Isotopic ratios and concentrations for mineral-associated and particulate organic fractions of sediment core Wilson_Lake samples

The flux of sediment and organic carbon from continents to the coastal ocean is an important factor governing organic burial in coastal sediments, and these systems preserve important records of environmental and biogeochemical conditions during past global change events. Burial of organic materials in coastal systems can be promoted by chemical resilience or through protection by association with mineral surfaces, but the role and influence of these processes on organic records from ancient sediments is poorly known. We studied sediment and organic matter burial as particulate organic matter (POM) and mineral-bound organic matter (MOM) in near-shore marine sediments from the Wilson Lake core (New Jersey, USA) that span the Paleocene-Eocene thermal maximum (PETM), a climatic perturbation 55.9 Myr ago. Our results show that distinct POM and MOM fractions can be isolated from sediments. Both fractions appear to be dominated by terrestrial material, but POM consisted primarily of recently synthesized material whereas MOM included a significant fraction of pre-aged organic matter from soils or ancient sediments. Variation in organic burial through the PETM is associated with changes in inorganic nitrogen burial, clay mineralogy, and clastic grain size that we associate with enhanced continental weathering, erosion and redeposition of ancient kaolinites, and eustatic sea level variation, respectively. These results provide a new perspective on factors governing carbon burial and carbon isotope records in ancient marine margin settings and offer information on rate and phasing of late Paleocene/early Eocene Earth system changes that may constrain interpretations of the cause of the PETM climate change event.

Elemental data for composites from DSDP Sites 417A, 417D, and 418A

While the input of river-alkalinity into seawater is relatively well known, the complementary acidity production is poorly understood. Using the major-element budget of seafloor alteration of the upper 500 m of 120-Ma-old oceanic crust at DSDP/ODP Sites 417A, 417D and 418A in the central western Atlantic, we estimate the acidity flux associated with the low-temperature weathering of the upper oceanic crust. The acidity flux is calculated based on major-element fluxes and charge-balance considerations. The relevant chemical fluxes from seawater to the upper crust are 4.1+-0.1; 1.4+-1.4; 2.2+-0.6 and -12+-2 10**11 mol/yr for K, Mg, Na and silicate-Ca, respectively. The associated acidity flux is (3.5+-3)10**11 eq/y. Relative to continental weathering, these fluxes are significant for K and silicate-Ca, but are minor for Na, Mg and acidity. Thus, riverine fluxes of alkalinity are not significantly balanced by acidity fluxes from low-temperature upper ocean crust alteration.

Tab.1: Composition of salt crusts and host rocks

Gypsum and calcite crusts were found on many outcrops of the metamorphic basement and on moraines in Dronning Maud Land. For the first time the copper mineral connellite was found in such crusts. Salt crust and efflorescences indicate an important role of chemical weathering even in a cold and arid climate such as the Antarctic interior. Findings of salt efflorescenees few centimetres beneath the rock surface suggest the contribution of salt crystallization to the formation of the typical Antarctic cavernous or honeycomb weathering features.

(Table 1) Neodymium and Strontium measurements from sediment core MD01-2451

In the nineties, cold-water coral mounds were discovered in the Porcupine Seabight (NE Atlantic, west of Ireland). A decade later, this discovery led to the drilling of the entire Challenger cold-water coral mound (Eastern slope, Porcupine Seabight) during IODP Expedition 307. As more than 50% of the sediment within Challenger Mound consists of terrigenous material, the terrigenous component is equally important for the build-up of the mound as the framework-building corals. Moreover, the terrigenous fraction contains important information on the dynamics and the conditions of the depositional environment during mound development. In this study, the first in-depth investigation of the terrigenous sediment fraction of a cold-water coral mound is performed, combining clay mineralogy, sedimentology, petrography and Sr-Nd-isotopic analysis on a gravity core (MD01-2451G) collected at the top of Challenger Mound. Sr- and Nd-isotopic fingerprinting identifies Ireland as the main contributor of terrigenous material in Challenger Mound. Besides this, a variable input of volcanic material from the northern volcanic provinces (Iceland and/or the NW British Isles) is recognized in most of the samples. This volcanic material was most likely transported to Challenger Mound during cold climatic stages. In three samples, the isotopic ratios indicate a minor contribution of sediment deriving from the old cratons on Greenland, Scandinavia or Canada. The grain-size distributions of glacial sediments demonstrate that ice-rafted debris was deposited with little or no sorting, indicating a slow bottom-current regime. In contrast, interglacial intervals contain strongly current-sorted sediments, including reworked glacio-marine grains. The micro textures of the quartz-sand grains confirm the presence of grains transported by icebergs in interglacial intervals. These observations highlight the role of ice-rafting as an important transport mechanism of terrigenous material towards the mound during the Late Quaternary. Furthermore, elevated smectite content in the siliciclastic, glaciomarine sediment intervals is linked to the deglaciation history of the British-Irish Ice Sheet (BIIS). The increase of smectite is attributed to the initial stage of chemical weathering processes, which became activated following glacial retreat and the onset of warmer climatic conditions. During these deglaciations a significant change in the signature of the detrital fraction and a lack of coral growth is observed. Therefore, we postulate that the deglaciation of the BIIS has an important effect on mound growth. It can seriously alter the hydrography, nutrient supply and sedimentation processes, thereby affecting both sediment input and coral growth and hence, coral mound development.

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.

(Table 1) Rare earth element contents in basalts and glasses of DSDP Legs 45 and 51

Rare-earth element (REE) distributions in altered basalts and glasses collected during some Legs of the Deep Sea Drilling Project show that a fractionation of these elements occurs during submarine weathering. When the alteration is well-marked, the REE distribution in altered glasses shows an enrichment in light rare-earths relative to the fresh glass. In particular, Ce is selectively enriched in palagonitized glasses that comprise, besides polymetallic nodules, another phase liable to explain the Ce depletion in seawater. Taking in account these processes of submarine weathering of the oceanic crust, a geochemical balance of Ce between authigenic phases of the marine environment is attempted.

Clay and smectite content in sediment core CRP-3

The Cenozoic sediments of the CRP-3 drill core from the continental shelf of McMurdo Sound in Ross Sea, Pacific sector of the Southern Ocean, have been investigated for their clay mineral assemblages, especially for the smectite abundances, concentrations and crystallinities. The assemblages of CRP-3 are very different from those of the CRP-1 and CRP-2/2A drill cores. Thus, an almost monomineralic assemblage characterizes the sequence below 330 mbsf. This assemblage is made of well-crystallized smectite with probably authigenic origin between 800 mbsf and 625 mbsf. From 625 mbsf to 330 mbsf the assemblage consists of moderately crystallized smectite that, at least in part, seems to be of detrital origin and thus indicates weathering under a relatively warm and wet climate. In the interval 330-145 mbsf, smectite concentrations fluctuate between 50% and 100% and probably document alternating phases of chemical weathering under a warm and wet climate and physical weathering under a relatively cool and dry climate. Above 145 mbsf the smectite decreases dramatically to concentrations of about 20% and becomes poorly crystalline. In contrast, illite and chlorite become more abundant. Such an assemblage is typical for early Oligocene and younger sediments in McMurdo Sound and reflects physical weathering conditions under a cool climate on a glaciated Antarctic continent. Correlations of the changes in the clay mineral spectrum of CRP-3 with other cores from McMurdo Sound and from other parts of the Southern Ocean has to remain speculative at this stage, because of the poor age control.

Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.

Matlab scripts for modeled obliquity amplitude modulations

The start of the Mesozoic Era is marked by roughly five million years (myr) of Earth system upheavals, including unstable biotic recovery, repeated global warming, ocean anoxia, and perturbations in the global carbon cycle. Intervals between crises were comparably hospitable to life. The causes of these upheavals are unknown, but are thought to be linked to recurrent Siberian volcanism. Here, two marine sedimentary successions at Chaohu and Daxiakou, South China are evaluated for paleoclimate change from astronomical forcing. In these sections, gamma-ray variations indicative of terrestrial weathering reveal enhanced obliquity cycling over prolonged intervals, characterized by a periodicity of 32.8 kiloyear and strong 1.2 myr modulations. This suggests a 22-hour length-of-day and 1.2 myr interaction between the orbital inclinations of Earth and Mars. The 1.2 myr obliquity modulation cycles in these sections are compared with Early Triassic records of global sea-level, temperature, redox and biotic evolution. The evidence collectively suggests that long-term astronomical forcing was involved in the repeated climatic and biotic upheavals that took place throughout the Early Triassic.

Sediment microstructures of ODP Leg 105 holes

Possible genetic relationships between syn- and post-depositional processes and sediment microstructure were investigated. Samples from cores at Sites 646 and 647 of Ocean Drilling Program (ODP) Leg 105 included examples of bottom current deposition (contourites), turbidity current deposition, consolidation, and diagenesis. Examination of nearly 200 micrographs of 14 samples from Site 646 and 13 samples from Site 647 leads to the conclusion that sedimentation processes do not appear to have an obvious influence on fabric. The effects of post-depositional processes, such as bioturbation, coring disturbance, and even remolding, appear to be less significant than one might expect as a result of the relatively coarse grain size of the sediments studied. Consolidation resulting from increased overburden stress results in increased particle alignment and compression of fabric elements with depth. The transition from open, random fabric in shallow samples to preferred orientation at depth represents the only change in these sediments that can be ascribed directly to a specific depositional or post-depositional process. Mineralogical variations, owing to changes in weathering processes and growth of authigenic/diagenetic minerals, also have a pronounced effect on sediment fabric.

Clay and smectite analysis of sediment core CRP-2A

Sediments of the CRP-2/2A drill core from the continental shelf of McMurdo Sound in Ross Sea, Pacific sector of the Southern Ocean, have been investigated for their clay mineral assemblages, especially for the smectite contents and smectite crystallinities. Highest smectite amounts and best crystallinities occur in three intervals below 485 mbsf in CRP-2/2A. They indicate deposition of sediments during a time when chemical weathering was active on large ice-free areas on the nearby Antarctic continent. In he upper part of the core, smectite contents are much lower and crystallinities are worse. This clay mineral composition indicates deposition of sediments during a time when physical weathering prevailed on an ice-covered continent. At deep-sea sites around Antarctica the shift from smectite-dominated to smectite-poor and illite-rich assemblages is well dated as earliest Oligocene, 33.9-33.1 Ma, and documents the onset of continental glaciation in East Antarctica. At CIROS-1 a corresponding shift in the clay mineralogy was observed at a depth of 425-445 mbsf.

Stable isotopes and XRF data over the Paleocene-Eocene Thermal Maximum from IODP Sites U1403 and U1409

During the Paleocene-Eocene Thermal Maximum (PETM) about 56 million years ago, thousands of petagrams of carbon were released into the atmosphere and ocean in just a few thousand years, followed by a gradual sequestration over approximately 200,000 years. If silicate weathering is one of the key negative feedbacks that removed this carbon, a period of seawater calcium carbonate saturation greater than pre-event levels is expected during the event's recovery phase. In marine sediments, this should be recorded as a temporary deepening of the depth below which no calcite is preserved - the calcite compensation depth (CCD). Previous and new sedimentary records from sites that were above the pre-PETM calcite compensation depth show enhanced carbonate accumulation following the PETM. A new record from an abyssal site in the North Atlantic that lay below the pre-PETM calcite compensation depth shows a period of carbonate preservation beginning about 70,000 years after the onset of the PETM, providing the first direct evidence for an over-deepening of the calcite compensation depth. This record confirms an overshoot in ocean carbonate saturation during the PETM recovery. Simulations with two earth system models support scenarios for the PETM that involve both a large initial carbon release followed by prolonged low-level emissions, consistent with the timing of CCD deepening in our record. Our findings indicate that sequestration of these carbon emissions was most likely the result of both globally enhanced calcite burial above the calcite compensation depth and, at least in the North Atlantic, by a temporary over-deepening of the calcite compensation depth.