Pore water and solid phase geochemistry of sediment core US5B

Studies of authigenic phosphorus (P) minerals in marine sediments typically focus on authigenic carbonate fluorapatite, which is considered to be the major sink for P in marine sediments and can easily be semi-quantitatively extracted with the SEDEX sequential extraction method. The role of other potentially important authigenic P phases, such as the reduced iron (Fe) phosphate mineral vivianite (Fe(II)3(PO4)*8H2O) has so far largely been ignored in marine systems. This is, in part, likely due to the fact that the SEDEX method does not distinguish between vivianite and P associated with Fe-oxides. Here, we show that vivianite can be quantified in marine sediments by combining the SEDEX method with microscopic and spectroscopic techniques such as micro X-ray fluorescence (µXRF) elemental mapping of resin-embedded sediments, as well as scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) and powder X-ray diffraction (XRD). We further demonstrate that resin embedding of vertically intact sediment sub-cores enables the use of synchrotron-based microanalysis (X-ray absorption near-edge structure (XANES) spectroscopy) to differentiate between different P burial phases in aquatic sediments. Our results reveal that vivianite represents a major burial sink for P below a shallow sulfate/methane transition zone in Bothnian Sea sediments, accounting for 40-50% of total P burial. We further show that anaerobic oxidation of methane (AOM) drives a sink-switching from Fe-oxide bound P to vivianite by driving the release of both phosphate (AOM with sulfate and Fe-oxides) and ferrous Fe (AOM with Fe-oxides) to the pore water allowing supersaturation with respect to vivianite to be reached. The vivianite in the sediment contains significant amounts of manganese (~4-8 wt.%), similar to vivianite obtained from freshwater sediments. Our results indicate that methane dynamics play a key role in providing conditions that allow for vivianite authigenesis in coastal surface sediments. We suggest that vivianite may act as an important burial sink for P in brackish coastal environments worldwide.

Depth, age, strontium isotopic ratios and trace elemental ratios of samples from thirteen DSDP and ODP holes

Large variations exist between published mid-Cretaceous (late Barremian to early Turonian stages) seawater Sr-isotope stratigraphies; this has resulted in disparate interpretations of crustal production rates. We report on a detailed investigation of seawater Sr-isotope stratigraphy based on foraminifers and, where available, on inoceramid bivalves from 12 mid-Cretaceous Deep Sea Drilling Project and Ocean Drilling Program sections. The effects of diagenesis are assessed using scanning electron microscope observations and trace-elemental analyses, but are best distinguished by comparing the 87Sr/86Sr values of similar-age samples from different sites. Strontium-isotope analyses compiled from 9 of 12 sites that have detailed age control define one band of common values. This band is used as a composite curve, which presumably represents seawater 87Sr/86Sr values. The composite curve shows a "trough" of markedly lower 87Sr/86Sr values in the Aptian and early Albian stages, higher but constant values for the middle Albian-Cenomanian stages, followed by a decrease in 87Sr/86Sr values in the early Turonian. Variations between published mid-Cretaceous Sr-isotope records result from diagenetic alteration, analytical problems, and the diverse biostratigraphic approaches and assumptions used to estimate sample ages. When preexisting age data are made consistent, the composite record shows close similarities with data sets derived from measurements of macrofossils in land sections of Europe and North America. The interval of decreased 87Sr/86Sr values in the Aptian-Albian stages overlaps with the pulse of mid-plate volcanic activity that produced the Ontong Java, Manihiki, and Kerguelen Plateaus. The exact age and the shape of the trough, however, are consistent with increased spreading rates at oceanic ridges, given the existing data on the timing of mid-plate volcanic activity.

Surface seawater carbonate chemistry, nutrients and phytoplankton community composition on a transect between North Sea and Arctic Ocean, 2008

This data was collected during the 'ICE CHASER' cruise from the southern North Sea to the Arctic (Svalbard) in July-Aug 2008. This data consists of coccolithophore abundance, calcification and primary production rates, carbonate chemistry parameters and ancillary data of macronutrients, chlorophyll-a, average mixed layer irradiance, daily irradiance above the sea surface, euphotic and mixed layer depth, temperature and salinity.

Planktic foraminifera of sediment core GeoB1710-3

In this study, we test various parameters in deep-sea sediments (bulk sediment parameters and changes in microfossil abundances and preservation character) which are generally accepted as indicators of calcium carbonate dissolution. We investigate sediment material from station GeoB 1710-3 in the northern Cape Basin (eastern South Atlantic), 280 km away from the Namibian coast, well outside today's coastal upwelling. As northern Benguela upwelling cells were displaced westward and periodically preceded the core location during the past 245 kyr (Volbers et al., submitted), GeoB 1710-3 sediments reflect these changes in upwelling productivity. Results of the most commonly used calcium carbonate dissolution proxies do not only monitor dissolution within these calcareous sediments but also reflect changes in upwelling intensity. Accordingly, these conventional proxy parameters misrepresent, to some extent, the extent of calcium carbonate dissolution. These results were verified by an independent dissolution proxy, the Globigerina bulloides dissolution index (BDX') (Volbers and Henrich, 2002, doi:10.1016/S0025-3227(02)00333-X). The BDX' is based on scanning electronic microscope ultrastructural investigation of planktonic foraminiferal tests and indicates persistent good carbonate preservation throughout the past 245 kyr, with the exception of one pronounced dissolution event at early oxygen isotopic stage (OIS) 6. The early OIS 6 is characterized by calcium carbonate contents, sand contents, and planktonic foraminiferal concentrations all at their lowest levels for the last 245 kyr. At the same time, the ratio of radiolarian to planktonic foraminiferal abundances and the ratio of benthic to planktonic foraminiferal tests are strongly increased, as are the rain ratio, the fragmentation index, and the BDX'. The sedimentary calcite lysocline rose above the core position and GeoB 1710-3 sediments were heavily altered, as attested to by the unusual accumulation of pellets, aggregates, sponge spicules, radiolaria, benthic foraminifera, and planktonic foraminiferal assemblages. Solely the early OIS 6 dissolution event altered the coarse fraction intensely, and is therefore reflected by all conventional calcium carbonate preservation proxies and the BDX'. We attribute the more than 1000 m rise of the sedimentary calcite lysocline to the combination of two processes: (a) a prominent change in the deep-water mass distribution within the South Atlantic and (b) intense degradation of organic material within the sediment (preserved as maximum total organic carbon content) creating microenvironments favorable for calcium carbonate dissolution.

Seawater carbonate chemistry and Mytilus edulis biological processes during experiments, 2010

CO2 emissions are leading to an acidification of the oceans. Predicting marine community vulnerability towards acidification is difficult, as adaptation processes cannot be accounted for in most experimental studies. Naturally CO2 enriched sites thus can serve as valuable proxies for future changes in community structure. Here we describe a natural analogue site in the Western Baltic Sea. Seawater pCO2 in Kiel Fjord is elevated for large parts of the year due to upwelling of CO2 rich waters. Peak pCO2 values of >230 Pa (>2300 µatm) and pHNBS values of <7.5 are encountered during summer and autumn, average pCO2 values are ~70 Pa (~700 µatm). In contrast to previously described naturally CO2 enriched sites that have suggested a progressive displacement of calcifying auto- and heterotrophic species, the macrobenthic community in Kiel Fjord is dominated by calcifying invertebrates. We show that blue mussels from Kiel Fjord can maintain control rates of somatic and shell growth at a pCO2 of 142 Pa (1400 µatm, pHNBS = 7.7). Juvenile mussel recruitment peaks during the summer months, when high water pCO2 values of ~100 Pa (~1000 µatm) prevail. Our findings indicate that calcifying keystone species may be able to cope with surface ocean pHNBS values projected for the end of this century when food supply is sufficient. However, owing to non-linear synergistic effects of future acidification and upwelling of corrosive water, peak seawater pCO2 in Kiel Fjord and many other productive estuarine habitats could increase to values >400 Pa (>4000 µatm). These changes will most likely affect calcification and recruitment, and increase external shell dissolution.

Tab. 1: Proportion of glacial quartz grains contained in the deposits

The Yari-Hotaka Mountain Range is one of the most famous formerly-glaciated areas of Japan. Many glacial landforms remain in three neighbouring U-shaped valleys, named Yarisawa, Yokoo and Migimata. Moraines and outwash terraces can be classified into four groups according to their location and to the amount of glacial quartz grains contained in the deposits. A glaciation is proved for other parts of the Northern Japanese Alps before 100 000 years B.P., but not for the Yari-Hotaka Mountain Range, because the corresponding glacial landforms cannot be found here. The oldest known Ichinomata stage before and after 60 000 years B.P. corresponds to the Yokoo glacial which is proved wirhin the whole Japanese Alps. The three younger stages, Babadaira stage (before 30 000 years B.P.), Yarisawa stage I (about 30000 years B.P.) and Yarisawa stage II (about 15000 years B.P.), belong to the Karasawa glacial. About 10 000 years B.P. the glaciers melted away. At all times the relief-influence was especially important for Ihe mass-balances of Japanese glaciers. Wind-drifted snow from the west-exposed windward slopes to the slopes in eastern (lee) exposition, and a voluminous snow accumulation by avalanches from the high rocky walls onto the glacier surfaces beneath, caused very low situated glaciers as well as low equilibrium-lines. In most cases the snow-lines were situated 100 m or more above the equilibrium-lines. During the Ichinomata stage the snow-line reached an altitude of 2400-2450 m. It rose about 100 m to the Babadaira stage, 300 m to Yarisawa stage I and about 450 m to Yarisawa stage II. At present the snow-line is situated above the Northern Japanese Alps at over 4000 m. Therefore only perennial snow-patches exist. If the snow-line would go down by a few hundred meters, this region would be highly interesting Ifor studies on the beginning of mountain glaciation.

Phytoplanktonic microfossil groups of sediments from the South and Equatorial Atlantic

Individual planktonic microfossil species, or assemblage groups of different species, are often used to, qualitatively and/or quantitatively, reconstruct past (sub)surface-water conditions of the world's oceans and seas. Until now, little information has been available on the surface sediment distribution patterns and paleoenvironmental reconstruction potential of coccolith, calcareous dinoflagellate cyst and organic-walled dinoflagellate cyst assemblages of the South and equatorial Atlantic, especially at the species level. This paper (i) summarizes the distributions of these three phytoplanktonic microfossil groups in numerous Atlantic surface sediments from 20°N-50°S and 30°E-65°W and determines their relationship with the physicochemical and trophic conditions of the overlying (sub)surface-waters, and (ii) determines the synecology of the three phytoplankton groups by carrying out statistical analyses (i.e. detrended and canonical correspondence analyses) on all groups simultaneously. Ecological relationships are additionally strengthened by statistically comparing the distribution patterns of the phytoplankton groups with those of planktonic foraminifera (Pflaumann et al. 1996; Niebler et al. 1998), as the ecological preferences of the latter are much better known. Many of the analyzed phytoplanktonic microfossil species or groups of species in the surface sediments do show restricted distributions which primarily reflect the environmental conditions of the upper water masses above them (e.g. sea-surface temperature, productivity, stratification). The acquired 'reference' data sets are large and diverse enough to allow future development of transfer functions for the reconstruction of past surface-water conditions, and show that there is still an enormous paleoenvironmental reconstruction potential concealed in many fossil coccolith and dinoflagellate cyst assemblages.

(Table 1) Distribution of upper Campanian-lower Maestrichtian calcareous nannofossils at DSDP Hole 71-511

Calcareous nannofossils from upper Campanian-lower Maestrichtian Deep Sea Drilling Project Leg 71 Cores 511-23 and 511-24 are described and correlated with assemblages of similar age from piston and drill cores on the Falkland Plateau, South Atlantic Ocean. The Leg 71 cores partially fill a drilling gap of at least 20 meters left within a thick (50 m) carbonate section first drilled by DSDP Leg 36 at Site 327. Cores 511-23 and 511-24 both fall within the upper portion of the Biscutum coronum Zone of Wind and demonstrate an overlap in the range of Monomarginatus quaternarius with the ranges of M. pectinatus, Misceomarginatus pleniporus, and Biscutum coronum across the Campanian/ Maestrichtian boundary. Resolution of the sequence of highest occurrence datums for the latter species must await the recovery of a more complete section. Comparison of the Site 511 assemblages with those from Mas Orcadas Core 07-75-44 to the north confirms earlier speculation that the Falkland Plateau served as an important boundary between major water masses during the Late Cretaceous.

Quartz grain microtextures of sediments from ODP Hole 188-1166A (Table 1)

This paper presents the results of the scanning electron microscopic (SEM) analysis of quartz grains from a selection of samples at Site 1166. Ocean Drilling Program Leg 188 drilled Site 1166 on the Prydz Bay continental shelf, Antarctica, to document onset and fluctuations of East-Antarctic glaciation. This site recovered Upper Pliocene-Holocene glacial sediments directly above Cretaceous through Lower Oligocene sediments recording the transition from preglacial to early glacial conditions. SEM analysis of quartz grains at Site 1166 was used to characterize the glacial and preglacial sediments by their diagnostic textures. Angular edges, edge abrasion as well as arcuate to straight steps, are the most frequent features in glacial deposits. The highest frequency of grains with round edges is present in Middle-Late Eocene fluvio-deltaic sands. However, angular outlines, fractured plates with subparallel linear fractures and edge abrasion indicating glacier influence are also present. Preglacial carbonaceous mudstone and laminated gray claystone show distinctive high relief quartz grains and some chemical weathering on grain surfaces. The results of the microtextural analysis of quartz grains are used to verify some critical periods of ice sheet evolution, such as the transition from the East Antarctic preglacial to glacial conditions on the continental shelf from Middle/Late Eocene to Late Eocene/Early Oligocene time.

Occurrence of microtextures recorded from quartz sand grains of ODP Hole 178-1101A (Table 1)

Sediment drifts on the continental rise are located proximal to the western side of the Antarctic Peninsula and recorded changes in glacial volume and thermal regime over the last ca. 15 m.y. At Ocean Drilling Program (ODP) Site 1101 (Leg 178), which recovered sediments back to 3.1 Ma, glacial-interglacial cyclicity was identified based on the biogenic component and sedimentary structures observed in X-radiographs, magnetic susceptibility and lithofacies descriptions. Glacial intervals are dominated by fine-grained laminated mud and interglacial units consist of bioturbated muds enriched in biogenic components. From 2.2 to 0.76 Ma, planktonic foraminifera and calcareous nannofossils dominate in the interglacials suggesting a shift of the Antarctic Polar Front (APF) to the south near the drifts. Prior to 2.2 Ma, cyclicity cannot be identified and diatoms dominate the biogenic component and high percent opal suggests warmer conditions south of the APF and reduced sea ice over the drifts. Analyses of the coarse-grained terrigenous fraction (pebbles and coarse sand) from Sites 1096 and 1101 record glaciers at sea-level releasing iceberg-rafted debris (IRD) throughout the last 3.1 m.y. Analyses of quartz sand grains in IRD with the scanning electron microscope (SEM) show an abrupt change in the frequency of occurrence of microtextures at ~1.35 Ma. During the Late Pliocene to Early Pleistocene, the population of quartz grains included completely weathered grains and a low frequency of crushing and abrasion, suggesting that glaciers were small and did not inundate the topography. Debris shed from mountain peaks was transported supraglacially or englacially allowing weathered grains to pass through the glacier unmodified. During glacial periods from 1.35-0.76 Ma, glaciers expanded in size. The IRD flux was very high and dropstones have diverse lithologies. Conditions resembling those at the Last Glacial Maximum (LGM) have been episodically present on the Antarctic Peninsula since ~0.76 Ma. Quartz sand grains show high relief, fracture and abrasion common under thick ice and the IRD flux is low with a more restricted range of dropstone lithologies.

A Mineralogical Study of a Dravitic Tourmaline from the Grenville Province

Tourmaline from a gem-quality deposit in the Grenville province has been studied with X-ray diffraction, visible-near infrared spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, electron microprobe and optical measurements. The tourmaline is found within tremolite-rich calc-silicate pods hosted in marble of the Central Metasedimentary Belt. The crystals are greenish-greyish-brown and have yielded facetable material up to 2.09 carats in size. Using the classification of Henry et al. 2011 the tourmaline is classified as a dravite, with a representative formula shown to be (Na0.73Ca0.2380.032)(Mg2+2.913Fe2+0.057Ti4+0.030) (Al3+5.787Fe3+0.017Mg2+0.14)(Si6.013O18)(BO3)3(OH)3((OH,O)0.907F0.093). Rietveld analysis of powder diffraction data gives a = 15.9436(8) Å, c = 7.2126(7) Å and a unit cell volume of 1587.8 Å3. A polished thin section was cut perpendicular to the c-axis of one tourmaline crystal, which showed zoning from a dark brown core into a lighter rim into a thin darker rim and back into lighter zonation. Through the geochemical data, three key stages of crystal growth can be seen within this thin section. The first is the core stage which occurs from the dark core to the first colourless zone; the second is from this colourless zone increasing in brown colour to the outer limit before a sudden absence of colour is noted; the third is a sharp change from the end of the second and is entirely colourless. These events are the result of metamorphism and hydrothermal fluids resulting from nearby felsic intrusive plutons. Scanning electron microscope, and electron microprobe traverses across this cross-section revealed that the green colour is the result of iron present throughout the system while the brown colour is correlated with titanium content. Crystal inclusions in the tourmaline of chlorapatite, and zircon were identified by petrographic analysis and confirmed using scanning electron microscope data and occur within the third stage of formation.

Analysis of Evidence from Core Sample Fractures in Stewardson Lake Uranium Prospect

This study was performed to characterize evidence of potential unconformity-type U mineralizing fluids in drill core fractures from the Stewardson Lake prospect, in the Athabasca Basin, located in Northern Saskatchewan and Alberta, Canada. Fractures were visually classified into eight varieties. This classification scheme was improved with the use of mineralogical characterization through SEM (Scanning Electron Microscope) and XRD analyses of the fracture fills and resulted in the identification of various oxides, hydroxides, sulfides, and clays or clay-sized minerals. Fractures were tallied to a total of ten categories with some commonalities in color. The oxidative, reductive or mixed nature of the fluids interacting with each fracture was determined based on its fill mineralogy. The measured Pb isotopic signature of samples was used to distinguish fractures affected solely by fluids emanating from a U mineralization source, from those affected by mixed fluids. Anomalies in U and U-pathfinder elements detected in fractures assisted with attributing them to the secondary dispersion halo of potential mineralization. Three types of fracture functions (chimney, composite and drain) were defined based on their interpreted flow vector and history. A secondary dispersion halo boundary with a zone of dominance of infiltrating fluids was suggested for two boreholes. The control of fill mineralogy on fracture color was investigated and the indicative and non-indicative colors and minerals, with respect to a secondary dispersion halo, were formally described. The fracture colors and fills indicative of proximity to the basement host of the potential mineralization were also identified. In addition, three zones of interest were delineated in the boreholes with respect to their geochemical dynamics and their relationship to the potential mineralization: a shallow barren overburden zone, a dispersion and alteration zone at intermediate depth, and a second deeper zone of dispersion and alteration.