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

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

Magnesium/Calcium ratios and sea surface temperature estimation for sediments of the Timor Sea

We use a multiproxy approach to monitor changes in the vertical profile of the Indonesian Throughflow as well as monsoonal wind and precipitation patterns in the Timor Sea on glacial-interglacial, precessional, and suborbital timescales. We focus on an interval of extreme climate change and sea level variation: marine isotope (MIS) 6 to MIS 5e. Paleoproductivity fluctuations in the Timor Sea follow a precessional beat related to the intensity of the Australian (NW) monsoon. Paired Mg/Ca and d18O measurements of surface- and thermocline-dwelling planktonic foraminifers (G. ruber and P. obliquiloculata) indicate an increase of >4°C in both surface and thermocline water temperatures during Termination II. Tropical sea surface temperature changed synchronously with ice volume (benthic d18O) during deglaciation, implying a direct coupling of high- and low-latitude climate via atmospheric and/or upper ocean circulation. Substantial cooling and freshening of thermocline waters occurred toward the end of Termination II and during MIS 5e, indicating a change in the vertical profile of the Indonesian Throughflow from surface- to thermocline-dominated flow.

(Table 1) Boron, carbon, magnesium and calcium isotope data, post-Marinoan Neoproterozoic carbonate sections, Namibia

A marked ocean acidification event and elevated atmospheric carbon dioxide concentrations following the extreme environmental conditions of the younger Cryogenian glaciation have been inferred from boron isotope measurements. Calcium and magnesium isotope analyses offer additional insights into the processes occurring during this time. Data from Neoproterozoic sections in Namibia indicate that following the end of glaciation the continental weathering flux transitioned from being of mixed carbonate and silicate character to a silicate-dominated one. Combined with the effects of primary dolomite formation in the cap dolostones, this caused the ocean to depart from a state of acidification and return to higher pH after climatic amelioration. Differences in the magnitude of stratigraphic isotopic changes across the continental margin of the southern Congo craton shelf point to local influences modifying and amplifying the global signal, which need to be considered in order to avoid overestimation of the worldwide chemical weathering flux.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Stable isotope and Magnesium/Calcium ratios of 4 profiles from the equatorial Pacific/Caribbean

This thesis examines the closure history of the Central American Seaway (CAS) and its effect on changes in ocean circulation and climate during the time interval from ~6 - 2.5 Ma. It was accomplished within the DFG Research Unit "Impact of Gateways on Ocean Circulation, Climate and Evolution" at the University of Kiel. Proxy records from Ocean Drilling Program (ODP) Sites 999 and 1000 (Caribbean), and from ODP Sites 1237, 1239 and 1241 (low-latitude east Pacific) are developed and examined. In addition, previously established proxy data from Atlantic Sites 925/926 (Ceara Rise) and 1006 (western Great Bahama Bank) and from two east Pacific sites (851, 1236) are included for interpretations. The main objectives of this study are (1) to acquire a consistent stratigraphic framework for all sites, (2) to reconstruct Pliocene changes in Caribbean and tropical east Pacific upper ocean water masses (i.e. temperature, salinity, thermocline depth), and (3) to identify potential underlying forcing mechanisms.

Haemolymph inorganic ion composition, physiology and behaviour dependent on temperature and ambient magnesium concentration in early life history stages of Paralomis granulosa (Decapoda, Anomura, Lithodidae)

Marine brachyuran and anomuran crustaceans are completely absent from the extremely cold (-1.8 °C) Antarctic continental shelf, but caridean shrimps are abundant. This has at least partly been attributed to low capacities for magnesium excretion in brachyuran and anomuran lithodid crabs ([Mg2+]HL = 20-50 mmol/L) compared to caridean shrimp species ([Mg2+]HL = 5-12 mmol/L). Magnesium has an anaesthetizing effect and reduces cold tolerance and activity of adult brachyuran crabs. We investigated whether the capacity for magnesium regulation is a factor that influences temperature-dependent activity of early ontogenetic stages of the Sub-Antarctic lithodid crab Paralomis granulosa. Ion composition (Na+, Mg2+, Ca2+, Cl-, [SO4]2-) was measured in haemolymph withdrawn from larval stages, the first and second juvenile instars (crabs I and II) and adult males and females. Magnesium excretion improved during ontogeny, but haemolymph sulphate concentration was lowest in the zoeal stages. Neither haemolymph magnesium concentrations nor Ca2+:Mg2+ ratios paralleled activity levels of the life stages. Long-term (3 week) cold exposure of crab I to 1 °C caused a significant rise of haemolymph sulphate concentration and a decrease in magnesium and calcium concentrations compared to control temperature (9 °C). Spontaneous swimming activity of the zoeal stages was determined at 1, 4 and 9 °C in natural sea water (NSW, [Mg2+] = 51 mmol/L) and in sea water enriched with magnesium (NSW + Mg2+, [Mg2+] = 97 mmol/L). It declined significantly with temperature but only insignificantly with increased magnesium concentration. Spontaneous velocities were low, reflecting the demersal life style of the zoeae. Heart rate, scaphognathite beat rate and forced swimming activity (maxilliped beat rate, zoea I) or antennule beat rate (crab I) were investigated in response to acute temperature change (9, 6, 3, 1, -1 °C) in NSW or NSW + Mg2+. High magnesium concentration reduced heart rates in both stages. The temperature-frequency curve of the maxilliped beat (maximum: 9.6 beats/s at 6.6 °C in NSW) of zoea I was depressed and shifted towards warmer temperatures by 2 °C in NSW + Mg2+, but antennule beat rate of crab I was not affected. Magnesium may therefore influence cold tolerance of highly active larvae, but it remains questionable whether the slow-moving lithodid crabs with demersal larvae would benefit from an enhanced magnesium excretion in nature.

Haemolymph inorganic ion composition, physiology and behaviour dependent on temperature and magnesium in adult Paralomis granulosa (Decapoda, Anomura, Lithodidae)

A low capacity for regulation of extracellular Mg2+ has been proposed to exclude reptant marine decapod crustaceans from temperatures below 0°C and thus to exclude them from the high Antarctic. To test this hypothesis and to elaborate the underlying mechanisms in the most cold-tolerant reptant decapod family of the sub-Antarctic, the Lithodidae, thermal tolerance was determined in the crab Paralomis granulosa (Decapoda, Anomura, Lithodidae) using an acute stepwise temperature protocol (-1°, 1°, 4°, 7°, 10°, and 13°C). Arterial and venous oxygen partial pressures (Po2) in hemolymph, heartbeat and ventilation beat frequencies, and hemolymph cation composition were measured at rest and after a forced activity (righting) trial. Scopes for heartbeat and ventilation beat frequencies and intermittent heartbeat and scaphognathite beat rates at rest were evaluated. Hemolymph [Mg2+] was experimentally reduced from 30 mmol/L to a level naturally observed in Antarctic caridean shrimps (12 mmol/L) to investigate whether the animals remain more active and tolerant to cold (-1°, 1°, and 4°C). In natural seawater, righting speed was significantly slower at -1° and 13°C, compared with acclimation temperature (4°C). Arterial and venous hemolymph Po2 increased in response to cooling even though heartbeat and ventilation beat frequencies as well as scopes decreased. At rest, ionic composition of the hemolymph was not affected by temperature. Activity induced a significant increase in hemolymph [K+] at -1° and 1°C. Reduction of hemolymph [Mg2+] did not result in an increase in activity, an increase in heartbeat and ventilation beat frequencies, or a shift in thermal tolerance to lower temperatures. In conclusion, oxygen delivery in this cold-water crustacean was not acutely limiting cold tolerance, and animals may have been constrained more by their functional capacity and motility. In contrast to earlier findings in temperate and subpolar brachyuran crabs, these constraints remained insensitive to changing Mg2+ levels.

Magnesium/Calcium ratios measured on planktonic foraminifera of the LGM

As part of the Multi-proxy Approach for the Reconstruction of the Glacial Ocean (MARGO) incentive, published and unpublished temperature reconstructions for the Last Glacial Maximum (LGM) based on planktonic foraminiferal Mg/Ca ratios have been synthesised and made available in an online database. Development and applications of Mg/Ca thermometry are described in order to illustrate the current state of the method. Various attempts to calibrate foraminiferal Mg/Ca ratios with temperature, including culture, trap and core-top approaches have given very consistent results although differences in methodological techniques can produce offsets between laboratories which need to be assessed and accounted for where possible. Dissolution of foraminiferal calcite at the sea-floor generally causes a lowering of Mg/Ca ratios. This effect requires further study in order to account and potentially correct for it if dissolution has occurred. Mg/Ca thermometry has advantages over other paleotemperature proxies including its use to investigate changes in the oxygen isotopic composition of seawater and the ability to reconstruct changes in the thermal structure of the water column by use of multiple species from different depth and or seasonal habitats. Presently available data are somewhat limited to low latitudes where they give fairly consistent values for the temperature difference between Late Holocene and the LGM (2-3.5 °C). Data from higher latitudes are more sparse, and suggest there may be complicating factors when comparing between multi-proxy reconstructions.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Chemical and mineral compositions of altered peridotites from ODP Leg 209

Abyssal peridotite from the 15°20'N area of the Mid-Atlantic Ridge show complex geochemical variations among the different sites drilled during ODP Leg 209. Major element compositions indicate variable degrees of melt depletion and refertilization as well as local hydrothermal metasomatism. Strongest evidence for melt-rock interactions are correlated Light Rare Earth Element (LREE) and High Field Strength Element (HFSE) additions at Sites 1270 and 1271. In contrast, hydrothermal alteration at Sites 1274, 1272, and 1268 causes LREE mobility associated with minor HFSE variability, reflecting the low solubility of HFSE in aqueous solutions. Site 1274 contains the least-altered, highly refractory, peridotite with strong depletion in LREE and shows a gradual increase in the intensity of isochemical serpentinization; except for the addition of H2O which causes a mass gain of up to 20 g/100 g. The formation of magnetite is reflected in decreasing Fe(2+)/Fe(3+) ratios. This style of alteration is referred to as rock-dominated serpentinization. In contrast, fluid-dominated serpentinization at Site 1268 is characterized by gains in sulfur and development of U-shaped REE pattern with strong positive Eu anomalies which are also characteristic for hot (350 to 400°C) vent-type fluids discharging from black smoker fields. Serpentinites at Site 1268 were overprinted by talc alteration under static conditions due to interaction with high a_SiO2 fluids causing the development of smooth, LREE enriched patterns with pronounced negative Eu anomalies. These results show that hydrothermal fluid-peridotite and fluid-serpentinite interaction processes are an important factor regarding the budget of exchange processes between the lithosphere and the hydrosphere in slow spreading environments.