Azoic sediments and benthic foraminifera: Environmental quality in a subtropical coastal lagoon in the gulf of California.

Marine transitional environments play an important role in human sustainability. Around these ecosystems, coastal lagoons are subject to high anthropogenic pressure from population growth. The increased demand for goods and services is associated with the elevated discharge of untreated and treated wastewater into lagoon systems. The absence of benthic organisms in lagoon environments has been linked to extreme natural conditions and severe anthropogenic impact at both spatial and temporal scales. However, the mechanisms that lead to the presence of azoic sediments in lagoon environments have yet to be studied. This study aimed to determine the vertical variability of textural groups, geochemistry, and benthic foraminiferal fauna to understand how natural and anthropogenic components generate a vertical sediment sequence with low or absent benthic foraminifera in a subtropical coastal lagoon in the southwestern end of the Gulf of California. A 41 cm-long sediment core was collected from La Paz Lagoon at a 1-m depth. The core was sectioned every centimeter, and sediment subsamples were dried and homogenized for grain size, calcium carbonate, elemental and isotopic carbon and nitrogen analyses, and benthic foraminifera quantification. Muds with fine sands towards the core's base characterized the sedimentary sequence. Organic carbon and total nitrogen increased from the base (1.4% and 0.06%, respectively) to the core-top (CT, 3.0% and 0.14%, respectively), significant from the 27 cm interval. Calcium carbonate content was very low (<0.8%). The relationship of δ13C vs. C:N ratio indicated that sedimentary organic carbon was derived from the marine and sewage source mixture. The δ15N of organic matter increased by 3.7‰, starting from the 27 cm interval towards the CT. The nitrogen sewage input source was relatively more significant than nitrogen fixation. The few individuals (<18 ind. in 10 g) and genera (Ammonia and Elphidium), as well as the absence of foraminifera in 19 of 41 intervals in the core, indicated that environmental conditions were unfavorable, even for colonization of environmentally stress-tolerant genera. The frequency of azoic sediments was higher from the 25 cm interval to the CT vs. from the base to the 25 cm interval. Moreover, the AEI revealed severe to moderate hypoxia in the study area. The limited presence of benthic foraminifera and calcium carbonate preservation corroborated that the quality of the lagoon's environment has deteriorated along with population growth, which requires strategic programs to sustain this transitional ecosystem.

Assessing the effect of Amphistegina lobifera invasion on infralittoral benthic foraminiferal assemblages in the Sicily Channel (Central Mediterranean).

This article documents, through a quantitative approach, the negative effect of the highly invasive species Amphistegina lobifera Larsen, 1976 on native benthic foraminiferal assemblages of coastal areas in the Sicily Channel (Central Mediterranean). A nested sampling design was applied through the comparison of benthic foraminiferal community structure across three areas that are known to be at different stages of invasion (i.e. Maltese Islands - advanced, southern Sicily - medium, and eastern Sicily - early). Results suggested that both diversity and richness of benthic foraminiferal community from the Maltese Islands were strongly modified by increased abundances of A. lobifera. In contrast, this phenomenon is less evident in southern and eastern Sicily, where the invader displayed lower abundances and the community structure was more diversified. Collected data also allowed for predicting what could happen in the near future in the whole Sicily Channel, as well as in the rest of the Mediterranean Sea.

Benthic Foraminifera as Pollution Biomarkers: a Morphological Approach.

Coastal areas are often intervened by anthropic activities, which increase the contamination of toxic agents such as heavy metals. This causes adverse morphological effects on benthic microorganisms, such as foraminifera. This group is one of the most susceptible to environmental deterioration, so they can be used as pollution biomarkers by identifying shell abnormalities. Therefore, 28 sediment samples from northern Chile were analyzed, calculating the Abnormality Index-FAI and its spatio-temporal distributions in benthic foraminifera, as well as the minimum and maximum abnormality percentages and their relationship with heavy metal concentrations, using a generalized non-linear model and a principal component analysis. The results indicated a proportion of abnormal shells within the ranges described for polluted areas conditions, revealing environmental stress conditions. This reflected a change in the environmental conditions in the most recent sediments of the bay. The highest FAI values were observed to the southwest of the bay, caused by the local current system. The species Bolivina seminuda, Buliminella elegantissima, and Epistominella exigua presented a greater number of deformities, allowing them to be used as contamination biomarkers. A significant correlation was found between Ti, Mn, Ni, Va, and Ba with decreased chamber sizes, wrong coiling, scars, and number of abnormality types. This suggests the effect of the particular geochemical conditions of the area on the heavy metals that cause toxic effects on foraminifera. These analyses are an efficient tool for identifying the effects of environmental stress before they occur in higher organisms, mitigating the environmental impact on marine biodiversity.

Benthic foraminifera as bioindicators for the heavy metals in the severely polluted Hurghada Bay, Red Sea coast, Egypt.

Twenty-nine sediment samples were collected from the Hurghada Bay, a heavily polluted bay on the Red Sea of Egypt, to inspect the environmental quality status and anthropogenic consequences on benthic foraminifera. Some foraminiferal species showed deformations in their apertures and coiling directions as a response to environmental stresses. In addition, the FoRAM index, an index used for evaluating the growth of coral reefs, indicated a hazard in the proximity of nearshore stations. To elucidate the relationships between the biological response and chemistry of sediments, eight heavy metals concentrations (Cu, Cd, Zn, Pb, As, Cr, Ni, and Mn) were analyzed using inductively coupled plasma-atomic emission spectrometers (ICP-AES). Interestingly, two groups of benthic foraminiferal associations were illustrated using multivariate statistical analyses. Group I have extremely high heavy metal concentrations, an enriched total organic matter (TOM)%, high deformation percentages, and mud content. Moreover, it is dominated by Ammonia tepida which is regarded as an opportunistic species. Group II includes low to moderately polluted stations, highly enriched living foraminiferal assemblages, and is dominated by the sensitive rotaliids Neorotalia calcar and Amphistegina lobifera. Alternatively, four geochemical indices, EF, CF, Igeo, and PLI, are used to assess the contamination level that shown ominous spots for the nearshore stations of the Hurghada Bay. The pollution indices (HQ and HI) were also conducted to evaluate the risks of carcinogenic heavy metals on human health. Our findings demonstrated that ingestion and dermal exposure have greater carcinogenic hazards for adults and children than inhalation. The lifetime carcinogenic risk (LCR) is significantly higher than the permissible limit and follows this order: Pb > As > Cr > Cd > Ni. To that end, developing strategies to lessen the negative impact of pollution on human health and/or the Red Sea's biodiversity is an inevitable issue in the present day and future.

Metabarcoding reveals high diversity of benthic foraminifera linked to water masses circulation at coastal Svalbard.

Arctic marine biodiversity is undergoing rapid changes due to global warming and modifications of oceanic water masses circulation. These changes have been demonstrated in the case of mega- and macrofauna, but much less is known about their impact on the biodiversity of smaller size organisms, such as foraminifera that represent a main component of meiofauna in the Arctic. Several studies analyzed the distribution and diversity of Arctic foraminifera. However, all these studies are based exclusively on the morphological identification of specimens sorted from sediment samples. Here, we present the first assessment of Arctic foraminifera diversity based on metabarcoding of sediment DNA samples collected in fjords and open sea areas in the Svalbard Archipelago. We obtained a total of 5,968,786 reads that represented 1384 amplicon sequence variants (ASVs). More than half of the ASVs (51.7%) could not be assigned to any group in the reference database suggesting a high genetic novelty of Svalbard foraminifera. The sieved and unsieved samples resolved comparable communities, sharing 1023 ASVs, comprising over 97% of reads. Our analyses show that the foraminiferal assemblage differs between the localities, with communities distinctly separated between fjord and open sea stations. Each locality was characterized by a specific assemblage, with only a small overlap in the case of open sea areas. Our study demonstrates a clear pattern of the influence of water masses on the structure of foraminiferal communities. The stations situated on the western coast of Svalbard that are strongly influenced by warm and salty Atlantic water (AW) are characterized by much higher diversity than stations in the northern and eastern part, where the impact of AW is less pronounced. This high diversity and specificity of Svalbard foraminifera associated with water mass distribution indicate that the foraminiferal metabarcoding data can be very useful for inferring present and past environmental conditions in the Arctic.

Insights from Fossil-Bound Nitrogen Isotopes in Diatoms, Foraminifera, and Corals.

Nitrogen is a major limiting element for biological productivity, and thus understanding past variations in nitrogen cycling is central to understanding past and future ocean biogeochemical cycling, global climate cycles, and biodiversity. Organic nitrogen encapsulated in fossil biominerals is generally protected from alteration, making it an important archive of the marine nitrogen cycle on seasonal to million-year timescales. The isotopic composition of fossil-bound nitrogen reflects variations in the large-scale nitrogen inventory, local sources and processing, and ecological and physiological traits of organisms. The ability to measure trace amounts of fossil-bound nitrogen has expanded with recent method developments. In this article, we review the foundations and ground truthing for three important fossil-bound proxy types: diatoms, foraminifera, and corals. We highlight their utility with examples of high-resolution evidence for anthropogenic inputs of nitrogen to the oceans, glacial-interglacial-scale assessments of nitrogen inventory change, and evidence for enhanced CO2 drawdown in the high-latitude ocean. Future directions include expanded method development, characterization of ecological and physiological variation, and exploration of extended timescales to push reconstructions further back in Earth's history.

Fast and pervasive diagenetic isotope exchange in foraminifera tests is species-dependent.

Oxygen isotope compositions of fossil foraminifera tests are commonly used proxies for ocean paleotemperatures, with reconstructions spanning the last 112 million years. However, the isotopic composition of these calcitic tests can be substantially altered during diagenesis without discernible textural changes. Here, we investigate fluid-mediated isotopic exchange in pristine tests of three modern benthic foraminifera species (Ammonia sp., Haynesina germanica, and Amphistegina lessonii) following immersion into an 18O-enriched artificial seawater at 90 °C for hours to days. Reacted tests remain texturally pristine but their bulk oxygen isotope compositions reveal rapid and species-dependent isotopic exchange with the water. NanoSIMS imaging reveals the 3-dimensional intra-test distributions of 18O-enrichment that correlates with test ultra-structure and associated organic matter. Image analysis is used to quantify species level differences in test ultrastructure, which explains the observed species-dependent rates of isotopic exchange. Consequently, even tests considered texturally pristine for paleo-climatic reconstruction purposes may have experienced substantial isotopic exchange; critical paleo-temperature record re-examination is warranted.

Calcite crystal orientation patterns in the bilayers of laminated shells of benthic rotaliid foraminifera.

Shells of calcifying foraminifera play a major role in marine biogeochemical cycles; fossil shells form important archives for paleoenvironment reconstruction. Despite their importance in many Earth science disciplines, there is still little consensus on foraminiferal shell mineralization. Geochemical, biochemical, and physiological studies showed that foraminiferal shell formation might take place through various and diverse mineralization mechanisms. In this study, we contribute to benthic foraminiferal shell calcification through deciphering crystallite organization within the shells. We base our conclusions on results gained from electron backscattered diffraction (EBSD) measurements and describe microstructure/texture characteristics within the laminated shell walls of the benthic, symbiontic foraminifera: Ammonia tepida, Amphistegina lobifera, Amphistegina lessonii. We highlight crystallite assembly patterns obtained on differently oriented cuts and discuss crystallite sizes, morphologies, interlinkages, orientations, and co-orientation strengths. We show that: (i) crystals within benthic foraminiferal shells are mesocrystals, (ii) have dendritic-fractal morphologies and (iii) interdigitate strongly. Based on crystal size, we (iv) differentiate between the two layers that comprise the shells and demonstrate that (v) crystals in the septa have different assemblies relative to those in the shell walls. We highlight that (vi) at junctions of different shell elements the axis of crystal orientation jumps abruptly such that their assembly in EBSD maps has a bimodal distribution. We prove (vii) extensive twin-formation within foraminiferal calcite; we demonstrate (viii) the presence of two twin modes: 60°/[001] and 77°/~[6 -6 1] and visualize their distributions within the shells. In a broader perspective, we draw conclusions on processes that lead to the observed microstructure/texture patterns.

Seasonal origin of the thermal maxima at the Holocene and the last interglacial.

Proxy reconstructions from marine sediment cores indicate peak temperatures in the first half of the last and current interglacial periods (the thermal maxima of the Holocene epoch, 10,000 to 6,000 years ago, and the last interglacial period, 128,000 to 123,000 years ago) that arguably exceed modern warmth1-3. By contrast, climate models simulate monotonic warming throughout both periods4-7. This substantial model-data discrepancy undermines confidence in both proxy reconstructions and climate models, and inhibits a mechanistic understanding of recent climate change. Here we show that previous global reconstructions of temperature in the Holocene1-3 and the last interglacial period8 reflect the evolution of seasonal, rather than annual, temperatures and we develop a method of transforming them to mean annual temperatures. We further demonstrate that global mean annual sea surface temperatures have been steadily increasing since the start of the Holocene (about 12,000 years ago), first in response to retreating ice sheets (12 to 6.5 thousand years ago), and then as a result of rising greenhouse gas concentrations (0.25 ± 0.21 degrees Celsius over the past 6,500 years or so). However, mean annual temperatures during the last interglacial period were stable and warmer than estimates of temperatures during the Holocene, and we attribute this to the near-constant greenhouse gas levels and the reduced extent of ice sheets. We therefore argue that the climate of the Holocene differed from that of the last interglacial period in two ways: first, larger remnant glacial ice sheets acted to cool the early Holocene, and second, rising greenhouse gas levels in the late Holocene warmed the planet. Furthermore, our reconstructions demonstrate that the modern global temperature has exceeded annual levels over the past 12,000 years and probably approaches the warmth of the last interglacial period (128,000 to 115,000 years ago).

Fatty Acids of Abyssal Echinodermata, the Sea Star Eremicaster vicinus and the Sea Urchin Kamptosoma abyssale: A New Polyunsaturated Fatty Acid Detected, 22:6(n-2).

Fatty acids (FA) of two species of abyssal Echinodermata-the sea star (Asteroidea) Eremicaster vicinus and the sea urchin (Echinoidea) Kamptosoma abyssale-from the Kuril-Kamchatka Trench, collected at depths of 5210 and 6183 m, were analyzed. Lipids of these deposit-feeding animals showed similar FA compositions: 20.05-16.08% saturated, 42.20-39.50% monoenoic, and 37.75-44.42% polyunsaturated FA, respectively. The contents of odd- and branched-chain FA were 17.35% and 8.80%, respectively. A significant part of FA was represented by uncommon FA such as 21:4(n-7), 22:4(n-8), 22:5(n-5), and 23:4(n-9), earlier discovered in deep-sea foraminifera. Also, the newly found acid, related to the ω2 family, Δ5,8,11,14,17,20-22:6(n-2), amounted 1.60% and 0.33% of total FA, respectively, for the two species. Such unusual FA composition of these abyssal species can be explained by the transfer and modification of FA from consumed foraminifera, which in turn, feed on bacteria.

Impact of drill cutting releases on benthic foraminifera at three exploration wells drilled between 1992 and 2012 in the SW Barents Sea, Norway.

The aim of this study is to identify the environmental impact of drill cuttings (DC) released around three wells drilled in 1992, 2000 and 2012 in the SW Barents Sea. Foraminiferal assemblages are studied in cores taken along transects <250 m from wells. Well E-1992 shows no impact of DC on foraminifera indicating that low amounts of released DC limit environmental impact. Impact at wells G-2000 and S-2012, is confined to <30 m, and attributable to smothering of fauna, resulting in low foraminiferal density. We therefore argue that previous monitoring studies, mainly focusing on samples collected >250 m from wellheads, might not capture the full impact of DC. In well G-2000, a recovery layer indicates partial recovery 15 years after DC releases. In well S-2012, no recovery is observed, 3 years after release. Released DC did not result in faunal composition changes.

Rapid ocean acidification and protracted Earth system recovery followed the end-Cretaceous Chicxulub impact.

Mass extinction at the Cretaceous-Paleogene (K-Pg) boundary coincides with the Chicxulub bolide impact and also falls within the broader time frame of Deccan trap emplacement. Critically, though, empirical evidence as to how either of these factors could have driven observed extinction patterns and carbon cycle perturbations is still lacking. Here, using boron isotopes in foraminifera, we document a geologically rapid surface-ocean pH drop following the Chicxulub impact, supporting impact-induced ocean acidification as a mechanism for ecological collapse in the marine realm. Subsequently, surface water pH rebounded sharply with the extinction of marine calcifiers and the associated imbalance in the global carbon cycle. Our reconstructed water-column pH gradients, combined with Earth system modeling, indicate that a partial ∼50% reduction in global marine primary productivity is sufficient to explain observed marine carbon isotope patterns at the K-Pg, due to the underlying action of the solubility pump. While primary productivity recovered within a few tens of thousands of years, inefficiency in carbon export to the deep sea lasted much longer. This phased recovery scenario reconciles competing hypotheses previously put forward to explain the K-Pg carbon isotope records, and explains both spatially variable patterns of change in marine productivity across the event and a lack of extinction at the deep sea floor. In sum, we provide insights into the drivers of the last mass extinction, the recovery of marine carbon cycling in a postextinction world, and the way in which marine life imprints its isotopic signal onto the geological record.

The amplitude and origin of sea-level variability during the Pliocene epoch.

Earth is heading towards a climate that last existed more than three million years ago (Ma) during the 'mid-Pliocene warm period'1, when atmospheric carbon dioxide concentrations were about 400 parts per million, global sea level oscillated in response to orbital forcing2,3 and peak global-mean sea level (GMSL) may have reached about 20 metres above the present-day value4,5. For sea-level rise of this magnitude, extensive retreat or collapse of the Greenland, West Antarctic and marine-based sectors of the East Antarctic ice sheets is required. Yet the relative amplitude of sea-level variations within glacial-interglacial cycles remains poorly constrained. To address this, we calibrate a theoretical relationship between modern sediment transport by waves and water depth, and then apply the technique to grain size in a continuous 800-metre-thick Pliocene sequence of shallow-marine sediments from Whanganui Basin, New Zealand. Water-depth variations obtained in this way, after corrections for tectonic subsidence, yield cyclic relative sea-level (RSL) variations. Here we show that sea level varied on average by 13 ± 5 metres over glacial-interglacial cycles during the middle-to-late Pliocene (about 3.3-2.5 Ma). The resulting record is independent of the global ice volume proxy3 (as derived from the deep-ocean oxygen isotope record) and sea-level cycles are in phase with 20-thousand-year (kyr) periodic changes in insolation over Antarctica, paced by eccentricity-modulated orbital precession6 between 3.3 and 2.7 Ma. Thereafter, sea-level fluctuations are paced by the 41-kyr period of cycles in Earth's axial tilt as ice sheets stabilize on Antarctica and intensify in the Northern Hemisphere3,6. Strictly, we provide the amplitude of RSL change, rather than absolute GMSL change. However, simulations of RSL change based on glacio-isostatic adjustment show that our record approximates eustatic sea level, defined here as GMSL unregistered to the centre of the Earth. Nonetheless, under conservative assumptions, our estimates limit maximum Pliocene sea-level rise to less than 25 metres and provide new constraints on polar ice-volume variability under the climate conditions predicted for this century.

Constraints on global mean sea level during Pliocene warmth.

Reconstructing the evolution of sea level during past warmer epochs such as the Pliocene provides insight into the response of sea level and ice sheets to prolonged warming1. Although estimates of the global mean sea level (GMSL) during this time do exist, they vary by several tens of metres2-4, hindering the assessment of past and future ice-sheet stability. Here we show that during the mid-Piacenzian Warm Period, which was on average two to three degrees Celsius warmer than the pre-industrial period5, the GMSL was about 16.2 metres higher than today owing to global ice-volume changes, and around 17.4 metres when thermal expansion of the oceans is included. During the even warmer Pliocene Climatic Optimum (about four degrees Celsius warmer than pre-industrial levels)6, our results show that the GMSL was 23.5 metres above the present level, with an additional 1.6 metres from thermal expansion. We provide six GMSL data points, ranging from 4.39 to 3.27 million years ago, that are based on phreatic overgrowths on speleothems from the western Mediterranean (Mallorca, Spain). This record is unique owing to its clear relationship to sea level, its reliable U-Pb ages and its long timespan, which allows us to quantify uncertainties on potential uplift. Our data indicate that ice sheets are very sensitive to warming and provide important calibration targets for future ice-sheet models7.

Natural and anthropogenic oil impacts on benthic foraminifera in the southern Gulf of Mexico.

The Campeche Sound is the major offshore oil producing area in the Southern Gulf of Mexico (SGoM). To evaluate the impact of oil related activities in the ocean floor sediments, we analyzed the geochemical (major and trace element, organic carbon and hydrocarbon concentrations) and biological (benthic foraminifera) composition of 62 superficial sediment samples, from 13 to 1336 m water depth. Cluster and Factor analysis of all the variables indicate that their distribution patterns are mainly controlled by differences between the terrigenous and carbonate platforms in the SGoM. Benthic foraminiferal assemblages were abundant and diverse, and their distribution patterns are mainly determined by water depth and sedimentary environment. However, most of the abundant species are opportunistic and/or low-oxygen tolerant, and many of their tests show oil stains and infillings, characteristic of oil polluted locations, suggesting the environment has been modified by natural seepage or oil-related activities. To determine if these conditions are natural or anthropogenic in origin, pre - industrial settings should be studied. Organic carbon (Corg) content (0.6-2.9%) and total hydrocarbon concentrations (PAHs 1.0-29.5 µg kg-1) were usually higher around the oil platforms area, the natural hydrocarbon seeps ("chapopoteras") area and offshore rivers, but there is no accumulation of oil related trace elements in these areas. However, the comparison with international sediment quality benchmarks indicates that Cd, Cr and Ni concentrations are above the threshold effect level, and also As, Ba and Cu are above the probable effect level benchmarks, which indicate that these element concentrations might be of potential ecological concern. Comprehensive studies involving different proxies, and assessing pre-industrial conditions, must be undertaken before assessing environmental health of marine benthic ecosystems.

Scaling laws explain foraminiferal pore patterns.

Due to climate warming and increased anthropogenic impact, a decrease of ocean water oxygenation is expected in the near future, with major consequences for marine life. In this context, it is essential to develop reliable tools to assess past oxygen concentrations in the ocean, to better forecast these future changes. Recently, foraminiferal pore patterns have been proposed as a bottom water oxygenation proxy, but the parameters controlling foraminiferal pore patterns are still largely unknown. Here we use scaling laws to describe how both gas exchanges (metabolic needs) and mechanical constraints (shell robustness) control foraminiferal pore patterns. The derived mathematical model shows that only specific combinations of pore density and size are physically feasible. Maximum porosity, of about 30%, can only be obtained by simultaneously increasing pore size and decreasing pore density. A large empirical data set of pore data obtained for three pseudocryptic phylotypes of Ammonia, a common intertidal genus from the eastern Atlantic, strongly supports this conclusion. These new findings provide basic mechanistic understanding of the complex controls of foraminiferal pore patterns and give a solid starting point for the development of proxies of past oxygen concentrations based on these morphological features. Pore size and pore density are largely interdependent, and both have to be considered when describing pore patterns.

Advanced approach to analyzing calcareous protists for present and past pelagic ecology: Comprehensive analysis of 3D-morphology, stable isotopes, and genes of planktic foraminifers.

Marine protists play an important role in oceanic ecosystems and biogeochemical cycles. However, the difficulties in culturing pelagic protists indicate that their ecology and behavior remain poorly understood; phylogeographic studies based on single-cell genetic analyses have often shown that they are highly divergent at the biological species level, with variable geographic distributions. This indicates that their ecology could be complex. On the other hand, the biomineral (calcareous) shells of planktic foraminifers are widely used in geochemical analyses to estimate marine paleoenvironmental characteristics (i.e., temperature), because the shell chemical composition reflects ambient seawater conditions. Among the pelagic protists, planktic foraminifers are ideal study candidates to develop a combined approach of genetic, morphological, and geochemical methods, thus reflecting environmental and ecological characteristics. The present study precisely tested whether the DNA extraction process physically and chemically affects the shells of the planktic foraminifer Globigerinoides ruber. We used a nondestructive method for analyzing physical changes (micro-focus X-ray computed tomography (MXCT) scanning) to compare specimens at the pre- and post-DNA extraction stages. Our results demonstrate that DNA extraction has no significant effect on shell density and thickness. We measured stable carbon and oxygen isotopes on the shell of each individual in a negative control or one of two DNA-extracted groups and detected no significant differences in isotopic values among the three groups. Moreover, we evaluated isotopic variations at the biological species level with regard to their ecological characteristics such as depth habitat, life stages, and symbionts. Thus, our examination of the physiochemical effects on biomineral shells through DNA extraction shows that morphological and isotopic analyses of foraminifers can be combined with genetic analysis. These analytical methods are applicable to other shell-forming protists and microorganisms. In this study, we developed a powerful analytical tool for use in ecological and environmental studies of modern and past oceans.

Calcareous Foraminiferal Shells as a Template for the Formation of Hierarchal Structures of Inorganic Nanomaterials.

A microorganism template approach has been explored for the fabrication of various well-defined three-dimensional (3D) structures. However, most of these templates suffer from small size (few µm), difficulty to remove the template, or low surface area, which affect their potential use in different applications or makes industrial scale-up difficult. Conversely, foraminifer's microorganisms are large (up to 200 mm), consist of CaCO3 (easy to dissolve in mild acid), and have a relatively high surface area (≈5 m2 g-1). Herein, we demonstrate the formation of hierarchical structures of inorganic materials using calcareous foraminiferal shells such as Sorites, Globigerinella siphonifera, Lox-ostomina amygdaleformis, Calcarina baculatus or hispida, and Peneroplis planatus. Several techniques, such as thermal decomposition of single-source precursors of metal oxides or sulfides, reduction of metal salts directly on the surfaces, and redox reactions, were used for coating of different shell materials and several hybrid compositions, which possess nanofeatures. Finally, we examined the role of the prepared 3D structures on the reduction of 4-nitrophenol (4-NP), ethanol electrooxidation, and water purification. A remarkable performance was achieved in each application. The hierarchical structure leads to the reduction of 4-NP within several minutes, a 27 mA cm-2 current density peak was obtained for ethanol electrooxidation, and more than 95% of the organic dye contaminants were successfully removed. These results show that using foraminiferal shells offers a new way for designing complex hierarchical structures with unique properties.

Influence of surface ocean density on planktonic foraminifera calcification.

This study provides evidence that ambient seawater density influences calcification and may account for the observed planktonic foraminifera shell mass increase during glacial times. Volumes of weighed fossil Globigerina bulloides shells were accurately determined using X-ray Computer Tomography and were combined with water density reconstructions from Mg/Ca and δ18O measurements to estimate the buoyancy force exerted on each shell. After assessment of dissolution effects, the resulting relationship between shell mass and buoyancy suggests that heavier shells would need to be precipitated in glacial climates in order for these organisms to remain at their optimum living depth, and counterbalance the increased buoyant force of a denser, glacial ocean. Furthermore, the reanalysis of bibliographic data allowed the determination of a relationship between G. bulloides shell mass and ocean density, which introduces implications of a negative feedback mechanism for the uptake of atmospheric CO2 by the oceans.

Glacial expansion of oxygen-depleted seawater in the eastern tropical Pacific.

Increased storage of carbon in the oceans has been proposed as a mechanism to explain lower concentrations of atmospheric carbon dioxide during ice ages; however, unequivocal signatures of this storage have not been found1. In seawater, the dissolved gases oxygen and carbon dioxide are linked via the production and decay of organic material, with reconstructions of low oxygen concentrations in the past indicating an increase in biologically mediated carbon storage. Marine sediment proxy records have suggested that oxygen concentrations in the deep ocean were indeed lower during the last ice age, but that near-surface and intermediate waters of the Pacific Ocean-a large fraction of which are poorly oxygenated at present-were generally better oxygenated during the glacial1-3. This vertical opposition could suggest a minimal net basin-integrated change in carbon storage. Here we apply a dual-proxy approach, incorporating qualitative upper-water-column and quantitative bottom-water oxygen reconstructions4,5, to constrain changes in the vertical extent of low-oxygen waters in the eastern tropical Pacific since the last ice age. Our tandem proxy reconstructions provide evidence of a downward expansion of oxygen depletion in the eastern Pacific during the last glacial, with no indication of greater oxygenation in the upper reaches of the water column. We extrapolate our quantitative deep-water oxygen reconstructions to show that the respired carbon reservoir of the glacial Pacific was substantially increased, establishing it as an important component of the coupled mechanism that led to low levels of atmospheric carbon dioxide during the glacial.