Code and readme of a MATLAB-based graphical user interface program for computing functionals of the geopotential

We present a novel graphical user interface program GrafLab (GRAvity Field LABoratory) for spherical harmonic synthesis (SHS) created in MATLAB®. This program allows to comfortably compute 38 various functionals of the geopotential up to ultra-high degrees and orders of spherical harmonic expansion. For the most difficult part of the SHS, namely the evaluation of the fully normalized associated Legendre functions (fnALFs), we used three different approaches according to required maximum degree: (i) the standard forward column method (up to maximum degree 1800, in some cases up to degree 2190); (ii) the modified forward column method combined with Horner's scheme (up to maximum degree 2700); (iii) the extended-range arithmetic (up to an arbitrary maximum degree). For the maximum degree 2190, the SHS with fnALFs evaluated using the extended-range arithmetic approach takes only approximately 2-3 times longer than its standard arithmetic counterpart, i.e. the standard forward column method. In the GrafLab, the functionals of the geopotential can be evaluated on a regular grid or point-wise, while the input coordinates can either be read from a data file or entered manually. For the computation on a regular grid we decided to apply the lumped coefficients approach due to significant time-efficiency of this method. Furthermore, if a full variance-covariance matrix of spherical harmonic coefficients is available, it is possible to compute the commission errors of the functionals. When computing on a regular grid, the output functionals or their commission errors may be depicted on a map using automatically selected cartographic projection.

Element concentrations of plagioclase and clinopyroxene in poikilitic olivine gabbros from ODP Hole 153-923A (Table 4)

Ocean Drilling Program Hole 923A, located on the western flank of the Mid-Atlantic Ridge south of the Kane Fracture Zone, recovered primitive gabbros that have mineral trace element compositions inconsistent with growth from a single parental melt. Plagioclase crystals commonly show embayed anorthitic cores overgrown by more albitic rims. Ion probe analyses of plagioclase cores and rims show consistent differences in trace element ratios, indicating variation in the trace element characteristics of their respective parental melts. This requires the existence of at least two distinct melt compositions within the crust during the generation of these gabbros. Melt compositions calculated to be parental to plagioclase cores are depleted in light rare earth elements, but enriched in yttrium, compared to basalts from this region of the Mid-Atlantic Ridge, which are normal mid-ocean ridge basalt (N-MORB). Clinopyroxene trace element compositions are similar to those predicted to be in equilibrium with N-MORB. However, primitive clinopyroxene crystals are much more magnesian than those produced in one-atmosphere experiments on N-MORB, suggesting that the major element composition of the melt was unlike N-MORB. These data require that the diverse array of melt compositions generated within the mantle beneath mid-ocean ridges are not always fully homogenised during melt extraction from the mantle and that the final stage of mixing can occur efficiently within crustal magma chambers. This has implications for the process of melt extraction from the mantle and the liquid line of descent of MORB

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Hydrocarbon gases in Tertiary and Quaternary sediments offshore Peru

Hydrocarbon gases (methane, ethane, propane, isobutane, n-butane, ethene, and propene) are present in Tertiary and Quaternary shelf, upper-slope, and lower-slope deposits of the Peruvian continental margin. Methane dominates the composition of the hydrocarbon gas at all 10 sites examined during Ocean Drilling Program (ODP) Leg 112. Generation of methane is regulated by the amount of sulfate in pore water. Wherever sulfate concentrations approach or equal zero, methane concentrations increase rapidly, reaching values near 100,000 µL/L of wet sediment at eight of the 10 sites. Methane at all 10 sites results from methanogenesis, which is inhibited where sulfate is present and microbial reduction of sulfate occurs. Hydrocarbon gases heavier than methane also are present, but at much lower concentrations than methane. These hydrocarbons are thought to result from early thermal and microbial diagenesis, based on relative gas compositions and trends of concentrations with depth. With few exceptions, the results obtained in the shipboard and shore-based laboratories are comparable for methane and ethane in sediments of Leg 112. Reanalyses of canned sediments from ODP Leg 104 and from Deep Sea Drilling Project (DSDP) Legs 76 and 84 show that gas samples can be stored for as long as 8 yr, but the amounts of individual hydrocarbon gases retained vary. Nevertheless, the trends of the data sets with depth are similar for fresh and stored samples.

Total organic carbon content and isorenieratene concentrations from three holes of ODP Leg 160

Carotenoids were analysed in ca. 1-cm thick subsamples of three laterally time-equivalent sapropels from a west-east transect of the eastern Mediterranean Basin to study euxinic periods during Pliocene sapropel formation. The amount of intact isorenieratene (summed all-trans and cis isomers), ranged from non-detectable at the base and top of a sapropel up to 140 µg/g sediment in the central parts. Isorenieratene accumulation rates at the central and western site are remarkably similar and increase sharply to levels of up to 3.0 mg/m**2/ yr in the central part of the sapropel and then drop to low levels. This pattern indicates an expansion of euxinic conditions reaching into the photic zone, followed by deepening of the chemocline during deposition of this Pliocene sapropel. The sapropel from the easternmost site of the basin, which contains less organic carbon, shows much lower isorenieratene accumulation rates and even absence of isorenieratene in the central part of the sapropel. Ba/Al ratios indicate enhanced palaeoproductivity during sapropel formation, supporting previously proposed models, according to which increased productivity is the driving force for the generation of euxinic conditions.

Fecal pellets flux at DYFAMED sediment traps

Because zooplankton feces represent a potentially important transport pathway of surface-derived organic carbon in the ocean, we must understand the patterns of fecal pellet abundance and carbon mobilization over a variety of spatial and temporal scales. To assess depth-specific water column variations of fecal pellets on a seasonal scale, vertical fluxes of zooplankton fecal pellets were quantified and their contribution to mass and particulate carbon were computed during 1990 at 200, 500, 1000, and 2000 m depths in the open northwestern Mediterranean Sea as part of the French-JGOFS DYFAMED Program. Depth-averaged daily fecal pellet flux was temporally variable, ranging from 3.04 * 10**4 pellets m**2/d in May to a low of 6.98 * 10**2 pellets m**2/d in September. The peak flux accounted for 50% of the integrated annual flux of fecal pellets and 62% of pellet carbon during only two months in mid-spring (April and May). Highest numerical fluxes were encountered at 1000 m, suggesting fecal pellet generation well below the euphotic zone. However, there was a trend toward lower pellet carbon with increasing depth, suggesting bacterial degradation or in situ repackaging as pellets sink through the water column. At 500 m, both the lowest pellet numerical abundance and carbon flux were evident during the spring peak. Combined with data indicating that numerical and carbon fluxes are dominated at 500 m by a distinct type of pellet found uniquely at this depth, these trends suggest the presence of an undescribed mid-water macro-zooplankton or micro-nekton community. Fecal pellet carbon flux was highest at 200 m and varied with depth independently of overall particulate carbon, which was greatest at 500 m. Morphologically distinct types of pellets dominated the numerical and carbon fluxes. Small elliptical and spherical pellets accounted for 88% of the numerical flux, while larger cylindrical pellets, although relatively rare (<10%), accounted for almost 40% of the overall pellet carbon flux. Cylindrical pellets dominated the pellet carbon flux at all depths except 500 m, where a large subtype of elliptical pellet, found only at that depth, was responsible for the majority of pellet carbon flux. Overall during 1990, fecal pellets were responsible for a depth-integrated annual average flux of 1.03 mgC/m**2/d, representing 18% of the total carbon flux. The proportion of vertical carbon flux attributed to fecal pellets varied from 3 to 35%, with higher values occurring during periods when the water column was vertically mixed. Especially during these times, fecal pellets are a critical conveyor of carbon to the deep sea in this region.

Trace element concentrations in zircons from ODP Holes 147-894G and 153-923A

The trace element compositions of Hadean zircons have been used in two ways to argue for the existence of Hadean continental crust. One argument is based on low crystallization temperatures of Hadean zircons that have been determined using a novel geothermometer based on the Ti content of zircons in equilibrium with rutile. The second argument is based on using the trace element abundances in zircons to calculate their parental melt compositions, especially the rare earth elements. Here we demonstrate that zircons that grow from a melt formed by basalt differentiation at modern mid-ocean ridges cannot be unambiguously distinguished from Hadean zircons on either of these grounds. Thus, we conclude that the trace element compositions of Hadean zircons are permissive of models that do not include the generation of continental crust in the Hadean.

Mineralogical and grain size analysis of ODP Hole 119-745B from the Southern Ocean

The upper Miocene to Pleistocene sediments recovered at ODP Sites 745 and 746 in the Australian-Antarctic Basin are characterized by cyclic facies changes. Sedimentological investigations of a detailed Quaternary section reveal that facies A is dominated by a high content of siliceous microfossils, a relatively low terrigenous sediment content, an ice-rafted component, low concentrations of fine sediment particles, and a relatively high smectite content. This facies corresponds to interglacial sedimentary conditions. Facies B, in contrast, is characteristic of glacial conditions and is dominated by a large amount of terrigenous material and a smaller opaline component. There is also a prominent ice-rafted component. The microfossils commonly are reworked and broken. The clay mineral assemblages show higher proportions of glacially derived illite and chlorite. A combination of four different processes, attributed to glacial-interglacial cycles, was responsible for the cyclic facies changes during Quaternary time: transport by gravity, ice, and current and changes in primary productivity. Of great importance was the movement of the grounding line of the ice shelves, which directly influenced the intensity of ice rafting and of gravitational sediment transport to the deep sea. The extension of the ice shelves was also responsible for the generation of cold and erosive Antarctic Bottom Water, which controlled the grain-size distribution, particularly of the fine fraction, in the investigated area.

Petrology and geochemistry of volcanic rocks from ODP Sites 134-827, 134-829 and 134-830

Igneous rocks recovered from Ocean Drilling Program (ODP) Leg 134 Sites 827, 829, and 830 at the toe of the forearc slope of New Hebrides Island Arc were investigated, using petrography, mineral chemistry, major and trace element, and Sr, Nd, and Pb isotopic analyses. Basaltic and andesitic clasts, together with detrital crystals of plagioclase, pyroxenes, and amphiboles embedded in sed-lithic conglomerate or volcanic siltstone and sandstone of Pleistocene age, were recovered from Sites 827 and 830. Petrological features of these lava clasts suggest a provenance from the Western Belt of New Hebrides Island Arc; igneous constituents were incorporated into breccias and sandstones, which were in turn reworked into a second generation breccia. Drilling at Site 829 recovered a variety of igneous rocks including basalts and probably comagmatic dolerites and gabbros, plus rare ultramafic rocks. Geochemical features, including Pb isotopic ratios, of the mafic rocks are intermediate between midocean ridge basalts and island arc tholeiites, and these rocks are interpreted to be backarc basin basalts. No correlates of these mafic rocks are known from Espiritu Santo and Malakula islands, nor do they occur in the Pleistocene volcanic breccias at Sites 827 and 830. However, basalts with very similar trace element and isotopic compositions have been recovered from the northern flank of North d'Entrecasteaux Ridge at Site 828. It is proposed that igneous rocks drilled at Site 829 represent material from the North d'Entrecasteaux Ridge accreted onto the over-riding Pacific Plate during collision. An original depleted mantle harzburgitic composition is inferred for a serpentinite clast recovered at 407 meters below seafloor (mbsf) in Hole 829A. Its provenance is a matter of speculation. It could have been brought up along a deep thrust fault affecting the Pacific Plate at the colliding margin, or analogous to the Site 829 basaltic lavas, it may represent material accreted from the North d'Entrecasteaux Ridge.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Geochemistry of basalts from ODP Hole 113-690C

Basalts from Maud Rise, Weddell Sea, are vesicular and olivine-phyric. Major, trace, and rare earth element concentrations are similar to those of alkali basalts from ocean islands and seamounts. The rocks are low in MgO, Cr, Ni, and Sc, and high in TiO2, K2O, P2O5, Zr, and LREE contents. The abundance of "primary" biotite and apatite in the matrix indicates the melting of a hydrous mantle. Prevalence of olivine and absence of plagioclase in the rocks suggests that the volatile in the melt was an H2O-CO2 mixture, where H2O was <0.5. Mantle derived xenocrysts in the basalt include corroded orthopyroxene, chromite, apatite, and olivine. Olivine (Fo90) is too magnesian to be in equilibrium with the basalts, as they contain only 5-6 wt% MgO. Based on the presence of mantle xenocrysts, the high concentration of incompatible elements, the spatial and chemical affinity with other ocean island basalts from the area, and the relative age of the basalt (overlain by late Campanian sediments), it is suggested that Maud Rise was probably generated by hot-spot activity, possible during a ridge crest jump prior to 84 Ma (anomaly 34 time). Iddingsite, a complex intergrowth of montmorillonite and goethite, is the major alteration product of second generation olivine. It is suggested that iddingsite crystallized at low temperatures (<200°C) from an oxidized fluid during deuteric alteration. Vesicles are commonly filled by zeolites which have been replaced by K-feldspars.

Miocene to Pleistocene sedimentation at ODP Site 133-823

More than 2000 turbidite, debris-flow, and slump deposits recovered at Site 823 record the history of the Queensland Trough since the middle Miocene and provide new insights about turbidites, debris flow, and slump deposits (herein termed gravity deposits). Changes in the composition and nature of gravity deposits through time can be related to tectonic movements, fluctuations in eustatic sea level, and sedimentological factors. The Queensland Trough is a long, relatively narrow, structural depression that formed as a result of Cretaceous to Tertiary rifting of the northeastern Australia continental margin. Thus, tectonics established the geometry of this marginal basin, and its steep slopes set the stage for repeated slope failures. Seismic data indicate that renewed faulting, subsidence, and associated tectonic tilting occurred during the early late Miocene (continuing into the early Pliocene), resulting in unstable slopes that were prone to slope failures and to generation of gravity deposits. Tectonic subsidence, together with a second-order eustatic highstand, resulted in platform drowning during the late Miocene. The composition of turbidites reflects their origin and provides insights about the nature of sedimentation on adjacent shelf areas. During relative highstands and times of platform drowning, planktonic foraminifers were reworked from slopes and/or drowned shelves and were redeposited in turbidites. During relative lowstands, quartz and other terrigenous sediment was shed into the basin. Quartzose turbidites and clay-rich hemipelagic muds also can record increased supply of terrigenous sediment from mainland Australia. Limestone fragments were eroded from carbonate platforms until the drowned platforms were buried under hemipelagic sediments following the late Miocene drowning event. Bioclastic grains and neritic foraminifers were reworked from neritic shelves during relative lowstands. During the late Pliocene (2.6 Ma), the increased abundance of bioclasts and quartz in turbidites signaled the shallowing and rejuvenation of the northeastern Australia continental shelf. However, a one-for-one relationship cannot be recognized between eustatic sea-level fluctuations and any single sedimentologic parameter. Perhaps, tectonism and sedimentological factors along the Queensland Trough played an equally important role in generating gravity deposits. Turbidites and other gravity deposits (such as those at Site 823) do not necessarily represent submarine fan deposits, particularly if they are composed of hemipelagic sediments reworked from drowned platforms and slopes. When shelves are drowned and terrigenous sediment is not directly supplied by nearby rivers/point sources, muddy terrigenous sediments blanket the entire slope and basin, rather than forming localized fans. Slope failures affect the entire slope, rather than localized submarine canyons. Slopes may become destabilized as a result of tectonic activity, inherent sediment weaknesses, and/or during relative sea-level lowstands. For this reason, sediment deposits in this setting reflect tectonic and eustatic events that caused slope instabilities, rather than migration of different submarine fan facies.

Authigenic carbonate of ODP SIte 104-643

Different generations of complex authigenic carbonates formed in siliceous muds (lithologic Unit IV) and hemipelagic clays (lithologic Unit V) of ODP Site 643, Leg 104 Norwegian Sea. The dominant phase in Unit IV is an early diagenetic Mn, Fe-calcite with a strong negative d13C ( -14 to -16 per mil) signature, and slightly negative d180 values. The strong negative d13C results from extensive incorporation of 12C-enriched CO2 derived from bacterial degradation of marine organic matter into early Mn, Fe - calcite cements. Concomitant framboidal pyrite precipitation and abundant SEM microtextures showing excellent preservation of delicate structures of fragile diatom valves by outpourings with early Mn-calcites strongly support their shallow burial formation before the onset of compaction. Later generations of authigenic mineralizations in lithologic Unit IV include minor amounts of a second generation of calcite with platy crystals, possibly precipitated along with opal-A dissolution, and finally opal-CT crystallization in deeper seated environments overgrowing earlier precipitates with films and lepispheres. The last mineralization is collophane (fluor apatite) forming amorphous aggregates and tiny hexagonal crystals. Authigenic mineral assemblages in lithologic Unit V consist of rhodochrosites, transitional rhodochrosite/manganosiderites, and apatite. A negative d13C ( -7.1 to -15.6 per mil) and a fluctuating d18O signal indicates that the micritic to sparitic rhodochrosites, transitional rhodochrosites/manganosiderites were formed at various burial depths. CO2 resulted from organic matter degradation in the lowermost sulfate reduction zone and from biogenic methane generation in the lowermost sediments, resulting in variable and negative d13C signals. The change in carbonate mineralogy reflects major compositional differences compared to sediments in Unit IV. Most prominent is an increase in altered ash as a primary sediment component and a sudden decrease of siliceous microfossils. Upward diffusion of cations, lowered salinities in pore waters, and elevated temperatures provide diagenetic environments favoring increased remobilization processes.