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.

Stable oxygen isotopes of calcite veins in ODP Site 146-892

In situ secondary ionization mass spectrometry (SIMS) analyses of oxygen isotopes in authigenic calcite veins were obtained from an active thrust fault system drilled at Ocean Drilling Program (ODP) Site 892 (44°40.4'N, 125°07.1'W) along the Cascadia subduction margin. The average d18OPDB value of all samples is -9.9 per mil and the values are the lowest of any measured in active accretionary prisms. Ranges in individual veins can be as much as 19.6 per mil. There is an isotopic stratigraphy related to the structural stratigraphy. Mean isotope values in the hanging wall, thrust, and footwall are -14.4 per mil, -9.5 per mil, and -5.2 per mil, respectively. Several veins and crosscutting vein sequences show a general trend from lower to higher d18O values over time. Isotopic and textural data indicate several veins formed by a crack-seal mechanism and growth into open fractures. The best explanation for the strong 18O depletions is periodic rapid flow from 2-3 km deeper in the prism. Relatively narrow isotopic ranges for most veins suggest that fluids were derived from a similar source depth for each episode of fluid pulse and calcite crystallization. Structural and mass balance considerations are consistent with a record preserved in the veins of ten to hundreds of thousands of years. The fluid pulses may relate to periodic large earthquake events such as those recognized in the paleoseismicity records from the Cascadia margin.

Benthic foraminifera in Lower Cretaceous sediments from various DSDP samples

From the DSDP Legs 1, 11, 13, 17, 25, 27, 32, 36, 41, 43, 44, 50, and 62 the Lower Cretaceous foraminifers have been investigated for biostratigraphical, taxonomical, and palaeoecological purposes. An overview of the cored Lower Cretaceous sections of Leg 1-80 is given. In the Northern Atlantic Ocean characteristic foraminiferal faunas are missing from the Upper Tithonian to the Valanginian due to a marked regression which caused hiatuses. In areas without black shale conditions Valanginian to Barremian medium rich to poor microfaunas with Praedorothia ouachensis (Sigal) of the Praedorothia ouachensis Zone (Valanginian-Hauterivian). The Hauterivian-Aptian interval is characterized by zones of Gavelinella barrerniana, Gaudryina dividens, and Conorotalites aptiensis. During the Albian a world-wide fauna consisting of agglutinated and calcareous foraminifers of the Pseudoclavulina gaultina Zone is established in areas lacking the wide-spread black-shale conditions. The Upper Albian and the Cenomanian are represented by the Gavelinella eenomanica Zone. Some ornamented species of the nodosariids (Citharina, Lenticulina), Gavelinella, Conorotatites, Pleurostomella, Vatvulineria, and Osangularia are of some importance for the biostratigraphy of the Berriasian-Albian interval. The Berriasian to Albian zones introduced for the Tethys and the DSDP by Moullade (1984) could only be of some local importance due to the long stratigraphical range of the foraminiferal species used. In the Indian Ocean an exact stratigraphical age cannot be assigned to the few Neocomian foraminiferal faunas of a cooler sea water (Site 261). These faunas mainly contain primitive agglutinated foraminifers, because in most cases the calcareous tests are dissolved or redeposited. In the Pacific Ocean most of the Berriasian to Aptian microfaunas are of minor biostratigraphical and palaeoecological importance for reasons of poor core recoveries, contaminations or original foraminiferal poverty (black shales). Since the Albian there are somewhat higher-diverse faunas of calcareous and agglutinated foraminifers with index species of the Pseudoclavulina gaultina Zone. As a rule, the boundary Albian/Cenomanian is set by means of planktonic foraminifers because no other foraminifer has its first appearance datum during this interval, except Gavelinella cenornanica. During the Albian very uniform, world-wide foraminiferal faunas without a marked provincialism are obvious.

Campanian-Maestrichtian planktonic foraminifera of the southern South Atlantic

Campanian-Maestrichtian planktonic foraminifers were examined from Sites 698 (2128 m water depth) and 700 (3611 m water depth) on the Northeast Georgia Rise (southern South Atlantic, 51°S). Site 698 penetrated 72.5 m of Campanian-Maestrichtian chalk and limestone with only 18.2% recovery, whereas Site 700 recovered 66.8% of a 152.7-m section of Coniacian-Maestrichtian limestone. Preservation of planktonic foraminifers from both sites is moderate in Maestrichtian samples, but worsens with increasing depth in the Campanian. The Northeast Georgia Rise planktonic foraminifers are typical of Late Cretaceous Austral Province faunas described from other southern high-latitude sites; species diversity is low and the assemblages are dominated by species of Heterohelix, Globigerinelloides, Hedbergella, and Archaeoglobigerina. Five species, including Globigerinelloides impensus Sliter, Archaeoglobigerina australis Huber, Archaeoglobigerina mateola Huber, Hedbergella sliteri Huber, and Rugotruncana circumnodifer (Finlay), are considered to be endemic to the Austral Province. Formation of a cool temperate water mass in the circum-Antarctic region, resulting from the final breakup of the Gondwana continents, may have led to increased provincialism of the Austral Province planktonic foraminifers during Campanian-Maestrichtian time. Magnetobiostratigraphic correlation of eight planktonic foraminifer datum events at Hole 700B with ages determined for datums at ODP Leg 113 Holes 689B and 690C (Maud Rise, 65°S) demonstrates regional synchroneity of first and last occurrences within the Austral Province. As was observed at the Maud Rise, several keeled and nonkeeled species previously thought to have been restricted to warmer low-latitude regions first occur later at the Northeast Georgia Rise than at the low-latitude sites. The causes for high-latitude diachroneity among these immigrant species are not clear; neither oxygen and carbon isotope data from the Maud Rise sites nor calcareous nannoplankton distributions for the southern South Atlantic region show conspicuous changes that correlate to the delayed first occurrences.

Calcareous nannofossils of ODP Hole 123-765C and DSDP Hole 27-261

Sediments from the Argo Abyssal Plain (AAP), northwest of Australia, are the oldest known from the Indian Ocean and were recovered from ODP Site 765 and DSDP Site 261. New biostratigraphic and sedimentologic data from these sites, as well as reinterpretations of earlier findings, indicate that basal sediments at both localities are of Late Jurassic age and delineate a history of starved sedimentation punctuated by periodic influx of calcareous pelagic turbidites. Biostratigraphy and correlation of Upper Jurassic-Lower Cretaceous sediments is based largely on calcareous nannofossils. Both sites yielded variably preserved nannofossil successions ranging from Tithonian to Hauterivian at Site 765 and Kimmeridgian to Hauterivian at Site 261. The nannofloras are comparable to those present in the European and Atlantic Boreal and Tethyan areas, but display important differences that reflect biogeographic differentiation. The Argo region is thought to have occupied a position at the southern limit of the Tethyan nannofloral realm, thus yielding both Tethyan and Austral biogeographic features. Sedimentary successions at the two sites are grossly similar, and differences largely reflect Site 765's greater proximity to the continental margin. Jurassic sediments were deposited at rates of about 2 m/m.y. near the carbonate compensation depth (CCD) and contain winnowed concentrations of inoceramid prisms and nannofossils, redeposited layers rich in calcispheres and calcisphere debris, manganese nodules, and volcanic detritus. Lower Cretaceous and all younger sediments accumulated below the CCD at rates that were highest (about 20 m/m.y.) during mid-Cretaceous and Neogene time. Background sediment in this interval is noncalcareous claystone; turbidites dominate the sequence and are thicker and coarser grained at Site 765. AAP turbidites consist mostly of calcareous and siliceous biogenic components and volcanogenic smectite clay; they were derived from relatively deep parts of the continental margin that lay below the photic zone, but above the CCD. The Jurassic-Lower Cretaceous section is about the same thickness across the AAP; turbidites in this interval appear to have had multiple sources along the Australian margin. The Upper Cretaceous-Cenozoic section, however, is three times thicker at Site 765 than at Site 261; turbidites in this interval were derived predominantly from the south. Patterns of sedimentation across the AAP have been influenced by shifts in sea level, the CCD, and configuration of the continental margin. Major pulses of calcareous turbidite deposition occurred during Valanginian, Aptian, and Neogene time-all periods of eustatic lowstands and depressed CCD levels. Sediment redeposited on the AAP has come largely from the Australian outer shelf, continental slope, or rise, rather than the continent itself. Most terrigenous detritus was trapped in epicontinental basins that have flanked northwestern Australia since the early Mesozoic.

Flow rates, hydraulic conductivities and permeabilities of sediments from ODP Holes 190-1173A and 190-1174B

Understanding the role of fluids in active accretionary prisms requires quantitative knowledge of parameters such as permeability. We report here the results of permeability tests on four samples from Ocean Drilling Program Leg 190 at the Nankai Trough accretionary prism-two from Site 1173 and two from Site 1174. Volcanic ash is present in one of the samples; otherwise, the material is hemipelagic mud. A constant-rate-of-flow technique was used at various effective pressures and rates of flow. The permeability of the four samples ranges between 10**-15 and 10**-18 m**2, with the ash-bearing sample showing the highest values.

(Table 1) Experimental results of Kd at various conditions from ODP Hole 131-808C

A comprehensive experimental study, utilizing a rocking autoclave hydrothermal apparatus with isotope tracers, was applied to evaluate the temperature of squeezing artifacts on B contents and isotopic compositions in pore waters. The partition coefficient (KD) was determined at temperatures from 25 ° to 350 °C, at 800 bars, and this information was applied to reconstruct pore water B and d11B in ODP drill sites, where pH, T, and porosity are known. The partition coefficient of B is a function of temperature, pH, and sediment mineralogy. The solution pH exerts a dominant control at low temperatures; however, KD decreases to a value of essentially zero (compared to that of KD = ~3.5 at 25 °C) at high temperatures indicating no adsorption. Two empirical equations were derived to represent most of the available experimental results. For pelagic clay rich sediments, a KD = -3.84-0.020T + 0.88pH (R = 0.84; 1sigma = 0.25) is established. For sediments that have experienced progressive metamorphism, a KD = -1.38-0.008T + 0.59pH (R = 0.81; 1sigma = 0.37) can be applied. Similarly the effect on pore water d11B can be corrected if the fractionation factors at different temperatures are assumed. The corrected B and d11B in ODP Sites 671, 672, and 808 indicate significant mobilization of bulk B in sediment (exchangeable + lattice bound) at depth, especially near the décollement zone or other potential flow conduits. Tectonically expelled fluids from mud diapirs of Barbados Ridge Complex, hot springs of Rumsey Hills, California, and mud pot waters of the Salton Sea geothermal field, are enriched in B (up to 20 mM) with lower d11B, supporting the argument of B mobilization as a result of fluid expulsion in accretionary prisms.

Distribution of planktonic foraminifera and other biogenic components in ODP Hole 113-693A (Figure 2)

A planktonic foraminiferal fauna of probable late Aptian age is recorded in Cores 113-693A-47R and -48R, located on the Antarctic continental margin. Moderate to highly productive surface waters and upper bathyal paleodepths are inferred from benthic and planktonic foraminifers, and other biotic and mineral components in the >63 µm size fraction.

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.

Seawater carbonate chemistry and shell weights of Laternula elliptica, Yoldia eightsi, Nacella concinna and Liothyrella uva during experiments, 2009

Antarctic calcified macroorganisms are particularly vulnerable to ocean acidification because many are weakly calcified, the dissolution rates of calcium carbonate are inversely related to temperature, and high latitude seas are predicted to become undersaturated in aragonite by the year 2100. We examined the post-mortem dissolution rates of aragonitic and calcitic shells from four species of Antarctic benthic marine invertebrates (two bivalves, one limpet, one brachiopod) and the thallus of a limpet shell-encrusting coralline alga exposed to acidified pH (7.4) or non-acidified pH (8.2) seawater at a constant temperature of 4 C. Within a period of only 14-35 days, shells of all four species held in pH 7.4 seawater had suffered significant dissolution. Despite calcite being 35% less soluble in seawater than aragonite, there was surprisingly, no consistent pattern of calcitic shells having slower dissolution rates than aragonitic shells. Outer surfaces of shells held in pH 7.4 seawater exhibited deterioration by day 35, and by day 56 there was exposure of aragonitic or calcitic prisms within the shell architecture of three of the macroinvertebrate species. Dissolution of coralline algae was confirmed by differences in weight loss in limpet shells with and without coralline algae. By day 56, thalli of the coralline alga held in pH 7.4 displayed a loss of definition of the conceptacle pores and cracking was evident at the zone of interface with limpet shells. Experimental studies are needed to evaluate whether there are adequate compensatory mechanisms in these and other calcified Antarctic benthic macroorganisms to cope with anticipated ocean acidification. In their absence, these organisms, and the communities they comprise, are likely to be among the first to experience the cascading impacts of ocean acidification.

Miocene foraminiferal, bolboformid, dinoflagellate and diatom age calibrations for the northeastern North Atlantic

This study presents a new Miocene biostratigraphic synthesis for the high-latitude northeastern North Atlantic region. Via correlations to the bio-magnetostratigraphy and oxygen isotope records of Ocean Drilling Program and Deep Sea Drilling Project Sites, the ages of shallower North Sea deposits have been better constrained. The result has been an improved precision and documentation of the age designations of the existing North Sea foraminiferal zonal boundaries of King (1989) and Gradstein and Bäckström (1996). All calibrations have been updated to the Astronomically Tuned Neogene Time Scale (ATNTS) of Lourens et al. (2004). This improved Miocene biozonation has been achieved through: the updating of age calibrations for key microfossil bioevents, identification of new events, and integration of new biostratigraphic data from a foraminiferal analysis of commercial wells in the North Sea and Norwegian Sea. The new zonation has been successfully applied to two commercial wells and an onshore research borehole. At these high latitudes, where standard zonal markers are often absent, integration of microfossil groups significantly improves temporal resolution. The new zonation comprises 11 Nordic Miocene (NM) Zones with an average duration of 1 to 2 million years. This multi-group combination of a total of 92 bioevents (70 foraminifers and bolboformids; 16 dinoflagellate cysts and acritarchs; 6 marine diatoms) facilitates zonal identification throughout the Nordic Atlantic region. With the highest proportion of events being of calcareous walled microfossils, this zonation is primarily suited to micropaleontologists. A correlation of this Miocene biostratigraphy with a re-calibrated oxygen isotope record for DSDP Site 608 suggests a strong correlation between Miocene planktonic microfossil turnover rates and the inferred paleoclimatic trends. Benthic foraminifera zonal boundaries appear to often coincide with Miocene global sequence boundaries. The biostratigraphic record is punctuated by four main stratigraphic hiati which show variation in their geographic and temporal extent. These are related to the following regional unconformities: basal Neogene, Lower/Middle Miocene ("mid-Miocene unconformity"), basal Upper Miocene and basal Messinian unconformities. Further coring of Neogene sections in the North Sea and Norwegian Sea may better constrain their extent and their effect on the biostratigraphic record.

10Be data for sediments from DSDP Leg 56 and ODP Leg 170

Sediment accretion and subduction at convergent margins play an important role in the nature of hazardous interplate seismicity (the seismogenic zone) and the subduction recycling of volatiles and continentally derived materials to the Earth's mantle. Identifying and quantifying sediment accretion, essential for a complete mass balance across the margin, can be difficult. Seismic images do not define the processes by which a prism was built, and cored sediments may show disturbed magnetostratigraphy and sparse biostratigraphy. This contribution reports the first use of cosmogenic 10Be depth profiles to define the origin and structural evolution of forearc sedimentary prisms. Biostratigraphy and 10Be model ages generally are in good agreement for sediments drilled at Deep Sea Drilling Project Site 434 in the Japan forearc, and support an origin by imbricate thrusting for the upper section. Forearc sediments from Ocean Drilling Program Site 1040 in Costa Rica lack good fossil or paleomagnetic age control above the decollement. Low and homogeneous 10Be concentrations show that the prism sediments are older than 3-4 Ma, and that the prism is either a paleoaccretionary prism or it formed largely from slump deposits of apron sediments. Low 10Be in Costa Rican lavas and the absence of frontal accretion imply deeper sediment underplating or subduction erosion.

Boron concentrations and isotope ratios of authigenic carbonates from the Oregon margin

Boron contents and boron, carbon and oxygen stable isotopes were determined for authigenic carbonates recovered from Ocean Drilling Program Leg 146, Oregon margin. Carbonate precipitates are the most widespread authigenic phase in the shallow accretionary wedge and carry chemical information about long-term variations in pore fluid origin and flow paths in the Cascadia subduction zone. Drilling the first ridge (toe area including the frontal thrust) and the second ridge (or Hydrate Ridge) of the prism demonstrated different fluid regimes, with higher B contents in the authigenic precipitates at the toe. The delta11B of 18 authigenic precipitates analysed ranges from 13.9 per mil to as high as 39.8 per mil, extending the upper range of previously reported carbonate delta11B values considerably. When related to the delta11B ratio of their parent solutions, these data are characteristic of fluid-related processes in accretionary prisms. Together with delta13C and delta18O, delta11B ratios of the carbonate concretions, nodules and crusts allow one to distinguish between precipitation influenced by (i) seawater, (ii) fluid reservoirs at different depth levels within the accretionary prism and (iii) cage water from dissociated gas hydrates, the latter possibly indicating a fluctuation of the bottom simulating reflector during most recent Earth's history. From this first systematic boron study on authigenic precipitates from an accretionary prism it is suggested that B contents of such carbonate crusts and concretions exceed those reported for other marine carbonates. Given the abundance of such precipitates at convergent margins, they represent a significant B sink in geochemical cycling. Isotopic compositions of the parent fluids to the carbonates mirror B chemistry of modern pore waters from convergent margins. The precipitates carry information of different subduction-related fluid processes over a certain period of time, and hence are a crucial tracer in the investigation of palaeo-fluid flow.