Ancient Marine Research Articles

Chloride in the Chalk aquifer of East Anglia, UK, Part 1: Distribution of chloride in brackish and saline groundwater

The Chalk aquifer of East Anglia is heavily exploited as a groundwater source. During exploration and exploitation, it has become clear that some of the groundwater in the Chalk is brackish and unsuitable for drinking (>250 mg/l chloride). Data comprising chemical analyses of pumped water samples and borehole depth samples (> 900 results in total), and downhole geophysical surveys have been used to assemble maps of the distribution of chloride areally and with depth. Brackish or saline water is probably present at depth in the Chalk, even where shallow fresh water is present, over much of the area where Crag Group marine sediments have been deposited. The depth below surface at which brackish water is encountered varies between 50 to >100 m, and the elevation of the transition varies from +16 mAOD to below 91 mAOD. From its chemistry it is deduced that most of the brackish water is of ancient marine origin, but that there has been localised intrusion of modern seawater in coastal areas, especially around Ipswich. Saline water most probably entered the aquifer during Crag Group times (late Pliocene-early Pleistocene) and its chemistry has been modified subsequently. The most saline old water that has been encountered has full marine salinity.

Mapping the habitat distribution of horseshoe crabs (Tachypleus gigas) in Pamekasan, Madura Island, Indonesia

Abstract Horseshoe crabs, often known as Belangkas or Mimi, is one of the ancient marine faunas with protected conservation status. Horseshoe crabs are distributed in coastal waters of Indonesia of the islands of Sumatra, Java, Kalimantan, and Sulawesi, which are often caught as bycatch. Horseshoe crabs’s bloods were uniquewhich contain amebocytes as a test material for the presence of endotoxin bacteria. The purpose of this study was to identify the species of horseshoe crabs and to analyze environmental conditions, as well as the distribution of horseshoe crabs in the coastal waters of Pamekasan, Madura Island. This study was conducted in June 2023 by collecting data from crab fishers. ArcGIS was applied to delineate the distribution of horseshoe crab. The identification results showed that there was one species horseshoe crab of the Tachypleus gigas in the waters of Polagan Village, Galis District, Pamekasan Regency. The environmental condition of the waters in Polagan Village, Galis District, and Pamekasan Regency was relatively good. Habitat mapping is one way to protect these animals from the threat of extinction and support conservation efforts.

Genesis and reservoir preservation mechanism of 10 000‐m ultradeep dolomite in Chinese craton basin

AbstractThe 10 000‐m ultradeep dolomite reservoir holds significant potential as a successor field for future oil and gas exploration in China's marine craton basin. However, major challenges such as the genesis of dolomite, the formation time of high‐quality reservoirs, and the preservation mechanism of reservoirs have always limited exploration decision‐making. This research systematically elaborates on the genesis and reservoir‐forming mechanisms of Sinian–Cambrian dolomite, discussing the ancient marine environment where microorganisms and dolomite develop, which controls the formation of large‐scale Precambrian–Cambrian dolomite. The periodic changes in Mg isotopes and sedimentary cycles show that the thick‐layered dolomite is the result of different dolomitization processes superimposed on a spatiotemporal scale. Lattice defects and dolomite embryos can promote dolomitization. By simulating the dissolution of typical calcite and dolomite crystal faces in different solution systems and calculating their molecular weights, the essence of heterogeneous dissolution and pore formation on typical calcite and dolomite crystal faces was revealed, and the mechanism of dolomitization was also demonstrated. The properties of calcite and dolomite (104)/(110) grain boundaries and their dissolution mechanism in carbonate solution were revealed, showing the limiting factors of the dolomitization process and the preservation mechanism of deep buried dolomite reservoirs. The in situ laser U‐Pb isotope dating technique has demonstrated the timing of dolomitization and pore formation in ancient carbonate rocks. This research also proposed that dolomitization occurred during the quasi‐contemporaneous or shallow‐burial periods within 50 Ma after deposition and pores formed during the quasi‐contemporaneous to the early diagenetic periods. And it was clear that the quasi‐contemporaneous dolomitization was the key period for reservoir formation. The systematic characterization of the spatial distribution of the deepest dolomite reservoirs in multiple sets of the Sinian and the Cambrian in the Chinese craton basins provides an important basis for the distribution prediction of large‐scale dolomite reservoirs. It clarifies the targets for oil and gas exploration at depths over 10 000 m. The research on dolomite in this study will greatly promote China's ultradeep oil and gas exploration and lead the Chinese petroleum industry into a new era of 10 000‐m deep oil exploration.

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.

Assessment of water supply to the east European arctic agglomeration from groundwater, taking into account their quality and health risks

The purpose of the study is to assess the possibilities of using groundwater for water supply in the East European Arctic agglomeration based on an assessment of their quality and health risks. For this purpose, high-precision determinations of the complete macro- and microcomponent composition were carried out in sixty-six water samples taken from wells up to 180 m deep. It was found that in some samples the concentrations of Na+, Fe, B, Ba, Mn and U exceeded WHO standards. The least mineralized young waters are characterized by the processes of dissolution of carbonates with the transition of Ca, Mg, Ba, Sr into water, and the processes of leaching of Fe and Mn by acidic swamp waters from near-surface sediments. Waters of high mineralization, enriched in Na+, Cl-, B, Mo, Cd, Pb, were formed as a result of the dissolution of aluminosilicate rocks over thousands of years and mixing with relics of ancient and modern marine transgressions. An assessment of the average Water Quality Index value of the studied aquifer showed that, in general, the water is of excellent quality. Non-carcinogenic risks were determined primarily by uranium concentrations. The average danger index values for this element for children were 1.22. In adults it was slightly lower and amounted to 0.83. Carcinogenic risks are associated primarily with arsenic concentrations. The average total carcinogenic risk associated with this element was 3.8.10−5, which is acceptable, but samples from two wells showed total carcinogenic risk values above 10−4, which is in the high-risk area. For drinking purposes, it is preferable to use low-mineralized water with a minimum content of toxic elements. If necessary, preliminary aeration of the water is possible, during which precipitation of iron, arsenic and uranium occurs. Due to the typical nature of the problem under consideration for the Arctic regions, the results obtained can be used at other sites in the Subpolar zone.

Stable Isotope Variation in East and Southeast Asian Marine Ecosystems and its Relevance for Archaeological Analysis

ABSTRACT This paper delves into the utilisation of stable isotope analysis as a tool for understanding ancient human adaptations to diverse marine environments, with a specific geographical focus on Southeast Asia and the Pacific. It analyzes stable isotope data from modern fish bones and tooth enamel, focusing on δ13C, δ15N, and δ18O values. The data confirm the reliability of δ13C as a proxy for marine consumption in archaeological contexts and emphasises the potential of combining δ13C and δ15N measurements to reconstruct marine food consumption and trophic level. This, in turn, helps us gain insights into ancient marine consumption and ecosystems in Southeast Asia. While distinctions between marine niches are not clear, δ15N shows potential for distinguishing feeding behaviours among fish species. The data also suggests geographical and ecological variations in stable isotope values, highlighting the need for locally-based baseline datasets in archaeological studies of marine subsistence strategies.

Asymmetric fin shape changes swimming dynamics of ancient marine reptiles’ soft robophysical models

Animals have evolved highly effective locomotion capabilities in terrestrial, aerial, and aquatic environments. Over life’s history, mass extinctions have wiped out unique animal species with specialized adaptations, leaving paleontologists to reconstruct their locomotion through fossil analysis. Despite advancements, little is known about how extinct megafauna, such as the Ichthyosauria one of the most successful lineages of marine reptiles, utilized their varied morphologies for swimming. Traditional robotics struggle to mimic extinct locomotion effectively, but the emerging soft robotics field offers a promising alternative to overcome this challenge. This paper aims to bridge this gap by studying Mixosaurus locomotion with soft robotics, combining material modeling and biomechanics in physical experimental validation. Combining a soft body with soft pneumatic actuators, the soft robotic platform described in this study investigates the correlation between asymmetrical fins and buoyancy by recreating the pitch torque generated by extinct swimming animals. We performed a comparative analysis of thrust and torque generated by Carthorhyncus, Utatsusaurus, Mixosaurus, Guizhouichthyosaurus, and Ophthalmosaurus tail fins in a flow tank. Experimental results suggest that the pitch torque on the torso generated by hypocercal fin shapes such as found in model systems of Guizhouichthyosaurus, Mixosaurus and Utatsusaurus produce distinct ventral body pitch effects able to mitigate the animal’s non-neutral buoyancy. This body pitch control effect is particularly pronounced in Guizhouichthyosaurus, which results suggest would have been able to generate high ventral pitch torque on the torso to compensate for its positive buoyancy. By contrast, homocercal fin shapes may not have been conducive for such buoyancy compensation, leaving torso pitch control to pectoral fins, for example. Across the range of the actuation frequencies of the caudal fins tested, resulted in oscillatory modes arising, which in turn can affect the for-aft thrust generated.

The first Protosiren remains preserved in ornamental limestones, Middle Eocene, North Eastern Desert, Egypt

A recent revelation has come to our attention, revealing the remarkably well-preserved post-cranial remains belonging to Protosiren. These remains include vertebrae, ribs, and fragmentary bones, and were discovered from two different horizons located in the Mokattam Formation of El-Galala Plateau, North Eastern Desert of Egypt. The first specimen, GCU0101, is identified as Protosiren sp., whereas the GCU0201 specimen is recognised as Protosiren cf. P. fraasi due to certain distinguishing features. These include vertebrae with wide keyhole-shaped neural canals, reduced tuberculum on the ribs, lack of pachyostotic ribs, and the possession of rugose articular rib head. This discovery is remarkable, as it offers a unique opportunity to study the ancient marine mammal's morphology and osteology, shedding light on its evolutionary history and ecological niche. The study documents the first occurrence of Protosiren from an ornamental limestone of the Middle Eocene (Bartonian) Observatory Formation from El-Galala Plateau, Northeastern Desert, Egypt.

Impacts of Groundwater Pumping on Subterranean Microbial Communities in a Deep Aquifer Associated with an Accretionary Prism.

Accretionary prisms are composed mainly of ancient marine sediment scraped from the subducting oceanic plate at convergent plate boundaries. Anoxic groundwater is stored in deep aquifers associated with accretionary prisms and can be collected via deep wells. We investigated how such groundwater pumping affects the microbial community in a deep aquifer. Groundwater samples were collected from a deep well drilled down to 1500 m every six months (five times in total) after completion of deep well construction and the start of groundwater pumping. Next-generation sequencing and clone-library analyses of 16S rRNA genes were used to describe the subterranean microbial communities in the samples. The archaea: the prokaryote ratio in groundwater increased significantly from 1 to 7% (0 and 7 months after initiating groundwater pumping) to 59 to 72% (13, 19, and 26 months after initiating groundwater pumping), and dominant prokaryotes changed from fermentative bacteria to sulfate-reducing archaea. The optimal growth temperature of the sulfate-reducing archaea, estimated based on the guanine-plus-cytosine contents of their 16S rRNA genes, was 48-52 °C, which agreed well with the groundwater temperature at the deep-well outflow. Our results indicated that, in deep aquifers, groundwater pumping enhances groundwater flow, and the supply of sulfate-containing seawater activates the metabolism of thermophilic sulfate-reducing archaea.

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.

Impact of hypoxia on glucose metabolism and hypoxia signaling pathways in juvenile horseshoe crabs Tachypleus tridentatus

Marine hypoxia poses a significant challenge in the contemporary marine environment. The horseshoe crab, an ancient benthic marine organism, is confronted with the potential threat of species extinction due to hypoxia, making it an ideal candidate for studying hypoxia tolerance mechanisms. In this experiment, juvenile Tachypleus tridentatus were subjected to a 21-day trial at DO:2 mg/L (hypoxia) and DO:6 mg/L conditions. The experimental timeline included a 14-day exposure phase followed by a 7-day recovery period. Sampling occurred on days 0, 7, 14, and 21, where the period from day 14 to day 21 corresponds to seven days of recuperation. Several enzymatic activities of important proteins throughout this investigation were evaluated, such as succinate dehydrogenase (SDH), phosphofructokinase (PFK), hexokinase (HK), lactate dehydrogenase (LDH), and pyruvate kinase (PK). Concurrently, the relative expression of hexokinase-1 (HK), hypoxia-inducible factor 1-alpha inhibitor (FIH), and hypoxia-inducible factor 1-alpha (HIF-1α), pyruvate dehydrogenase phosphatase (PDH), succinate dehydrogenase assembly factor 4 (SDH), and Glucose-6-phosphatase (G6Pase) were also investigated. These analyses aimed to elucidate alterations in the hypoxia signaling pathway and respiratory energy metabolism. It is revealed that juvenile T. tridentatus initiated the HIF pathway under hypoxic conditions, resulting in an upregulation of HIF-1α and FIH-1 gene expression, which in turn, influenced a shift in metabolic patterns. Particularly, the activity of glycolysis-related enzymes was promoted significantly, including PK, HK, PKF, LDH, and the related HK gene. In contrast, enzymes linked to aerobic respiration, PDH, and SDH, as well as the related PDH and SDH genes, displayed down-regulation, signifying a transition from aerobic to anaerobic metabolism. Additionally, the activity of gluconeogenesis-related enzymes such as PK and G6Pase gene expression were significantly elevated, indicating the activation of gluconeogenesis and glycogenolysis pathways. Consequently, juvenile T. tridentatus demonstrated an adaptive response to hypoxic conditions, marked by changes in respiratory energy metabolism modes and the activation of hypoxia signaling pathways.

Chemical and isotopic evidence to clarify the salinity of the bedrock groundwater at Finnish mining site

Study regionLithium mine in Ostrobothnia, Western Finland. Study focusClear anomalous electrical conductivity horizons and high salinity (Cl, Na, Ca) of groundwater were identified in several exploration boreholes. As these could not be explained thoroughly with geological variations, further studies on the origin of the anomalies were suggested. It was speculated that the abrupt rise in electrical conductivity shows a horizon of waters of different ages, the lower being either old brine, or having ancient marine origin. To understand the processes controlling the hydrochemistry and the evolution of the salinity of the groundwater, the hydrogeochemistry and isotopic composition (δ2H, δ18O, 87 Sr/86 Sr, 3 H, 14 C, δ13C) was analysed in 13 boreholes, two lakes, a test pit and a stream. New Hydrological insights for the regionThe isotope and geochemistry results indicate long residence times (up to 10,000 years BP), but no strong water-rock interaction and a typical Litorina SO4 layer is missing. The mismatching results could be explained by 1) the fact that even a small amount of ancient brine or ancient sea water mixing with fresh groundwater would affect water geochemistry, while the isotopic composition would stay immutable, or 2) the salinity originates from pre-Litorina SO4-poor brackish groundwater due to an earlier uplift from the Baltic Sea. Therefore, the groundwaters of the site are interpreted as a mixture of modern meteoric and fresh HCO3 water, brackish pre-Litorina subglacial groundwater, and glacial melt water.

Refining vanadium hyper‐enrichment in black shales of the Late Devonian–Early Mississippian Bakken Formation (USA)

AbstractVanadium hyper‐enrichment (V ≥ 500 μg g−1) is widespread in ancient marine organic‐rich sedimentary rocks and is controlled by its source and accumulation. To understand how V source and accumulation control V hyper‐enrichment, the V hyper‐enriched organic‐rich black shales of the Late Devonian–Early Mississippian Bakken Formation (USA) were investigated here. The results imply that V in the Bakken Formation black shales is mainly derived from detritus and open ocean. Its hyper‐enrichment was always related to the complexation of V(IV) species by organic matter and/or fine clay mineral adsorption, though extremely reducing (i.e. euxinic) depositional conditions sometimes assisted in accumulating V through forming V(IV)–sulphur structure and/or V(III). Vanadium is a frequently used seawater redox indicator, but its hyper‐enrichment in marine sediments/sedimentary rocks does not always need to be redox driven. This study, thus, reminds us to be more careful when reconstructing palaeoceanographic redox states using V‐involved proxies.

Paleozoic cave system preserves oldest-known evidence of amniote skin.

The richest and most diverse assemblage of early terrestrial tetrapods is preserved within the infilled cave system of Richards Spur, Oklahoma (289-286 Mya1). Some of the oldest-known terrestrial amniotes2,3 are exquisitely preserved here because of early impregnation and encasement of organic material by oil-seep hydrocarbons within rapidly deposited clay-rich cave sediments under toxic anoxic conditions.4 This phenomenon has also afforded the preservation of exceedingly rare integumentary soft tissues, reported here, providing critical first evidence into the anatomical changes marking the transition from the aquatic and semiaquatic lifestyles of anamniotes to the fully terrestrial lifestyles of early amniotes. This is the first record of a skin-cast fossil (3D carbonization of the skin proper) from the Paleozoic Era and the earliest known occurrence of epidermal integumentary structures. We also report on several compression fossils (carbonized skin impressions), all demonstrating similar external morphologies to extant crocodiles. A variety of previously unknown ossifications, as well as what are likely palpebral ossifications of the deeper dermis layer of the skin, are also documented. These fossils also serve as invaluable references for paleontological reconstructions. Chromatographic analysis of extractable hydrocarbons from bone and cave samples indicates that the source rock is the Devonian age Woodford Shale. Hydrocarbons derived from ancient marine organisms interacting with geologically younger terrestrial vertebrates have therefore resulted in the oldest-known preservation of amniote skin proper.

Revitalizing the Population of Tachypleus tridentatus: A Comprehensive Study Tachypleus tridentatus Conservation in China

Tachypleus tridentatus is an ancient marine arthropod. Currently, the population of Tachypleus tridentatus has decreased rapidly, in 2019, the IUCN Red List officially updated the endangered status of Tachypleus tridentatus to Endangered (EN), indicating a global decline in the resources of this species. However, the lack of data, such as population baseline data, acts as a barrier for this nearshore habitat and medically important species. The results of this paper suggest that the main causes of the decline in the population of the Tachypleus tridentatus darter are overfishing and habitat destruction. In addition, the discussion focuses on three techniques presently employed in China to revive the population of Tachypleus tridentatus, including fisheries enhancement, habitat designation for conservation, and educational programs. The study also examines the advantages and disadvantages of conservation methods implemented in China, and while certain methods, such as moratoriums on aquaculture, show significant advantages, others, such as the establishment of protected habitats, have limitations due to incomplete findings. These methods provide a solid foundation for the conservation of the Tachypleus tridentatus, and also point to possible future directions, such as the implementation of polyculture. However, there is a need to improve the efficiency of existing methods through further development and additional data collection studies. To address the acknowledged limitations and gaps in this study, additional exploration and discourse are imperative to advance the preservation of Tachypleus tridentatus.

Streamlined Arsenolipid Identification via Direct Arsenic Detection Using RPLC-ESI-QTOF-MS with Collision-Induced Dissociation.

Arsenolipids are organoarsenicals with a long aliphatic chain that have been identified in a wide array of marine organisms. Precise analysis of arsenolipids is crucial for evaluating their toxicity, ensuring food safety, monitoring the environment, and gaining insights into the evolution of arsenic biogeochemistry. However, the discovery of new arsenolipids is often impeded by existing analytical challenges, notably the need for multiple instruments, such as the combination of liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) and inductively coupled plasma mass spectrometry (LC-ICP-MS). This study introduces a high-throughput untargeted analytical method on the basis of an unsophisticated instrumental configuration, LC-ESI-MS with collision-induced dissociation (CID) at 200 eV. This approach provides efficient dissociation of arsenic atoms from their precursor lipids and direct detection of the organic-bound arsenic as monatomic cations, As+. Application of this method has shown promise in rapidly characterizing arsenolipids in diverse samples, which has led to the discovery of a wide range of novel arsenolipids, including seven previously unidentified thioxoarsenolipids in ancient marine sediments.

Recognition of an extended record of euglenoid cysts: Implications for the end-Triassic mass extinction

The enigmatic non-pollen palynomorph Chomotriletes, occurs consistently within sediments associated with the end-Triassic mass-extinction. Based on a detailed palynological survey and other published records from Europe, Chomotriletes is prevalent within the uppermost Rhaetian Contorta and Triletes Beds and its equivalents elsewhere. Chomotriletes is now a senior synonym for Permian Circulisporites, Meso- to Cenozoic Pseudoschizaea, and Quaternary to Recent Concentricystes. Its widespread occurrence has significance for our understanding of the end-Triassic mass-extinction, but its biological affinity and ecological preference have remained contentious for almost a century. We undertook a TEM examination of a Holocene and a Pliocene example of Concentricystes and found their structure to be a close match to the wall of Jurassic Pseudoschizaea from Italy that has been interpreted to belong to cysts of the Euglenophyceae. Together with a nascent understanding of a deep time record of the euglenoid, Moyeria, Chomotriletes helps document a terrestrial signature of the Euglenophyceae in the fossil record. An extensive literature survey indicates that Chomotriletes is associated with wetlands and riverine floodplain soils, and that it inhabited mainly temperate to tropical latitudes and continues to do so to the present day. Its presence in ancient marine sediments therefore indicates transport via weathering and erosion. The association with wetlands is in line with the ecological preferences of species of the Euglenophyceae. The presence of euglenoid cysts in association with the end-Triassic extinction fits a scenario in which enhanced rainfall followed by strong soil erosion resulted in the release and redeposition of Chomotriletes into shallow marine settings.

Enigmatic carbonate isotope values in shark teeth: Evidence for environmental and dietary controls

Shark teeth are abundant in the fossil record and integrate physiological information, ecological interactions, and paleo-oceanographic conditions in their chemistry. Fossil shark teeth are well suited for stable isotope analysis because their enameloid is resistant to diagenetic alteration due to its high chemical stability. Although often used in paleoecological studies of mammals, carbonate carbon isotope compositions (δ13CCO3) in shark enameloid have remained enigmatic. Here, we investigate multiple stable isotope systems (δ13Corg, δ13CCO3, δ18OCO3, δ18OPO4) within modern shark teeth to determine relationships between the different systems and build an interpretative framework for future studies of both modern and fossil sharks. There is a weaker than expected correlation between δ18OPO4 and δ18OCO3 values in modern shark teeth (r2 = 0.44), which contrasts with mammalian studies to date and suggests this metric is not an appropriate test for diagenetic alteration in fossil shark teeth. Organic carbon isotope composition (δ13Corg) measured from modern dental collagen ranges from −16.0‰ to −10.8‰. The enameloid δ13CCO3 values we measured are much higher than collagen, ranging from −6.0‰ to 10.3‰, and there is no direct relationship between δ13Corg and δ13CCO3 values in shark teeth. Instead, we found the fractionation (ε) between δ13Corg and δ13CCO3 values to correspond with δ18OCO3 values but not δ18OPO4 values. This could be due to the carbon source in shark enameloid being partitioned between dietary carbon and dissolved inorganic carbon (DIC) or physiological differences in the tooth formation process changing the fractionation of carbonate isotopes. We applied the fractionation factor from modern teeth to carbonate isotope compositions of fossil shark teeth to predict δ13Corg values. Although the carbon sources to shark enameloid carbonate needs further investigation, our results suggest that fossil shark teeth could provide insights into carbon cycling of ancient marine ecosystems.

Evaluating methods for determining mercury concentrations in ancient marine fish and mammal bones as an approach to assessing millennial-scale fluctuations in marine ecosystems

Millennial-scale datasets of heavy metals in biota are difficult to obtain but are important for determining patterns and underlying drivers of toxicant concentrations. This is particularly important to better discriminate contemporary natural and anthropogenic sources. Globally mercury is a contaminant of concern. Post-industrial increases in mercury in arctic biota have been documented and monitoring of Steller sea lions (Eumetopias jubatus) in the Aleutian Islands, Alaska, has revealed a high proportion of pups with fur mercury concentrations above thresholds of concern in some regions. As bone is a tissue that is well preserved in archeological middens, it may prove useful for developing long-term mercury data sets under appropriate conditions. The goal of this study was to evaluate methodologies for measuring mercury concentration in Steller sea lion bone using a direct mercury analyzer, considering sample preparation methods and variability among bone tissue types (e.g., compact versus spongy bone). Finally, we directly compare sensitivity and precision of two different direct mercury analyzer models. Based on the methods presented here, direct mercury analysis using the Nippon MA-3000 can quantify small (ppb) quantities of Hg accurately and precisely in 20 to 60mg of bone with minimal specimen processing. The described method is efficient, relatively inexpensive, and requires minimal bone, conserving rare and valuable specimens. Hydrogen peroxide cleaning and collagen extraction were not required, and may be detrimental for optimal Hg quantification in bone. Further, while homogenization of distinct compact and spongy bone did not impact concentration determination, variance of technical replicates was lower improving quantitation precision. Most importantly, significant differences between compact and spongy bone exist within some individual specimen; however, the difference is not consistent and may indicate differential Hg exposure windows influenced by turnover rate of bone types. We conclude bone provides a natural archive for mercury ecosystem dynamics over millennial time scales in regions where appropriate samples are available. Compact bone has lower and less variable [THg] simplifying analysis and interpretation of data; however, the more dynamic concentrations observed in spongy bone should not be dismissed as invaluable due to their variability in [THg]. Comparisons of [THg] between bone type within individual may provide insight into more acute changes in mercury exposure within an individual’s lifetime.

A chlorophyll c synthase widely co-opted by phytoplankton.

Marine and terrestrial photosynthesis exhibit a schism in the accessory chlorophyll (Chl) that complements the function of Chl a: Chl b for green plants versus Chl c for most eukaryotic phytoplankton. The enzymes that mediate Chl c biosynthesis have long remained elusive. In this work, we identified the CHLC dioxygenase (Phatr3_J43737) from the marine diatom Phaeodactylum tricornutum as the Chl c synthase. The chlc mutants lacked Chl c, instead accumulating its precursors, and exhibited growth defects. In vitro, recombinant CHLC protein converted these precursors into Chl c, thereby confirming its identity. Phylogenetic evidence demonstrates conserved use of CHLC across phyla but also the existence of distinct Chl c synthases in different algal groups. Our study addresses a long-outstanding question with implications for both contemporary and ancient marine photosynthesis.