Ocean Chemistry Research Articles

The effects of bathymetry on the long-term carbon cycle and CCD

The shape of the ocean floor (bathymetry) and the overlaying sediments provide the largest carbon sink throughout Earth's history, supporting ~one to two orders of magnitude more carbon storage than the oceans and atmosphere combined. While accumulation and erosion of these sediments are bathymetry dependent (e.g., due to pressure, temperature, salinity, ion concentration, and available productivity), no systemic study has quantified how global and basin scale bathymetry, controlled by the evolution of tectonics and mantle convection, affects the long-term carbon cycle. We reconstruct bathymetry spanning the last 80 Myr to describe steady-state changes in ocean chemistry within the Earth system model LOSCAR. We find that both bathymetry reconstructions and representative synthetic tests show that ocean alkalinity, calcite saturation state, and the carbonate compensation depth (CCD) are strongly dependent on changes in shallow bathymetry (ocean floor ≤600 m) and on the distribution of the deep marine regions (>1,000 m). Limiting Cenozoic evolution to bathymetry alone leads to predicted CCD variations spanning 500 m, 33 to 50% of the total observed variations in the paleoproxy records. Our results suggest that neglecting bathymetric changes leads to significant misattribution to uncertain carbon cycle parameters (e.g., atmospheric CO2 and water column temperature) and processes (e.g., biological pump efficiency and silicate-carbonate riverine flux). To illustrate this point, we use our updated bathymetry for an Early Paleogene C cycle case study. We obtain carbonate riverine flux estimates that suggest a reversal of the weathering trend with respect to present-day, contrasting with previous studies, but consistent with proxy records and tectonic reconstructions.

Elemental Uptake by Different Calcite Crystal Faces: An In Situ Study

This study aims to evaluate relationships between elemental signatures in calcite and the crystallographic orientation of its planes. The ability of calcite (a widespread calcium carbonate mineral) to entrap various trace and minor elements in its structure is the foundation of multiple methods (also called proxies) to reconstruct paleoenvironment conditions (e.g., temperature, pH, and marine chemistry). Although several element-to-calcium ratios (E/Ca) are routinely measured in marine carbonates and are widely used in paleoclimate studies, some of the controls on the incorporation of these elements are still unclear. Here, we examine the effect of crystallography on (E/Ca)calcite by growing thin layers of calcite on differently oriented Iceland Spar substrates immersed in modified seawater solution. Newly grown calcite layers were examined with Laser Ablation Inductivity–Coupled Plasma Mass Spectrometry (LA-ICP-MS), Backscattered Electron Imaging (BSE), and Energy Dispersive X-ray Spectroscopy (EDS). We propose that the crystallographic orientation might slightly influence the incorporation of lithium (Li), sodium (Na), magnesium (Mg), sulfur (S), and barium (Ba) into the studied calcite faces and have no impact on the incorporation of boron (B), potassium (K), and strontium (Sr) at least under the conditions of our experiment.

Characterizing the stable oxygen isotopic composition of the southeast Indian Ocean

New seawater stable oxygen isotope (δ18O) samples were collected from the southeast Indian Ocean as part of the Coring to Reconstruct Ocean Circulation and Carbon dioxide Across 2 Seas (CROCCA-2S) expedition in November – December of 2018. These data fill a gap in the δ18O sampling coverage of the southern Indian basin, providing new insights into the hydrologic and oceanographic processes influencing the δ18O distribution of the region and its relationship to salinity in the upper ocean. Our surface ocean data (<100 m)—in combination with decades of observations from the broader south Indian Ocean—show distinct δ18O – salinity characteristics on either side of ∼85°E. The balance between evaporation and precipitation yields a strong, robust δ18O – salinity relationship west of 85°E (δ18O = 0.50(±0.01) * S – 17.2(±0.22)). However, within the mesoscale eddy field initiated by the Leeuwin Current further east (∼85–120°E), our observations fall along a mixing line between the southwest Indian Ocean and data collected from the Australian coastal margin, illustrating for the first time how the unique eastern boundary system of the south Indian Ocean drives regional-scale variability in the δ18O – salinity relationship of the surface ocean. A comparison between our observations in the shallow subsurface (100–1000 m) and those from neighboring surveys reinforces this upper ocean connection across the Indo-Australian basin. Antarctic Intermediate Water from the Indian Ocean can be isotopically distinguished from the more regional Tasman Intermediate Water occupying the South Australian Bight, suggesting exchange between the two regions is most prevalent at surface and mode water depths. In deeper waters (> ∼1500 m), we observe a notable 0.87‰ spread in δ18O. This variability may represent interactions between distinct deep water masses in the region, although additional data are needed to confirm. Overall, our data provide a new look at the hydrography and isotopic chemistry of the southeast Indian Ocean, emphasizing the impact of the region's mesoscale eddy field and its interconnectivity with neighboring basins.

Toxicity of Cadmium (Cd) on Artemia salina

Cd is a non-essential metal and a widespread micropollutant that has physiological effects on aquatic organisms. Cd heavy metal poisoning can be acutely caused by contamination at high doses, while chronic poisoning is generally caused by low levels of contamination and long exposure time. This research was conducted in June 2022 at the Marine Chemistry Laboratory Faculty of Fisheries and Marine, Universitas Riau, which aims to determine the value of LC50 (Lethal Concentration) for 24 hours after being given a toxicant in the form of Cd and to determine the level of Cd toxicity in A. salina. The method used in this research is the experimental method with the experimental unit A. salina. The LC50 of Cd on A. salina revealed 11.7109 mg/L. This concentration is capable of causing the death of 50% of the test animals. Furthermore, the water quality in the acute toxicity test, P0 (control), was classified as good to support the life of A. salina, while at P1 (3.13 mg/L) - P5 (50 mg/L), it was classified as polluted.

GASTROPOD DIVERSITY AS A BIO-INDICATOR OF AQUATIC POLLUTION IN SIRONJONG GADANG ISLAND PESISIR SELATAN DISTRICT

This study aims to determine the diversity of gastropods and water conditions on Sironjong Gadang Island, Pesisir Selatan Regency. This research was conducted in August 2022 in the waters of Sironjong Gadang Island and the Marine Biology Laboratory and Marine Chemistry Laboratory of the Department of Marine Science, Universitas Riau. The method used in this research is the survey method, which is direct observation of the research area and sampling and measurement of water quality parameters in the field. The results of the study found gastropod species consisting of 4 (four) families, 4 (four) genera, and 8 (eight) species. The diversity value (H') was at a moderate level of diversity. The highest gastropod density was found at Station I, with a density value of 16.33 ind/m², and the lowest density was found at Station III, with a density value of 13.89 ind/m². The highest relative density was Monodonta labia species, with a relative density value of 27.6%, while the lowest relative density was Haustrum-scoring species, with a relative density value of 3.3%. Temperature 28-29˚C; salinity 25-27 ppt; pH 7.91-7.95; brightness 1.55-2.65 m. The sediment type at Station I was dominated by muddy gravel, Station II was dominated by sandy gravel, and Station III was defeated by sandy gravel with a total sediment organic matter content of 6.10-10.05%.

Seasonal variations in chlorophyll–a and sea surface temperature in the exclusive economic zone of Sri Lanka

Oceanic phytoplankton plays a crucial role in regulating the biogeochemical cycle in marine ecosystems. Light harvesting pigments such as chlorophyll–a (chl–a) can be used to understand marine primary productivity, especially phytoplankton abundance. Sea surface temperature is closely linked with phytoplankton abundance and climatic changes. The objective of the current study is to determine spatial and temporal variations of chl–a and sea surface temperature and their co-variation, over 12 years using statistical methodologies and Remote Sensing, Geographic Information System (GIS) and Cloud Computing Approach. In this study, the available sea surface temperature and chl–a data acquired from a Moderate Resolution Imaging Spectroradiometer (MODIS) satellite sensor were proceeded through Google Earth Engine and Earth Science Data System. Data visualization was carried out using ArcMap™ software. Results show a weak negative linear relationship (−0.40, P < 0.05) between sea surface temperature and chl–a. Therefore, additional favorable environmental factors such as coastal upwelling, and nutrient discharge through river run-off can control the primary productivity of phytoplankton. We also illustrated spatial and temporal maps for chl–a and sea surface temperature distribution in the exclusive economic zone of Sri Lanka. Chlorophyll–a concentration is enhanced during the southwest monsoon, and the lowest concentration is observed during the first inter-monsoon period. Next, the highest sea surface temperature is recorded during the first inter-monsoon period, and the lowest sea surface temperature is observed during the northeast monsoon. Seasonal behavior of chl–a concentration and sea surface temperature are changed as chl–a (SWM) > chl–a (NEM) > chl–a (SIM) > chl–a (FIM) and SST (FIM) > SST (SIM) > SST (SWM) > SST (NEM), respectively. In addition, both trend lines for each variable show a positive gradient, which may be attributed to global warming. Finally, we observed the alteration of chl–a and sea surface temperature that linked to changes in ocean chemistry during the global COVID–19 pandemic.

Functional diversity and metabolic response in benthic communities along an ocean acidification gradient

Altered ocean chemistry caused by ocean acidification (OA) is expected to have negative repercussions at different levels of the ecological hierarchy, starting from the individual and scaling up to the community and ultimately to the ecosystem level. Understanding the effects of OA on benthic organisms is of primary importance given their relevant ecological role in maintaining marine ecosystem functioning. The use of functional traits represents an effective technique to investigate how species adapt to altered environmental conditions and can be used to predict changes in the resilience of communities faced with stresses associated with climate change. Artificial supports were deployed for 1-y along a natural pH gradient in the shallow hydrothermal systems of the Bottaro crater near Panarea (Aeolian Archipelago, southern Tyrrhenian Sea), to explore changes in functional traits and metabolic rates of benthic communities and the repercussions in terms of functional diversity. Changes in community composition due to OA were accompanied by modifications in functional diversity. Altered conditions led to higher oxygen consumption in the acidified site and the selection of species with the functional traits needed to withstand OA. Calcification rate and reproduction were found to be the traits most affected by pH variations. A reduction in a community's functional evenness could potentially reduce its resilience to further environmental or anthropogenic stressors. These findings highlight the ability of the ecosystem to respond to climate change and provide insights into the modifications that can be expected given the predicted future pCO2 scenarios. Understanding the impact of climate change on functional diversity and thus on community functioning and stability is crucial if we are to predict changes in ecosystem vulnerability, especially in a context where OA occurs in combination with other environmental changes and anthropogenic stressors.

Combined cadmium and chromium isotopes record a collapse of bioproductivity across the Cretaceous—Paleogene boundary in the Danish basin

Cadmium (Cd) isotope signatures (δ114Cd) deduced from modern and ancient marine deposits are often used as a proxy for bioproductivity and for micronutrient cycling, whereas chromium (Cr) isotope signatures (δ53Cr) are used as a potential proxy for oxygenation. The Cretaceous—Paleogene (K/Pg) boundary records one of Earth's five big mass extinctions, which contains geochemical fingerprints of the Chixculub asteroid impact and is coeval with the Deccan Trap volcanism. Here we present for the first time a combined record of Cd and Cr isotopes from the Danish Basin to interrogate the effects on bioproductivity across the K/Pg boundary. The δ114Cd values range between −0.28‰ and 0.27‰ defining an average of 0.05‰ ± 0.24 (2σ, n = 87). Authigenic δ53Cr values range between 0.06‰ and 1.06‰ and define an average of 0.59‰ ± 0.51 (2σ, n = 81). An abrupt jump, across the K/Pg boundary layer, from consistently positively fractionated Cd and Cr isotope signatures recorded in Late Maastrichtian white chalks towards less positively fractionated δ114Cd values and heterogeneous δ53Cr values in the Early Danian carbonates, likely indicates a decrease in surface water bioproductivity. This decrease is accompanied by redox fluctuations in the water column as a consequence of environmental changes either related to the Chixculub impact event and/or to the Deccan volcanic eruptions coeval with this boundary. Assuming an efficient removal of Cd and Cr through consumption and/or adsorption by primary producers, or by incorporation into the skeleton/shells of calcifiers, and using the fractionation factor of Cd into carbonates, we reconstruct surface water conditions during the Late Masstrichtian—Early Danian that are compatible with those of modern oceans, with δ114Cd varying from 0.17 to 0.72‰. Overall, the combined Cr-Cd isotope fluctuations over the K/Pg boundary are consistent with a scenario characterized by climate-induced changes of nutrient availability and concomitant responses of primary production levels, ultimately related to the asteroid impact and to the proceeding volcanic activities that influenced the ocean's chemistry. We anticipate our results to point for further studies of other stratigraphic sections worldwide to reveal an extensive Cd-Cr record for the Cretaceous—Paleogene boundary and its corresponding collapse of bioproductivity and decreasing ocean oxygenation.

Continental Emissions Influence the Sources and Formation Mechanisms of Marine Nitrate Aerosols in Spring Over the Bohai Sea and Yellow Sea Inferred From Stable Isotopes

AbstractThe influence of continental emissions on the origin and formation mechanisms of atmospheric particulate nitrate (ρ‐NO3−) aerosols in the marine boundary layer remains unclear. Here, synchronous observations of nitrogen isotope ratios (δ15N–NO3−) and oxygen isotope anomaly (Δ17O–NO3−) in ρ‐NO3− were conducted across the Yellow Sea and Bohai Sea in Eastern China. Nitrate concentrations, δ15N–NO3− and Δ17O–NO3− exhibited a pronounced north‐to‐south latitudinal gradient. Combined with backward air mass trajectory analysis, the high nitrate concentration and isotopic characteristics in the northern sea area were found to be affected by the continental outflow near China while the low values in the southern sea area were more related to the oceanic inflow. Stable isotope analysis in R (SIAR) indicated that near the northern sea area, the nitrate radicals (NO3) reacted with hydrocarbons (HC) or dimethyl sulfides (DMS) pathway (NO3 + HC/DMS) played a leading role in nitrate production, whereas the NO2 + OH pathway dominated near the southern sea area. Nitrate in the northern seas originated mainly from nitrogen oxides (NOx = NO + NO2, the gaseous precursor of nitrate) emitted from continental sources, especially coal combustion and biomass burning. While closer to the southern seas, the proportion of NOx generated in the marine environment (from ship and biogenic emissions) increased. Overall, the differential relative contributions of continental and marine atmospheric chemistry and NOx sources lead to the spatial distribution characteristics of atmospheric nitrate concentrations and isotopic values over the Yellow and Bohai Seas.

Synglacial carbonate records of snowball Earth ocean composition—Evidence from the Nantuo Formation, South China

Abstract The Cryogenian (ca. 717–635 Ma) snowball Earth glaciations ended with the precipitation of “cap” carbonate successions with negative carbon isotope (δ13Ccarb) values, which have been explained by the addition of various 13C-depleted carbon sources in the deglacial process. These arguments assumed that marine dissolved inorganic carbon (DIC) was enriched in 13C in the synglacial ocean. However, this assumption has not yet been tested, because the synglacial ocean chemistry is unknown. In this study, we carried out detailed analyses of the petrology, carbonate carbon (δ13Ccarb) and oxygen (δ18Ocarb) isotopes, organic carbon (δ13Corg) isotopes, major and minor elemental compositions (Ca, Mg, Mn, Fe, Sr), and iron speciation (total Fe, highly reactive Fe, pyrite Fe) of the carbonate layers (also called synglacial carbonate layers) from the Nantuo Formation (ca. 650–635 Ma) on the Yangtze block, South China. Petrographic observations indicated that the synglacial carbonate comprises dolomicrite, mud-crystal powder dolomite, lime dolomite, and dolomitic limestone, supporting an authigenic carbonate origin, and thus, it potentially recorded the ocean chemistry during the Marinoan ice age. The synglacial carbonate is characterized by extreme Mn enrichment, low Fe/Mn ratios, and low δ13Ccarb (−7‰) values. High Mn contents and low Fe/Mn ratios imply marine redox conditions favoring Mn2+ accumulation and Fe2+ oxidation, while low δ13Ccarb values might be attributed to CO2 degassing of submarine volcanoes as well as low primary burial during the glaciation. Since the δ13CDIC value of the synglacial ocean was lower than the δ13Ccarb values of most cap carbonates, we infer the addition of 13C-enriched DIC or removal of 12C during cap carbonate precipitation, such as through carbonate weathering or organic carbon burial. These findings provide new insights into the nature of Cryogenian glaciation, the origin of cap carbonates, and the aftermath of global glaciation.

Ocean salinity, early-life health, and adaptation

We study the effects of in utero exposure to climate change induced high ocean salinity levels on children's anthropometric outcomes. Leveraging six geo-referenced waves of the Bangladesh Demographic and Health Surveys merged with gridded data on ocean salinity, ocean chemistry and weather indicators (temperature, rainfall and humidity) from 1993 to 2018, we find that a one standard deviation increase in in utero salinity exposure leads to a 0.11 standard deviation decline in height-for-age. Effects on weight-for-height and weight-for-age for a similar magnitude increase in salinity are 0.13 and 0.15 standard deviations, respectively. Analyses of parental investments and health-seeking behaviors demonstrate that compensating actions along these dimensions to attenuate the detrimental effects of salinity are few and restricted to poorer households. Using satellite-sourced datasets on agriculture and land-use, we find that increasing salinity constrains farmers' land use choices, restricting cultivation in the more profitable seasons which leads to lower agricultural potential. In particular, the effects of salinity on child health originate in areas with lower agricultural intensity caused by the progressive salinization of productive lands. These results highlight the climate change related costs of environmental insults on early-life health outcomes in vulnerable populations.

Copper and zinc isotopic compositions of methane-derived carbonates: Implications for paleo-methane seepage and paleoenvironmental proxies

Copper and zinc isotopic compositions of methane-derived carbonates: Implications for paleo-methane seepage and paleoenvironmental proxies

The Paleoecological Environment during the Ediacaran–Cambrian Transition in Central Guizhou Province, China: Evidence from Zn Isotopes

During the Ediacaran–Cambrian transition, a series of stratal continuous and well-preserved siliceous rock and phosphorite assemblages developed in Qingzhen, Guizhou Province, China, facilitating research on the biological evolution, marine chemistry, and palaeoecological environment of this period. Therefore, we investigated the paleontology, trace and rare earth elements, total organic carbon, total sulfur content, and Zn isotopes of the phosphorus-bearing rock series in the Taozichong Formation of the Cambrian period in Qingzhen. Geochemical analysis reveals that the sedimentary rocks in this area were formed in the oxygen-rich seawater environment and were not affected by high-temperature hydrothermal activity. The upwelling ocean current provided abundant rare earth elements and other nutrient elements, as well as conditions for the prosperity of biota in Qingzhen. In addition, the δ66Zn value (−0.21‰–0.41‰ range and 0.17‰ mean) in the Qingzhen phosphorous rock series was much lower than that in seawater, indicating a strong level of biological productivity. The variation trend of δ13C, δ18O, and δ66Zn exhibited four stages and three obvious drift events. The results suggest that climate change during this period led to the intermittent flourishing and extinction of organisms, which triggered the negative drift of δ13C and δ18O in the ocean, resulting in a coordinated response of δ66Zn. The unique ecological environment of the Taozichong Formation in Qingzhen also provides favorable conditions for the population continuation of Ediacaran-type benthic soft-bodied metazoon dominated by discoid fossils, Shaanxilithes, worm fossils, and sponge fossils in the Cambrian strata, as well as participation in the global biological explosion events. The study area provides new insights for rebuilding the global Ediacaran–Cambrian ecosystem during the transition period.

Impact of marine carbon removal on atmospheric CO2

Abstract A computer simulation of Earth’s climate is used to study if marine carbon removal will lead to a reduced atmospheric carbon dioxide concentration, and if there are potential secondary impacts on marine life and chemistry. We find that for stationary carbon removal plants the ocean cannot supply sufficient carbon rich water to allow a meaningful reduction of atmospheric CO2. This also means that outside the location of carbon removal there is no noticeable impact on plankton concentrations. It can be speculated that putting carbon removal plants on ships would lead to a significant increase in removal efficiency, although the engineering and energy aspects of this approach would need to be investigated.

Biodegradation of Ancient Organic Carbon Fuels Seabed Methane Emission at the Arctic Continental Shelves

AbstractThis study explores the carbon stability in the Arctic permafrost following the sea‐level transgression since the Last Glacial Maximum (LGM). The Arctic permafrost stores a significant amount of organic carbon sequestered as frozen particulate organic carbon, solid methane hydrate and free methane gas. Post‐LGM sea‐level transgression resulted in ocean water, which is up to 20°C warmer compared to the average annual air mass, inundating, and thawing the permafrost. This study develops a one‐dimensional multiphase flow, multicomponent transport numerical model and apply it to investigate the coupled thermal, hydraulic, microbial, and chemical processes occurring in the thawing subsea permafrost. Results show that microbial methane is produced and vented to the seawater immediately upon the flooding of the Arctic continental shelves. This microbial methane is generated by the biodegradation of the previously frozen organic carbon. The maximum seabed methane flux is predicted in the shallow water where the sediment has been warmed up, but the remaining amount of organic carbon is still high. It is less likely to cause seabed methane emission by methane hydrate dissociation. Such a situation only happens when there is a very shallow (∼200 m depth) intra‐permafrost methane hydrate, the occurrence of which is limited. This study provides insights into the limits of methane release from the ongoing flooding of the Arctic permafrost, which is critical to understand the role of the Arctic permafrost in the carbon cycle, ocean chemistry and climate change.

Submesoscale‐Permitting Physical/Biogeochemical Future Projections for the Main Hawaiian Islands

AbstractGlobal climate models provide useful tools to forecast large‐scale anthropogenic trends and the impacts on ocean physics and marine biology and chemistry. Due to coarse spatial resolution, they typically lack the ability to represent important regional processes while underestimating mesoscale variability and vertical mixing. This means they provide limited value when it comes to regional climate projections. We developed a regional submesoscale‐permitting physical/biogeochemical model to dynamically downscale the output of a CMIP6 Earth System Model for three different Socioeconomic Pathways for the main Hawaiian Islands. We describe the methodology for downscaling the CMIP6 ocean physics and biogeochemistry along with atmospheric conditions in order to offline nest a regional model. We expect the large‐scale spatial and temporal features of the global model to be retained by the regional model, while adding representation of the regional processes that are crucial to understanding climate change on a local scale. We compare the regional model representation against both observed data and a regional reanalysis over the first two decades of the century. We show that the regional model maintains the large‐scale trends and interannual variability provided by the CMIP6 model while well‐representing the regional dynamics that drive the short‐term variability. To better illustrate the benefit of the downscaling, we present preliminary analysis of the downscaled results to examine climate impacts on the island corals that are not resolved by the global models. This analysis reveals that coastal corals are likely to experience unprecedented ocean acidification and substantial warming over the course of the century.

Nanoparticulate apatite and greenalite in oldest, well-preserved hydrothermal vent precipitates.

Paleoarchean jaspilites are used to track ancient ocean chemistry and photoautotrophy because they contain hematite interpreted to have formed following biological oxidation of vent-derived Fe(II) and seawater P-scavenging. However, recent studies have triggered debate about ancient seawater Fe and P deposition. Here, we report greenalite and fluorapatite (FAP) nanoparticles in the oldest, well-preserved jaspilites from the ~3.5-billion-year Dresser Formation, Pilbara Craton, Australia. We argue that both phases are vent plume particles, whereas coexisting hematite is linked to secondary oxidation. Geochemical modeling predicts that hydrothermal alteration of seafloor basalts by anoxic, sulfate-free seawater releases Fe(II) and P that simultaneously precipitate as greenalite and FAP upon venting. The formation, transport, and preservation of FAP nanoparticles indicate that seawater P concentrations were ≥1 to 2 orders of magnitude higher than in modern deepwater. We speculate that Archean seafloor vents were nanoparticle "factories" that, on prebiotic Earth, produced countless Fe(II)- and P-rich templates available for catalysis and biosynthesis.

State-of-the-art multimodal scanning hard X-ray imaging and tomography sheds light at multiple length-scales on biomineralization related processes

Biomineralization is a widespread process among living organisms, playing a significant role in the formation and preservation of geological structures, biogeochemical cycles, regulation of ocean chemistry, and carbon sequestration. Moreover pathological biomineralization has a huge impact on human health. The growth of biominerals provides a rich area for research at multiple length-scales since they have controlled hierarchical structures from nano-to macroscopic scales. Here, we provide an overview on the potentials of the state-of-the-art scanning hard X-ray imaging and tomography methods developed at the NANOSCOPIUM beamline at Synchrotron Soleil in such studies. Multimodal scanning imaging provides simultaneous information on the elemental composition by X-ray fluorescence (XRF) spectrometry, on the sample morphology by absorption contrast imaging, on the crystalline structure by X-ray diffraction, and on the luminescence characteristics by X-ray Excited Optical Luminescence. As illustrated through diverse research cases about biomineralization in stromatolites and pathological calcification, such a versatile portfolio of X-ray imaging techniques provides unique complementary information to conventional laboratory techniques on biominerals and the underlying mineral precipitation processes.

A novel method for extracting potassium (K) from K-poor and sodium-rich samples for high-precision stable K isotope analysis

Reconstruction of stable potassium isotope composition (41K/39K) in ancient seawater has significant implications for our understanding of the fundamental controls on the long-term stability of Earth’s climate and ocean chemistry,...

Fluctuating oxygenation and dynamic iron cycling in the late Paleoproterozoic ocean

The mid-Proterozoic (1.8–0.8 billion years ago, Ga) is generally considered to have been an interval of relative stasis in terms of environmental and biological evolution. Indeed, in terms of ocean redox chemistry, deeper ocean waters are considered to have dominantly remained anoxic and ferruginous throughout this interval. Despite the persistence of ferruginous conditions, the mid-Proterozoic has long been considered notable for a general absence of iron formations (IFs), in stark contrast to the major intervals of IF deposition that occurred in the ferruginous oceans of the earlier Precambrian. In recent years, however, sporadic IFs have been found in the mid-Proterozoic, but controls on the genesis of these IFs, as well as implications for the evolution of ocean chemistry, remain poorly understood. Here, we present major and trace element data, iron speciation systematics, and organic carbon and iron isotope data for the ∼1.64 Ga Chuanlinggou Formation, which hosts a sudden reappearance of substantial IF deposition on the North China Craton. The Chuanlinggou IF has low Y/Ho ratios (24–26), slightly positive Eu anomalies (Eu/Eu* = 1.14–1.47), no Ce anomalies, slightly positive δ56Fe values (0.05 to 0.35 ‰), and high δ13Corg values (−29 ‰) relative to deeper water facies (down to −33.4 ‰). These observations provide support for a redox-stratified ocean with oxic surface waters overlying ferruginous deeper waters, and further suggest that IF deposition occurred in a stratified ocean with a shallow redoxcline during an interval of elevated Fe concentrations. Specifically, we suggest that the development of relatively intense ferruginous conditions was likely a consequence of hydrothermal activity during the breakup of the Columbia supercontinent. Microaerophilic iron-oxidizing bacteria and/or anoxygenic photosynthesizers likely played a key role in the generation of the Chuanlinggou IF. Importantly, however, data for shales that overly the Chuanlinggou IF suggest episodic intervals of deeper water oxygenation. Thus, similar to recent studies of the later Mesoproterozoic ocean, our data indicate that ocean chemistry during the latest Paleoproterozoic may have been more dynamic than previously considered, with fluctuating oxygen and iron levels likely exerting a limiting constraint on both the evolution of eukaryotes and the deposition of IFs across the immense interval of time encapsulated by the mid-Proterozoic.