Total organic carbon, metal concentrations and metal and aluminium ratios in bulk sediment from the ODP sample 169-1033B-4H-4,54-74

Holocene laminated sediments in Saanich Inlet, British Columbia, are interrupted by frequent, non-laminated, massive layers. These layers may be debris flows released by earthquakes or bioturbated sediments deposited during periods of relatively high bottom water oxygen concentration and/or low surface productivity, or both. We determined the organic carbon content and the concentration of a suite of redox-sensitive metals in bulk sediments at approximately 1-cm resolution across a laminated-massive-laminated interval (ODP Leg 169S Sample 1033B-4H-4,54-74), to determine the redox conditions under which the massive layer was deposited. Our results indicate that this massive interval was deposited under anoxic bottom waters. Manganese/Al ratios are consistently low throughout the massive section, while Mo/Al, Cd/Al, Re/Al, and U/Al ratios are enriched relative to their metal/Al ratios in detrital material (represented by Cowichan River suspended sediments). The concentration of organic carbon in the lower portion of the massive layer is higher than in the upper portion, which has a concentration similar to that in the overlying and underlying laminated sediments. Well-defined peaks in Mo/Al, Cd/Al, and Re/Al and a broad peak in U/Al occur in the lower portion of the massive layer. The positions of the Cd/Al, Re/Al, and Mo/Al peaks, as well as the increase in organic carbon content with depth in the massive layer, are best explained by a process of diagenetic redistribution of metals that occurred after the massive layer was emplaced.

Adenylate concentration and energy charge in different thallus regions and after UV radiation in brown, red and green algae

A method was developed to extract adenine nucleotides AMP, ADP, and ATP from marine macroalgal tissue to gain information on the cellular energy charge. Quantification was carried out by high performance liquid chromatography (HPLC). Three species from the rocky shore of the island of Helgoland (German Bight) were examined: Laminaria saccharina (Phaeophyta), Chondrus crispus (Rhodophyta), and Ulva lactuca (Chlorophyta). In L. saccharina and C. crispus, the adenylate energy charge (AEC) was determined in different thallus regions. AEC varied in relation to tissue age and function. Higher AEC values typically occurred in thallus regions with meristematic activity. Furthermore, L. saccharina and U. lactuca were exposed to UV-A and elevated UV-B radiation. The AEC was calculated and the maximal quantum yield of photosystem II (Fv/Fm) was determined as indicators for UV stress. In both species, the AEC remained at high values (0.72 ± 0.04), while Fv/Fm dropped rapidly. The results show that the photosynthesis of the phaeophyte is more resistant to UV radiation than the chlorophyte.

(Table 2) Collection sites and number of specimens of Usnea subgenus Neuropogon species

Usnea species of the Neuropogon group are amongst the most widespread and abundant macrolichens in Antarctic regions. Four principal species, U. antarctica, U. aurantiaco-atra, U. sphacelata and U. subantarctica, have been described on morphological grounds. However, identification to species level is often difficult and atypical morphologies frequently arise. Over 400 specimens were collected on the Antarctic Peninsula and Falkland Islands. Both morphological and molecular characters (ITS and RPB1) were used to compare samples to clarify taxonomic relationships. Morphological characteristics used included presence of apothecia, apothecial rays, soredia, papillae, fibrils, pigmentation and the diameter of the central axis as a proportion of branch diameter. Results revealed a very close relationship between U. antarctica and U. aurantiaco-atra, suggesting that they might constitute a species pair or be conspecific. Usnea sphacelata was comprised of at least two genetically distinct groups with no clear differences in morphology. One group included the first reported fertile specimen of this species. Usnea subantarctica was phylogenetically distinct from the other main Antarctic Usnea species, but clustered with U. trachycarpa. Genetic variation was evident within all species although there was no clear correlation between geographic origin and genetic relatedness. Phylogenetic analyses indicated that species circumscription in the Neuropogon group needs revision, with the principal species being non-monophyletic. None of the morphological characters, or groups of characters, used in this study proved to be completely unambiguous markers for a single species. However, axis thickness was supported as being informative for the identification of monophyletic lineages within the group.

d11B and metal/Ca ratios versus size fractions in the Surface and deep dwelling species, ODP Holes 130-806B and 108-664C

We have assessed the reliability of several foraminifer-hosted proxies of the ocean carbonate system (d11B, B/Ca, and U/Ca) using Holocene samples from the Atlantic and Pacific oceans. We examined chemical variability over a range of test sizes for two surface-dwelling foraminifers (Globigerinoides sacculifer and Globigerinoides ruber). Measurements of d11B in G. ruber show no significant relationship with test size in either Atlantic or Pacific sites and appear to provide a robust proxy of surface seawater pH. Likewise there is no significant variability in the d11B of our Atlantic core top G. sacculifer, but we find that d11B increases with increasing test size for G. sacculifer in the Pacific. These systematic differences in d11B are inferred to be a consequence of isotopically light gametogenic calcite in G. sacculifer and its preferential preservation during postdepositional dissolution. The trace element ratio proxies of ocean carbonate equilibria, U/Ca and B/Ca, show systematic increases in both G. ruber and G. sacculifer with increasing test size, possibly as a result of changing growth rates. This behavior complicates their use in paleoceanographic reconstructions. In keeping with several previous studies we find that Mg/Ca ratios increase with increasing size fraction in our well-preserved Atlantic G. sacculifer but not in G. ruber. In contrast to previous interpretations we suggest that these observations reflect a proportionally larger influence of compositionally distinct gametogenic calcite in small individuals compared to larger ones. As with d11B this influences G. sacculifer but not G. ruber, which has negligible gametogenic calcite.

Temporal variation of temperature and related proxies from the penultimate glacial towards the Eemian in the Black Sea

The last glacial-interglacial transition or Termination I (T I) is well documented in the Black Sea, whereas little is known about climate and environmental dynamics during the penultimate Termination (T II). Here we present a multi-proxy study based on a sediment core from the SE Black Sea covering the penultimate glacial and almost the entire Eemian interglacial (133.5 ±0.7-122.5 ±1.7 ka BP). Proxies comprise ice-rafted debris (IRD), O and Sr isotopes as well as Sr/Ca, Mg/Ca, and U/Ca ratios of benthic ostracods, organic and inorganic sediment geochemistry, as well as TEX86 and UK'37derived water temperatures. The ending penultimate glacial (MIS 6, 133.5 to 129.9 ±0.7 ka BP) is characterised by mean annual lake surface temperatures of about 9°C as estimated from the TEX86 palaeothermometer. This period is impacted by two Black Sea melt water pulses (BSWP-II-1 and 2) as indicated by very low Sr/Ca ostracods but high sedimentary K/Al values. Anomalously high radiogenic 87Sr/86Sr ostracod values (max. 0.70945) during BSWP-II-2 suggest a potential Himalayan source communicated via the Caspian Sea. The T II warming started at 129.9 ±0.7 ka BP, witnessed by abrupt disappearance of IRD, increasing d18O ostracod values, and a first TEX86 derived temperature rise of about 2.5°C. A second, abrupt warming step to ca. 15.5°C as the prelude of the Eemian warm period is documented at 128.3 ka BP. The Mediterranean-Black Sea reconnection most likely occurred at 128.1 ±0.7 ka BP as demonstrated by increasing Sr/Ca ostracods and U/Ca ostracods values. The disappearance of ostracods and TOC contents >2% document the onset of Eemian sapropel formation at 127.6 ka BP. During sapropel formation, TEX86 temperatures dropped and stabilised at around 9°C, while UK'37 temperatures remain on average 17°C. This difference is possibly caused by a habitat shift of Thaumarchaeota communities from surface towards nutrient-rich deeper and colder waters located above the gradually establishing halo-and redoxcline.

Recent benthic foraminifera of the Scotia Sea and Argentine Basin

We investigated 88 surface sediment samples taken with a multiple corer from the southwestern South Atlantic Ocean for their live (Rose Bengal stained) and dead benthic foraminiferal content. Using Q-Mode Principal Component Analysis six live and six dead associations are differentiated. Live and dead association distributions correspond fairly well; differences are mainly caused by downslope transport and selective test destruction. In addition, four potential fossil associations are calculated from the dead data set after removal of non-fossilizable species. These potential fossil associations are expected to be useful for paleoceanographic reconstructions. Environments are described in detail for the live and potential fossil associations and for selected species. Along the upper Argentine continental slope strong bottom currents control the occurrence of live, dead and potential fossil Angulogerina angulosa associations. Here, particles of a high organic carbon flux rate remain suspended. Below this high energy environment live, dead and potential fossil Uvigerina peregrina dominated associations correlate with enhanced sediment organic carbon content and still high organic carbon flux rates. The live A. angulosa and U. peregrina associations correlate with high standing crops. Furthermore, live and dead Epistominella exigua-Nuttallides umbonifer associations were separated. Dominance of a Nuttallides umbonifer potential fossil association relates to coverage by Antarctic Bottom Water (AABW) and Lower Circumpolar Deep Water (LCDW), above the Calcite Compensation Depth (CCD). Three associations of mainly agglutinated foraminifera occur in sediments bathed mainly by AABW or CDW. A Reophax difflugiformis association was found in mud-rich and diatomaceous sediments. Below the CCD, a Psammosphaera fusca association occurs in coarse sediments poor in organic carbon while a Cribrostomoides subglobosus-Ammobaculites agglutinans association covers a more variable environmental range with mud contents exceeding 30%. One single Eggerella bradyi-Martinottiella communis association poor in both species and individuals remains from the agglutinated associations below the CCD if only preservable species are considered for calculation.

Element analyses of DSDP/ODP Hole 504B basalt and breccia (Table 2)

Geochemical well logs were used to measure the dry weight percent oxide abundances of Si, Al, Ca, Mg, Fe, Ti, and K and the elemental abundances of Gd, S, Th, and U at 0.15-m intervals throughout the basement section of Hole 504B. These geochemical data are used to estimate the integrated chemical exchange resulting from hydrothermal alteration of the oceanic crust that has occurred over the last 5.9 Ma. A large increase in Si in the transition zone between pillows and dikes (Layers 2B and 2C) indicates that mixing of hot, upwelling hydrothermal fluids with cold, downwelling seawater occurred in the past at a permeability discontinuity at this level in the crust, even though the low-to-high permeability boundary in Hole 504B is now 500 m shallower (at the Layer 2A/2B boundary). The observations of extensive Ca loss and Mg gain agree with chemical exchanges recorded in the laboratory in experiments on the reactions that occur between basalt and seawater at high temperatures. The K budget requires significant addition to Layer 2A from both high-temperature depletion in Layers 2B and 2C and low-temperature alteration by seawater. Integrated water/rock ratios are derived for the mass of seawater required to add enriched elements and for the mass of hydrothermal fluid required to remove depleted elements in the crust at Hole 504B.

Sm-Nd isotopic investigation for rocks of Prince Charles Mountains, East Antarctica

The Prince Charles Mountains have been subject to extensive geological and geophysical investigations by former Soviet, Russian and Australian scientists from the early 1970s. In this paper we summarise, and review available geological and isotopic data, and report results of new isotopic studies (Sm-Nd, Pb-Pb, and U-Pb SHRIMP analyses); field geological data obtained during the PCMEGA 2002/2003 are utilised. The structure of the region is described in terms of four tectonic terranes. Those include Archaean Ruker, Palaeoproterozoic Lambert, Mesoproterozoic Fisher, and Meso- to Neoproterozoic Beaver Terranes. Pan-African activities (granite emplacement and probably tectonics) in the Lambert Terrane are reported. We present a summary of the composition of these terranes, discuss their origin and relationships. We also outline the most striking geological features, and problems, and try to draw attention to those rocks and regional geological features which are important in understanding the composition and evolution of the PCM and might suggest targets for further investigations.

Geochemistry of phosphatic crusts from the shelf off Peru

Authigenic phosphorite crusts from the shelf off Peru (9°40°S to 13°30°S) consist of a facies with phosphatic coated grains covered by younger phosphatic laminite. The crusts are composed of carbonate fluorapatite, which probably formed via an amorphous precursor close to the sediment water interface as indicated by low F/P2O5 ratios, Sr and Ca isotopes, as well as rare earth element patterns agreeing with seawater-dominated fluids. Small negative Ce anomalies and U enrichment in the laminite suggest suboxic conditions close to the sediment-water interface during its formation. Increased contents of chalcophilic elements and abundant sulfide minerals in the facies with phosphatic coated grains as well as in the laminite denote sulfate reduction and, consequently, point to episodical development of anoxic conditions during phosphogenesis. The Peruvian phosphorites formed episodically over an extended period of time lasting from Middle Miocene to Pleistocene. Individual phosphatic coated grains show a succession of phosphatic layers with varying contents of organic matter and sulfide-rich phosphatic layers. Coated grains supposedly formed as a result of episodic suspension caused by high turbulence and shifting redox conditions. Episodic anoxia in the pore water induced pyritization in the outermost carbonate fluorapatite layer. Phosphatic coated grains were later transported to the place of crust formation, where subsequent laminite formation was favored under lower energy conditions. A similar succession of phosphatic layers with varying contents of organic matter and sulfide-rich layers in the laminite suggests a formation mechanism analogous to that of individual coated grains.

Geochemistry of sediment cores of the Southern Ocean

We examine the possibility that glacial increase in the areal extent of reducing sediments might have changed the oceanic Cd inventory, thereby decoupling Cd from PO4. We suggest that the precipitation of Cd-sulfide in suboxic sediments is the single largest sink in the oceanic Cd budget and that the accumulation of authigenic Cd and U is tightly coupled to the organic carbon flux into the seafloor. Sediments from the Subantarctic Ocean and the Cape Basin (South Atlantic), where oxic conditions currently prevail, show high accumulation rates of authigenic Cd and U during glacial intervals associated with increased accumulation of organic carbon. These elemental enrichments attest to more reducing conditions in glacial sediments in response to an increased flux of organic carbon. A third core, overlain by Circumpolar Deep Water (CPDW) as are the other two cores but located south of the Antarctic Polar Front, shows an approximately inverse pattern to the Subantarctic record. The contrasting patterns to the north and south of the Antarctic Polar Front suggest that higher accumulation rates of Cd and U in Subantarctic sediments were driven primarily by increased productivity. This proposal is consistent with the hypothesis of glacial stage northward migration of the Antarctic Polar Front and its associated belt of high siliceous productivity. However, the increase in authigenic Cd and U glacial accumulation rates is higher than expected simply from a northward shift of the polar fronts, suggesting greater partitioning of organic carbon into the sediments during glacial intervals. Lower oxygen content of CPDW and higher organic carbon to biogenic silica rain rate ratio during glacial stages are possible causes. Higher glacial productivity in the Cape Basin record very likely reflects enhanced coastal up-welling in response to increased wind speeds. We suggest that higher productivity might have doubled the areal extent of suboxic sediments during the last glacial maximum. However, our calculations suggest low sensitivity of seawater Cd concentrations to glacial doubling of the extent of reducing sediments. The model suggests that during the last 250 kyr seawater Cd concentrations fluctuated only slightly, between high levels (about 0.66 nmol/kg) on glacial initiations and reaching lowest values (about 0.57 nmol/kg) during glacial maxima. The estimated 5% lower Cd content at the last glacial maximum relative to modern levels (0.60 nmol/kg) cannot explain the discordance between Cd and delta13C, such as observed in the Southern Ocean. This low sensitivity is consistent with foraminiferal data, suggesting minimal change in the glacial Cd mean oceanic content.

Geochemical traces across the Paleocene-Eocene thermal maximum on Walvis Ridge

An understanding of sediment redox conditions across the Paleocene-Eocene thermal maximum (PETM) (?55 Ma) is essential for evaluating changes in processes that control deep-sea oxygenation, as well as identifying the mechanisms responsible for driving the benthic foraminifera extinction. Sites cored on the flanks of Walvis Ridge (Ocean Drilling Program Leg 208, Sites 1262, 1266, and 1263) allow us to examine changes in bottom and pore water redox conditions across a ~2 km depth transect of deep-sea sediments of PETM age recovered from the South Atlantic. Here we present measurements of the concentrations of redox-sensitive trace metals manganese (Mn) and uranium (U) in bulk sediment as proxies for redox chemistry at the sediment-water interface and below. All three Walvis Ridge sites exhibit bulk Mn enrichment factors (EF) ranging between 4 and 12 prior to the warming, values at crustal averages (Mn EF = 1) during the warming interval, and a return to pre-event values during the recovery period. U enrichment factors across the PETM remains at crustal averages (U EF = 1) at Site 1262 (deep) and Site 1266 (intermediate depth). U enrichment factors at Site 1263 (shallow) peaked at 5 immediately prior to the PETM and dropped to values near crustal averages during and after the event. All sites were lower in dissolved oxygen content during the PETM. Before and after the PETM, the deep and intermediate sites were oxygenated, while the shallow site was suboxic. Our geochemical results indicate that oxygen concentrations did indeed drop during the PETM but not sufficiently to cause massive extinction of benthic foraminifera.

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.

Trace element geochemistry of zircons frim in situ ocean lithoshere

We characterize the textural and geochemical features of ocean crustal zircon recovered from plagiogranite, evolved gabbro, and metamorphosed ultramafic host-rocks collected along present-day slow and ultraslow spreading mid-ocean ridges (MORs). The geochemistry of 267 zircon grains was measured by sensitive high-resolution ion microprobe-reverse geometry at the USGS-Stanford Ion Microprobe facility. Three types of zircon are recognized based on texture and geochemistry. Most ocean crustal zircons resemble young magmatic zircon from other crustal settings, occurring as pristine, colorless euhedral (Type 1) or subhedral to anhedral (Type 2) grains. In these grains, Hf and most trace elements vary systematically with Ti, typically becoming enriched with falling Ti-in-zircon temperature. Ti-in-zircon temperatures range from 1,040 to 660°C (corrected for a TiO2 ~ 0.7, a SiO2 ~ 1.0, pressure ~ 2 kbar); intra-sample variation is typically ~60-15°C. Decreasing Ti correlates with enrichment in Hf to ~2 wt%, while additional Hf-enrichment occurs at relatively constant temperature. Trends between Ti and U, Y, REE, and Eu/Eu* exhibit a similar inflection, which may denote the onset of eutectic crystallization; the inflection is well-defined by zircons from plagiogranite and implies solidus temperatures of ~680-740°C. A third type of zircon is defined as being porous and colored with chaotic CL zoning, and occurs in ~25% of rock samples studied. These features, along with high measured La, Cl, S, Ca, and Fe, and low (Sm/La)N ratios are suggestive of interaction with aqueous fluids. Non-porous, luminescent CL overgrowth rims on porous grains record uniform temperatures averaging 615 ± 26°C (2SD, n = 7), implying zircon formation below the wet-granite solidus and under water-saturated conditions. Zircon geochemistry reflects, in part, source region; elevated HREE coupled with low U concentrations allow effective discrimination of ~80% of zircon formed at modern MORs from zircon in continental crust. The geochemistry and textural observations reported here serve as an important database for comparison with detrital, xenocrystic, and metamorphosed mafic rock-hosted zircon populations to evaluate provenance.

Chemical composition of bottom sediments from the Baltic Sea

According to geochemical analyses carbonaceous sediments from deep basins of the Baltic Sea containing 3-5% of organic carbon are enriched in some metals such as Cu, Mo, Ni, Pb, Zn, V, and U relative to shallow-water facies of the Bay of Finland. These metals also enrich (relative to background values in clayey rocks) ancient carbonaceous shales, where the average Cu and V contents are slightly higher and that of Mo, Pb, and Zn lower than in deep-sea carbonaceous sediments of the Baltic Sea. In addition, the deep-sea carbonaceous sediments of the Baltic Sea are enriched (but less notably than ancient shales) in Ag, As, Bi, and Cd. These data confirm previous assumptions that carbonaceous sediments accumulating now in seas and oceans can be considered as recent analogs of ancient metalliferous shales.