Calcium isotopic composition of planktonic foraminifera from ODP Site 154-925

An 18 million year record of the Ca isotopic composition (d44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. ?44/42Ca in this record averages +0.37+/-0.05 (1 sigma SD) and ranges from +0.21? to +0.52?. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25? lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their d44/42Ca (i.e., by 0.06+/-0.06? (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in d44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (d44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (D_sed) results in unrealistically large variations in the total mass of Ca2+ in the oceans over the Neogene. Alternatively, variations of +/-0.05? in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in d44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in D_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in d44/42Ca_w and D_sed have been established, modeling the Ca2+ content of seawater from Ca isotope curves should be approached cautiously.

Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and U1 S.D., N=30 samples) (except one felsic vein with 87Sr/86Sr=0.7045), 143Nd/144Nd=0.51304-0.51314, average 0.51310+/-0.00002 (1 S.D., N=28), 206Pb/204Pb=17.43-18.55, 207Pb/204Pb=15.40-15.61 and 208Pb/204Pb=37.19-38.28. The range of Sr and the almost constant Nd isotopic composition resemble that found in the upper 500 m of Hole 735B, while Pb ranges to more radiogenic compositions. In general, there is a decrease in isotopic variation of Sr and Pb as well as ? (238U/204Pb), U and Pb with depth, with a trend towards relatively unradiogenic compositions. This correlates with a decrease in alteration and frequency of evolved rock-types in the core. Leached samples generally have less radiogenic Pb with values trending towards 206Pb/204Pb=17.35, 207Pb/204Pb=15.35 and 208Pb/204Pb=37.0, while their 87Sr/86Sr ratios deviate less systematically from unleached rocks and reach both higher, 0.70307, and lower values, 0.70276. Separated clinopyroxene has elevated 87Sr/86Sr up to 0.7035, while plagioclase generally has close to whole rock Sr. Leaching reduced 87Sr/86Sr in clinopyroxene and in two (out of nine) cases leached separates and whole rock display isotopic equilibrium. Relatively minor hydrothermal seawater alteration is thought to have increased 87Sr/86Sr in the rocks, while a secondary high temperature percolation of a mantle-derived agent is thought to be the cause for the trend towards radiogenic Pb. This material had intermediate 87Sr/86Sr and may have originated from non-MORB off axis mantle. The main primary igneous isotopic variation of the gabbros is suggested to have been derived from the MORB-mantle and is defined mainly by leached samples from both ODP Leg 176 and Leg 118 and can be explained by two-component mixing of an end-member with composition like Central Indian Ridge basalts and an end-member with composition unlike any MORB. The latter is characterized by very unradiogenic Pb, in particular 207Pb/204Pb, and may have an origin with affinity to old depleted mantle (DM). The isotopic composition of the magmas parental to the FeTi-oxide rich rocks cannot be distinguished from the magmas parental to the primitive gabbros and an intimate relationship is indicated. The small-scale inhomogeneity indicated for the SWIR MORB-mantle at the Atlantis II Fracture Zone was probably inherited by the lower crustal rocks due to small-scale melting and monogenetic magma chambers at this slow spreading ridge.

Measurements of stable carbon isotope ratios of CO2 over the last 24000 years and CO2 concentration measurements on Antarctic ice cores using three different methods

The stable carbon isotope ratio of atmospheric CO2 (d13Catm) is a key parameter in deciphering past carbon cycle changes. Here we present d13Catm data for the past 24,000 years derived from three independent records from two Antarctic ice cores. We conclude that a pronounced 0.3 per mil decrease in d13Catm during the early deglaciation can be best explained by upwelling of old, carbon-enriched waters in the Southern Ocean. Later in the deglaciation, regrowth of the terrestrial biosphere, changes in sea surface temperature, and ocean circulation governed the d13Catm evolution. During the Last Glacial Maximum, d13Catm and atmospheric CO2 concentration were essentially constant, which suggests that the carbon cycle was in dynamic equilibrium and that the net transfer of carbon to the deep ocean had occurred before then.

Climate reconstruction and oxygen isotope composition of sediment core Dethlingen, Germany

To gain insights into the mechanisms of abrupt climate change within interglacials, we have examined the characteristics and spatial extent of a prominent, climatically induced vegetation setback during the Holsteinian interglacial (Marine Isotope Stage 11c). Based on analyses of pollen and varves of lake sediments from Dethlingen (northern Germany), this climatic oscillation, here termed the "Older Holsteinian Oscillation" (OHO), lasted 220 years. It can be subdivided into a 90-year-long decline of temperate tree taxa associated with an expansion of Pinus and herbs, and a 130-year-long recovery phase marked by the expansion of Betula and Alnus, and the subsequent recovery of temperate trees. The climate-induced nature of the OHO is corroborated by changes in diatom assemblages and ?18O measured on biogenic silica indicating an impact on the aquatic ecosystem of the Dethlingen paleolake. The OHO is widely documented in pollen records from Europe north of 50° latitude and is characterized by boreal climate conditions with cold winters from the British Isles to Poland, with a gradient of decreasing temperature and moisture availability, and increased continentality towards eastern Europe. This pattern points to a weakened influence of the westerlies and/or a stronger influence of the Siberian High. A comparison of the OHO with the 8.2 ka event of the Holocene reveals close similarities regarding the imprint on terrestrial ecosystems and the interglacial boundary conditions. Hence, in analogy to the 8.2 ka event, a transient, meltwater-induced slowdown of the North Atlantic Deep Water formation appears as a plausible trigger mechanism for the OHO. If correct, meltwater release into the North Atlantic may be a more common agent of abrupt climate change during interglacials than previously thought. We conclude that meltwater-induced climate setbacks during interglacials preferentially occurred when low rates of summer insolation increase during the preceding terminations facilitated the persistence of large-scale continental ice-sheets well into the interglacials.

Lithogenic sediment deposition of 7 sediment cores from the Pacific Southern Ocean

Dust deposition in the Southern Ocean constitutes a critical modulator of past global climate variability, but how it has varied temporally and geographically is underdetermined. Here, we present data sets of glacial-interglacial dust-supply cycles from the largest Southern Ocean sector, the polar South Pacific, indicating three times higher dust deposition during glacial periods than during interglacials for the past million years. Although the most likely dust source for the South Pacific is Australia and New Zealand, the glacial-interglacial pattern and timing of lithogenic sediment deposition is similar to dust records from Antarctica and the South Atlantic dominated by Patagonian sources. These similarities imply large-scale common climate forcings such as latitudinal shifts of the southern westerlies and regionally enhanced glaciogenic dust mobilization in New Zealand and Patagonia.

Whole-rock and mineral geochemistry of ODP Hole 176-735B gabbros

We report mineral chemistry, whole-rock major element compositions, and trace element analyses on Hole 735B samples drilled and selected during Leg 176. We discuss these data, together with Leg 176 shipboard data and Leg 118 sample data from the literature, in terms of primary igneous petrogenesis. Despite mineral compositional variation in a given sample, major constituent minerals in Hole 735B gabbroic rocks display good chemical equilibrium as shown by significant correlations among Mg# (= Mg/[Mg + Fe2+]) of olivine, clinopyroxene, and orthopyroxene and An (=Ca/[Ca + Na]) of plagioclase. This indicates that the mineral assemblages olivine + plagioclase in troctolite, plagioclase + clinopyroxene in gabbro, plagioclases + clinopyroxene + olivine in olivine gabbro, and plagioclase + clinopyroxene + olivine + orthopyroxene in gabbronorite, and so on, have all coprecipitated from their respective parental melts. Fe-Ti oxides (ilmenite and titanomagnetite), which are ubiquitous in most of these rocks, are not in chemical equilibrium with olivine, clinopyroxene, and plagioclase, but precipitated later at lower temperatures. Disseminated oxides in some samples may have precipitated from trapped Fe-Ti-rich melts. Oxides that concentrate along shear bands/zones may mark zones of melt coalescence/transport expelled from the cumulate sequence as a result of compaction or filter pressing. Bulk Hole 735B is of cumulate composition. The most primitive olivine, with Fo = 0.842, in Hole 735B suggests that the most primitive melt parental to Hole 735B lithologies must have Mg# 0.637, which is significantly less than Mg# = 0.714 of bulk Hole 735B. This suggests that a significant mass fraction of more evolved products is needed to balance the high Mg# of the bulk hole. Calculations show that 25%-45% of average Eastern Atlantis II Fracture Zone basalt is needed to combine with 55%-75% of bulk Hole 735B rocks to give a melt of Mg# 0.637, parental to the most primitive Hole 735B cumulate. On the other hand, the parental melt with Mg# 0.637 is far too evolved to be in equilibrium with residual mantle olivine of Fo > 0.89. Therefore, a significant mass fraction of more primitive cumulate (e.g., high Mg# dunite and troctolite) is yet to be sampled. This hidden cumulate could well be deep in the lower crust or simply in the mantle section. We favor the latter because of the thickened cold thermal boundary layer atop the mantle beneath slow-spreading ridges, where cooling and crystallization of ascending mantle melts is inevitable. These observations and data interpretation require reconsideration of the popular concept of primary mantle melts and relationships among the extent of mantle melting, melt production, and the composition and thickness of igneous crust.

Geochemistry of Indian Ocean tephra and Afro-Arabian lavas

Widespread silicic pyroclastic eruptions of the Oligocene Afro-Arabian flood volcanic province (ignimbrites and airfall tuffs) produced up to 20% of the total flood volcanic stratigraphy (>6*10**4 km**3). Volumes of individual ignimbrites and tuffs exposed on land range from ~150 to >2000 km**3 and eight major units (15-100 m thick) were erupted in <2 Myr, placing these amongst the largest-magnitude silicic pyroclastic eruptions on Earth. They are compositionally distinctive time-stratigraphic markers which were deposited as co-ignimbrite ashfall deposits on a near-global scale around the time of the Oi2 cooling anomaly at ~30 Ma. Two ignimbrites from the lower part of the flood volcanic succession in Yemen have been correlated to: (a) the conjugate rifted margin of Ethiopia (>500 km distant); and (b) to two deep sea ash layers sampled by ODP Leg 115 in the Indian Ocean ~2700 km to the southeast. This correlation is based on whole rock analyses of silicic units for isotope ratios (Pb, Nd) and rare earth element compositions, in conjunction with novel in situ Pb isotope laser ablation multicollector inductively coupled plasma mass spectroscopy analysis of groundmass and glass shards. Compositional diversity preserved on the scale of individual ash shards in these deep sea tephra layers record chemical heterogeneity present in the silicic magma chambers that is not evident in the welded on-land deposits. Ages of the ash layers can be established by correlation to precisely dated on-land ignimbrites, and current evidence suggests that while these eruptions may have exacerbated already changing climatic conditions, they both marginally post-date the Oi2 global cooling anomaly.

Rock magnetic properties and radiocarbon dates of samples obtained on Ile de Possession, South Indian Ocean

A 6200 year old peat sequence, cored in a volcanic crater on the sub-Antarctic Ile de la Possession (Iles Crozet), has been investigated, based on a multi-proxy approach. The methods applied are macrobotanical (mosses, seeds and fruits) and diatom analyses, complemented by geochemical (Rock-Eval6) and rock magnetic measurements. The chronology of the core is based on 5 radiocarbon dates. When combining all the proxy data the following changes could be inferred. From the onset of the peat formation (6200 cal yr BP) until ca. 5550 cal yr BP, biological production was high and climatic conditions must have been relatively warm. At ca. 5550 cal yr BP a shift to low biological production occurred, lasting until ca. 4600 cal yr BP. During this period the organic matter is well preserved, pointing to a cold and/or wet environment. At ca. 4600 cal yr BP, biological production increased again. From ca. 4600 cal yr BP until ca. 4100 cal yr BP a 'hollow and hummock' micro topography developed at the peat surface, resulting in the presence of a mixture of wetter and drier species in the macrobotanical record. After ca. 4100 cal yr BP, the wet species disappear and a generally drier, acidic bog came into existence. A major shift in all the proxy data is observed at ca. 2800 cal yr BP, pointing to wetter and especially windier climatic conditions on the island probably caused by an intensification and/or latitudinal shift of the southern westerly belt. Caused by a stronger wind regime, erosion of the peat surface occurred at that time and a lake was formed in the peat deposits of the crater, which is still present today.

AMS 14C dating points, isotopic compositions, Mg/Ca ratios and sea surface temperatures of sediment cores GeoB10029-4 and GeoB10038-4

Quantifying the spatial and temporal sea surface temperature (SST) and salinity changes of the Indo-Pacific Warm Pool is essential to understand the role of this region in connection with abrupt climate changes particularly during the last deglaciation. In this study we reconstruct SST and seawater d18O of the tropical eastern Indian Ocean for the past 40,000 years from two sediment cores (GeoB 10029-4, 1°30'S, 100°08'E, and GeoB 10038-4, 5°56'S, 103°15'E) retrieved offshore Sumatra. Our results show that annual mean SSTs increased about 2-3 °C at 19,000 years ago and exhibited southern hemisphere-like timing and pattern during the last deglaciation. Our SST records together with other Mg/Ca-based SST reconstructions around Indonesia do not track the monsoon variation since the last glacial period, as recorded by terrestrial monsoon archives. However, the spatial SST heterogeneity might be a result of changing monsoon intensity that shifts either the annual mean SSTs or the seasonality of G. ruber towards the warmer or the cooler season at different locations. Seawater d18O reconstructions north of the equator suggest fresher surface conditions during the last glacial and track the northern high-latitude climate change during the last deglaciation. In contrast, seawater ?18O records south of the equator do not show a significant difference between the last glacial period and the Holocene, and lack Bølling-Allerød and Younger Dryas periods suggestive of additional controls on annual mean surface hydrology in this part of the Indo-Pacific Warm Pool.

Radiocarbon age, and sedimentation and accumulation rate of core JM05-G001 obtained during Jan Mayen cruise JM050704 to the Barents Sea

Instrumental monitoring of the climate at high northern latitudes has documented the ongoing warming of the last few decades. Climate modelling has also demonstrated that the global warming signal will be amplified in the polar region. Such temperature increases would have important implications on the ecosystem and biota of the Barents Sea. This study therefore aims to reconstruct the climatic changes of the Barents Sea based on benthic foraminifera over approximately the last 1400 years at the decadal to sub-decadal scale. Oxygen and carbon isotope analysis and benthic foraminiferal species counts indicate an overall warming trend of approximately 2.6°C through the 1400-year record. In addition, the well-documented cooling period equating to the 'Little Ice Age' is evident between c. 1650 and 1850. Most notably, a series of highly fluctuating temperatures are observed over the last century. An increase of 1.5°C is shown across this period. Thus for the first time we are able to demonstrate that the recent Arctic warming is also reflected in the oceanic micro-fauna.

Geochemistry of sediments beneath the Tonga-Kermadec arc

The fate of subducted sediment and the extent to which it is dehydrated and/or melted before incorporation into arc lavas has profound implications for the thermo-mechanical nature of the mantle wedge and models for crustal evolution. In order to address these issues, we have undertaken the first measurements of 10Be and light elements in lavas from the Tonga-Kermadec arc and the sediment profile at DSDP site 204 outboard of the trench. The 10Be/9Be ratios in the Tonga lavas are lower than predicted from flux models but can be explained if (a) previously estimated sediment contributions are too high by a factor of 2-10, (b) the top 1-22 m of the incoming sediment is accreted, (c) large amounts of sediment erosion are proposed, or (d) the sediment component takes several Myr longer than the subducting plate to reach the magma source region beneath Tonga. The lavas form negative Th/Be-Li/Be arrays that extend from a depleted mantle source composition to lower Th/Be and Li/Be ratios than that of the bulk sediment. Thus, these arrays are not easily explained by bulk sediment addition and, using partition coefficients derived from experiments on the in-coming sediment, we show that they are also unlikely to result from fluid released during dehydration of the sediment (or altered oceanic crust). However, partial melts of the dehydrated sediment residue formed at ~800 °C during the breakdown of amphibole +/- plagioclase and in the absence of cordierite have significantly lowered Th/Be ratios. The lava arrays can be successfully modelled as 10-15% partial melts of depleted mantle after it has been enriched by the addition of 0.2-2% of these partial melts. Phase relations suggest that this requires that the top of the subducting crust reaches temperatures of ~800 °C by the time it attains ~ 80 km depth which is in excellent agreement with the results of recent numerical models incorporating a temperature-dependent mantle viscosity. Under these conditions the wet basalt solidus is also crossed yet there is no recognisable eclogitic signal in the lavas suggesting that on-going dehydration or strong thermal gradients in the upper part of the subducting plate inhibit partialmelting of the altered oceanic crust.

Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

Permeability measurements on sheared and unsheared samples from different IODP Holes of Leg 316 and from IODP Hole 315-C0001E and ODP Hole 190-1174B

At subduction zones, the permeability of major fault zones influences pore pressure generation, controls fluid flow pathways and rates, and affects fault slip behavior and mechanical strength by mediating effective normal stress. Therefore, there is a need for detailed and systematic permeability measurements of natural materials from fault systems, particularly measurements that allow direct comparison between the permeability of sheared and unsheared samples from the same host rock or sediment. We conducted laboratory experiments to compare the permeability of sheared and uniaxially consolidated (unsheared) marine sediments sampled during IODP Expedition 316 and ODP Leg 190 to the Nankai Trough offshore Japan. These samples were retrieved from: (1) The décollement zone and incoming trench fill offshore Shikoku Island (the Muroto transect); (2) Slope sediments sampled offshore SW Honshu (the Kumano transect) ~ 25 km landward of the trench, including material overriden by a major out-of-sequence thrust fault, termed the "megasplay"; and (3) A region of diffuse thrust faulting near the toe of the accretionary prism along the Kumano transect. Our results show that shearing reduces fault-normal permeability by up to 1 order of magnitude, and this reduction is largest for shallow (< 500 mbsf) samples. Shearing-induced permeability reduction is smaller in samples from greater depth, where pre-existing fabric from compaction and lithification may be better developed. Our results indicate that localized shearing in fault zones should result in heterogeneous permeability in the uppermost few kilometers in accretionary prisms, which favors both the trapping of fluids beneath and within major faults, and the channeling of flow parallel to fault structure. These low permeabilities promote the development of elevated pore fluid pressures during accretion and underthrusting, and will also facilitate dynamic hydrologic processes within shear zones including dilatancy hardening and thermal pressurization.

Abundance of organic-walled dinoflagellate cysts and geochemical analysis of sediment core GeoB5546-2

NW African climate shows orbital and millenial-scale variations, which are tightly connected to changes in marine productivity. We present an organic-walled dinoflagellate cyst (dinocyst) record from a sediment core off Cape Yubi at about 27°N in the Canary Basin covering the time period from 47 to 3ka before present (BP). The dinocyst record reflects differences in upwelling intensity and seasonality as well as the influence of fluvial input. Sea-level changes play an important role for the upwelling pattern and productivity signals at the core site. Within the studied time interval, four main phases were distinguished. (1) From 45 to 24ka BP, when sea-level was mostly about 75m lower than today, high relative abundances of cysts of heterotrophic taxa point to enhanced upwelling activity, especially during Heinrich Events, while relatively low dinocyst accumulation rates indicate that filament activity at the core location was strongly reduced. (2) At sea-level lowstand during the LGM to H1, dinocyst accumulation rates suggest that local filament formation was even more inhibited. (3) From the early Holocene to about 8ka BP, extraordinary high accumulation rates of most dinocyst species, especially of Lingulodinium machaerophorum, suggest that nutrient supply via fluvial input increased and rising sea-level promoted filament formation. At the same time, the upwelling season prolongated. (4) A relative increase in cysts of photoautotrophic taxa from about 8ka BP on indicates more stratified conditions while fluvial input decreased. Our study shows that productivity records can be very sensitive to regional features. From the dinocyst data we infer that marine surface productivity off Cape Yubi during glacial times was within the scale of modern times but extremely enhanced during deglaciation.

Radiocarbon ages and major n-alkane homologues of peat cores LVPS4 and LVPS5B, Russian Arctic

Coupled analyses of n-alkane biomarkers and plant macrofossils from a peat plateau deposit in the northeast European Russian Arctic were carried out to assess the effects of past hydrology on the molecular contributions of plants to the peat. The n-alkane biomarkers accumulated over 9.6 kyr of local paleohydrological changes in this complex peat profile in which a succession of vegetation changes occurred during a transition from a wet fen to a relatively dry peat plateau bog. This study shows that the contribution of the n-C31 alkane from rootlets to peat layers rich in fine and dark roots is important. The results further indicate that the n-alkane Paq and n-C23/n-C29 biomarker proxies that have been useful to reconstruct past water table levels in many peat deposits can be misleading when the contributions of Betula and Sphagnum fuscum to the peat are large. Under these conditions, the C23/(C27 + C31) n-alkane ratio seems to correct for the presence of Betula and S. fuscum and provides a better description for the relative amounts of moisture. The average chain length (ACL) n-alkane proxy also appears to be a good paleohydrology proxy in having larger values during dry and cold conditions in this Arctic bog setting.