Tab. 1+2: Representative electron-microprobe analyses of minerals from Du Toit Nunataks

An example of cordierite-bearing gneiss that is part of a high-grade gneiss-migmatite sequence is described from the Hatch Plain in the Read Mountains of the Shackleton Range, Antarctica, for the first time. The cordierite-bearing rocks constitute the more melanosomic portions of the metatectic and migmatitic rocks that are associated with relict granulite facies rocks such as enderbitic granulite and enderbitic garnet granulite. The predominant mineral assemblage in the cordierite-bearing rocks is chemically homogeneous cordierite (XMg 0.61) and biotite (XMg 0.47), strongly zoned garnet (XMg 0.18-0.11), sillimanite, K-feldspar (Or81-94Ab5-18An0.6), plagioclase (An28), and quartz. Inclusions of sillimanite and biotite relics in both garnet and cordierite indicate that garnet and cordierite were produced by the coupled, discontinuous reaction biotite + sillimanite + quartz = cordierite + garnet + K-feldspar + H2O. Various garnet-biotite and garnet-cordierite geothermometers and sillimanite-quartz-plagioclase-garnet-cordierite geobarometers yield a continuous clockwise path in the P-T diagram. The P-T conditions for equilibrium between garnet core and cordierite and between garnet core and biotite during peak metamorphism and migmatization were estimated to be 690 °C at 5-6 kb. This was followed by cooling and unloading with continuously changing conditions down to 515 °C at 2-3 kb. This low-pressure re-equilibration correlates with the pressure conditions evaluated by SCHULZE (1989) for the widespread granitic gneisses of the Read Group in the Shackleton Range. The associated relict enderbitic granulites representing low-pressure type granulite (8 kb; 790 °C) are comparable to similar low-pressure granulites from the East Antarctic craton. They were either formed by under-accretion processes after collision (WELLS 1979, p. 217) or they are a product of remetamorphism at P-T conditions intermediate between granulite and amphibolite facies. A model of a multiple imbrication zone with crustal thickening (CUTHBERT et al. 1983) is discussed for the formation of the relict granulites of the central and eastern Read Mountains which show higher pressure conditions (8-12 kb, SCHULZE & OLESCH 1990), indicating a Proterozoic crustal thickness of at least 40 km.

Geochemistry and stable isotopes of peridotites of ODP Hole 103-637A

A ridge of strongly serpentinized, plagioclase-bearing peridotite crops out at the boundary between the Atlantic oceanic crust and the Galicia continental margin (western Spain). These peridotites, cored at Hole 637A (ODP Leg 103) have been mylonitized at high-temperature, low-pressure conditions and under large deviatoric stress during their uplift (Girardeau et al., 1988, doi:10.2973/odp.proc.sr.103.135.1988). After this main ductile deformation event, the peridotite underwent a polyphase metamorphic static episode in the presence of water, with the crystallization of Ti- and Cr-rich pargasites at high-temperature (800°-900°C) interaction with a metasomatic fluid or alkaline magma. Introduction of water produced destabilization of the pyroxenes and the subsequent development of hornblendes and tremolite at temperatures decreasing from 750° to 350°C. The main serpentinization of the peridotite occurred at a temperature below 300°C, and possibly around 50°C, as a consequence of the introduction of a large amount of seawater, which is suggested by stable isotope (d18O and SD) data. Finally, calcite derived from seawater precipitated in late-formed fractures or locally pervasively impregnated the peridotite at low temperature (~10°C).

Magnetic properties, grain sizes and minerals at DSDP Site 83-504B

Twenty-seven samples from the Leg 83 section of Hole 504B have been investigated using magnetic, optical, and electron optical methods. The primary magnetic mineral to crystallize was titanomagnetite of approximate composition Fe2.4Ti0.6O4 (TM60), but none survives, nor is there evidence of titanomaghemite produced by oxidation of TM60. The average measured magnetic properties can be interpreted in terms of magnetite, Fe3O4, having average grain size of <1 µm and present in average volume concentration of - 0.5%. The intensity of the natural remanent magnetization (NRM) of the rocks could also be accounted for as being a thermoremanence carried by this mineral. Although the heterogeneity of the titanomagnetite grains could be detected optically, the texture of the intergrown phases is poorly developed. In some samples from the massive units of the lower part of the section, trellis patterns were visible. The Fe3O4 present in the intergrowths is too intimately mixed with the other intergrown phases to be revealed by electron microprobe analysis that simply returns the bulk composition of the intergrowth (oxidized TM60). The path by which the mineral assemblage evolved from TM60 to an Fe304-containing intergrowth, under the temperature and pressure conditions obtaining in the Leg 83 section, makes interesting speculation. Deuteric oxidation, maghemitization/inversion, or some hypothetical low-temperature/high-pressure oxidation by a leaching-of-iron process may all play roles.

Diagenetic development of deep-sea carbonate sediments from DSDP Holes 30-228, 30-289 and 33-316

Laboratory measurements of ultrasonic velocity (VP, VS) and attenuation (QP**-1, QS**-1) in deep-sea carbonate sequences at DSDP Sites 288, 289 and 316 in the equatorial Pacific were made in conjunction with studies of sediment density, porosity and pore geometry in order to investigate the role of diagenesis in the development of physical properties. Bulk porosity decrease appears to be related more significantly to depth of burial than to age of strata. Both depth of burial and age, however, are important factors controlling the modal pore diameter. In deep-burial diagenesis the modification of pore geometry is influenced by the presence of silica during diagenesis. In carbonate sequences at the three DSDP sites studied, shear wave attenuation anisotropy (QSHH**-1/QSHV**-1) correlates with the shear wave velocity anisotropy. Pore orientation, resulting from overburden pressure and other deep-burial diagenetic processes, is an important factor controlling the increase of VP anisotropy with age and depth of burial. On the basis of observed minor changes in anisotropy values with increasing pressure for some samples, other contributions to VP anisotropy such as grain orientation and bedding lamination cannot be ruled out.

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

(Table 1) Geochemical and geothermometry data from fibrous calcite vein fills in the Dabashan Fold Belt, China

Fibrous calcite veins with organic inclusions have been widely considered as indicators of oil and gas generation and migration under overpressure. Abundant fibrous calcite veins containing organic-bearing inclusions occur in faulted Lower Paleozoic through Triassic hydrocarbon source rocks in the Dabashan Foreland Belt (DBF). d13CPDB and d18OPDB values of the fibrous calcite range from - 4.8 to -1.9 to per mil and - 12.8 to - 8.4 per mil respectively, which is lighter than that of associated carbonate host rocks ranging from - 1.7 to + 3.1 per mil and - 8.7 to - 4.5 per mil. A linear relationship between d13CPDB and d18OPDB indicates that the calcite veins were precipitated from a mixture of basinal and surface fluids. The fibrous calcite contains a variety of inclusions, such as solid bitumen, methane bearing all-liquid inclusions, and vapor-liquid aqueous inclusions. Homogenization temperatures of aqueous inclusions range from 140 to 196° with an average of 179°. Salinities of aqueous inclusions average 9.7 wt% NaCl. Independent temperatures from bitumen reflectance and inclusion phase relationships of aqueous and methane inclusions were used to determine fluid pressures. Results indicate high pressures, elevated above typical lithostatic confining pressure, from 150 to 200 MPa. The elevated salinity and high temperature and pressure conditions of the fibrous calcite veins argue against an origin solely from burial overpressure resulting from clay transformation and dehydration reactions. Instead fluid inclusion P-T data and geochemistry results and regional geology indicate abnormally high pressures during fluid migration. These findings indicate that tectonic stress generated fracture and fault fluid pathways and caused migration of organic bearing fluids from the DBF during the Yanshan orogeny.

Permeabilities, grain size and carbon composition of sediments from ODP Hole 170-1040C and two Leg 205 holes

Constant-pressure difference and constant-flow permeability tests were conducted on core samples from Ocean Drilling Program Legs 170 and 205 from the Costa Rica subduction zone representing pelagic carbonate and hemipelagic mud lithologies. Seven whole-round core samples from Sites 1040, 1253, and 1255 were tested for vertical permeabilities. The permeabilities of the pelagic carbonate sediments range from ~4 x 10**-16 to ~1 x 10**-15 m**2. The permeabilities of the hemipelagic mud sediments vary from ~2 x 10**-18 to ~4 x 10**-18 m**2. To further characterize the sediments, grain size, total carbon, and total inorganic carbon analyses were conducted.

Laser ablation data of benthic foraminifera from surface sediments collected from the muddy intertidal flats near Dorum, Northwestern Germany in Autumn 2008

Biological activity introduces variability in element incorporation during calcification and thereby decreases the precision and accuracy when using foraminifera as geochemical proxies in paleoceanography. This so-called 'vital effect' consists of organismal and environmental components. Whereas organismal effects include uptake of ions from seawater and subsequent processing upon calcification, environmental effects include migration- and seasonality-induced differences. Triggering asexual reproduction and culturing juveniles of the benthic foraminifer Ammonia tepida under constant, controlled conditions allow environmental and genetic variability to be removed and the effect of cell-physiological controls on element incorporation to be quantified. Three groups of clones were cultured under constant conditions while determining their growth rates, size-normalized weights and single-chamber Mg/Ca and Sr/Ca using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Results show no detectable ontogenetic control on the incorporation of these elements in the species studied here. Despite constant culturing conditions, Mg/Ca varies by a factor of similar to 4 within an individual foraminifer while intra-individual Sr/Ca varies by only a factor of 1.6. Differences between clone groups were similar to the intra-clone group variability in element composition, suggesting that any genetic differences between the clone-groups studied here do not affect trace element partitioning. Instead, variability in Mg/Ca appears to be inherent to the process of bio-calcification itself. The variability in Mg/Ca between chambers shows that measurements of at least 6 different chambers are required to determine the mean Mg/Ca value for a cultured foraminiferal test with a precision of <= 10%

(Table 1) Lithium contents and isotopic composition in sediments from DSDP Holes 64-477 and 64-477A

Lithium isotopic compositions of hydrothermally altered sediments of Deep Sea Drilling Project (DSDP) site 477/477A, as well as high temperature vent fluids of the Guaymas Basin, have been determined to gain an understanding of lithium exchange during fluid-sediment interaction at this sediment-covered spreading center. Unaltered turbidite of the basin has a d6Li value of -10%, 5-7% heavier than fresh oceanic basalts. Contact metamorphism induced by a shallow sill intrusion results in a decrease of the lithium content of the adjacent sediments and a lighter isotopic value (-8%). Below the sill, sediments altered by a deep-seated hydrothermal system show strong depletions in lithium, while lithium isotopic compositions vary greatly, ranging from -11 to +1%. The shift to lighter composition is the result of preferential retention of the lighter isotope in recrystallized phases after destruction of the primary minerals. The complexity of the isotope profile is attributed to inhomogeneity in mineral composition, the tortuous pathway of fluids and the temperature effect on isotopic fractionation. The range of lithium concentration and d6Li values for the vent fluids sampled in 1982 and 1985 overlaps with that of the sediment-free mid-ocean ridge systems. The lack of a distinct expression of sediment input is explained in terms of a flow-through system with continuous water recharge. The observations on the natural system agree well with the results of laboratory hydrothermal experiments. The experimental study demonstrates the importance of temperature, pressure, water/rock ratio, substrate composition and reaction time on the lithium isotopic composition of the reacted fluid. High temperature authigenic phases do not seem to constitute an important sink for lithium and sediments of a hydrothermal system such as Guaymas are a source of lithium to the ocean. The ready mobility of lithium in the sediment under elevated temperature and pressure conditions also has important implications for lithium cycling in subduction zones.

Experiment: Organic matter exudation by Emiliania huxleyi under simulated future ocean conditions

Emiliania huxleyi (strain B 92/11) was exposed to different nutrient supply, CO2 and temperature conditions in phosphorus controlled chemostats to investigate effects on organic carbon exudation and partitioning between the pools of particulate organic carbon (POC) and dissolved organic carbon (DOC). 14C incubation measurements for primary production (PP) and extracellular release (ER) were performed. Chemical analysis included the amount and composition of high molecular weight (>1 kDa) dissolved combined carbohydrates (HMW-dCCHO), particulate combined carbohydrates (pCCHO) and the carbon content of transparent exopolymer particles (TEP-C). Applied CO2 and temperature conditions were 300, 550 and 900 µatm pCO2 at 14 °C, and additionally 900 µatm pCO2 at 18 °C simulating a greenhouse ocean scenario. Enhanced nutrient stress by reducing the dilution rate (D) from D = 0.3 /d to D = 0.1 /d (D = µ) induced the strongest response in E. huxleyi. At µ = 0.3 /d, PP was significantly higher at elevated CO2 and temperature and DO14C production correlated to PO14C production in all treatments, resulting in similar percentages of extracellular release (PER; (DO14C production/PP) × 100) averaging 3.74 ± 0.94%. At µ = 0.1 /d, PO14C production decreased significantly, while exudation of DO14C increased. Thus, indicating a stronger partitioning from the particulate to the dissolved pool. Maximum PER of 16.3 ± 2.3% were observed at µ = 0.1 /d at elevated CO2 and temperature. While cell densities remained constant within each treatment and throughout the experiment, concentrations of HMW-dCCHO, pCCHO and TEP were generally higher under enhanced nutrient stress. At µ= 0.3 /d, pCCHO concentration increased significantly with elevated CO2 and temperature. At µ = 0.1 /d, the contribution (mol % C) of HMW-dCCHO to DOC was lower at elevated CO2 and temperature while pCCHO and TEP concentrations were higher. This was most pronounced under greenhouse conditions. Our findings suggest a stronger transformation of primary produced DOC into POC by coagulation of exudates under nutrient limitation. Our results further imply that elevated CO2 and temperature will increase exudation by E. huxleyi and may affect organic carbon partitioning in the ocean due to an enhanced transfer of HMW-dCCHO to TEP by aggregation processes.

Direct linkage between dimethyl sulfide production and microzooplankton grazing, resulting from prey composition change under high partial pressure of carbon dioxide conditions

Oceanic dimethyl sulfide (DMS) is the enzymatic cleavage product of the algal metabolite dimethylsulfoniopropionate (DMSP) and is the most abundant form of sulfur released into the atmosphere. To investigate the effects of two emerging environmental threats (ocean acidification and warming) on marine DMS production, we performed a large-scale perturbation experiment in a coastal environment. At both ambient temperature and 2 °C warmer, an increase in partial pressure of carbon dioxide (pCO2) in seawater (160-830 ppmv pCO2) favored the growth of large diatoms, which outcompeted other phytoplankton species in a natural phytoplankton assemblage and reduced the growth rate of smaller, DMSP-rich phototrophic dinoflagellates. This decreased the grazing rate of heterotrophic dinoflagellates (ubiquitous micrograzers), resulting in reduced DMS production via grazing activity. Both the magnitude and sign of the effect of pCO2 on possible future oceanic DMS production were strongly linked to pCO2-induced alterations to the phytoplankton community and the cellular DMSP content of the dominant species and its association with micrograzers.

Ocean acidification slows nitrogen fixation and growth in the dominant diazotroph Trichodesmium under low-iron conditions

Dissolution of anthropogenic CO(2) increases the partial pressure of CO(2) (pCO(2)) and decreases the pH of seawater. The rate of Fe uptake by the dominant N(2)-fixing cyanobacterium Trichodesmium declines as pH decreases in metal-buffered medium. The slower Fe-uptake rate at low pH results from changes in Fe chemistry and not from a physiological response of the organism. Contrary to previous observations in nutrient-replete media, increasing pCO(2)/decreasing pH causes a decrease in the rates of N(2) fixation and growth in Trichodesmium under low-Fe conditions. This result was obtained even though the bioavailability of Fe was maintained at a constant level by increasing the total Fe concentration at low pH. Short-term experiments in which pCO(2) and pH were varied independently showed that the decrease in N(2) fixation is caused by decreasing pH rather than by increasing pCO(2) and corresponds to a lower efficiency of the nitrogenase enzyme. To compensate partially for the loss of N(2) fixation efficiency at low pH, Trichodesmium synthesizes additional nitrogenase. This increase comes partly at the cost of down-regulation of Fe-containing photosynthetic proteins. Our results show that although increasing pCO(2) often is beneficial to photosynthetic marine organisms, the concurrent decreasing pH can affect primary producers negatively. Such negative effects can occur both through chemical mechanisms, such as the bioavailability of key nutrients like Fe, and through biological mechanisms, as shown by the decrease in N(2) fixation in Fe-limited Trichodesmium.

Seawater carbonate chemistry, chlorophyll a and photosynthetic carbon fixation rate under different light and pCO2 conditions during experiments, 2010

We carried out short term pCO2/pH perturbation experiments in the coastal waters of the South China Sea to evaluate the combined effects of seawater acidification (low pH/high pCO2) and solar UV radiation (UVR, 280-400 nm) on photosynthetic carbon fixation of phytoplankton assemblages. Under photosynthetically active radiation (PAR) alone treatments, reduced pCO2 (190 ppmv) with increased pH resulted in a significant decrease in the photosynthetic carbon fixation rate (about 23%), while enriched pCO2 (700 ppmv) with lowered pH had no significant effect on the photosynthetic performance compared to the ambient level. The apparent photosynthetic efficiency decreased under the reduced pCO2 level, probably due to C-limitation as well as energy being diverged for up-regulation of carbon concentrating mechanisms (CCMs). In the presence of UVR, both UV-A and UV-B caused photosynthetic inhibition, though UV-A appeared to enhance the photosynthetic efficiency under lower PAR levels. UV-B caused less inhibition of photosynthesis under the reduced pCO2 level, probably because of its contribution to the inorganic carbon (Ci)-acquisition processes. Under the seawater acidification conditions (enriched pCO2), both UV-A and UV-B reduced the photosynthetic carbon fixation to higher extents compared to the ambient pCO2 conditions. We conclude that solar UV and seawater acidification could synergistically inhibit photosynthesis.