Stable oxygen isotope record and Mg/Ca ratios at the Mid-Pleistocene Climate Transition, ODP Site 181-1123

Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the Mid-Pleistocene Transition (MPT), when the dominant periodicity of climate cycles changed from 41,000 to 100,000 years in the absence of significant change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume at 900 ka. We see no evidence of a pattern of gradual cooling but near-freezing temperatures occur at every glacial maximum.

Nitrogen isotope, total organic carbon and element concentration data for piston core M77/2-024-5 from the Peruvian continental margin

Piston core M77/2-024-5 was retrieved during the M77/2 cruise of Research Vessel Meteor in December 2008. Total organic carbon concentrations were determined using a Carlo Erba Element Analyzer (NA1500). Prior to analysis carbon bound to carbonate minerals was removed by leaching the sediment with 1 M HCl. Bulk nitrogen isotope ratios were determined using a Carlo Erba Element Analyzer (NA1500) coupled to a DeltaPlusXL isotope ratio mass spectrometer. Major and trace metals were analyzed after microwave-assisted (CEM MARS-5) acid digestion (HCl, HNO3 and HF) by inductively coupled plasma optical emission spectrometry (aluminum, titanium and iron) (Teledyne Leeman Prodigy) and inductively coupled plasma mass spectrometry (molybdenum and uranium) (THERMO X-Series 2).

Petrography, microprobe analyses and isotope composition of ultramafic rock from the northern Haskard Highlands, Shackleton Range, East Antarctica

In the Shackleton Range of East Antarctica, garnet-bearing ultramafic rocks occur as lenses in supracrustal high-grade gneisses. In the presence of olivine, garnet is an unmistakable indicator of eclogite facies metamorphic conditions. The eclogite facies assemblages are only present in ultramafic rocks, particularly in pyroxenites, whereas other lithologies - including metabasites - lack such assemblages. We conclude that under high-temperature conditions, pyroxenites preserve high-pressure assemblages better than isofacial metabasites, provided the pressure is high enough to stabilize garnet-olivine assemblages (i.e. >=18-20 kbar). The Shackleton Range ultramafic rocks experienced a clockwise P-T path and peak conditions of 800-850 °C and 23-25 kbar. These conditions correspond to ~70 km depth of burial and a metamorphic gradient of 11-12 °C/km that is typical of a convergent plate-margin setting. The age of metamorphism is defined by two garnet-whole-rock Sm-Nd isochrons that give ages of 525 ± 5 and 520 ± 14 Ma corresponding to the time of the Pan-African orogeny. These results are evidence of a Pan-African suture zone within the northern Shackleton Range. This suture marks the site of a palaeo-subduction zone that likely continues to the Herbert Mountains, where ophiolitic rocks of Neoproterozoic age testify to an ocean basin that was closed during Pan-African collision. The garnet-bearing ultramafic rocks in the Shackleton Range are the first known example of eclogite facies metamorphism in Antarctica that is related to the collision of East and West Gondwana and the first example of Pan-African eclogite facies ultramafic rocks worldwide. Eclogites in the Lanterman Range of the Transantarctic Mountains formed during subduction of the palaeo-Pacific beneath the East Antarctic craton.

Beryllium, thorium and protactinium isotope ratios in sediments from the Galapagos microplate

Biogenic particle fluxes from highly productive surface waters, boundary scavenging, and hydrothermal activity are the main factors influencing the deposition of radionuclides in the area of the Galapagos microplate, eastern Equatorial Pacific. In order to evaluate the importance of these three processes throughout the last 100 kyr, concentrations of the radionuclides 10Be, 230Th, and 231Pa, and of Mn and Fe were measured at high resolution in sediment samples from two gravity cores KLH 068 and KLH 093. High biological productivity in the surface waters overlying the investigated area has led to 10Be and 231Pa fluxes exceeding production during at least the last 30 kyr and probably the last 100 kyr. However, during periods of high productivity at the up welling centers off Peru and extension of the equatorial high-productivity zone, a relative loss of 10Be and 231Pa may have occurred in these sediment cores because of boundary scavenging. The effects of hydrothermal activity were investigated by comparing the 230Thex concentrations to the Mn/Fe ratios and by comparing the fluxes of 230Th and 10Be which exceed production. The results suggest an enhanced hydrothermal influence during isotope stages 4 and 5 and to a lesser extent during isotope stage 1 in core KLH 093. During isotope stages 2 and 3, the hydrothermal supply of Mn was deposited elsewhere, probably because of changes in current regime or deep water oxygenation. A strong increase of the Mn/Fe ratio at the beginning of climatic stage 1 which is not accompanied by an increase of the 230Thex concentration is interpreted to be an effect of Mn remobilization and reprecipitation in the sediment.

Sedimentology and geochemistry of Oxygen Isotope Stage 3 and Holocene sediments from Laguna Potrok Aike, Patagonia

Seismic reflection studies in the maar lake Laguna Potrok Aike (51°58? S, 70°23? W) revealed an erosional unconformity associated with a sub-aquatic lake-level terrace at a water depth of 30m. Radiocarbon-dated, multi-proxy sediment studies of a piston core from this location indicate that the sediment below this discontinuity has an age of 45kyr BP (Oxygen Isotope Stage 3), and was deposited during an interval of high lake level. In comparison to the Holocene section, geochemical indicators of this older part of the record either point towards a different sediment source or to a different transport mechanism for Oxygen Isotope Stage 3 sediments. Holocene sedimentation started again before 6790cal. yr BP, providing a sediment record of hydrological variability until the present. Geochemical and isotopic data indicate a fluctuating lake level until 5310cal. yr BP. During the late Holocene the lake level shows a receding tendency. Nevertheless, the lake level did not drop below the 30m terrace to create another unconformity. The geochemical characterization of volcanic ashes reveals evidence for previously unknown explosive activity of the Reclús and Mt. Burney volcanoes during Oxygen Isotope Stage 3.

Auxiliary material and basic geochemical and benthic foraminiferal stable isotope data for the interval bracketing Eocene Thermal Maximum 2 (ETM2) at DSDP Sites 401 and 550 in the northeastern Atlantic Ocean

Ever since its discovery, Eocene Thermal Maximum 2 (ETM2; ~53.7 Ma) has been considered as one of the "little brothers" of the Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) as it displays similar characteristics including abrupt warming, ocean acidification, and biotic shifts. One of the remaining key questions is what effect these lesser climate perturbations had on ocean circulation and ventilation and, ultimately, biotic disruptions. Here we characterize ETM2 sections of the NE Atlantic (Deep Sea Drilling Project Sites 401 and 550) using multispecies benthic foraminiferal stable isotopes, grain size analysis, XRF core scanning, and carbonate content. The magnitude of the carbon isotope excursion (0.85-1.10 per mil) and bottom water warming (2-2.5°C) during ETM2 seems slightly smaller than in South Atlantic records. The comparison of the lateral d13C gradient between the North and South Atlantic reveals that a transient circulation switch took place during ETM2, a similar pattern as observed for the PETM. New grain size and published faunal data support this hypothesis by indicating a reduction in deepwater current velocity. Following ETM2, we record a distinct intensification of bottom water currents influencing Atlantic carbonate accumulation and biotic communities, while a dramatic and persistent clay reduction hints at a weakening of the regional hydrological cycle. Our findings highlight the similarities and differences between the PETM and ETM2. Moreover, the heterogeneity of hyperthermal expression emphasizes the need to specifically characterize each hyperthermal event and its background conditions to minimalize artifacts in global climate and carbonate burial models for the early Paleogene.

Chemical composition and sulfur-isotope ratios in DSDP Legs 69-and 70

As part of the geochemical-petrological study of basalts recovered from DSDP Hole 504B (Leg 70) on the southern flank of the Costa Rica Rift, we investigated specially the relationships between the distribution and isotopic composition of sulfur of scattered and vein sulfides on the one hand, and the observed pattern and processes of secondary alterations on the other. The following groups of observations are essential: (1) variations in the contents and isotopic composition of sulfur of different forms of sulfides are clearly interrelated and are observed solely in porous horizons established on the basis of detailed geophysical experiments; (2) the enrichment of sulfides in the light sulfur isotope decreases from the upper to the lower horizons, and within horizons in the direction of the less-altered rock; (3) the increase of d34S values of scattered sulfides in individual permeable zones parallels a decrease in the degree of iron oxidation in the contents of crystallization water, and in the concentrations of Mg, K, and Li in the rock.

Stable isotope composition of carbonates in the Tyrrhenian Sea

The Messinian evaporitic succession recovered at ODP Sites 652, 653, and 654 in the Tyrrhenian Sea was generated under various environmental conditions which ranged from brackish to hypersaline, as deduced from the sedimentary facies and stable isotope compositions of the carbonate and sulfate deposits. Water in the basins had to be shallow to undergo such rapid and large geochemical variations. The marine influence was omnipresent in the basin at least during the deposition of sulfate evaporites; seawater or marine brines might have been supplied either by direct input into evaporitic lagoons as at Sites 653 and 654, or by subterraneous infiltration in marginal areas as at Site 652. Episodes of severe dilution by continental waters occurred frequently throughout Messinian times in the more basinal areas at Sites 653 and 654, while a fresh water body was standing permanently at Site 652. The high heat flow present at Site 652 was responsible for a major late authigenesis of iron-rich dolomites, which was initiated during the subsidence of the basin and ended before Pliocene.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Chemical and isotope compositions of bottom sediments from ODP Leg 168, Eastern Flank of the Juan de Fuca Ridge

Ten sites were drilled in the eastern flank of the Juan de Fuca Ridge (North East Pacific) along a 100 km-long east-west transect during Leg ODP 168. This study focuses on the mineralogical and chemical study of sediments that overly basaltic basement through which seawater circulates. Silicate authigenesis was observed in the sediment layer just above basement at sites located more than 30 km from the ridge axis. This sediment alteration is particularly abundant at ODP Sites 1031 and 1029 where authigenic formation of Fe-Mg rich smectite and zeolite and the dissolution of biogenic calcite are observed. Comparison of the distribution of the alteration in the basal sediment collected along this transect suggests that diffusional transport of aqueous solutes from the basement into the overlying sediment cannot produce the mineralogical and chemical changes in the basal sediments at Sites 1031 located on a basement topographic high, and at Site 1029 located at about 50 km from the ridge axis on a buried basement area. Vertical advection of basement fluid though the sediment section is required to produce this alteration. These processes are still active at Site 1031, based on systematic variations in pore-water profiles and temperatures obtained from stable isotopic data on calcium carbonates and the nature of authigenic minerals. At Site 1029, there is no present-day advection of basement fluids though the sediment section, suggesting that this is a relic site for fluid flow.

Marine osmium isotope record across the Cretaceous-Tertiary boundary

A composite late Maastrichtian (65.5 to 68.5 Ma) marine osmium (Os) isotope record, based on samples from the Southern Ocean (ODP Site 690), the Tropical Pacific Ocean (DSDP Site 577), the South Atlantic (DSDP Site 525) and the paleo-Tethys Ocean demonstrates that subaerially exposed pelagic carbonates can record seawater Os isotope variations with a fidelity comparable to sediments recovered from the seafloor. New results provide robust evidence of a 20% decline in seawater 187Os/188Os over a period of about 200 kyr early in magnetochron C29r well below the Cretaceous-Paleogene Boundary (KPB), confirming previously reported low-resolution data from the South Atlantic Ocean. New results also confirm a second more rapid decline in 187Os/188Os associated with the KPB that is accompanied by a significant increase in Os concentrations. Complementary platinum (Pt) and iridium (Ir) concentration data indicate that the length scale of diagenetic remobilization of platinum group elements from the KPB is less than 1 m and does not obscure the pre-KPB decline in 187Os/188Os. Increases in bulk sediment Ir concentrations and decreases in bulk carbonate content that coincide with the Os isotope shift suggest that carbonate burial flux may have been lower during the initial decline in 187Os/188Os. We speculate that diminished carbonate burial rate may have been the result of ocean acidification caused by Deccan volcanism.

Isotope ratios, trace elements and ultrastructure results of Mytilus galloprovincialis shells and experimental site data off Ischia (Italy)

Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island. Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

Element concentrations and Osmium, Platinum and Rhenium isotope ratios of ODP Site 153-920 abyssal peridotites

Abyssal peridotites are normally thought to be residues of melting of the mid-ocean ridge basalt (MORB) source and are presumably a record of processes affecting the upper mantle. Samples from a single section of abyssal peridotite from the Kane Transform area in the Atlantic Ocean were examined for 190Pt-186Os and 187Re-187Os systematics. They have uniform 186Os/188Os ratios with a mean of 0.1198353 +/- 7, identical to the mean of 0.1198340 +/-12 for Os-Ir alloys and chromitites believed to be representative of the upper mantle. While the Pt/Os ratios of the upper mantle may be affected locally by magmatic processes, these data show that the Pt/Os ratio for the bulk upper mantle has not deviated by more than about +/- 30% from a chondritic Pt/Os ratio over 4.5 billion years. These observations are consistent with the addition of a chondritic late veneer after core separation as the primary control on the highly siderophile element budget of the terrestrial upper mantle. The 187Os/188Os of the samples range from 0.12267 to 0.12760 and correlate well with Pt and Pt/Os, but not Re/Os. These relationships may be explained by variable amounts of partial melting with changing D(Re), reflecting in part garnet in the residue, with a model-dependent melting age between about 600 and 1700 Ma. A model where the correlation between Pt/Os and 187Os/188Os results from multiple ancient melting events, in mantle peridotites that were later juxtaposed by convection, is also consistent with these data. This melting event or events are evidently unrelated to recent melting under mid-ocean ridges, because recent melting would have disturbed the relationship between Pt/Os and 187Os/188Os. Instead, this section of abyssal peridotite may be a block of refractory mantle that remained isolated from the convecting portions of the upper mantle for 600 Ma to >1 Ga. Alternatively, Pt and Os may have been sequestered during more recent melting and possibly melt/rock reaction processes, thereby preserving an ancient melting history. If representative of other abyssal peridotites, then the rocks from this suite with subchondritic 187Os/188Os are not simple residues of recent MORB source melting at ridges, but instead have a more complex history. This suite of variably depleted samples projects to an undepleted present-day Pt/Os of about 2.2 and 187Os/188Os of about 0.128-0.129, consistent with estimates for the primitive upper mantle.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.