Geochemistry on rocks from Shackleton Range

During the GEISHA expedition (Geologische Expedition in die Shackleton Range 1987/88), the Pioneers Escarpment was visited and sampled extensively for the first time. Most of the rock types encountered represent amphibolite facies metamorphics, but evidence for granulite facies conditions was found in cores of garnet. These conditions must have been at least partly reached during the peak of metamorphism. For the Pioneers Escarpment a varicolored succession of sedimentary and bimodal volcanic origin is typical. It comprises: quartzites muscovite quartzite, sericite quartzite, fuchsite quartzite, garnet-quartz schists etc.; pelites: mica schists and plagioclase or plagioclase-microcline gneisses, aluminous schists; marls and carbonates: grey meta-limestones, carbonaceous quartzites, but also pure white, often fine-grained, saccharoidal marble, or a variety of tremolite marble, olivine (forsterite) marble, diopside-clinopyroxene-tremolite marble, etc.; basic volcanic rocks: amphibole fels, amphibolite schist, garnet amphibolite, and acidic to intermediate volcanic rocks: garnet-biotite schist, epidote-biotite-plagioclase gneiss, microcline gneiss. These rocks are considered to be a supracrustal unit, called the Pioneers Group. In the easternmost parts of the Pioneers Escarpment, e.g. at Vindberget, nonmetamorphic shales, sandstones and greywackes crop out, which are cover rocks of possibly Jurassic age. These metasediments, which represent a quartz-pelite-carbonate (QPC) association, indicate that deposition took place on a stable shelf, i.e. on the submerged rim of a craton. Marine shallow-water sedimentation including marls and aluminous clays form the protoliths. The volcanics may be part of a bimodal volcanics-arkose-conglomerate (BVAC) association. Geochemical analyses support the assumption of volcanic protoliths. This is demonstrated especially by the elevated amounts of the immobile, incompatible high-field-strength elements (HFSE) Nb, Ta, Ti, Y, and Zr encountered in some of the gneisses. Microscopic investigation suggests the existence of ortho-amphibolites. This is confirmed by the geochemistry. A bimodal volcanic association is evident. The amphibolites plot in both the tholeiite and calc-alkaline fields. The acidic volcanics are mainly rhyolitic. The sediments and volcanics were subjected to conditions of 10-11 kbar and 600°C during the peak of metamorphism, i.e. granulite facies metamorphism, which can be deduced from the Fe mole ratios of 0.71-0.73 in the garnet cores. Due to the relatively low temperatures, no anatectic melting took placc. The rims of the garnets show a Fe mole ratio of 0.84-0.86, and the coexisting mineral association garnet-biotite-staurolite-kyanite indicate amphibolite facies. The thermobarometry shows P-T conditions of 5-6 kbar and 570-580°C for this stage. The metamorphic history indicates deep burial at depths down to 35 km (subduction?) i.e. high pressure metamorphism, followed by pressure release due to uplift associated with retrograde metamorphism. This may have happened during a pre-Ross metamorphic event or orogeny. The Ross Orogeny at about 500 Ma probably just led to the weak greenschist facies overprint that is evident in the rocks of the Pioneers Group. Finally, sedimentation resumed in the area of the present Shackleton Range, or at least in the eastern part of the Pioneers Escarpment, probably when detritus from erosion of the basement (Read Group and Pioneers Group) was deposited, forming sandstones and greywackes of possibly Jurassic age. There is no indication that these sediments belong to the former Turnpike Bluff Group.

Biological, physical and chemical characteristics of water and sediment samples from the Volga River delta, northern Caspian

Based on the data of synchronous observations of hydrophysical and biogeochemical parameters in the near-mouth and shallow-water areas of the northern Caspian in 2000-2001, the scale of spatiotemporal variability in the following characteristics of the water-bottom system was estimated (1) flow velocity and direction within vortex structures formed by the combined effect of wind, discharge current, and the presence of higher aquatic plants; (2) dependence of the spatial distribution of the content and composition of suspended particulate matter on the hydrodynamic regime of waters and development of phytoplankton; (3) variations in the grain-size, petrographic, mineralogical, and chemical compositions of the upper layer of bottom sediments at several sites in the northern Caspian related to the particular local combination of dominant natural processes; and (4) limits of variability in the group composition of humus compounds in bottom sediments. The acquired data are helpful in estimating the geochemical consequences of a sea level rise and during the planning of preventive environmental protection measures in view of future oil and gas recovery in this region.

Sandstone and siltstone beds overlying conglomerate at DSDP Hole 59-439

Massive sandstone and siltstone beds with many shallow-water megafossils overlie acidic volcanic conglomerates at DSDP Site 439. Smear-slides, thin sections from coarse fractions, and heavy minerals of the sandstone and siltstone beds were analyzed. The sandstones and siltstones are very rich in lithic fragments and are classified as lithic arenite and (or) lithic wacke. Hornblende and clinopyroxene are abundant, and zircon is present in most of the examined samples. The proportions of sandstone, chert, and volcanic rock in the coarse fraction are variable, but fragments of clastic rocks and cherts are predominant. Plagioclase crystals of volcanic-rock origin, such as highly zoned plagioclase and very fine, euhedral, lath-shaped plagioclase, are frequently observed. Metamorphic-rock fragments and metamorphic minerals are also observed. Thus, the provenance of the sandstone and siltstone beds appears to have been a slightly mature island arc, the Oyashio ancient landmass, consisting of clastic sediments and metamorphic and volcanic rocks.

Impacts of ocean acidification on sediment processes in shallow waters of the arctic ocean

Despite the important roles of shallow-water sediments in global biogeochemical cycling, the effects of ocean acidification on sedimentary processes have received relatively little attention. As high-latitude cold waters can absorb more CO2 and usually have a lower buffering capacity than warmer waters, acidification rates in these areas are faster than those in sub-tropical regions. The present study investigates the effects of ocean acidification on sediment composition, processes and sediment-water fluxes in an Arctic coastal system. Undisturbed sediment cores, exempt of large dwelling organisms, were collected, incubated for a period of 14 days, and subject to a gradient of pCO2 covering the range of values projected for the end of the century. On five occasions during the experimental period, the sediment cores were isolated for flux measurements (oxygen, alkalinity, dissolved inorganic carbon, ammonium, nitrate, nitrite, phosphate and silicate). At the end of the experimental period, denitrification rates were measured and sediment samples were taken at several depth intervals for solid-phase analyses. Most of the parameters and processes (i.e. mineralization, denitrification) investigated showed no relationship with the overlying seawater pH, suggesting that ocean acidification will have limited impacts on the microbial activity and associated sediment-water fluxes on Arctic shelves, in the absence of active bio-irrigating organisms. Only following a pH decrease of 1 pH unit, not foreseen in the coming 300 years, significant enhancements of calcium carbonate dissolution and anammox rates were observed. Longer-term experiments on different sediment types are still required to confirm the limited impact of ocean acidification on shallow Arctic sediment processes as observed in this study.

(Table 1) Some structural characteristics of communities and detritus flux through the lower boundary of a given water column in different regions of the Kara Sea

Vertical fluxes of autochtonous detritus at different levels were estimated using the algorithm of structure-function analysis. The calculations are based on pelagic ecosystem parameters in the Kara Sea observed in September 1993 (temperature, primary production, biomass of phytoplankton, bacteria, protozoa, and zooplankton, trophic and size composition, etc.). At eight stations in different parts of the sea where sedimentation traps were set, the range of calculated fluxes of autochtonous detritus through the lower boundary of the water column was 13-90 mgC/m**2/day. The flux was much higher in the estuary of the Yenisey River (55-90 mgC/m**2/day) than in the northeastern regions (I8-50 mgC/m**2/day) and, especially, in the relatively deep southwestern part of the sea (13-35 mgC/m**2/day). The calculated fluxes of autochtonous detritus in shallow water regions (where conditions are variable and poorly known hydrologically and where outflow of allochtonous detritus is substantial) cannot be compared to data from sedimentation traps.

Water chemistry and fluffy layer geochemistry and mineral content at four sites in the western Baltic Sea

The fluffy layer was sampled repeatedly during nine expeditions between October 1996 and December 1998 at four stations situated along a S-N-transect from the Oder Estuary to the Arkona Basin. Geochemical and mineralogical analyses of the fluff show regional differences (trends) in composition, attributed to provenance and to hydrographical conditions along their transport pathways. Temporal variability is very high at the shallow water station of the estuary, and decreases towards the deeper stations in the north. In the shallow water area, intensive resuspension of the fluff due to wind-driven waves and currents leads to an average residence time of only one to two days. Near-bottom lateral transport of the fluff is the main process that transfers the fine grained material, containing both nutrients and contaminants, from the coastal zone into the deeper basins of the Baltic Sea. Seasonal effects (e.g. biogenic production in relation to trace metal variation) are observed at the Tromper Wiek station, where the residence time of the fluffy material is in the scale of seasons. Thus, the fluffy layer offers suitable material for environmental monitoring programs.

Sediment fraction analysis and population density of living larger foraminifera in the Persian Gulf (Table 1A, 1B)

Living Heterostegina depressa were found in the Persian Gulf on shallows and sides of islands in the Central Basin. Preliminary culture experiments furnished information on life span, salinity tolerances and population density of species. Reproduction processes (probably asexual) could be observed several times. A possible carbonate production of ca. 150 g/year/m**2 has been estimated.

Oxygen and carbon isotope ratios for six planktonic foraminifer species from different water depth, Ontong-Java Plateau, Pacific (Table 2)

Stable isotope analyses and scanning electron micrographs have been carried out on six planktonic forminifera species, Pulleniatina obliquiloculata, Globorotalia tumida, Sphaeroidinella dehiscens, Globigerinoides ruber, Globigerinoides sacculifer and Globigerinoides quadrilobatus from eleven box-cores taken at increasing depths in the equatorial Ontong-Java Plateau (Pacific). This allows us to describe the way dissolution affects the microstructures of the tests of the different species and to quantify the changes of isotopic composition. We may conclude that: 1) dissolution effects on test morphology and stable isotope compositions are species dependent, species with a similar habitat showing a similar trend; 2) the shallow water, thin-shelled species are the first to disappear: scanning electron microscope (SEM) work shows alteration of outer layers. Deep water, thick-shelled species are present in all samples: SEM work shows breakdown and disparition of inner layers; 3) for all species there is a similar trend towards increasing delta18O values with increasing water depths and increasing dissolution. This effect may be as high as 0.6 ? per thousand meters for Globorotalia tumida; 4) below the lysocline, around 3500 m, it appears that 13C/12C ratios slightly increase towards equilibrium values for thick shelled species: G. tumida, P. obliquiloculata and S. dehiscens. 14C dates and isotope stratigraphy of two box-cores show that all samples are recent in age, and exclude upward mixing of glacial deposits as an important factor.

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

Water chemistry, carbonate system parameters, and macro-organism biomass of vent and off-vent sites in the Columbretes Islands Marine Reserve

Ocean acidification is receiving increasing attention because of its potential to affect marine ecosystems. Rare CO2 vents offer a unique opportunity to investigate the response of benthic ecosystems to acidification. However, the benthic habitats investigated so far are mainly found at very shallow water (less than or equal to 5 m depth) and therefore are not representative of the broad range of continental shelf habitats. Here, we show that a decrease from pH 8.1 to 7.9 observed in a CO2 vent system at 40 m depth leads to a dramatic shift in highly diverse and structurally complex habitats. Forests of the kelp Laminaria rodriguezii usually found at larger depths (greater than 65 m) replace the otherwise dominant habitats (i.e. coralligenous outcrops and rhodolith beds), which are mainly characterized by calcifying organisms. Only the aragonite-calcifying algae are able to survive in acidified waters, while high-magnesium-calcite organisms are almost completely absent. Although a long-term survey of the venting area would be necessary to fully understand the effects of the variability of pH and other carbonate parameters over the structure and functioning of the investigated mesophotic habitats, our results suggest that in addition of significant changes at species level, moderate ocean acidification may entail major shifts in the distribution and dominance of key benthic ecosystems at regional scale, which could have broad ecological and socio-economic implications.

Calcium carbonate content in surface sediments and benthic fauna on Antarctic shelves

We analyzed 214 new core-top samples for their CaCO3 content from shelves all around Antarctica in order to understand their distribution and contribution to the marine carbon cycle. The distribution of sedimentary CaCO3 on the Antarctic shelves is connected to environmental parameters where we considered water depth, width of the shelf, sea-ice coverage and primary production. While CaCO3 contents of surface sediments are usually low, high(> 15%) CaCO3 contents occur at shallow water depths (150-200 m) on narrow shelves of the eastern Weddell Sea and at a depth range of 600-900 m on the broader and deeper shelves of the Amundsen, Bellingshausen and western Weddell Seas. Regions with high primary production, such as the Ross Sea and the western Antarctic Peninsula region, have generally low CaCO3 contents in the surface sediments. The predominant mineral phase of CaCO3 on the Antarctic shelves is low-magnesium calcite. With respect to ocean acidification, our findings suggest that dissolution of carbonates in Antarctic shelf sediments may be an important negative feedback only after the onset of calcite undersaturation on the Antarctic shelves. Macrozoobenthic CaCO3 standing stocks do not increase the CaCO3 budget significantly as they are two orders of magnitude lower than the budget of the sediments. This first circumpolar compilation of Antarctic shelf carbonate data does not claim to be complete. Future studies are encouraged and needed to fill data gaps especially in the under-sampled southwest Pacific and Indian Ocean sectors of the Southern Ocean.

Boron isotope composition and seawater characteristics of cold water scleratinian corals

The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high d11B compositions ranging from 23.2 per mil to 28.7 per mil. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pH(cf)), being elevated by ~0.6-0.8 units (Delta pH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower d11B composition of 15.5 per mil, with a corresponding lower Delta pH value of ~0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pH(T) and shows an approximate linear correlation with Delta pH(Desmo) = 6.43 - 0.71 pH(T) (r**2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where Delta pH(Desmo) = 1.09 - 0.14 Omega(arag) (r**2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pH(cf), and consequently Omega(cf), of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+ -ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (d11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium.

Age analysis, aragonite and high magnesium calcite content from different IODP Holes from Exp 310

The widespread occurrence of microbialites in the last deglacial reef frameworks (16-6 Ka BP) implies that the accurate study of their development patterns is of prime importance to unravel the evolution of reef architecture through time and to reconstruct the reef response to sea-level variations and environmental changes. The present study is based on the sedimentological and chronological analysis (14C AMS dating) of drill cores obtained during the IODP Expedition #310 "Tahiti Sea Level" on the successive terraces which typify the modern reef slopes from Tahiti. It provides a comprehensive data base to investigate the microbialite growth patterns (i.e. growth rates and habitats), to analyze their roles in reef frameworks and to reconstruct the evolution of the reef framework architecture during sea-level rise. The last deglacial reefs from Tahiti are composed of two distinctive biological communities: (1) the coralgal communities including seven assemblages characterized by various growth forms (branching, robust branching, massive, tabular and encrusting) that form the initial frameworks and (2) the microbial communities developed in the primary cavities of those frameworks, a few meters (1.5 to 6 m) below the living coral reef surface, where they heavily encrusted the coralgal assemblages to form microbialite crusts. The dating results demonstrate the occurrence of two distinctive generations of microbialites: the "reefal microbialites" which developed a few hundred years after coralgal communities in shallow-water environments, whereas the "slope microbialites" grew a few thousands of years later in significantly deeper water conditions after the demise of coralgal communities. The development of microbialites was controlled by the volume and the shape of the primary cavities of the initial reef frameworks determined by the morphology and the packing of coral colonies. The most widespread microbialite development occurred in frameworks dominated by branching, thin encrusting, tabular and robust branching coral colonies which built loose and open frameworks typified by a high porosity (> 50%). In contrast, their growth was minimal in compact coral frameworks formed by massive and thick encrusting corals where primary cavities yielded a low porosity (~ 30%) and could not host a significant microbialite expansion.

Geochemistry and mineralogy at DSDP Holes 61-462, 61-462A and 33-315A

Sedimentary rocks of Barremian through early Maestrichtian age recovered on Deep Sea Drilling Project Leg 61 had their principal source in the complex of igneous rocks with which they are interlayered in the Nauru Basin. Relict textures and primary sedimentary structures show these Cretaceous sediments to be of hyaloclastic origin, in part reworked and redeposited by slumps and currents. The dominant composition now is smectite, but locally iron, titanium, and manganese oxides, plagioclase, pyroxene, analcime, clinoptilolite, chalcedonic quartz, cristobalite, amphibole, nontronite, celadonite, and pyrite are also present. The mineral assemblages and the geochemistry reflect the original basaltic composition and its subsequent alteration by one or more processes of submarine weathering, authigenesis, hydrothermal circulation, and contact metamorphism. Hyaloclastitic sandstone, siltstone, and breccia within the sheet flows below 729 meters sub-bottom depth have Barremian fossils, thus establishing the age of the lower, or extrusive, complex of post-ridge-crest volcanism. Similar hyaloclastites between 564 and 729 meters are invaded by hypabyssal sills of the upper igneous complex, and fossil ages of Albian or Cenomanian set an older limit to the age of that second post-ridge-crest episode. Cenomanian to early Campanian sedimentary rocks between 490 and 564 meters have a substantial contribution of clays of submarine-weathered-basalt origin, as well as hydrothermal and pelagic components. The interval of reworked hyaloclastitic siltstone, sandstone, and breccias between 450 and 490 meters is of late Campanian and early Maestrichtian age. These sediments probably formed from glassy basalt that fragmented upon eruption nearby, when sills were being emplaced. In addition to pelagic elements, these Upper Cretaceous volcanogenic sediments include redeposited material of shallow-water origin, apparently derived from the Marshall Islands.