Ocean Acidification Affects Redox-Balance and Ion-Homeostasis in the Life-Cycle Stages of Emiliania huxleyi

Ocean Acidification (OA) has been shown to affect photosynthesis and calcification in the coccolithophore Emiliania huxleyi, a cosmopolitan calcifier that significantly contributes to the regulation of the biological carbon pumps. Its non-calcifying, haploid life-cycle stage was found to be relatively unaffected by OA with respect to biomass production. Deeper insights into physiological key processes and their dependence on environmental factors are lacking, but are required to understand and possibly estimate the dynamics of carbon cycling in present and future oceans. Therefore, calcifying diploid and non-calcifying haploid cells were acclimated to present and future CO2 partial pressures (pCO2; 38.5 Pa vs. 101.3 Pa CO2) under low and high light (50 vs. 300 µmol photons/m**2 /s). Comparative microarray-based transcriptome profiling was used to screen for the underlying cellular processes and allowed to follow up interpretations derived from physiological data. In the diplont, the observed increases in biomass production under OA are likely caused by stimulated production of glycoconjugates and lipids. The observed lowered calcification under OA can be attributed to impaired signal-transduction and ion-transport. The haplont utilizes distinct genes and metabolic pathways, reflecting the stage-specific usage of certain portions of the genome. With respect to functionality and energy-dependence, however, the transcriptomic OA-responses resemble those of the diplont. In both life-cycle stages, OA affects the cellular redox-state as a master regulator and thereby causes a metabolic shift from oxidative towards reductive pathways, which involves a reconstellation of carbon flux networks within and across compartments. Whereas signal transduction and ion-homeostasis appear equally OA-sensitive under both light intensities, the effects on carbon metabolism and light physiology are clearly modulated by light availability. These interactive effects can be attributed to the influence of OA and light on the redox equilibria of NAD and NADP, which function as major sensors for energization and stress. This generic mode of action of OA may therefore provoke similar cell-physiological responses in other protists.

Magnetic susceptibility and electric conductivity of marine surficial sediments by benthic electromagnetic profiling

Distribution, accumulation and diagenesis of surficial sediments in coastal and continental shelf systems follow complex chains of localized processes and form deposits of great spatial variability. Given the environmental and economic relevance of ocean margins, there is growing need for innovative geophysical exploration methods to characterize seafloor sediments by more than acoustic properties. A newly conceptualized benthic profiling and data processing approach based on controlled source electromagnetic (CSEM) imaging permits to coevally quantify the magnetic susceptibility and the electric conductivity of shallow marine deposits. The two physical properties differ fundamentally insofar as magnetic susceptibility mostly assesses solid particle characteristics such as terrigenous or iron mineral content, redox state and contamination level, while electric conductivity primarily relates to the fluid-filled pore space and detects salinity, porosity and grain-size variations. We develop and validate a layered half-space inversion algorithm for submarine multifrequency CSEM with concentric sensor configuration. Guided by results of modeling, we modified a commercial land CSEM sensor for submarine application, which was mounted into a nonconductive and nonmagnetic bottom-towed sled. This benthic EM profiler Neridis II achieves 25 soundings/second at 3-4 knots over continuous profiles of up to hundred kilometers. Magnetic susceptibility is determined from the 75 Hz in-phase response (90% signal originates from the top 50 cm), while electric conductivity is derived from the 5 kHz out-of-phase (quadrature) component (90% signal from the top 92 cm). Exemplary survey data from the north-west Iberian margin underline the excellent sensitivity, functionality and robustness of the system in littoral (~0-50 m) and neritic (~50-300 m) environments. Susceptibility vs. porosity cross-plots successfully identify known lithofacies units and their transitions. All presently available data indicate an eminent potential of CSEM profiling for assessing the complex distribution of shallow marine surficial sediments and for revealing climatic, hydrodynamic, diagenetic and anthropogenic factors governing their formation.

Geochemistry of ODP Site 145-882

Measurements of benthic foraminiferal cadmium:calcium (Cd/Ca) have indicated that the glacial-interglacial change in deep North Pacific phosphate (PO4) concentration was minimal, which has been taken by some workers as a sign that the biological pump did not store more carbon in the deep glacial ocean. Here we present sedimentary redox-sensitive trace metal records from Ocean Drilling Program (ODP) Site 882 (NW subarctic Pacific, water depth 3244 m) to make inferences about changes in deep North Pacific oxygenation - and thus respired carbon storage - over the past 150,000 yr. These observations are complemented with biogenic barium and opal measurements as indicators for past organic carbon export to separate the influences of deep-water oxygen concentration and sedimentary organic carbon respiration on the redox state of the sediment. Our results suggest that the deep subarctic Pacific water mass was depleted in oxygen during glacial maxima, though it was not anoxic. We reconcile our results with the existing benthic foraminiferal Cd/Ca by invoking a decrease in the fraction of the deep ocean nutrient inventory that was preformed, rather than remineralized. This change would have corresponded to an increase in the deep Pacific storage of respired carbon, which would have lowered atmospheric carbon dioxide (CO2) by sequestering CO2 away from the atmosphere and by increasing ocean alkalinity through a transient dissolution event in the deep sea. The magnitude of change in preformed nutrients suggested by the North Pacific data would have accounted for a majority of the observed decrease in glacial atmospheric pCO2.

Iron isotope and trace metal record of Cenomanian-Turonian sediments

he global carbon cycle during the mid-Cretaceous (~125-88 million years ago, Ma) experienced numerous major perturbations linked to increased organic carbon burial under widespread, possibly basin-scale oxygen deficiency and episodes of euxinia (anoxic and H2S-containing). The largest of these episodes, the Cenomanian-Turonian boundary event (ca. 93.5 Ma), or oceanic anoxic event (OAE) 2, was marked by pervasive deposition of organic-rich, laminated black shales in deep waters and in some cases across continental shelves. This deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter. Enrichments of redox-sensitive, often bioessential trace metals, including Fe and Mo, indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production. Iron enrichments and bulk Fe isotope compositions track the sources and sinks of Fe in the proto-North Atlantic at seven localities marked by diverse depositional conditions. Included are an ancestral mid-ocean ridge and euxinic, intermittently euxinic, and oxic settings across varying paleodepths throughout the basin. These data yield evidence for a reactive Fe shuttle that likely delivered Fe from the shallow shelf to the deep ocean basin, as well as (1) hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province(s) and (2) local-scale Fe remobilization within the sediment column. This study, the first to explore Fe cycling and enrichment patterns on an ocean scale using iron isotope data, demonstrates the complex processes operating on this scale that can mask simple source-sink relationships. The data imply that the proto-North Atlantic received elevated Fe inputs from several sources (e.g., hydrothermal, shuttle and detrital inputs) and that the redox state of the basin was not exclusively euxinic, suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during OAE-2.

Seawater carbonate chemistry and combined mechanistic effects of CO2 and light on the N2-fixing cyanobacterium Trichodesmium IMS101, 2010

The marine diazotrophic cyanobacterium Trichodesmium responds to elevated atmospheric CO2 partial pressure (pCO2) with higher N2 fixation and growth rates. To unveil the underlying mechanisms, we examined the combined influence of pCO2(150 and 900 µatm) and light (50 and 200 µmol photons m-2 s-1) on TrichodesmiumIMS101. We expand on a complementary study that demonstrated that while elevated pCO2 enhanced N2 fixation and growth, oxygen evolution and carbon fixation increased mainly as a response to high light. Here, we investigated changes in the photosynthetic fluorescence parameters of photosystem II, in ratios of the photosynthetic units (photosystem I:photosystem II), and in the pool sizes of key proteins involved in the fixation of carbon and nitrogen as well as their subsequent assimilation. We show that the combined elevation in pCO2 and light controlled the operation of the CO2-concentrating mechanism and enhanced protein activity without increasing their pool size. Moreover, elevated pCO2 and high light decreased the amounts of several key proteins (NifH, PsbA, and PsaC), while amounts of AtpB and RbcL did not significantly change. Reduced investment in protein biosynthesis, without notably changing photosynthetic fluxes, could free up energy that can be reallocated to increase N2 fixation and growth at elevated pCO2 and light. We suggest that changes in the redox state of the photosynthetic electron transportchain and posttranslational regulation of key proteins mediate the high flexibility in resources and energy allocation in Trichodesmium. This strategy should enableTrichodesmium to flourish in future surface oceans characterized by elevated pCO2, higher temperatures, and high light.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Geochemistry of Eocene/Oligocene sediments of ODP Site 177-1090

The Agulhas Ridge, off the tip of Africa between the Atlantic and Indian Oceans, is ideally located to capture the evolution of Paleogene-early Neogene circulation patterns associated with global cooling. Multiproxy records of productivity (biogenic barium (Baex), opal, CaCO3 mass accumulation rates (MARs)), nutrient and organic carbon burial (reactive phosphorus (Pr) MARs), and redox state of deep waters (U enrichment) from Ocean Drilling Program (ODP) Site 1090 reflect hydrographic shifts in this region between the middle Eocene and early Oligocene (~9-33 Ma). Several peaks in increased export productivity and burial of organic matter occurred within the late Eocene (~36.5, ~34, and ~33.7 Ma), which along with surface hydrologic conditions favoring opaline organisms over calcareous organisms could have aided in the draw down of pCO2 to a threshold level that facilitated large ice sheet development on Antarctica in the earliest Oligocene. Our multiproxy approach illustrates the importance of vertical as well as spatial hydrographic reorganization in amplifying or driving climatic cooling of the middle Eocene to early Oligocene by facilitating increases in the relative or absolute burial of organic carbon.

Biomarkers in turbidites at ODP Sites 157-951 and 157-952

Free and ester-bound lipid biomarkers were analysed in oxidised and unoxidised parts of four distinct turbidites from the Madeira Abyssal Plain (MAP), which contained 1 to 2% organic carbon homogeneously distributed throughout the turbidites at the time they were deposited. These turbidites are well suited to study the effects of oxic degradation on lipid biomarkers without the complicating influence of varying organic matter sources, sedimentation rates, or bioturbation. One sample from the oxidised turbidite was compared with two samples from the unoxidised part of each turbidite. Postdepositional oxic degradation decreased concentrations of biomarkers by several orders of magnitude. The ester-bound lipids were degraded to a far lesser extent than their free counterparts were. The extent of degradation of different compounds differed substantially. Within a specific class of biomarkers, degradation also took place to a different extent, altering their distributions. This study shows that oxic degradation of the organic matter may have a profound effect on the biomarker fingerprint and may result in a severe bias in, for example, the interpretation of organic matter sources and the estimation of the palaeoproductivity of specific groups of phytoplankton.

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.