Marine Carbonate Sediments Research Articles

Isotopic and Sedimentologic Proxies of Palaeoexposure Events and Oceanic Anoxic Event 2 (OAE2) in the Cenomanian–Turonian Neritic Carbonates (the Sarvak Formation) in the Abadan Plain, Zagros Basin, Iran

ABSTRACTThe shallow marine carbonate deposits of the Sarvak Formation have been deposited in an active tectonic setting under warm and humid climatic conditions during the Cenomanian–Turonian (C–T). The focus of this study is on the sedimentological and geochemical analysis of this formation in the Abadan Plain, Zagros Basin. Petrographic studies led to the identification of five microfacies deposited in the restricted lagoon, tidal flat, reef, shoal and open marine environments. They indicate deposition of the Sarvak Formation on a homoclinal ramp–like carbonate platform. Sequence stratigraphy studies have led to the identification of two third‐order sequences named Cenomanian sequence (DSS‐1) and Turonian sequence (DSS‐2), along with six fourth‐order sequences. The upper boundary of DSS‐1, known as the C–T disconformity (CT‐ES), is subjected to meteoric diagenetic processes, as evidenced by meteoric dissolution (karstification), collapsed brecciation and the development of palaeosols. The upper SB of DSS‐2 is marked by the mid‐Turonian disconformity (mT‐ES), characterised by silicification, brecciation, meteoric dissolution and iron oxide staining of core samples. The significant decreases in δ18Ocarb and δ13Ccarb values indicate a strong effect of meteoric diagenesis beneath the palaeoexposure surfaces. The calculation of sea surface temperatures (SSTs) based on the δ18Ocarb values measured from the unaltered carbonates indicated that the average SST for the C–T is 31.8°C and 30.9°C in K‐01 and K‐02 wells, respectively. A decrease of about 1.5°C is measured during the C–T transition, which indicate a cooling trend of the Late Cretaceous in the Tethyan realm. The carbon isotopic pattern observed in the analysed sections shows correlation with previous studies conducted in the Tethyan region. Additionally, the isotopic composition indicative of Oceanic Anoxic Event 2 (OAE2) is identified around the C–T boundary. Nevertheless, the signature of OAE2 has been somewhat obscured by diagenetic processes associated with C–T palaeoexposure.

Carbon, iron and sulfur records of lacustrine paleo-environments during the middle Eocene in eastern China

It is widely recognized that anoxic conditions facilitate the preservation of organic carbon in marine sediments. However, the specific geological factors that lead to the development of such conditions in paleo-lakes are less well understood. Owing to their smaller size, paleolakes could experience more frequent and stronger changes in geochemical conditions than oceans. Such changes, such as volcanism, hydrothermal fluids, or ocean transgressions, can also strongly affect the lacustrine organic carbon burial thereby complicating sediment diagenesis record. Here, we used total organic carbon content (TOC), organic carbon isotope (δ13Corg), iron speciation, and pyrite sulfur isotope (δ34Spy) data to establish relationships between organic carbon preservation and anoxic conditions in fine-grained sediments from the middle Eocene lacustrine depositional environments from the Shahejie Formation of the Jiyang Depression, Bohai Bay Basin, eastern China. The results reveal TOC between 1 % and 10 %, highly-reactive iron to total iron ratios >0.38, and most TOC to total sulfur ratios exceeding 2. These data indicate that the organic-rich shales of the Shahejie Formation were formed as a result of high primary productivity during the warm and humid middle Eocene period, coupled with the efficient preservation of organic matter in anoxic bottom waters. Negative δ13Corg and δ34Spy excursions recorded in the Shahejie Formation indicate water column conditions to have been influenced by transient volcanic eruptions. Positive δ13Corg and negative δ34Spy excursions may have been caused by hydrothermal fluids input whereas δ34Spy values approaching 20 ‰ suggest frequent marine transgressions. In particular, despite potential inputs of S into the paleolake by volcanism, hydrothermal fluids, or marine transgressions, bacterial sulfate reduction efficiently depleted the sulfate pool to have created ferruginous geochemistry water conditions for the effective preservation of organic carbon in sediments. Our results establish a direct link between lacustrine shale geochemical signatures and geological phenomena that impact its sedimentation.

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.

Changes in the particulate organic carbon pump efficiency since the Last Glacial Maximum in the northwestern Philippine Sea

Changes in bottom and pore water oxygenation over glacial – interglacial cycles have influenced the ocean's capacity to store particulate organic carbon regardless of its source, either the marine primary productivity or the continent-to-ocean transfer of terrestrial organic matter. In the Philippine Sea, east off Taiwan, despite being currently oligotrophic, the enhanced East Asian Winter Monsoon during the Last Glacial Maximum and the Heinrich Stadial 1 might have altered the nutrient budget in surface waters by providing nutrients from the Eurasian loess dust and deepening the vertical mixing, bringing nutrients from the nutrient-enriched Kuroshio Current subsurface waters to the surface. During the deglaciation, previous studies also suggest an overall weakening of the marine biological pump during the Heinrich Stadial 1, and the rise in sea level is expected to have led to a global significant decline in the ability of continents to bury their particulate organic carbon in marine sediments. However, changes in the continent-ocean transfer of terrestrial organic matter and on the marine biological pump around Taiwan remain poorly constrained.In the present study, we have thus aimed to reconstruct bottom – pore water oxygenation, past marine primary productivity and continental-ocean transfer of terrestrial particulate organic carbon to the ocean since the end of the Last Glacial Maximum, in order to better constrain the ability of marine sediments to capture atmospheric carbon over the past 20,000 years. To this end, sediment core MD18-3523 has been recovered from a levee of Hoping Canyon, north-east of Taiwan, in the Ryukyu forearc basin. The reconstructions were made possible by the application of multivariate statistics and transfer functions on benthic foraminiferal assemblages, by the measurement of total organic carbon concentration and by the investigation of chemical element ratios obtained from X-ray fluorescence (XRF).We observed a transition across the Bølling–Allerød and the Younger Dryas from suboxic-dysoxic bottom – pore waters during Heinrich Stadial 1 to oxic-suboxic during the Holocene, and revealed an increase in marine primary productivity during Heinrich Stadial 1 in all probability due to intensified East Asian Winter Monsoon winds. We have also identified periods of enhanced terrestrial particulate organic carbon transfer to the ocean driven by short-lived extreme events, most likely typhoons, during the Bølling–Allerød, at the beginning of the Early Holocene and the end of the Late Holocene, when the typhoon dynamics affecting Taiwan were intensified. Overall, these findings suggest an enhanced marine biological pump during the Heinrich Stadial 1 and an efficient carbon turbidity pump during the Bølling–Allerød, the Early and Late Holocene, contrasting with the western coast of Taiwan.

Decoupling of carbon burial from productivity in the northeast Indian Ocean

The concentration of atmospheric carbon dioxide (CO2) is a crucial climate parameter as it has far-reaching implications on global temperature. The oceans are a significant sink for CO2. Biologically mediated carbon sequestration, in the form of both inorganic (CaCO3) and organic carbon (Corg), and its subsequent burial in marine sediments play a vital role in regulating atmospheric CO2. Understanding the distribution of carbon in marine sediments under different environments can help predict the fate of excess CO2 in the future. We studied the factors affecting the basin scale variation in carbon burial in the climatically sensitive northeast Indian Ocean, by using the data [CaCO3, Corg, Corg/Nitrogen, and isotopic ratio (δ13C, δ15N) of organic carbon] from a total of 718 surface sediments. The entire continental shelf and slope contain <10 % CaCO3. The highest CaCO3 is in the deepest parts of the central northeast Indian Ocean, away from the mouth of major river systems. Despite of the high productivity, the low Corg on the continental shelf is attributed to the well-oxygenated coarse-grained sediments. The lowest Corg is found in the well-oxygenated deeper central northeast Indian Ocean. Interestingly, the highest total carbon is in the deeper central and equatorial regions, far away from the highly productive marginal marine regions. Our study reveals that the grain size, terrigenous dilution, dissolved oxygen, and water masses strongly influence carbon accumulation in the northeast Indian Ocean, with only secondary influence of the productivity.

A modified dithionite reduction method for the quantification of iron-bound organic carbon in marine sediments

Iron-bound organic carbon (Fe-OC) plays a significant role in the global marine carbon cycle, facilitating the long-term accumulation and storage of organic carbon. However, the conventional method for quantifying Fe-OC, known as the citrate-bicarbonate-dithionite (CBD) method, has limitations in terms of its efficiency in extracting both Fe-OC and iron (Fe). Another CBD method, commonly used for Fe speciation analysis in paleoenvironmental reconstructions, has shown efficient and selective extraction of Fe oxides; however, its effectiveness in extracting Fe-OC remains uncertain. To evaluate the efficiency of the two CBD methods, synthetic samples spiked with organic acid/environmental organic matter‑iron (hydr)oxide coprecipitates and a marine sediment sample were subjected to extraction. The CBD approach for Fe speciation analysis at pH 4.8 on spiked samples demonstrated higher efficiency compared to the conventional CBD method, but not for samples of marine sediment. This result suggests that the synthetic Fe-OC in the spiked samples did not accurately represent the realistic state of Fe-OC in marine sediments. We found that the pH of the leaching solution during the CBD extraction significantly influenced the efficiency of the Fe-OC and Fe extraction. Our tests at pH 4.8, 5.5, 6.0, 6.5, and 7.0 revealed that lower pH enhanced the extraction of Fe, but hindered the release of Fe-OC. Our study revealed that the new CBD (pH 6.5) method resulted in approximately 30% higher yields of Fe-OC and Fe compared to the conventional CBD method, despite of significant variability in the Fe-OC data. The modified CBD (pH 6.5) method uses lower concentration of extraction reagent and reaction temperature, both of which is considered beneficial. Therefore, we suggest that the new CBD method (pH 6.5) is at least of similar efficiency as the conventional method, and can be employed alongside the established method to facilitate the evaluation of the role of Fe-OC in the marine carbon cycle.

Using stable isotopes in deciphering climate changes from travertine deposits: the case of the Lapis Tiburtinus succession (Acque Albule Basin, Tivoli, Central Italy)

Quaternary stable isotope records of marine and lacustrine carbonate deposits as well as speleothems were extensively studied to reconstruct global and regional climatic evolution. This study demonstrates how stable isotope records of travertine provide fundamental information about climate and the consequences of its evolution on groundwater level fluctuations. The deposition of the Lapis Tiburtinus travertine succession occurred during the Late Pleistocene (150–30 ka), coeval with the last activity of the Colli Albani volcanic complex. Two boreholes (Sn1 and Sn2) were drilled into the Acque Albule Basin (23 km E of Rome), crossing the entire Lapis Tiburtinus succession. The Sn1 borehole in the central part of the basin crosscuts a travertine succession of 62.1 m in thickness, while the Sn2 borehole in the southern part of the basin is characterized by a travertine succession 36.3 m in thickness. Carbon and oxygen stable isotope ratios were analysed on 118 samples (59 samples both for Sn1 and Sn2 boreholes) representative of the entire Lapis Tiburtinus travertine succession crossed by the boreholes. Values, measured and correlated in the two drilled boreholes, permitted determination of the sensitivity of the travertine depositional system to glacial and interglacial cycles, unravelling the complex oxygen and carbon cycle dynamic recorded in such sedimentary succession. Moreover, the results obtained correlated with available pollen curves of the Mediterranean area (from the Castiglione crater, 25 km E of Rome). Regional and global oxygen isotope continental and marine curves, calibrated with the stratigraphy of the Acque Albule Basin, and available U/Th dating allow the identification of at least three phases of the last interglacial (Marine Isotope Stage 5-MIS5). The carbon isotope record, compared with CO2 flux reconstructed and associated with the volcanic activity of the Colli Albani volcanic complex, instead shows an influence from groundwater level changes. In particular, positive shifts that occurred during arid phases are associated with a lower groundwater level and increased CO2 degassing, inducing a major fractionation effect on carbon isotopes. Instead, the negative shifts occurring during more humid periods indicate the inhibition of CO2 degassing and increase in pressure, attesting to a rise in groundwater level. In this view, travertine deposits, frequently studied to define the tectonic setting and activity of the area where they develop, can thus also be used as a tool to understand climate changes and groundwater variations apparent in their stable oxygen and carbon isotope signature.

The end of the Cretaceous: depositional palaeogeographical reconstruction of the Gulf of Mexico and adjacent areas just prior to the Chicxulub impact

Abstract Until recently, information about the end of the Cretaceous was based upon investigation of global outcrop sections. New subsurface drilling and characterization from well cores and logs in the Gulf of Mexico Basin have greatly illuminated the end Cretaceous event. However, the palaeogeography of the late Maastrichtian just prior to bolide impact is less well understood and is of great importance in terms of modelling the resulting distribution and composition of the Chicxulub impact material, as well as tsunami and seiche wave height. Here, we examine the Maastrichtian strata in the basin, synthesizing lithostratigraphy and chronostratigraphy, tectonic plate reconstructions, global and local sea level history, palaeoclimate and depositional systems. Our new Maastrichtian palaeogeographical reconstruction shows the basin prior to the Chicxulub impact at a time of globally high sea level, with widespread deposition of deepwater chalks and shallow marine carbonates and local siliciclastic shorelines fed by the nascent Cordilleran belt. Stratigraphic correlations of wells and outcrops illustrate the range of palaeoenvironments from coastal plain to deep marine. As much as 610 m (2000 ft) of Maastrichtian and Campanian section is mapped around the basin, reflecting accommodation provided by basin subsidence, salt deflation and palaeophysiography. A large thickness of carbonates accumulated in the basin centre, with steep shoreline to basin gradients particularly in Mexico. At the end of the Cretaceous, carbonate palaeoenvironments probably covered 96% of the Gulf of Mexico Basin, with less than 4% of the area likely occupied by siliciclastic systems, a distribution that evolved from the Early Cretaceous. Our maps thus explain dominance of carbonate breccia and chalks in K–Pg boundary units deposited over the basin sites proximal or distal to the Chicxulub impact crater. This also elucidates the large impedance contrast and high amplitude seismic response of the K–Pg boundary horizon, mappable over vast portions of the basin.

High-latitude platform carbonate deposition constitutes a climate conundrum at the terminal Mesoproterozoic

During the Mesoproterozoic Era, 1600 to 1000 million years ago, global climate was warm with very little evidence of glaciation. Substantial greenhouse warming would have been required to sustain this ice-free state given 5-18% lower solar luminosity. Paleomagnetic data reported here place voluminous ca. 1.2 Ga shallow marine carbonate deposits from India at an unexpectedly high latitude of around 70° from the equator. Previous studies noted high latitudes, but their implication was never considered. Here, we evaluate the temporal-latitudinal distribution of neritic carbonate deposits across the Proterozoic and identify similar deposits from North China that together with those from India are seemingly unique to the late Mesoproterozoic. A uniformitarian interpretation implies that this is cold-water carbonate deposition, but facies similarity with low-latitude neritic deposits rather suggests a hotter climate and elevated polar ocean temperatures of 15–20° or higher. This interpretation represents a climate conundrum that would require much greater greenhouse warming than documented for the Mesoproterozoic.

Bacteria-Driven Fossil Ecosystems as Paleoindicators of Active Continental Margins and the Role of Carbonate Sediment-Hosted Vents in Geodynamic Reconstructions

Continental rifting of the Tisza microplate started during the Late Jurassic and resulted in phreatic eruptions, peperite, and the construction of a volcanic edifice in the Early Cretaceous in the Mecsek Mountains (South Hungary). In the SE direction from the volcanic edifice at Zengővárkony, a shallow marine (depth 100–200 m) carbonate sediment hosted a vent environment, and iron ore deposition occurred at the end of the Valanginian to early Hauterivian, hosting a diverse, endemic fauna of approximately 60 species. The detailed mineralogical analysis of the transport conduits included Fe oxides (ferrihydrite, goethite, hematite, and magnetite), quartz, mixed carbonate, pyrite, feldspar, Fe-bearing clay minerals, apatite, sulfates (barite, gypsum, and jarosite), and native sulfur. Filamentous, microbially mediated microtextures with inner sequented, necklace-like spheric forms (diameter of 1 μm) and bacterial laminae are also observed inside decapod crustacean coprolites (Palaxius tetraochetarius) and in the rock matrix. This complex ecological and mineralogical analysis provided direct evidence for the presence of bacteria in fossil sediment-hosted vent (SHV) environments on the one hand and for the intimate connection between bacteria and decapod crustaceans in hydrothermal environments 135 Ma before. This observation completes the fossil food chain of chemosynthesis-based ecosystems, from primary producers to the top carnivores reported for the first time from this locality.

Unexpected carbon utilization activity of sulfate-reducing microorganisms in temperate and permanently cold marine sediments.

Significant amounts of organic carbon in marine sediments are degraded, coupled with sulfate reduction. However, the actual carbon and energy sources used in situ have not been assigned to each group of diverse sulfate-reducing microorganisms (SRM) owing to the microbial and environmental complexity in sediments. Here, we probed microbial activity in temperate and permanently cold marine sediments by using potential SRM substrates, organic fermentation products at very low concentrations (15-30μM), with RNA-based stable isotope probing. Unexpectedly, SRM were involved only to a minor degree in organic fermentation product mineralization, whereas metal-reducing microbes were dominant. Contrastingly, distinct SRM strongly assimilated 13C-DIC (dissolved inorganic carbon) with H2 as the electron donor. Our study suggests that canonical SRM prefer autotrophic lifestyle, with hydrogen as the electron donor, while metal-reducing microorganisms are involved in heterotrophic organic matter turnover, and thus regulate carbon fluxes in an unexpected way in marine sediments.

Influence of mineralized organic carbon in marine sediments on ecological heavy metal risk: Bohai Bay case study

The organic matter in sediments can mineralize over time, which impacts the morphology of the heavy metals therein, which in turn affects the assessment of the risks posed by heavy metals. We used the sediments of Bohai Bay as the study object and analyzed the effects of different organic carbon mineralization levels on the concentrations of heavy metals (Cr, Pb, Cu, Zn, and Cd) using water extraction and potassium permanganate oxidation. The mean concentrations of Cd, Pb, Cu, and Zn in Bohai Bay were within the limits recommended by the World Health Organization. The proportions of the active and inert organic carbon fractions were 61.72% and 32.94%, respectively. Organic carbon mineralization most strongly impacted Cd and Pb levels, with releases accounting for 47.92% and 25.75%, respectively, of the oxidizable fractions. The release of all heavy metals, except for Cr, increased with increases in organic carbon mineralization, and heavy metals were released at a maximum rate of 12.94% when the organic carbon was highly mineralized, whereas Cr was released at a maximum of 0.023% during the first stage of organic carbon mineralization. In terms of spatial distribution, the concentration of mineralizable organic carbon in the sediments of the estuaries was substantially higher than that in other marine areas. Estuary sediments were more easily affected by organic carbon mineralization; therefore, the heavy metals in the oxidizable fraction of the estuarine region were more easily transformed into unstable heavy metal forms, posing high risk levels. Therefore, this study highlights the effects of organic carbon mineralization on heavy metal morphology and stability, when evaluating the ecological risk of heavy metals in marine sediments.

Coring tools have an effect on lithification and physical properties of marine carbonate sediments

Abstract. The International Ocean Discovery Program (IODP) JOIDES Resolution Science Operator typically uses an advanced piston corer (APC) in soft ooze and sediments and an extended core barrel (XCB) in firm sediments. The coring tool exchange typically occurs around the same depth in adjacent holes of the same site. However, during IODP Expedition 356, the coring tool switch occurred at different depths: IODP Sites U1463 and U1464 are marked by a stratigraphic interval (&gt; 25 m thick) that was XCB cored in one hole and APC cored in other holes. Shipboard scientists remarked that APC-cored sediments were unlithified or partially lithified, while XCB-cored sediments were fully lithified. This difference in sedimentological description of the same formation seems to be an effect of coring technique. To provide further insight, we assessed the physical properties (bulk density, porosity, and P-wave velocity), downhole wireline logging data, scanning electron microscope (SEM) images, and micro-computed tomography (µCT) scans of those intervals. We find systematic differences between the different coring techniques. XCB cores are characterized by systematically lower bulk density, higher porosity, and higher P-wave velocity than APC cores. Downhole logging data suggest that the original P-wave velocity of the formation is better preserved in XCB cores, despite the typical “biscuit-and-gravy” core disturbance (i.e. well-preserved core fragments surrounded by squelched core material). In conjunction with SEM and µCT images, we conclude that the APC tool destroyed early lithification by breaking cements between individual grains. Moreover, µCT images reveal denser packing and smaller pore volumes in the APC cores. These sedimentary changes likely occur when the APC pressure wave passes through the sediment. The destruction of grain-to-grain cements provides an explanation for the significantly lower P-wave velocities in APC cores. Interestingly, the gravy sections in XCB drilled cores mimic the destruction of early lithification and reduction of pore volume. We conclude that APC remains the tool of choice for recovering soft sediments, especially for paleoclimate purposes. However, for the study of lithification, XCB biscuits provide a more representative image of the formation. For the study of early diagenesis, further studies are required to ascertain the preservation of key sedimentary features using existing and new drilling tools.

Quantifying the Extent of Authigenic Carbonate Formation in Shallow Marine Sediments Through a Correlation Between Carbonate Precipitation Rate and Sulfate Flux

AbstractThe accumulation of authigenic carbonate in marine sediments has been regarded as a significant contributor to the carbon cycle over Earth's history. However, accurate quantification of the extent of authigenic carbonate formation in both modern and ancient oceans has been challenging due to limited approaches. Here, we analyzed calcium, magnesium, dissolved inorganic carbon, and alkalinity pore‐water profiles of 153 sites influenced by methane diffusion from the northern South China Sea. By combining these data with published data of diffusive sulfate flux, we found a significant positive correlation between carbonate precipitation rate and sulfate flux in the subseafloor. This correlation can be used to quantify the regional extent of authigenic carbonate formation, representing an advantage over a spatial interpolation approach. We therefore propose that the observed correlation can serve as a new approach for quantifying authigenic carbonate formation in shallow sediments along continental margins for both modern and ancient oceans.

The Modern Ocean Sediment Archive and Inventory of Carbon (MOSAIC): version 2.0

Abstract. Marine sediments play a crucial role in the global carbon cycle by acting as the ultimate sink of both terrestrial and marine organic carbon. To understand the spatiotemporal variability in the content, sources, and dynamics of organic carbon in marine sediments, a curated and harmonized database of organic carbon and associated parameters is needed, which has prompted the development of the Modern Ocean Sediment Archive and Inventory of Carbon (MOSAIC) database (http://mosaic.ethz.ch/, last access: 26 July 2023; https://doi.org/10.5281/zenodo.8322094, Paradis, 2023; https://doi.org/10.5168/mosaic019.1, Van der Voort et al., 2019​​​​​​​). MOSAIC version 2.0 has expanded the spatiotemporal coverage of the original database by &gt;400 % and now holds data from more than 21 000 individual sediment cores from different continental margins on a global scale. Additional variables have also been incorporated into MOSAIC v.2.0 that are crucial to interpret the quantity, origin, and age of organic carbon in marine sediments globally. Sedimentological parameters (e.g. grain size fractions and mineral surface area) help understand the effect of hydrodynamic sorting and mineral protection on the distribution of organic carbon, while molecular biomarker signatures (e.g. lignin phenols, fatty acids, and alkanes) can help constrain the specific origin of organic matter. MOSAIC v.2.0 also stores data on specific sediment and molecular fractions, which provide further insight into the processes that affect the degradation and ageing of organic carbon in marine sediments. Data included within MOSAIC are continuously expanding, and version control will allow users to benefit from updated versions while ensuring reproducibility of their findings.

Substantial incorporation of isotopically heavy reduced U species into marine carbonate sediments

The uranium (U) isotope ratio (238U/235U, reported as δ238U) in marine carbonates is an important proxy for reconstructing changes in past oceanic redox conditions, based on the essential assumption that U in carbonates originates from dissolved U(VI) in seawater. However, diagenetic processes may induce the addition of isotopically heavy U(IV) into the carbonates, complicating the application of the U isotope proxy. So far, the valence states of trace amounts of U and its relation with U isotope composition in marine carbonate sediments have not been directly studied. In this study, we have calibrated an ion-exchange chromatographic method to separate U(IV) from U(VI) in geological carbonate samples (e.g., modern and fossil corals, stalagmites, cold seep carbonates) and quantified their contents by mass spectrometry. Our study confirms that modern coral carbonates are faithful archives of U(VI) sourced from seawater. Surprisingly, drill core samples from a modern coral carbonate platform, which bear no sign of alteration inferred from conventional diagenetic proxies (e.g., Mn/Sr), show significant positive correlation between U(IV) fraction and bulk carbonate δ238U, suggesting U(IV) is present in the marine carbonates and drives δ238U toward higher values than that of seawater. We therefore suggest that coupled valence and isotope analyses of U in marine carbonates could provide critical constraints toward reliable reconstruction of marine redox evolution in the Earth’s history.

The effect of iron on the preservation of organic carbon in marine sediments and its implications for carbon sequestration

The effect of iron on the preservation of organic carbon in marine sediments and its implications for carbon sequestration

Characterizing the water–rock interactions and groundwater flow processes in the Paleozoic to Cenozoic strata aquifer systems with contrasting mineralogy at basin scale: Qingyi river, east China

This study aims to identify water–rock interaction and groundwater flow processes in aquifer systems with contrasting mineralogy at the basin scale. Investigations have been carried out using major ion geochemistry and environmental isotopes (δ2H and δ18O of water, δ13C values, 87Sr/86Sr ratios, and 14C activities) within aquifers with contrasting mineralogy in the Qingyi river basin (QRB, east China) composed of marine carbonate and continental granitic sediments with successive strata during Paleozoic, Mesozoic and Cenozoic. Analysis of 95 rain, surface and groundwater, and 12 solid rock samples found that dissolution of limestone, silicate minerals, and evapotranspiration dominated the hydrogeochemical process in the lower, upper, and middle basin, respectively. The various major ion and 87Sr/86Sr ratios of groundwater in each aquifer suggest that local lithology minerals dissolution controls the water–rock equilibria in the groundwater system. The 87Sr/86Sr ratios are correlated with both major ion geochemistry and δ13C values, constraining the process of varying proportions of silicate and carbonate minerals dissolution. Percolating water from soils carrying dissolved CO2 plays an important role in controlling the hydrogeochemical processes in the groundwater system throughout the QRB. Inter-aquifer flow has been proved by the well correlated relations between 87Sr/86Sr ratios and δ13C values or/and Sr/Na and Ca/Na ratios, as well as the irregular groundwater apparent 14C ages (1.78 to 8.52 kyr) with respect to position in the basin. Admixture ratios of 9–50% are derived from the groundwater in limestone aquifer. The rapid decrease in carbonate groundwater mixing ratio is accompanied by an increase in 87Sr/86Sr ratios, indicating that groundwater is derived Sr from silicate weathering and abundant carbon from the soils. Regional inter-aquifer flow occurs in the buried carbonate aquifers based on isotopic evidence, which could result in karstic groundwater leakage in the Wuhu cityside and should be given special attention.

The Global Turbidity Current Pump and Its Implications for Organic Carbon Cycling.

Submarine turbidity currents form the largest sediment accumulations on Earth, raising the question of their role in global carbon cycles. It was previously inferred that terrestrial organic carbon was primarily incinerated on shelves and that most turbidity current systems are presently inactive. Turbidity currents were thus not considered in global carbon cycles, and the burial efficiency of global terrestrial organic carbon was considered low to moderate (∼10-44%). However, recent work has shown that burial of terrestrial organic carbon by turbidity currents is highly efficient (>60-100%) in a range of settings and that flows occur more frequently than once thought, although they were far more active at sea-level lowstands. This leads to revised global estimates for mass flux (∼62-90 Mt C/year) and burial efficiency (∼31-45%) of terrestrial organic carbon in marine sediments. Greatly increased burial fluxes during sea-level lowstands are also likely underestimated; thus, organic carbon cycling by turbidity currents could play a role in long-term changes in atmospheric CO2 and climate.

Comparisons of age estimates from Strontium-isotope values versus other Chronostratigraphy methods

Strontium-isotope stratigraphy enables estimates of numerical dates for marine carbonate-bearing sediments by comparing their 87Sr/86Sr ratio to a reference curve of 87Sr/86Sr variations of global seawater through geologic time. That seawater reference curve is a published statistical LOWESS fit to a very large dataset (ca. 14,000) of 87Sr/86Sr measurements of carbonate fossils from known biozones which is converted to numerical ages using published timescales. In this study, we compute the numerical dates projected by this method for suites 87Sr/86Sr ratios from seven stratigraphic sections ranging from Ordovician through Oligocene. The strontium-isotope stratigraphy from the Dawangou section in Tarim Basin of NW China that hosts the Auxiliary GSSP for the base of the Late Ordovician is a new dataset; and the others are published datasets. These 87Sr/86Sr-derived dates are compared to those estimated for the same horizons in these sections by other chronostratigraphic methods, including cyclostratigraphy calibrated to radioisotopic dates and standard biochronostratigraphy. Except for a published study of Lower Triassic strata from Chaohu section in Anhui, China and Middle Devonian strata Jebel Mech Lrdane section of Morocco, all the 87Sr/86Sr-derived dates are within the estimated uncertainties of the dates from the other chronostratigraphic methods, thereby validating the usefulness of strontium-isotope stratigraphy as one tool for obtaining the ages of marine carbonate-bearing deposits. However, the datasets from all three Paleozoic sections (two Ordovician, one Devonian) did display a noticeable offset bias toward older ages, which may be partly an artifact of inadequate adjustment of the LOWESS reference curve to current age models for the biozones. The 87Sr/86Sr-derived dates from Chaohu section of Early Triassic conodont zones were unacceptably systematically younger by ca. 1.45 Myr; thereby indicating higher-than-expected 87Sr/86Sr values, which may have been partially the result of a combination of a semi-restricted basin that was slightly diluted by 87Sr-enriched fluvial waters from the chemical weathering of adjacent landmasses and of the laser ablation (LA-ICP-MS) analytical method applied to those samples that seems to yield higher 87Sr/86Sr ratios than the solution-mode ICP-MS method for 87Sr/86Sr measurements. In summary, with rare exceptions, the method of strontium-isotope stratigraphy and the statistical 87Sr/86Sr seawater curve is an important method to obtain semi-precise numerical dates from marine carbonate sediments.