Major and trace element compositions of the Buendnerschiefer samples

The Bündnerschiefer of the Swiss-Italian Alps is a large sedimentary complex deposited on the Piemonte-Liguria and Valais oceans and associated continental margins from the upper Jurassic to Eocene. It is made of a large variety of sequences associated or not with an ophiolitic basement. The Bündnerschiefer makes an accretionary prism that developed syn-tectonically from the onset of alpine subduction, and it records orogenic metamorphism following episodes of HP metamorphism. The Bündnerschiefer shares important similarities with the Otago schists of New Zealand and with the Wepawaug schists of Connecticut, both of which form accretionary prisms and have an orogenic metamorphic imprint. With the aim of testing the hypothesis of mobility of chemical components as a function of metamorphic grade, in this work I present fifty-five bulk chemical analyses of various lithological facies of the Bündnerschiefer collected along the well-studied field gradient of the Lepontine dome of Central Switzerland, in the Prättigau half window of East Switzerland, and in the Tsaté Nappe of Valle d'Aosta (Italy). The dataset includes the concentration of major components, large ion lithophile elements (Rb, Sr, Ba, Cs), high field strength elements (Zr, Ti, Nb, Th, U, Ta, Hf), fluid-mobile light elements (B, Li), volatiles (CO2, S), REEs, and Y, V, Cr, Co, Sn, Pb, Cu, Zn, Tl, Sb, Be, and Au. These data are compared against the compositions of the global marine sediment reservoir, typical crustal reservoirs, and against the previously measured compositions of Otago and Wepawaug schists. Results reveal that, irrespective of their metamorphic evolution, the bulk chemical compositions of orogenic metasediments are characterized by mostly constant compositional ratios (e.g., K2O/Al2O3, Ba/Al2O3, Sr/CaO, etc.), whose values in most cases are undistinguishable from those of actual marine sediments and other crustal reservoirs. For these rocks, only volatile concentrations decrease dramatically as a function of metamorphic temperature, and significant deviations from the reservoir signatures are evident for SiO2, B, and Li. These results are interpreted as an indication of residual enrichment in the sediments, a process taking place during syn-metamorphic dehydration from the onset of metamorphism in a regime of chemical immobility. Residual enrichment increased the absolute concentrations of the chemical components of these rocks, but did not modify significantly their fundamental ratios. This poor compositional modification of the sediments indicates that orogenic metamorphism in general does not promote significant mass transfer from accretionary prisms. In contrast, mass transfer calculations carried out in a shear zone crosscutting the Bündnerschiefer shows that significant mass transfer occurs within these narrow zones, resulting in gains of H2O, SiO2, Al2O3, K2O, Ba, Y, Rb, Cu, V, Tl, Mo, and Ce during deformation and loss of Na2O, CO2, S, Ni, B, U, and Pb from the rock. These components were presumably transported by an aquo-carbonic fluid along the shear zone. These distinct attitudes to mobilize chemical elements from orogenic sediments may have implications for a potentially large number of geochemical processes in active continental margins, from the recycling of chemical components at plate margins to the genesis of hydrothermal ore deposits.

Dust flux records from the Subarctic North Pacific

We present a new record of eolian dust flux to the western Subarctic North Pacific (SNP) covering the past 27000 years based on a core from the Detroit Seamount. Comparing the SNP dust record to the NGRIP ice core record shows significant differences in the amplitude of dust changes to the two regions during the last deglaciation, while the timing of abrupt changes is synchronous. If dust deposition in the SNP faithfully records its mobilization in East Asian source regions, then the difference in the relative amplitude must reflect climate-related changes in atmospheric dust transport to Greenland. Based on the synchronicity in the timing of dust changes in the SNP and Greenland, we tie abrupt deglacial transitions in the 230Th-normalized 4He flux record to corresponding transitions in the well-dated NGRIP dust flux record to provide a new chronostratigraphic technique for marine sediments from the SNP. Results from this technique are complemented by radiocarbon dating, which allows us to independently constrain radiocarbon paleoreservoir ages. We find paleoreservoir ages of 745 ± 140 yr at 11653 yr BP, 680 ± 228 yr at 14630 yr BP and 790 ± 498 yr at 23290 yr BP. Our reconstructed paleoreservoir ages are consistent with modern surface water reservoir ages in the western SNP. Good temporal synchronicity between eolian dust records from the Subantarctic Atlantic and equatorial Pacific and the ice core record from Antarctica supports the reliability of the proposed dust tuning method to be used more widely in other global ocean regions.

Stable carbon and oxygen isotope ratios of bulk sediment from the Weddell Sea

Carbon isotope measurements were made on bulk sediments from the well preserved calcareous sequences recovered at ODP Sites 689 and 690 on the Maud Rise, Weddell Sea, Antarctica. The very positive delta13C values that characterize the late Paleocene and the rapid trend toward lighter values in the early Eocene established in other sites are clearly recorded here and may be of value for long-distance stratigraphic correlation. However, values in the late Eocene are significantly more positive than have been reported from other areas. The general pattern of the records from Sites 689 and 690 is sufficiently unlike those previously reported from lower latitudes that we suggest that carbon isotope data should be used only with considerable caution for correlating sequences from such high latitudes with lower latitude records.

Benthic foraminiferal carbon isotopic records and the development of abyssal circulation at DSDP Sites 9-77, 12-119, 30-289, 82-563 and 94-608

The North Atlantic at present is ventilated by overflow of the Denmark Strait, Iceland-Faeroe Ridge, Faeroe Bank Channel, and Wyville-Thompson Ridge. The evolution of Cenozoic abyssal circulation of this region was related to tectonic opening and subsidence of these sills. We used d13C records of the benthic foraminifer Cibicidoides to decipher the timing of tectonically controlled changes in bottom-water circulation in the eastern basins (Biscay and Iberian) of the northern North Atlantic. Records from Site 608 (Kings Trough, northeastern North Atlantic) show that from about 24 to 15 Ma (early to early middle Miocene), d13C values in the Kings Trough area were depleted relative to western North Atlantic values and were more similar to Pacific d13C values. This reflects less ventilation of the Kings Trough region as compared to the well-oxygenated western North Atlantic. Comparison of Oligocene d13C records from Site 119 (Bay of Biscay) with western North Atlantic records suggests that the eastern basin was also relatively isolated prior to 24 Ma. At about 15 Ma, d13C values at Site 608 attained values similar to the western North Atlantic, indicating increased eastern basin ventilation in the middle Miocene. This increased advection into the eastern basin predated a major d18O increase which occurred at about 14.6 Ma. Subsidence estimates of the Greenland-Scotland Ridge indicate that the deepening of the Iceland-Faeroe Ridge was coincident with the marked change in eastern basin deep-water ventilation.

Rare earth and other element contents in surface layer bottom sediments and ferromanganese nodules along the Transatlantic profile

Behavior of rare earth elements (REE) and Th is studied along the Transatlantic transect at 22°N. It is shown that both REE and Th contents relative to Al (the most lithogenic element) increase toward the pelagic region. The increasing trend becomes more complicated due to variations in content of biogenic calcium carbonate that acts as a diluting component in sediments. REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al+Mn+Fe) and (Fe+Mn)/Ti, do not reach critical values. Variations in REE content and composition allowed to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenous type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th contents depend on Fe content in Atlantic sediments. Therefore, one can suggest that only minor amount of phosphorus is bound with bone debris. Low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic Ocean, as compared with those in pelagic regions of the Pacific Ocean.

Bulk mineralogy of Cretaceous to Quaternary sediments from the Kerguelen Plateau

Carbonate-free portions of Upper Cretaceous to Holocene sediment samples from the Kerguelen Plateau in the southern Indian Ocean were investigated by X-ray diffraction. Downhole variations in the content of opal-A, opal-CT, quartz, feldspar, barite, and clinoptilolite were studied at Site 737 on the northern Kerguelen Plateau and at Sites 744 and 738 on the southern Kerguelen Plateau. The variation of these components reflects temporal changes in the depositional history of the Kerguelen Plateau as well as major differences in the sedimentary evolution between the northern plateau and the southern plateau. Carbonate is the dominant component in the pelagic sediments on the Kerguelen Plateau. In addition, biogenic opal sedimentation plays an important role throughout most of the sequence. A major increase in opal accumulation is documented at all sites in late Miocene time, which is in accordance with the well-known increase in silica productivity probably caused by a major cooling step. Because of its position near the Polar Frontal Zone, sediments from Site 737 show a more extensive opal deposition than at Sites 744 and 738. An earlier productivity pulse is documented at Site 744 on the southern plateau within the early Oligocene, following the initial phase of intense East Antarctic glaciation. This cooling event resulted in higher amounts of ice-rafted terrigenous quartz and, to a lesser extent, feldspar. With the exception of the Site 744 sediments, opal deposition in Paleogene and older sediments can be reconstructed only from the diagenetic transformation products of opal-CT and probably clinoptilolite. In contrast to the southern sequence, on the northern Kerguelen Plateau higher amounts of clinoptilolite and no opal-CT were found. These major differences in the diagenetic environments may be due to extensive volcanism in the northern area. The volcanic influence at Site 737 is well recorded by the higher feldspar content and higher amounts of volcanic glass shards.

Radioisotopes and He accumulation in deep sea sediments of the Ontong Java Plateau

The accumulation of extraterrestrial 3He, a tracer for interplanetary dust particles (IDPs), in sediments from the Ontong Java Plateau (OJP; western equatorial Pacific Ocean) has been shown previously to exhibit a regular cyclicity during the late Pleistocene, with a period of ~100 ka. Those results have been interpreted to reflect periodic variability in the global accretion of IDPs that, in turn, has been linked to changes in the inclination of Earth's orbit with respect to the invariable plane of the solar system. Here we show that the accumulation in OJP sediments of authigenic 230Th, produced by radioactive decay of 234U in seawater, exhibits a 100-ka cyclicity similar in phase and amplitude to that evident in the 3He record. We interpret the similar patterns of 230Th and 3He accumulation to reflect a common origin within the ocean-climate system. Comparing spatial and temporal patterns of sediment accumulation against regional patterns of biological productivity and against the well-established pattern of CaCO3 dissolution in the deep Pacific Ocean leads to the further conclusion that a common 100-ka cycle in accumulation of biogenic, authigenic and extraterrestrial constituents in OJP sediments reflects the influence of climate-related changes in sediment focusing, rather than changes in the rate of production or supply of sedimentary constituents.

Surface time series of nitrate, silicate and chlorophyll a (1999-2011) and CTD profiles (1999) at the PhytoCly station, Bay of Calvi, Corsica, Mediterranean Sea

This work is based on a long time series of data collected in the well-preserved Bay of Calvi (Corsica island, Ligurian Sea, NW Mediterranean) between 1979 and 2011, which include physical characteristics (31 years), chlorophyll a (chl a, 15 years), and inorganic nutrients (13 years). Because samples were collected at relatively high frequencies, which ranged from daily to biweekly during the winter-spring period, it was possible to (1) evidence the key role of two interacting physical variables, i.e. water temperature and wind intensity, on nutrient replenishment and phytoplankton dynamics during the winter-spring period, (2) determine critical values of physical factors that explained interannual variability in the replenishment of surface nutrients and the winter-spring phytoplankton bloom, and (3) identify previously unrecognized characteristics of the planktonic ecosystem. Over the >30 year observation period, the main driver of nutrient replenishment and phytoplankton (chl a) development was the number of wind events (mean daily wind speed >5 m s-1) during the cold-water period (subsurface water <13.5°C). According to winter intensity, there were strong differences in both the duration and intensity of nutrient fertilization and phytoplankton blooms (chl a). The trophic character of the Bay of Calvi changed according to years, and ranged from very oligotrophic (i.e. subtropical regime, characterized by low seasonal variability) to mesotrophic (i.e. temperate regime, with a well-marked increase in nutrient concentrations and chl a during the winter-spring period) during mild and moderate winters, respectively. A third regime occurred during severe winters characterized by specific wind conditions (i.e. high frequency of northeasterly winds), when Mediterranean "high nutrient - low chlorophyll" conditions occurred as a result of enhanced crossshore exchanges and associated offshore export of the nutrient-rich water. There was no long-term trend (e.g. climatic) in either nutrient replenishment or the winter-spring phytoplankton bloom between 1979 and 2011, but both nutrients and chl a reflected interannual and decadal changes in winter intensity.

Eolian deposition on the Ontong Java Plateau

The record of eolian deposition on the Ontong Java Plateau (OJP) since the Oligocene (approximately 33 Ma) has been investigated using dust grain size, dust flux, and dust mineralogy, with the goal of interpreting the paleoclimatology and paleometeorology of the western equatorial Pacific. Studies of modern dust dispersal in the Pacific have indicated that the equatorial regions receive contributions from both the Northern Hemisphere westerly winds and the equatorial easterlies; limited meteorological data suggest that low-altitude westerlies could also transport dust to OJP from proximal sources in the western Pacific. Previous studies have established the characteristics of the grain-size, flux, and mineralogy records of dust deposited in the North Pacific by the mid-latitude westerlies and in the eastern equatorial Pacific by the low-latitude easterlies since the Oligocene. By comparing the OJP records with the well-defined records of the mid-latitude westerlies and the low-latitude easterlies, the importance of multiple sources of dust to OJP can be recognized. OJP dust is composed of quartz, illite, kaolinite/chlorite, plagioclase feldspar, smectite, and heulandite. Mineral abundance profiles and principal components analysis (PCA) of the mineral abundance data have been used to identify assemblages of minerals that covary through all or part of the OJP record. Abundances of quartz, illite, and kaolinite/chlorite covary throughout the interval studied, defining a mineralogical assemblage supplied from Asia. Some plagioclase and smectite were also supplied as part of this assemblage during the late Miocene and Pliocene/Pleistocene, but other source areas have supplied significant amounts of plagioclase, smectite, and heulandite to OJP since the Oligocene. OJP dust is generally coarser than dust deposited by the Northern Hemisphere westerlies or the equatorial easterlies, and it accumulates more rapidly by 1-2 orders of magnitude. These relationships indicate the importance of the local sources on dust deposition at OJP. The grain-size and flux records of OJP dust do not exhibit most of the events observed in the corresponding records of the Northern Hemisphere westerlies or the equatorial easterlies, because these features are masked by the mixing of dust from several sources at OJP. The abundance record of the Asian dust assemblage at OJP, however, does contain most of the features characteristic of dust flux by means of the Northern Hemisphere westerlies, indicating that the paleoclimatic and paleometeorologic signal of a particular source area and wind system can be preserved in areas well beyond the region dominated by that source and those winds. Identifying such a signal requires "unmixing" the various dust assemblages, which can be accomplished by combining grain-size, flux, and mineralogic data.

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.

Benthic foraminiferal stable isotope stratigraphy of ODP Site 138-846 in the tropical Pacific Ocean

A stable-isotope stratigraphy at Site 846 (tropical Pacific, 3°06'S, 90°49'W, 3307 m water depth), based on the benthic foraminifers Cibicides wuellerstorfi and Uvigerina peregrina, yields a high-resolution record of deep-sea delta18O and delta13C over the past 1.8 Ma, with an average sampling interval of 3 k.y. Variance in the delta18O and delta13C records is concentrated in the well-known orbital periods of 100, 41, and 23 k.y. In the 100-k.y. band, both isotopic signals grow from relatively low amplitudes prior to 1.2 Ma, to high amplitudes in the late Quaternary since 0.7 Ma. The amplitude of delta18O and especially of delta13C decreases in the 41-k.y. band as it grows in the 100-k.y. band, consistent with a transfer of energy into an orbitally-paced internal oscillation. A weak 30-k.y. rhythm, present in both delta18O and delta13C, may reflect nonlinear interaction between the 41-k.y. and 100-k.y. bands in the evolving climate system. In the 23-k.y. and 19-k.y. bands associated with orbital precession, delta18O and delta13C are not coherent with each other on long time scales, and do not evolve like the 100-k.y. and 41-k.y. bands. This suggests that the source of the growing 100-k.y. oscillation is not a nonlinear response to precession, in contrast to predictions of some climate models. Sedimentation rates at this site also vary with a strong 100-k.y. cycle. Unlike the isotope records, the amplitude of 100-k.y. variations in sedimentation rate is relatively constant over the past 1.8 Ma, ranging from about 15 to 70 m/m.y. Prior to 0.9 Ma, sedimentation rates co-vary with orbital eccentricity, rather than with global climate as reflected by delta18O or delta13C. A source of this 100-k.y. cycle of sedimentation rate in the absence of similar ice volume fluctuations may be precessional heating of equatorial land masses, which in an energy balance climate model drives variations of monsoonal climates with a 100-k.y. rhythm. For the interval younger than 0.9 Ma, high sedimentation rates in the 100-k.y. band are consistently associated with glacial stages. This change of pattern suggests that when the amplitude of glacial cycles become large enough, their global effects overpower a local monsoon-driven variation in sedimentation rate at Site 846.

Carbon sources in the North Sea evaluated by means of carbon isotope tracers

A multitracer approach is applied to assess the impact of boundary fluxes (e.g., benthic input from sedi- ments or lateral inputs from the coastline) on the acid-base buffering capacity, and overall biogeochemistry, of the North Sea. Analyses of both basin-wide observations in the North Sea and transects through tidal basins at the North-Frisian coastline, reveal that surface distributions of the d13C signature of dissolved inorganic carbon (DIC) are predominantly controlled by a balance between biological production and respiration. In particular, variability in metabolic DIC throughout stations in the well-mixed southern North Sea indi- cates the presence of an external carbon source, which is traced to the European continental coastline using naturally occurring radium isotopes (224Ra and 228Ra). 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (AT) compared to the more conventional use of salinity. Coastal inputs of meta- bolic DIC and AT are calculated on a basin-wide scale, and ratios of these inputs suggest denitrification as a primary metabolic pathway for their formation. The AT input paralleling the metabolic DIC release prevents a significant decline in pH as compared to aerobic (i.e., unbuffered) release of metabolic DIC. Finally, long- term pH trends mimic those of riverine nitrate loading, highlighting the importance of coastal AT production via denitrification in regulating pH in the southern North Sea.