Ocean Chemistry Research Articles

Assessment of bi-metal paleo-redox proxies in the Bakken Formation black shales, Williston Basin, North Dakota, USA

The influence of paleoredox conditions and water-mass restriction on trace metal (TM) accumulation in the lower (LBS) and upper black shales (UBS) of the Devonian–Mississippian (D–M) Bakken Formation was assessed utilizing V/Cr, V/(V + Ni), Ni/Co, U/Th, and enrichment factors (EF) for Mo vs. U. These assessments were compared to previously published estimates based on degree of pyritization (DOPT), sulfur‑iron and C–S–Fe relationships, and sedimentological data. Bi–metal ratios suggest >80 % of samples were deposited under suboxic to anoxic/euxinic conditions, whereas DOPT results suggest >60 % of samples were deposited under dysoxic (0.42–0.75 DOPT) bottom–water conditions. DOPT results are in good agreement with C–S–Fe and total S vs. Fe assessments of paleoredox conditions and sedimentological evidence. Good agreement is also seen between Mo/TOC and Mo EF/U EF that both suggest the Bakken shales were deposited under a relatively unrestricted water mass conditions resulting in consistent renewal of TMs into the basin. With TM resupply outpacing drawdown, the basin could support enhanced primary productivity as well as high concentrations of TMs. Trace metal concentrations for the Bakken Fm. show considerable range for Co (0–10,324 ppm), Mo (0–2018 ppm), Ni (0–1574 ppm), U (0–1604 ppm), and V (0–3194 ppm), and bi–metal ratios for the Bakken Fm. are up to 5× greater than those reported for other D–M black shale formations. Bivariate and principal component analysis indicate Mo, Ni, U, and V accumulation was more closely associated with the organic fraction than with reducing conditions, thus accumulation of organic matter during deposition and generation, migration, and biodegradation of hydrocarbons during diagenesis may have influenced the accumulation and distribution of these TMs. Furthermore, changes in biogeochemical processes during the D–M transition may have fundamentally altered marine chemistry, with the evolution of vascular land plants and enhanced terrestrial weathering leading to an increased influx of nutrients into marine waters resulting in the Annulata, Dasberg, and Hangenberg black shale events. Factors controlling TM accumulation during time of deposition (e.g., TM availability, bottom-water redox conditions, adsorption onto organic matter) and during diagenesis and catagenesis (e.g., alteration and break down of organic matter, movement of fluid hydrocarbons or other basinal fluids) likely contribute to the lack of agreement between redox proxies, and subsequently, the lack of applicability of bi–metal ratios in assessing bottom–water conditions for the Bakken shales. Therefore, it is suggested that these bi-metal redox proxies are not an effective means to describe bottom-water conditions during the deposition of the Bakken shales.

Rare earth elements as indicators of post-Marinoan (∼635 Ma) paleoceanographic changes from the Amazon Craton

The extensive deglaciation linked to the Snowball Earth climate that elapsed in the terminal Neoproterozoic caused dramatic changes in ocean chemistry, exceptionally recorded in globally distributed cap carbonate successions. One of the most spectacular examples is the Puga cap carbonate (∼635 Ma), which is exposed in the Amazon Craton and associated with extensive sea level changes related to glacial-isostatic adjustment and local ice gravity, resulting in continuously mixed waters. This study meticulously evaluates complex post-Marinoan dynamics using a comprehensive multiproxy approach. The rare earth element + yttrium (REE+Y) patterns in the Puga cap carbonate do not accurately reflect the global ocean water composition; instead, they primarily fractionate in response to local expression of the post-Snowball Earth event, including alkalinity levels and freshwater mixing in the aftermath of the Marinoan glaciation. The flattened REE+Y pattern, accompanied by a positive Eu anomaly, may suggest the influence of continental weathering. Specifically, low Y/Ho ratios in the cap dolostone are consistent with seawater dilution due to meltwater influx (Y/Ho ∼ 29–32). Conversely, superchondritic Y/Ho ratios up to 71 in the basal cap dolostones suggest upwelling of hypersaline seawater in coastal areas. The shallow-water recurrence influenced by ice gravity resulted in continuous coastal uplift, forming isolated shelves and the deformation in diamicton, resulting in irregular substrate relief morphologies. This post-glaciation scenario was succeeded by significant landward shoreline migration concomitant with rapid recovery of primary productivity, with large microbial communities flourishing, inducing dolomite precipitation under restricted paleoenvironmental conditions on dolomitic platforms. The rapid rise in sea level led to the dilution of evaporative fluids, ultimately halting dolomicrite precipitation. Following the pos-tglacial transgression, the stratified waters gradually became more mixed, resulting in the termination of dolomitic platform deposition and coinciding with an increase in detrital components, as indicated by the increase of insoluble elements (e.g., REE, Zr, and Th), followed by abrupt replacement by CaCO3-oversaturated seas during the post-glacial transgression. These observations elucidate the interplay between post-glaciation and paleoceanographic dynamics during the Cryogenian-Ediacaran boundary.

Paired X‐Ray Micro CT Scanning and Individual Foraminifera Isotopic Analysis Reveal (De)coupled Changes in Carbonate Preservation and Temperature

AbstractThe composition and preservation state of biogenic carbonate archives, such as foraminiferal tests, record ocean chemistry during the lifetime of the organism and post‐depositional changes in ambient conditions via carbonate compensation. Depending upon the specific paleoclimate proxy, post‐depositional processes, including dissolution, may alter original paleoenvironmental signals captured by the foraminifer's test composition. Accordingly, quantifying dissolution independent of geochemical measurements can improve proxy interpretation. Developing independent tools may also be useful for investigating whether changes in paleoclimatic conditions are associated with changes in seawater carbonate chemistry. Such approaches can be improved further if they are applied to individual foraminiferal tests, as specimen‐to‐specimen differences can record higher‐frequency environmental changes compared to conventional bulk‐scale analyses. Here, we combine individual foraminiferal carbon and oxygen isotopic analyses (IFA) with X‐ray MicroCT Scanning to generate paired analyses of test density (a proxy for the extent of post‐depositional dissolution) and isotopic composition. As a proof‐of‐concept application of this approach, we analyze Globigerina bulloides tests from both coretop and latest Miocene/earliest Pliocene‐aged sediment from Ocean Drilling Project (ODP) Site 1088 (Agulhas Ridge). Our measurements and mixing model calculations show that within‐population differences in carbon and oxygen isotopic ratios are largely independent of dissolution extent. By comparing population averages from coretop and downcore sediments, we find that lower oxygen isotopic ratios (likely driven by higher calcification temperatures) are associated with greater extents of dissolution at ODP Site 1088. We interpret this finding to reflect coupled changes in carbonate chemistry and climatic conditions over million‐year timescales.

Reconstructing CO2 uptake capacity and pH dynamics in the Middle Ordovician Taebaeksan Basin, Korea

This study presents the first continuous carbonate boron isotope (δ11Bcarb) record from Middle Ordovician carbonate rocks, focusing on the Taebaek section in Korea. The δ11Bcarb values analyzed from the Makgol, Jigunsan, and Duwibong formations range between 7.5 ‰ and 17.8 ‰, falling within the published Paleozoic range. Samples exhibit minimal diagenetic alteration, as evidenced by weak correlations between isotopic factors and elemental ratios (δ11Bcarb, δ13Ccarb, δ15Nbulk, B/Ca, Mn/Sr, and Na/Ca) as well as mineralogical observations used to select unaltered micrite portions. Using the δ11Bcarb data, we reconstruct pH levels (8.4 to 9.1) which suggest that this shallow shelf environment acted as a CO2 sink during the Middle Darriwilian, despite periods of acidification coinciding with sea level rise and expansion of anoxic zones. Weakening of the basin's CO2 uptake capacity via reduced CaCO3 precipitation and photosynthesis accompanied these oceanographic changes. Our findings provide new insights into the dynamics of CO2 accumulation and pH in Middle Ordovician shallow marine settings in relation to sea level fluctuations. This work lays the foundation for further research into ocean chemistry and carbon cycle perturbations during this important period in Earth's history.

Genesis of Devonian volcanic-associated Lahn-Dill-type iron ores – part II: trace element fractionation evidences diffuse fluid venting

The iron (Fe)-oxide deposits of the Lahn-Dill-type are composed of haematite-quartz and rare siderite-haematite ores. These ores formed as marine chemical sediments on top of volcaniclastic rocks near the Middle to Late Devonian boundary (∼ 380 Ma). As such, their trace element fractionation patterns provide key information on venting style, ocean chemistry, particle-solution interaction, and depositional environment at the time of ore formation. This study combines WDXRF and ICP-MS/OES whole-rock geochemistry with complementary in-situ LA-ICP-MS analysis, and TEM element mapping of ore samples from the Fortuna Mine (Rhenish Massif, Germany). In-situ measurments were conducted on quartz-haematite, haematite, and siderite-haematite microdomains. Bulk major element contents of the ores indicate (volcani)clastic contamination and post-depositional hydrothermal alteration. Microdomain trace element distributions reveal four different trace element signatures, which are related to: (1) syngenetic apatite formation due to sorption of P and REY from seawater; (2) Fe-(oxyhydr)oxide-specific trace element scavenging and fractionation within the seawater column; (3) diagenetic Fe(III) reduction and trace element mobilisation in pore water; and (4) simultaneous deposition of (volcani)clastic material and Fe-(oxyhydr)oxides. These results show that Lahn-Dill-type iron ore formation resulted from mixing of a low-temperature vent fluid with ambient seawater at high seawater to vent fluid ratios. This likely was related to an environment in which diffuse venting dominated over focused venting, and in which quick Fe-particle precipitation led to formation of haematite-quartz ores. Local diagenetic Fe(III) reduction resulted in post-depositional siderite-haematite ore formation during which trace elements were partially remobilised in pore water.

The timing and duration of large-scale carbon release in the Early Jurassic

The Toarcian oceanic anoxic event (T-OAE, ca. 183 Ma) in the Early Jurassic was one of the most significant warming events of the Phanerozoic, associated with large-scale carbon emissions, mass extinction, and perturbations to hydrology and ocean chemistry. However, the age and duration of this hyperthermal have long been uncertain, hindering our understanding of the timing and pace of carbon release and the associated environmental and biotic changes. We present high-precision radioisotopic dates bracketing a biostratigraphically constrained record of the T-OAE in Japan. Our geochronology reveals an unexpectedly short T-OAE duration of ∼300 k.y. and a temporal coincidence with Ferrar large igneous province (LIP) magmatism. Our dates refute previous work linking the T-OAE to the earlier Karoo LIP, which was coincident with an earlier carbon cycle perturbation at the Pliensbachian−Toarcian boundary. Our results suggest both events were driven by extremely rapid (perhaps sub-millennial scale) thermogenic carbon degassing during LIP sill intrusion.

Middle Ordovician paleoenvironmental evolution of the western Laurentian carbonate platform: Evidence for persistent oxygenation of the shallow ocean and implications for biodiversification

The Great Ordovician Biodiversification Event (GOBE) encompasses a series of rapid and sustained diversification pulses unparalleled in Earth history. Despite the uniqueness and magnitude of the GOBE, a singular driving force for this critical interval has not been identified. Multiple hypotheses have been presented, some pairing the GOBE as cause and effect with extrinsic factors such as changing global temperatures, ocean chemistry, or paleogeography, while others have pointed to factors intrinsic to biology itself, such as the proliferation of skeletonization, predator-prey escalation, or the development of complex tiered seafloor communities. Sufficient data are not available at present to ascertain what combination of these factors was the key to generating the GOBE.Here, we present new paired carbon and sulfur isotope data (δ13Ccarb, δ13Corg, and δ34SCAS), along with iodine concentration data from a Darriwilian carbonate sequence exposed at Meiklejohn Peak in southwestern Nevada, USA. Within a detailed lithologic and biostratigraphic framework, these new data provide a robust correlation to chemostratigraphic zonation established in Baltica and eastern Laurentia along with insights into the evolution of Middle Ordovician biogeochemical cycling. Carbon isotope data indicate a slight (2 ‰) increase in the fractionation between carbonate carbon and organic matter (Δ13C) during the onset of the middle Darriwilian carbon isotope excursion (MDICE), and new carbonate-associated sulfate (CAS) sulfur isotope data are consistent with a decrease in global pyrite burial during this time. Both of these observations support previous work arguing for a synchronous increase in the [O2] of the global oceans. New iodine concentration data from Meiklejohn Peak also suggest a progressive and sustained increase in the [O2] of regional waters throughout the Darriwilian during a period of relative sea-level highstand. This expansion of stable and well‑oxygenated ecospace could have laid the foundation for rapid diversification during one of the largest pulses of the GOBE.

The Palaeo-Productivity Signals Chronicled from the Buxa Formation, North-East Lesser Himalaya, India

ABSTRACT The Mesoproterozoic era is known for its relatively stable ecological conditions and limited atmospheric oxygen. Despite this understanding, uncertainties remain about how ocean chemistry evolved during this time and its potential impact on the development of complex eukaryotic life forms. In response to these uncertainties; we have undertaken a study to investigate indicators of ancient productivity within the Buxa Formation of the Lesser Himalaya in Sikkim. By analyzing the isotopic values ( δ13 C and δ 18Ο values) as well as Rare Earth Element (REE) composition, a total n = 151 carbonate samples were investigated across three sections of the Buxa Formation: Jorethang to Mangalbare, Legship to Naya Bazar, and Reshi to Mangalbare, Sikkim. The study’s findings show that there was minimal variation in δ13C values, consistently ranging between –0.5 and +2.5 ‰ VPDB. This pattern suggests a relatively steady and moderately high level of productivity during that time. This productivity might have been influenced by a temporary increase in atmospheric oxygen levels. Additionally, we have also reviewed and examined stromatolites as part of the investigation.

Mesoproterozoic siliciclastic stromatolites of Chapada Diamantina (Brazil): Morphological types, genesis and environmental context

Laminations of organosedimentary structures can be formed by three distinct processes: (i) bio-induced mineral precipitation, (ii) trapping and binding, and (iii) abiotic mineral precipitation and each of these processes predominates in a certain geological time interval. Agglutinated stromatolites are rare and seem to form in specific environmental conditions. Siliciclastic stromatolites are an even rarer class of agglutinated stromatolites, which are formed in response to the process of trapping and binding of siliciclastic grains by upright filaments or by extracellular polymeric substances (EPS). This study describes and interprets one of the oldest siliciclastic stromatolites of the geological record and discusses the microbial evidence and mechanisms that controlled their accumulation and preservation. Two compound sections were analyzed and ten thin sections were prepared to characterize the siliciclastic stromatolites from the Mesoproterozoic Caboclo Formation (Brazil). Stromatolites are present in two different lithofacies associations: (i) shoreface and (ii) offshore transition. The shoreface stromatolites are characterized by silty to sandy texture and poor lamination, and the distal ones by clay, silt grains, less sand, and distinct lamination. The volume of siliciclastic grains composing the stromatolite fabric is >85% in the shoreface and >30% in offshore transition. These stromatolites were deposited in a favorable environment for trapping and binding of siliciclastic sediments: a wave-dominated siliciclastic ramp with the availability of siliciclastic grains and frequent water column agitation. The marine environment is favorable for forming EPS with good adhesive properties. Besides, the Caboclo Formation age (1.3–1.0 Ga) coincides with an abrupt fall in the amount of atmospheric CO2 reflected in CaCO3 saturation in the oceans. This change in ocean chemistry may have led to a change in stromatolite fabric, from the sparry crust and fine-grained precipitated to agglutinated.

Dolostone-barite-phosphorite sequence in the basal Doushantuo Formation: Origin and implications for post-Marinoan ocean chemistry and phosphogenesis

Barite (BaSO4) represents a major component of many post-Marinoan cap dolostones worldwide, recording important information on climate upheavals during the terminal Neoproterozoic. However, its origins and relations with other lithofacies remain to be explored. Here we report new occurrences of barite in the basal Ediacaran Doushantuo Formation at a major phosphate mine in Weng'an, South China, and present results of detailed petrographic and geochemical investigations on the barites and related phases. At the outcrop scale, barite is mainly present as a 1–2 cm-thick layer at the contact of the cap dolostones and overlying phosphorites. Detailed petrographic observations reveal a lithofacies transition from dolostone through a mixture of barite, dolomite and apatite to barite and finally to granular phosphorite. The barites can be categorized into three generations in stratigraphic order, which are present as loose, randomly-oriented blades (B1), dense aggregates (B2), and radially aligned crystal fans (B3), respectively. B1 is dispersed in a matrix of apatite and dolomite, which has an average δ13Ccarb of −0.61‰. This, along with the common presence of organic matter (OM) in this barite, point to a possible source of Ba from organic degradation. B3 forms a centimeter-scale layer of barite fans that laterally extends over the entire mining pit, whereas B2 is locally distributed between B1 and B3, and occurs as relatively unoriented aggregates. δ34S values of B3 show a narrow range between +25.9‰ and +30.9‰, which is similar to that of contemporaneous seawater and indicate a seawater source of sulfate in barite. Based on the present investigation and a compilation of published data, we propose that B1 is diagenetic barite with a main source of Ba from degradation of organic matter and possibly also from dissolution of previous pelagic barite, whereas B2 and B3 represent seafloor precipitates that resulted from interactions between deep, anoxic Ba-rich waters and oxic, sulfate-rich surface waters during the post-glacial transgression. This episode of barite precipitation was immediately followed by massive accumulations of phosphorites in Weng'an and many areas of South China. The consecutive deposition of cap dolostone, barite and phosphorite signifies the transition from an alkalinity-rich, stagnant anoxic ocean to a dynamic marine regime featuring oxygenated surface waters and upwelling currents. These pH and redox changes likely facilitated the cycling and enrichment of phosphate in the shallow waters that was necessitated by the unprecedented accumulation of Ediacaran phosphorites in South China.

Mixing behaviour and sources of Ag, Pd, and other trace elements in the Estuary and Gulf of St. Lawrence under winter conditions

The marine chemistry of platinum group elements is poorly documented despite robust evidence of their widespread emissions and deposition around the globe. Here, we report the concentrations and discuss the geochemical behaviours of Ag, Pd and other trace and ultra-trace elements in the Estuary and Gulf of St. Lawrence (EGSL). We highlight the contrasting mixing behaviours of these elements, i.e., conservative (Cd, Re) vs. non-conservative (Ag, Pd), in samples collected during the winter and under ice-covered conditions. We ascribe the contrasting geochemical behaviour of these elements to their differential affinity for reactive surfaces carried into the estuary from the frozen watersheds. We also report an increase of the concentrations of Ag (up to 40 pmol L−1), Pd (up to 10 pmol L−1) and Pt (up to 0.4 pmol L−1) in the bottom and oxygen-depleted waters of the Gulf of St. Lawrence (GSL). A strong correlation between dissolved Pt concentrations and the stable carbon isotopic composition of the dissolved inorganic carbon (δ13C-DIC) suggests that the increased mobility of Pt may result from the aerobic mineralization of organic carbon or the oxidation of Pt-bearing organic complexes. Molar Pt/Pd ratios in the three water masses that compose the water column in the EGSL highlight a potential influence of anthropogenic sources near urban centers. The signature of continental end-members will be required to confirm the impacts of road traffic on the estuarine geochemistry of these elements.

A Study on Isotopic Analysis of Trace Metals in Geochemistry and Marine Chemistry

A Study on Isotopic Analysis of Trace Metals in Geochemistry and Marine Chemistry

Marine coastal chemistry related to inland inputs in San Jorge gulf and the adjacent north coast

Coastal regions are sectors where human activities impact the marine ecosystem, and if necessary control measures are not taken, they can generate negative consequences for health and ecosystem services. Within the framework of the Pampa Azul initiative and under the One Health paradigm, the interconnection between the terrestrial and marine environments of the San Jorge Gulf and the adjacent north coast has been studied. In November, 2022, a campaign was carried out aboard the R/V “Mar Argentino” at thirty-four stations near the coast. There, for the first time, simultaneously with in-situ measurements of physical variables, macronutrients (NO3−, PO4−3, Si(OH)4 and NH4+), particulate silica (BSi and LSi), trace metals in the particulate material (Cd, Cu, Cr, Fe and Pb) and the phytoplankton community were analyzed. The results showed a high nutrient dynamic, with a significant influence of natural stratification and anthropogenic condition due to the discharge of effluents off the cities of Comodoro Rivadavia and Caleta Olivia. Under natural conditions, NO3− and Si(OH)4 limited the surface primary production by 47 % and 41 %, respectively. Additionally, due to the anthropogenic contribution, NH4+ concentration reached 3 μM, increasing the proliferation of nanophytoplankton, among other consequences. As a result of nutrient dynamics, the uptake of Si(OH)4, the growth rate of diatoms and their production of BSi were decoupled. Furthermore, a significant correlation between LSi and Fe in particulate matter was evidenced, opening new lines of research that relate dust storms to primary productivity in this marine environment. The measured concentrations of trace metals do not appear to be a biological risk; however, contamination by Cd (37.6 μg g− 1 d.w.) and Cu (214.97 μg g− 1 d.w.) off Camarones poses a significant concern that must be addressed in the immediate future.

On the emission-path dependency of the efficiency of ocean alkalinity enhancement

Ocean alkalinity enhancement (OAE) deliberately modifies the chemistry of the surface ocean to enhance the uptake of atmospheric CO2. The chemical efficiency of OAE (the amount of CO2 sequestered per unit of alkalinity added) depends, among other factors, on the background state of the surface ocean, which will significantly change until the end of this century and beyond. Here, we investigate the consequences of such changes for the long-term efficiency of OAE. We show, using idealized and scenario simulations with an Earth system model, that under doubling (quadrupling) of pre-industrial atmospheric CO2 concentrations, the simulated mean efficiency of OAE increases by about 18% (29%) from 0.76 to 0.90 (0.98). We find that only half of this effect can be explained by changes in the sensitivity of CO2 sequestration to alkalinity addition itself. The remainder is due to the larger portion of anthropogenic emissions taken up by a high-alkalinity ocean. Importantly, both effects are reversed if atmospheric CO2 concentrations were to decline due to large-scale deployment of land-based (or alternative ocean-based) carbon dioxide removal (CDR) methods. By considering an overshoot pathway that relies on large amounts of land-based CDR, we demonstrate that OAE efficiency indeed shows a strong decline after atmospheric CO2 concentrations have peaked. Our results suggest that the assumption of a constant, present-day chemical efficiency of OAE in integrated assessment modeling and carbon credit assignments could lead to economically inefficient OAE implementation pathways.

The depositional redox conditions of Fe‐speciation reference materials (BHW and WHIT) using redox‐sensitive trace metal enrichment

Iron speciation has emerged as a robust proxy for discerning oceanic redox conditions; nonetheless, it is subject to certain limitations. Specifically, the applicability of the degree of pyritization is contingent upon the presence of unequivocal evidence of an anoxic water column and its discriminatory capacity is limited to distinguish between ferruginous (anoxic) and euxinic conditions. This study highlights that through the integration of redox‐sensitive trace metal enrichment data with Fe‐speciation data, the depositional redox conditions for marine sediments can be established with greater certainty. Recently, a set of dedicated geological reference materials (BHW and WHIT) have been developed for validating the Fe‐speciation analytical results for redox reconstruction studies; however, to the best of our knowledge, these reference materials are not characterized for trace and rare earth elements (REEs). In this connection, the BHW (oxic) and WHIT (anoxic) reference materials are measured for major, trace and REEs. After careful statistical considerations for these reference standards, a complete set of trace and REEs is reported. Furthermore, considering BHW and WHIT as oxic and anoxic end‐members, respectively, the utility of trace metal enrichment and Fe‐speciation data in combination has been discussed. The trace and REE concentrations of BHW and WHIT reported in this study will enhance their applicability as a reference material to understand ocean chemistry and the oxidation state of the ancient oceans.

Depositional facies and evolution of sponge-microbial-constructed carbonate platforms in the lower Cambrian (Stage 3), Tarim basin, China: Understanding from anatomy

The early Cambrian was generally considered the earliest time interval while the archaeocyaths could act as the constructors in building reef framework although commonly coexisting with the microbial constructors (Epiphyton and Renalcis) in the course of the “Cambrian explosion”; however, this kind of metazoan-microbial buildups has not yet been reported in Tarim Basin. To delineate facies (associations), spatiotemporal variations, reef-building processes of metazoan-microbial constructed ramps/shelves and evolution, detailed anatomy was carried out upon the lower Cambrian Xiaoerbulak Formation (or Stage 3) exposed continuously along a marginal transect (∼2 km wide) in Aksu area, northwestern Tarim Basin. Three platform types with distinctive facies associations are distinguished: (1) sponge-microbial biostrome/mound-colonized homoclinal and distally-steepened ramps recorded respectively in the Lower Member and basal Middle Member, (2) Archaeocyath-Epiphyton reef- and microbial reef-rimmed platforms (or shelves) in the mid-upper Middle Member, and (3) microbial biostrome-colonized ramp in the Upper Member, thus illustrating the evolution from the ramp to reef-rimmed platform and final reversion to the ramp system. Four and a half third-order depositional sequences are further identified: one in the Lower Member, two in the Middle Member and one and half (TST) in the Upper Member, although, at least, one sequence was absent in the platform/ramp interior. All these can be well correlated with those in equivalent successions identified elsewhere around the world, implying a basic control of eustatic changes on platform development and evolution. Moreover, syndepositional faulting/sliding that occurred off the ramp margin, as demonstrated by slope failure/collapse, may have enhanced the relief difference between the inner and mid-outer ramps, promoting metazoan-microbes to colonize and build up wave-resistant architecture on the uplifting margin, forming the reef-rimmed platform (or shelf) system as typified in the Middle Member. Meanwhile, the development of wave-resistant, metazoan-microbial reef complexes also benefited from their concurrently-gained calcifying ability, which likely resulted from the instinctive biotic responses to the changes in climate and oceanic chemistry (i.e., pCO2, seawater Mg/Ca ratio) in the early Cambrian. The new datasets of this study fill previous information gap on the early Cambrian metazoan-involved buildups that had controlled the platform configuration and evolution in Tarim Basin, which thus are critically important for better understanding of climatic/environmental controls on their occurrence and evolution of the time-specific reef complexes in the course of “Cambrian Explosion”. Additionally, these datasets would provide a useful analogue for perceiving the facies-constrained porosity and heterogeneity in the deeply buried counterparts in the basin, helpful for making exploration strategy for the deeply-buried hydrocarbon resources.

Exploring Sources, Biological Functions, and Potential Applications of the Ubiquitous Marine Cyclic Dipeptide: A Concise Review of Cyclic Glycine-Proline.

Cyclic glycine-proline (cGP), a prevalent marine cyclic dipeptide, possesses a distinct pyrrolidine-2,5-dione scaffold, which contributes to the chemical diversity and broad bioactivities of cGP. The diverse sources from marine-related, endogenous biological, and synthetic pathways and the in vitro and in vivo activities of cGP are reviewed. The potential applications for cGP are also explored. In particular, the pivotal roles of cGP in regulating insulin-like growth factor-1 homeostasis, enhancing neuroprotective effects, and improving neurotrophic function in central nervous system diseases are described. The potential roles of this endogenous cyclic peptide in drug development and healthcare initiatives are also highlighted. This review underscores the significance of cGP as a fundamental building block in drug discovery with exceptional drug-like properties and safety. By elucidating the considerable value of cGP, this review aims to reignite interest in cGP-related research within marine medicinal chemistry and synthetic biology.

Spatio-temporal dynamics of the carbonate system during macroalgae farming season in a semi-closed bay in southeast China

Ocean Negative Carbon Emission (ONCE) involves utilizing natural marine chemistry and biology, along with mariculture, to achieve carbon sink goals. Growing awareness of the interplay between aquaculture and the coastal carbonate system has drawn researchers’ attention amid ring CO2 concentrations and the negative impacts of aquaculture on the environment. In this study, twelve sites representing different maricultural types were selected, including macroalgae, shellfish, fish, and non-farming areas. The environmental factors, dissolved inorganic carbon (DIC), total alkalinity (TA), and pCO2, were measured monthly during kelp farming periods. Nitrate is a major component of total nitrogen, and the NO3-N concentration in the macroalgal culture zone was lower than others, indicating effective nitrogen removal by macroalgae aquaculture. TA and DIC in non-farmed areas demonstrated larger variation ranges than in farming areas, probably due to the effects of precipitation on salinity. Aquaculture activities effectively maintained TA and DIC, with macroalgae cultivation playing an important role in TA stability, potentially resisting acidification. The pCO2sea-air of macroalgae culture areas in spring was slightly negative, suggesting carbon sink potential. However, further research is needed to assess the full extent of this “fourth type” of blue carbon, including accurate carbon footprint calculation and the contributions of particulate organic carbon and recalcitrant dissolved organic carbon. This study provided insight into the comprehensive contribution of different aquaculture types to the fishery environment and carbonate system, which can help guide aquaculture management and facilitate the carbon-neutral transition of aquaculture.

The salinity anomalies due to nutrients and inorganic carbon in the Bohai Sea

As a new seawater standard, the International Thermodynamic Equation of Seawater-2010 (TEOS-10) has made it possible to accurately calculate salinity changes caused by small changes in the relative proportions of inorganic dissolved constituents in the open ocean and thus to accurately calculate the thermodynamic properties of seawater. However, offshore and semi-enclosed seas are subject to the dual influence of geo-biochemical processes and terrestrial inputs, and the spatial and temporal variations in the relative composition of their seawater are more complex, resulting in very few studies of salinity change due to changes in the relative composition in these regions, and the applicability of the TEOS-10 in these seas needs to be further evaluated. The Bohai Sea is a typical semi-enclosed sea that has accumulated a large amount of physical oceanography and marine chemistry measurements, making it an ideal area to study the effects of changes in the relative composition of seawater on salinity. Based on repeated measurements of Section B in the Bohai Sea from 1985 to 2020, complemented by quasi-synchronous large-scale measurements of the Bohai Sea from 2006 to 2007, this study found that [HCO3−] and [Ca2+] ions anomalies dominate the relative composition anomalies of dissolved substances in this sea relative to the Standard Sea Water (SSW). These additional components could increase the absolute salinity SA by up to 0.1 g·kg-1 and the practical salinity SP by 0~0.04 according to the TEOS-10 algorithm and the mathematical model Pa08. Based on the specific environmental characteristics of the Bohai Sea, the sources, spatial and temporal variations, and influencing factors of the relative compositional anomalies are analyzed, and the empirical formulas of the absolute salinity anomaly δSA and practical salinity anomaly δSP for the Bohai Sea are further fitted, with the uncertainty of 0.007~0.021 g·kg-1 for δSA and 0.003~0.008 for δSP. The above results can not only improve the accuracy of the thermodynamic properties of the Bohai Seawater, but also provide the compatibility level of the long-term salinity changes in the Bohai Sea and its adjacent waters.

Early Mississippian global δ13C excursion is not a diagenetic artifact

Shallow-water platform carbonate δ13C may provide a record of changes in ocean chemistry through time, but early marine diagenesis and local processes can decouple these records from the global carbon cycle. Recent studies of calcium isotopes (δ44/40Ca) in shallow-water carbonates indicate that δ44/40Ca can be altered during early marine diagenesis, implying that δ13C may also potentially be altered. Here, we tested the hypothesis that the platform carbonate δ13C record of the Kinderhookian-Osagean boundary excursion (KOBE), ∼353 m.y. ago, reflects a period of global diagenesis using paired isotopic (δ44/40Ca and clumped isotopes) and trace-element geochemistry from three sections in the United States. There is little evidence for covariation between δ44/40Ca and δ13C during the KOBE. Clumped isotopes from our shallowest section support primarily sediment-buffered diagenesis at relatively low temperatures. We conclude that the δ13C record of the KOBE as recorded in shallow-water carbonate is consistent with a shift in the dissolved inorganic carbon reservoir and that, more generally, ancient shallow-water carbonates can retain records of primary seawater chemistry.