Early Diagenetic Processes Research Articles

High-Resolution Reconstruction of Oxidation–Reduction Conditions: Raman Spectroscopy and μ-XRF Analysis of Manganese Nodule and Crust on Tabletop of Western Pacific Magellan Seamounts

Ferromanganese (Fe-Mn) deposits are widely used in paleoenvironmental reconstructions owing to their mineralogical and geochemical properties. We analyzed Fe-Mn deposits using micro-X-ray fluorescence and Raman spectroscopy to study the paleo-ocean environment. Samples were collected from the OSM-XX seamount in the western Pacific. The Fe-Mn crust was divided into three parts: phosphatized, massive non-phosphatized, and porous non-phosphatized. Vernadite was identified in all layers. Furthermore, in the nodule, high values of Mn, Ni, and Cu were observed near the nucleus, with vernadite and todorokite, and these values decreased outward. A high Mn/Fe ratio near the nucleus indicates early diagenetic processes. Formation of Fe-Mn nodules began around 19–16 Ma, and this period corresponded to a minor phosphatization event and persistent reducing conditions. From 11–10 Ma, the Mn/Fe and Co/Mn ratios decreased due to the formation of a western Pacific warm pool during this period. Subsequently, with the opening of the Indonesian seaway and global cooling, the Mn/Fe and Co/Mn ratios in the Fe-Mn deposits increased again. The comparative analysis of variations in Mn/Fe ratio and vernadite crystallinity in the Fe-Mn deposits confirmed that it is possible to reconstruct paleo-productivity and redox condition changes in the western Pacific Magellan Seamount.

Diatom silicon isotope ratios in Quaternary research: Where do we stand?

Silicon stable isotope ratios (expressed as δ30Si) in biogenic silica have been widely used as a proxy for past and present biogeochemical cycling in both marine and lacustrine settings, in particular for nutrient utilization reconstructions. Yet an analysis of publication trends suggests a significant decline in the application of δ30Si to Quaternary science questions in the last five years. At the same time as δ30Si proxy applications have decreased, we are learning more about its complexities: an expanding body of work is highlighting biases, caveats or complications involved in the application of δ30Si-based approaches to the sediment record. These include the demonstration of species-specific silicon isotope fractionation factors (i.e. ‘vital effects’) or the potential for Fe or other trace metals to influence silicon isotope fractionation. Others have inferred the potential of biogenic silica dissolution to alter an initial δ30Si value, or questioned the preservation of the initial δ30Si through early diagenetic processes more generally. Another challenge receiving more attention is centered around deconvolving a δ30Si-value into a signal reflecting biological productivity and a signal reflecting changes in the δ30Si of dissolved silicon driven by whole-system and/or circulation changes. Finally, a number of studies focus on analytical difficulties, especially during sample preparation related to achieving and demonstrating a contaminant free biogenic silica. These challenges lead us to posit that the Quaternary science community is moving away from silicon isotope proxies because they are losing confidence in their reliability and usefulness. Here, focusing on the diatoms – the dominant biosilicifiers in both lakes and the ocean – we synthesize progress in understanding nuances and caveats of δ30Si-based proxies in order to answer whether the fall-off in δ30Si-based Quaternary research is warranted. We suggest that with some simple steps that can be readily implemented, and with the closing of key knowledge gaps, there is no reason to believe silicon isotopes do not have a promising future in the Quaternary sciences.

Study of the Geological Context of the 7th–6th Century BC Phoenician Era Shipwreck “Mazarrón 2” (Murcia, Spain)

The Mazarrón 2 shipwreck was found in 1994 on the beach of Playa de la Isla (Mazarrón, Murcia, Spain). This finding is extremely important because the boat and its lead cargo were still in a reasonable conservation state and, therefore, provided new data on naval construction, commercial goods, navigation routes, and the relationships between the Phoenicians and the local population in the 7th–6th century BC. Currently, the shipwreck remains underwater, protected by a metallic coffer. In the last 2 years, a Preliminary Studies Project has been carried out, supported by national and regional public institutions. This research aims to know the shipwreck’s conservation state and to determine the extraction and conservation methods at the Museo Nacional de Arqueología Subacuática ARQVA (Cartagena, Spain), where the conservation and restoration treatment will be conducted. The sampling strategy and analytical study included not only wood and other materials from the shipwreck and its cargo but also the seawater and the seabed materials in the vicinity of the shipwreck. This paper presents the results of the geochemical study of the archeological site. The applied methodology included physico-chemical tests, X-ray diffraction, optical microscopy, FTIR spectroscopy, field-emission scanning electron microscopy coupled with X-ray microanalysis, and X-ray microscopy. The results indicated that, despite the wreck being buried at a shallow depth (less than 50 cm) in a marine environment with a water column of 2–2.5 m, influenced by complex coastal dynamics that favor an oxic environment, early diagenetic processes like the formation of pyrite framboids are particularly intense in the pores and internal channels of the wreck’s wood, where a different dysoxic–anoxic environment prevails. These processes have been the main mechanisms to have affected the wreck and are related to the biogeochemistry of sediments. The sediments have been confirmed to be closely related to the geological context of the Mazarrón region. The conducted study found no significant evidence of pollution due to the lead cargo.

Investigating the impact of paleoclimatic conditions and diagenesis on the genesis of Permian Continental Red Beds: A case study from the Bohemian Massif, Czechia

The processes responsible for reddening of Continental Red Beds (CRBs) and the relationship between color variation and paleoenvironmental conditions are presented focusing on a comprehensive multi-proxy study of Permian sediments in the Bohemian Massif, Czechia. The investigation incorporates facies analysis, quantitative color assessment using diffuse Vis-spectral reflectance (DRS), optical and electron microprobe microscopy, bulk-rock (XRF and XRD), and in-situ geochemistry (laser-ablation ICP-MS). Results indicate a progressive drying trend from the Cisuralian to Guadalupian series in studied continental red sediments. Different facies indicate the change of the sedimentary environment from a deep lacustrine environment (lower part of Rudník Member, Cisuralian) to a fluvial floodplain and eolian environment (Trutnov Formation, Guadalupian). Examination of the three major categories (white, gray–green and red sediments) identified in the studied continental red beds indicates that diagenetic alteration of clay minerals and biotite was the main source of iron fueling the growth of hematite responsible for their red color. Early diagenetic processes and paleoenvironmental conditions, particularly the oxidizing or reducing conditions play a key role in the red sediment formation. It is suggested that later diagenetic stages are incapable of coloring non-red, iron-rich sediments formed in deep anoxic lacustrine environments. Microbial activities and reducing fluids have been identified as the main factors in the formation of gray–green sediments forming distinct reduction zones. The reduction spots formed during the early stages of diagenesis (eodiagenesis), and they were likely never red. In contrast, reduction strips, initially exhibiting a red hue, underwent a color change during more advanced stages of diagenesis (mesodiagenesis).

Sediment colour as a marker of syn-depositional and early diagenetic processes in glaciofluvial sediments

The continental red beds, encompassing a broad spectrum of genetic types, can serve as important palaeoclimatological and palaeoenvironmental archives. The origin of sediment colouration is a complex process involving abiotic processes (e.g., breakdown of original and precipitation of newly-formed minerals), which, together with biogenic factors, lead to mobilisation of redox-sensitive elements and precipitation of Fe- and Mn-(oxy)hydroxides. There is still discussion about the interpretation of the continental red beds as palaeoclimatological archives or the colour patterns reflecting ancient redox gradients. The layers coloured in red, yellow or black can be found in the Quaternary glaciofluvial sediments in the Czech Republic. We are using a combination of field study with multi-spectral petrophysical, petrological and geochemical analyses to investigate the mechanism and timing of the origin of coloured coatings in glaciofluvial sediments, and causes of cycling of Fe, Mn, and other redox sensitive elements and isotopes. The results show that both syn-depositional and early diagenetic processes are responsible for the origin of colour patterns in the Quaternary glaciofluvial sediments. The stable molybdenum and iron isotope fractionation is primarily driven by the breakdown of the primary Fe and Mn-bearing silicates and the precipitation of the secondary Fe- and Mn-(oxy)hydroxides, such as goethite and birnessite. These precipitates are the main components of colouring coatings on the detrital grains and are able to bind other redox-sensitive elements, such as Cu, As, Mo, U, and REEs. The textural patterns and geochemistry suggest that the colour features were developed in the time range of decades to several thousand years after the deposition along ancient subsurface redox gradients due to changes in groundwater flow associated with primary lithology, glaciotectonics, and seasonal changes in the active layer of permafrost. The coatings show morphological features (rods, botryoids) and geochemical signatures (e.g., increased P contents) suggesting involvement of microorganisms to their precipitation.

The adsorption of cerium on synthetic δ-MnO2: Implications for Ce uptake behavior of hydrogenetic and early diagenetic ferromanganese nodules from the Western Pacific

Cerium (Ce) anomalies can be used to distinguish diagenetic and hydrogenetic nodules, making them an important discriminator for the genesis of marine ferromanganese nodules. To understand the enrichment and adsorption mechanisms of Ce in different types of ferromanganese nodules, we conducted mineralogical and geochemical studies on ferromanganese nodule layers formed through both hydrogenetic and early diagenetic processes as well as adsorption experiments on synthetic δ-MnO2 to monitor the Ce uptake during the different processes. The major and trace element contents of natural ferromanganese nodule layers were investigated by SEM, EPMA and LA-ICP-MS analysis. The marine nodule studied in this study consisted of a core of fish tooth and a rim that could be divided into the hydrogenetic (type I) and early diagenetic (type II) layers based on their mineralogy and Mn/Fe ratios. The Mn oxide mineral assemblage is composed of todorokite, buserite, birnessite, and vernadite (δ-MnO2) and occurred in both type I and II layers. The type I layer has laminated structures with a low Mn/Fe ratio (1.1–3.2; averaging at 1.7), and low Cu, Ni and Mg contents consistent with a hydrogenetic genesis. The type II layer has a columnar and stromatolitic structure with a high Mn/Fe ratio (5.1–54.0; averaging at 23.3) and high Cu, Ni and Mg contents that are similar to early diagenetic nodules. The ΣREE contents in type I and type II layers are 1405–3506 ppm (averaging at 2091 ppm) and 199–1232 ppm (averaging at 674 ppm), respectively, indicating that the REE is enriched in the hydrogenetic type I layers. Strong positive Ce anomalies are present type I layers ranging from 1.2 to 2.5 (averaging 1.9), but only slightly positive are seen in type II ranging from 0.4 to 2.4 (averaging at 1.0). Synthetic experiments to monitor the Ce uptake process show that Ce can be adsorbed onto δ-MnO2 with the XRD and FTIR patterns suggesting that the structure of δ-MnO2 did not change significantly, consistent with Ce behavior in hydrogenetic nodules. The results suggest that Ce is predominantly concentrated in hydrogenetic nodules in an oxic environment, whereas in the early diagenetic layer, there is less oxidation and fixation of Ce due to the suboxic conditions. Our findings are consistent with Ce anomalies in marine Fe-Mn nodules being the result of Mn oxide oxidation adsorption and then fixation (oxidation) after adsorption.

Extracting paleo-weathering signals from authigenic phases in lake sediments: A case-study of Lake Baikal

Authigenic phases in lake sediments hold the potential to record changes in the isotope compositions of past lake water, potentially yielding valuable information on secular changes in continental weathering patterns and rates, including over past glacial cycles.Here, different leaching approaches are investigated with the aim of extracting Sr, Nd, Pb, and Be hosted in authigenic Fe-Mn (oxy)hydroxide sediment phases for precise isotope measurements. Elemental Al/Mn, Ca/Mn, and P/Mn ratios obtained via a mild reductive leach agree well with the composition of marine authigenic Fe-Mn phases. For core top sediments, leached Sr isotope compositions obtained with this leach agree well with the composition of lake water. The Be and Nd isotope compositions of core top leachates are consistent with the spatial variability observed in the water column. Due to high concentrations in Fe-Mn phases, leachate compositions are dominated by authigenic Be, Sr, Nd, and Pb, even in cases when as much as 40% of leached phases (by mass) are non-authigenic. These lines of evidence suggest that the mild reductive leach successfully extracts the modern lake isotope composition from modern sediments in terms of the isotope systems investigated. We further show that the leaching method is also reliable for older sediments (<340 ka): leached paleo-Sr isotope compositions are consistent between the current and previous interglacial periods, as well as for glacial periods. This suggests that reconstructed water isotope compositions are not affected by early diagenetic processes, instead reflecting environmental factors around the lake that determine the composition of weathering fluxes. Although more difficult to assess for Be, Nd, and Pb due to the heterogeneity of modern lake water, the data we present indicate the overall robustness of the leaching approach.These promising results open up lakes as archives for paleo-weathering reconstructions. Given that marine reconstructions face some important limitations (e.g., integration of basin-wide changes in weathering processes, long residence times for Sr, etc.Fe), lake records provide an avenue to improve our understanding of changes in regional weathering processes over glacial-interglacial timescales. The mild reductive leach used here may also be useful for meteoric Be studies in marine shelf settings, to prevent leaching of terrestrial sedimentary Fe-Mn oxy(hydroxide) phases.

Influence of goethite nanophase on rare-earth element patterns and enrichment in marine phosphates during early diagenesis

Although rare-earth elements (REEs) in authigenic phosphates and carbonates derived from marine sediments are potential proxies (e.g., REE patterns) for reconstructing paleoenvironmental conditions, the REE patterns appear to be inconsistent. Some marine authigenic phosphates show a “bell-shaped” pattern with an enrichment of the middle REEs (MREEs; NdHo), while others exhibit a “modern seawater-like” pattern characterized by a strong depletion in cerium and an enrichment in heavy REEs (ErLu, Y, and Sc). Although the origin of the “bell-shaped” pattern in phosphates has been extensively debated, the evidence is often ambiguous; therefore, the origin of the pattern remains unclear. In this study, we investigate the microscale and nanoscale mineralogical and geochemical characteristics of the REE-enriched Early Cambrian phosphorites. In situ elemental analyses reveal that the codeposited phosphates (“bell-shaped” REE pattern) and carbonates (“modern seawater-like” pattern) have different REE patterns. A microscale investigation shows that phosphate grains contain some dispersed goethite nanophase, and a nanoscale investigation using transmission electron microscopy coupled with electron energy-loss spectroscopy shows that Fe2+ is distributed along the rim of the goethite nanophase, indicating that the goethite were reduced. These findings suggest that the REE pattern and concentration in phosphates could have been influenced by the release of REEs during the reduction of Fe (oxyhydr)oxide in the early diagenetic process before the final deposition. Although additional evidence is required, our results are important for understanding the effects of Fe redox cycling on the REE pattern and enrichment in marine authigenic phosphates. In addition, our results suggest that compared with authigenic phosphates, authigenic carbonates would provide a more reliable reconstruction of paleoenvironmental conditions.

Early Diagenetic Processes in the Sediments of the Krka River Estuary

To study the processes that govern the post-depositional mobility of metals in the estuarine sediment, five sediment cores were sampled in the Krka River estuary (Croatia). The obtained concentration ranges in the pore water were 0.057–49.7 μM for Fe, 0.310–100 μM for Mn, 0.068–26.8 nM for Co, 0.126–153 nM for Cu, 11.5–2793 nM for Zn, 0.222–31.3 nM for Pb, 4.09–59.4 nM for U, 38.8–2228 nM for Mo, and 0.065–2.29 nM for As. The vertical distribution of metals in the dissolved and solid fraction of the sediment, coupled with other diagenetic tracers (e.g., dissolved sulphide), demonstrate the importance of early diagenetic reactions, in particular Fe and Mn oxyhydroxide and sulphate reduction, for the cycling of metals in the sediment. The redox zonation in the sediment was compressed, and the suboxic zone occurs immediately below the sediment–water interface. The estimated benthic fluxes in the estuary were 5220 kg y−1 for Fe, 27,100 kg y−1 for Mn, 6.00 kg y−1 for Co, 20.5 kg y−1 for Cu, 5.16 kg y−1 for Pb, 111 kg y−1 for Mo, and 87.3 kg y−1 for As. The riverine input was more important than the benthic flux, except in the case of Mn and Fe.

Spatial Distribution, Ecological Risk Assessment, and Source Identification of Metals in Sediments of the Krka River Estuary (Croatia)

To evaluate the level of contamination and predict the potential toxicity risk, selected metal concentrations (Cd, Pb, Cr, Mn, Co, Ni, Cu, Zn, and As) were determined in 40 surface sediment samples from the stratified karstic Krka River estuary (Croatia). In addition, diffusive gradients in thin films (DGT) probes were deployed in situ to understand the mobilization mechanisms and bioavailability of metals in the sediment. The results show significant spatial differences between the upper and lower estuary, with the latter being more affected by anthropogenic pollution. The pollution assessment using the enrichment factor (EF), the geoaccumulation index (Igeo), and the pollution load index (PLI) showed a strong enrichment of metals in the lower part of the estuary, especially of Mn, Cu, Zn, Pb, and As. The statistical analysis (PCA) revealed the former ferromanganese factory and the port as major sources of pollution in the area. Nickel, Co, and Cr, although slightly elevated, may be attributed to the natural origin. The metal mobility in the estuarine sediment was primarily governed by early diagenetic processes (aerobic organic matter mineralization, Fe and Mn oxyhydroxide reduction), which caused the release of metals from the sediment into the pore water and subsequently into the overlying water column.

Extracting Meaningful Environmental and Age Information From a c. 2.4–2.2 Ga Peritidal Phosphorite: The Turee Creek Group, Western Australia

AbstractPhosphorites can record oceanic conditions during their deposition, but the faithful retention of primary information in Paleoproterozoic deposits can be mitigated by post‐depositional processes. Here, we examine a peritidal phosphorite within a microbialite reef complex in the 2.4–2.2 Ga Turee Creek Group in Western Australia to assess the environmental information retained. Field mapping and petrography distinguishes between authigenic and locally transported phosphorite fragments, each of which contains unique information regarding the deposit. Elemental mapping and laser‐ablation analyses differentiate the impact of depositional versus early diagenetic versus metamorphic processes within these fragments. Samples within a near‐shore pebble conglomerate have mixed riverine‐oceanic signals and lack cerium anomalies, consistent with the depositional environment. Clasts from off‐shore peloidal grainstone beds retain “hat‐shaped” patterns with small negative cerium anomalies, reflective of transport and redeposition within potentially oxic seawater. U‐Pb isotopic dates range from ∼1.8 to 2.3 Ga and are generally uncorrelated with rare earth element and yttrium data. The youngest date (∼1.8 Ga) is associated with recrystallized apatite, with concave down, middle rare earth element enriched patterns. A potential depositional age, ∼2.3 Ga, is associated with massive apatite in a chert‐rich clast that has rare earth element patterns reflective of riverine‐oceanic signals. Overall, the peritidal system in the reef was dynamic, with potentially oxic seawater that had a strong riverine influence. Local recycling and reworking, early diagenesis, and later orogenic events impacted the preserved geochemical signals and together show that spatially resolved geochronological and geochemical data are ideal for interpreting ancient phosphorites.

Searching for microbial contribution to micritization of shallow marine sediments.

Micritization is an early diagenetic process that gradually alters primary carbonate sediment grains through cycles of dissolution and reprecipitation of microcrystalline calcite (micrite). Typically observed in modern shallow marine environments, micritic textures have been recognized as a vital component of storage and flow in hydrocarbon reservoirs, attracting scientific and economic interests. Due to their endolithic activity and the ability to promote nucleation and reprecipitation of carbonate crystals, microorganisms have progressively been shown to be key players in micritization, placing this process at the boundary between the geological and biological realms. However, published research is mainly based on geological and geochemical perspectives, overlooking the biological and ecological complexity of microbial communities of micritized sediments. In this paper, we summarize the state-of-the-art and research gaps in micritization from a microbial ecology perspective. Since a growing body of literature successfully applies in vitro and in situ 'fishing' strategies to unveil elusive microorganisms and expand our knowledge of microbial diversity, we encourage their application to the study of micritization. By employing these strategies in micritization research, we advocate promoting an interdisciplinary approach/perspective to identify and understand the overlooked/neglected microbial players and key pathways governing this phenomenon and their ecology/dynamics, reshaping our comprehension of this process.

Sulphide petrology and ore genesis of the stratabound Sheep Creek sediment-hosted Zn–Pb–Ag–Sn prospect, and U–Pb zircon constraints on the timing of magmatism in the northern Alaska Range

The Sheep Creek prospect is a stratabound Zn–Pb–Ag–Sn massive sulfide occurrence in the Bonnifield mining district, northern Alaska Range. The prospect is within a quartz–sericite–graphite–chlorite schist unit associated with Devonian carbonaceous and siliceous metasedimentary rocks. Volcanogenic massive sulfide (VMS) deposits in the district are hosted in felsic metavolcanic rocks (362 ± 2 Ma) associated with siliciclastic and carbonaceous sedimentary rocks that overlie the stratigraphic sequence hosting the Sheep Creek prospect. Felsic metaigneous rocks in underlying units are 372 ± 4 to 366 ± 4 Ma. Sheep Creek is atypical of the other sulfide deposits in the district in (1) having Sn grades up to 1.2%; (2) being contained in fine-grained, quartz-rich rocks and quartz–pebble conglomerate that likely originated as chert and chert-clast sediment, respectively; and (3) showing minimal evidence of volcanic components in the host rocks. Comparison of immobile trace-element proportions for graphitic and siliceous rocks from the Sheep Creek area with those for argillite associated with the Bonnifield VMS deposits indicates a continental volcanic-arc provenance for the former and a within-plate and passive margin provenance for the latter. In contrast to previously published interpretations, our data analysis supports a clastic-dominated (CD) rather than a VMS affinity for the Sheep Creek prospect. In our model, Zn–Pb–Ag–Sn mineralization formed by syngenetic or early diagenetic processes on or beneath the seafloor, possibly in the shallow-water environment of an outer continental shelf setting. Potential analogues are the Paleozoic CD deposits in the Canadian Selwyn Basin outboard of the Laurentian continental margin.

The staged growth of bedding-parallel fibrous calcite veins, from synsedimentary period to oil-generative window

Bedding-parallel fibrous calcite veins are commonly found in low-permeability strata rich in organic matter from various geological periods. Despite their importance in examining the fluid flow in sedimentary basins, dynamics of crustal permeability and mineralization, microbial mineralization, detection of early life signatures, and hydrocarbon production and accumulation, the growth processes of these veins remain inconclusive. Here we show a two-stage model to explain the growth of bedding-parallel fibrous calcite veins, by analyzing a wide range of organic geochemical, elemental, isotopic, and petrographic data from both new and published sources. This model consists of the early diagenetic stage and oil-generative window, with a focus on samples from the middle Eocene strata of the Bohai Bay Basin and the Cavan Bluff Limestone. This study emphasizes the crucial role of early diagenetic processes, such as anaerobic microbial activities, in initiating the formation of bedding-parallel fibrous calcite veins at the sediment-water interface. Additionally, the further modification and secondary enlargement of these veins by fluids generated from hydrocarbon production and clay evolution are described. While this model may not be applicable to all bedding-parallel fibrous calcite veins, it provided valuable insights and helped reconcile seemingly contradictory findings regarding these veins. Furthermore, the study indicates the potential of bedding-parallel fibrous calcite veins in paleoenvironmental reconstruction and emphasizes the significance of reevaluating certain existing knowledge within the fields that employ these veins as specimens.

Rock physics diagnostics to characterize early diagenetic processes in hemipelagic calcareous ooze in the northern South China Sea margin

Rock physics diagnostics to characterize early diagenetic processes in hemipelagic calcareous ooze in the northern South China Sea margin

Early marine carbonate cementation in a relict shelf-edge coral reef North of Miami, Florida: Pseudo-coupled depositional and diagenetic modeling

Carbonate depositional and early diagenetic processes overlap in time because of the high chemical reactivity of calcite. Previous studies have modeled early diagenesis in a static depositional framework. They followed a rule-based modeling approach instead of applying rigorous thermodynamics and reaction kinetics.This study has developed a pseudo-coupled approach based on a dynamic depositional framework and reactive transport modeling for diagenesis. It has been tested for the “Pompano” reef north of Miami, Florida. The model includes five reef parasequences deposited over 9.0 kyr with five facies zones. After deposition of the first parasequence, diagenetic processes are modeled. The resulting framework forms the starting condition for depositing the next parasequence. Subsequently, its diagenetic overprint and the continued overprint in the underlying parasequence(s) are modeled. These workflow steps are repeated until all five parasequences are covered.The results show the spatial and temporal development of calcite cementation and porosity distribution. During the reef catch-up phase, cement mainly developed at the depositional surface (up to 10% of the total sediment volume). During the keep-up phase, cement abundance increases to a maximum value of ∼17%. After the reef's demise, cement forms a crust at the sediment-water interface with up to 38% of the total sediment volume. In general, controlling factors of cement distribution include facies-specific flow velocities, reef facies, relative sea-level changes, depositional gaps, and seawater salinity.The modeling results of this study are well aligned with the actual cement and porosity distribution in the Pompano reef and with other sub-recent and ancient examples described in the literature. Pseudo-coupled depositional-diagenetic modeling represents a suitable approach for quantitative porosity prediction in comparable depositional and diagenetic settings. It reduces uncertainties in prediction at inter-well to prospect scale for oil and gas exploration, geothermal exploration, and subsurface storage of CO2.

Early diagenetic REE migration from Fe-Mn nodules to fish teeth in deep sea sediments

In deep sea sediments, rare earth elements and yttrium (REYs) are predominantly carried by bioapatite and Fe-Mn (oxyhydr)oxides. According to recent studies, REYs can migrate into bioapatite after the dissolution of Fe-Mn (oxyhydr)oxides. However, the REY migration mechanism from Fe-Mn (oxyhydr)oxides to bioapatite are still unclear. Here, we integrated in situ trace element and Nd isotope analyses to elucidate the geochemical characteristics of fish tooth-bearing Fe-Mn nodules from the Northwest Pacific Ocean. Our Fe-Mn nodule samples can be classified into different morphological and geochemical types of the different periods in early diagenesis: (I) completely overgrown around bioapatite; II) overgrown around half of the bioapatite. Type I nodules grow around a bioapatite core, which has high LaN/SmN (0.41–0.50, avg. 0.46) and LaN/YbN (0.49–0.90, avg. 0.62). The ΣREY content is non-uniform in the two bioapatite types (WP-01 & WP-02) in Type I nodules, i.e., 475–2150 ppm and 272–431 ppm, respectively. The REY results show that the bioapatite is mainly adsorbed REY in early diagenesis. Type II nodules were covered both inside and at the tip of the tooth. The LaN/SmN (0.34–0.38, avg. 0.36) and LaN/YbN (0.26–0.61, avg. 0.37) ratios of the bioapatite samples are relatively low. Meanwhile, the ΣREY content is very uneven (229–3521 ppm). The REY data show that the bioapatite is mainly substituted during strong early diagenesis. The intercrystalline pores in some authigenic apatite may have closed upon recrystallization, causing REY redistribution and fractionation. The Y/Ho vs. ΣREE/Th plot shows a higher REY proportion from pore water in type II nodules than in type I ones. The widespread distribution of high Mn content and the gradual decrease of REY content from the nodule rim to core reflect the transport of REY from dissolved Fe-Mn (oxyhydr)oxides to bioapatite during early diagenesis under suboxic conditions. From type I to type II nodules, the mean εNd value of bioapatite increases from −6.69 to −5.56. The comparison of εNd values between REY-rich mud and bioapatite indicate that the REYs were derived from the bottom water and pore water in deep sea sediments. Our findings comprehensively document the transport and enrichment mechanisms of REY in early diagenetic processes from Fe-Mn (oxyhydr)oxides to bioapatite, which we argued to be relatively localized.

The marine redox evolution and the formation model for the early Cambrian Gongxi-Tianzhu barite deposits in the South China Block

Late Ediacaran to early Cambrian is marked as a vital ore-formation interval of the Earth’s history, particularly for the bedded barite deposits hosted in cherts and shales. Although plenty of work has been carried out, controversies still exist, such as how the marine paleoenvironment changed in this critical interval, and where the origin of ore-formation materials (i.e., barium ions) was. To address these questions, here, we conducted systematic geochemical research on Gongxi-Tianzhu barite deposits in the South China Block, using redox proxies (MoEF-UEF, Mo-TOC, U-TOC patterns, and elemental ratios), REY patterns, and Sr isotopes. Redox proxies were used to reconstruct the paleoenvironment evolution in the Gongxi-Tianzhu region during the early Cambrian interval. Redox proxy results revealed that the bottom water was oxygen-depleted during most of the depositional time of the Niutitang Formation. The bedded and nodular barites in the Niutitang Formation were formed in the Sulfate-Methane Transition Zone (SMTZ) during the synsedimentary and early diagenetic processes. Formation of the barite ores depended greatly on the redox state variation of the bottom water and the barium remobilization in the sediments. The ore-formation event ceased when the supply of oxygen and sulfate from the upper water stopped, and the pre-stored Ba ions in the anoxic bottom seawater were exhausted and the SMTZ rose back into the water again. REY patterns and 87Sr/86Sr values recorded coeval seawater signals without hydrothermal activities during the studied interval. Based on the elemental and isotopic evidence, a three-stage redox-diagenetic model was established for the formation of the barite deposits in South China.

Critical assessment of U, Ba and Ni as redox and productivity proxies in organic-rich sediments underneath dynamic, highly productive waters

Sediments of the continental shelf anoxic zones of the Benguela upwelling system (BUS) and the Peruvian upwelling system are present-day hotspots of trace element accumulation. However, contribution of the lithogenic trace element fraction and early diagenetic transformation processes are poorly constrained. The identification of source and accumulation mechanisms is necessary for the validation of trace elements as proxies for productivity and redox cycling, notably in highly dynamic upwelling systems such as the BUS. Here, we analyzed redox- and biosensitive elements (U, Ba, Ni), lithogenic tracers (Al, Ti, Zr), total organic carbon (TOC) and P in eleven short sediment cores from the Namibian shelf (ca. 22–25°S) as well as grain size fractionated hinterland samples from the Tsauchab Valley at Sossusvlei (∼25°S). These samples help to constrain the lithogenic trace element contributions, a prerequisite for a realistic interpretation of marine authigenic trace element data. Our findings corroborate previous findings that Zr is a sensitive tracer of the coarse fraction in marine sediment for dust input and/or sediment reworking. Hence, the combined analysis of the coarse fraction (Zr), organic matter, and P enrichments (TOC/P) differentiates between a calm, organic matter-rich central shelf environment and a more energetic phosphorite-rich southern shelf environment. A significant correlation of U with P in cores from the southern shelf corroborates previous findings of U incorporation into apatite, the initial formation of which requires oscillating oxic to sulfidic redox conditions. Non-apatite associated U dominates in the cores from the central shelf, where it is only enriched in the buried, anoxic parts of the sediment. This also supports oscillating oxic to sulfidic redox conditions in surface sediment, where U may be recycled. Hence, U accumulates either (i) in apatite under oscillating oxic to sulfidic conditions or (ii) in buried anoxic sediment sections. This strongly questions the use of U as indicator of suboxic conditions but rather anoxic conditions. While lithogenic fractions of U were negligible, the lithogenic fractions of Ba and Ni were found to be elevated. The calculation of authigenic Ba when accounting for lithogenic Ba from the Sossusvlei fine fractions gives more realistic authigenic Ba values. The high Ba enrichment in the BUS is interpreted as uptake of Ba by diatoms and/or nucleation of barite in P-rich diatom remains, as suggested previously. Given the shallow water depth of the cores, barite formation must already take place in subsurface waters (<50 m water depth) as opposed to previous suggesting greater water depths. The lithogenic background of Ni strongly varies from 23°S to 25°S based on Sossusvlei data and the literature. When authigenic Ni contents are calculated accordingly and plotted versus TOC, more systematic trends are seen (compared to total Ni versus TOC). Essentially all cores show an increase in the authigenic Ni/TOC ratio with sediment depth suggesting better preservation and retention of Ni as compared to TOC consistent with previous observations in sediments from the Peruvian upwelling system. This trend corroborates the use of Ni as a productivity indicator for upwelling sediments.

Impact of depositional and diagenetic controls on reservoir quality of syn-rift sedimentary systems: An example from Oligocene-Miocene Al Wajh Formation, northwest Saudi Arabia

Tertiary, syn-rift clastic reservoirs offer a unique opportunity to investigate the pivotal role of depositional and early diagenetic controls on reservoir quality. The Al Wajh Formation is a vital exploration target for petroleum in the Red Sea, and is characterized by early, near-surface diagenetic signatures. An integrated petrographic-mineralogical study is conducted to assess the role of depositional factors (e.g., sand grain size and clay matrix) and early diagenetic overprints on reservoir quality. The Al Wajh sandstones are primarily subarkose and lithic arkose, deposited in alluvial fan, braided fluvial, and nearshore environments. Braided fluvial sandstones of the formation have the best quality reservoirs (average porosity: 23.2 %; average permeability: 3025 mD) because of medium to coarse grain size and small proportion of clay matrix, whereas the nearshore sandstones form reservoirs of far lower quality (average porosity: 12.6 %; average permeability: 486 mD) owing to predominantly finer grain size and higher proportion of clay matrix. Clay volume between 10 and 20 % generally reduces the reservoir properties to <10 % porosity and 100 mD permeability. Compaction and grain dissolution are the major near-surface, early diagenetic processes that have strongly affected the sandstones reservoir quality. High mechanical compaction has been recorded in sandstones characterized by abundant matrix content and ductile rock fragments. Dissolution of labile grains (e.g., feldspars) has created secondary, intragranular porosity of up to 13.5 % (average 4.7 %). Kaolinite is the primary authigenic pore-filling clay in the continental units of the formation, whereas detrital and authigenic smectites are the key pore-filling clays in the nearshore units of the formation. Grain-coating smectite (up to 18.7 %; average: 7.1 %) was mainly emplaced through mechanical infiltration and has the potential for inhibiting quartz cementation should deep burial occur. The findings of the study can be utilized for modelling reservoir quality in the subsurface analogue of the Al Wajh Formation in the Red Sea or elsewhere, thereby improving reservoir quality prediction.