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

Chemical characterization and quantification of the brown algal storage compound laminarin

In search of a meaningful stress indicator for Fucus vesiculosus we found that the often used quantitative determination procedures for the polysaccharide laminarin (beta-1,3-glucan) result in different kind of problems, uncertainties and limitations. This chemical long-term storage form of carbon enables perennial brown algae in seasonally fluctuating ecosystems to uncouple growth from photosynthesis. Because of this high ecological relevance a reliable and precise method for determination and quantification of laminarin is needed. Therefore, a simple, cold water extraction method coupled to a new quantitative liquid chromatography-mass spectrometrical method (LC-MS) was developed. Laminarin was determined in nine out of twelve brown algal species, and its expected typical molar mass distribution of 2000-7000 Da was confirmed. Furthermore, laminarin consisted of a complex mixture of different chemical forms, since fifteen chemical laminarin species with distinct molecular weights were measured in nine species of brown algae. Laminarin concentrations in the algal tissues ranged from 0.03 to 0.86% dry weight (DW). The direct chemical characterization and quantification of laminarin by LC-MS represents a powerful method to verify the biochemical and ecological importance of laminarin for brown algae. Single individuals of Laminaria hyperborea, L. digitata, Saccharina latissima, F. serratus, F. vesiculosus, F. spiralis, Himanthalia elongata, Cystoseira tamariscifolia, Pelvetia canaliculata, Ascophyllum nodosum, Halidrys siliquosa and Dictyota dichotoma were collected in fall (18.11.2013) during spring low tide from the shore of Finavarra, Co. Clare, west coast of Ireland (53° 09' 25'' N, 09° 06' 58'' W). After sampling, the different algae were immediately transported to the lab, lyophilized and sent to the University of Rostock. Laminarin was extracted with cold ultrapure water from the algal samples. Before extraction they were ground to < 1 mm grain size with an analytical mill (Ika MF 10 Basic). The algal material (approx. 1.5 g DW) was extracted in ultrapure water (8 mL) on a shaker (250 rpm) for 5 h. After the addition of surplus ultrapure water (4 mL) and shaking manually, 1 mL of the sample was filter centrifuged (45 µm) at 14,000 rpm (Hettich Mikro 22 R). The slightly viscous supernatant was free of suspended material and converted into a microvial (300 µL) for further analysis. The extracts were analyzed using liquid chromatography-mass spectrometry (LC-MS) analysis (LTQ Velos Pro ion trap spectrometer with Accela HPLC, Thermo Scientific). Laminarin species were separated on a KinetexTM column (2.6 µm C18, 150 x 3 mm). The mobile phase was 90 % ultrapure water and 10 % acetonitrile, run isocratically at a flow rate of 0.2 mL min-1. MS was working in ESI negative ion mode in a mass range of 100 - 4000 amu. Glucose contents were determined after extraction using high-performance liquid chromatography (HPLC). Extracted samples were analyzed in an HPLC (SmartLine, Knauer GmbH) equipped with a SUPELCOGELTM Ca column (30 x 7,8 mm without preColumn) and RI-detector (S2300 PDA S2800). Water was used as eluent at a flow rate of 0.8 mL min-1 at 75 °C. Glucose was quantified by comparison of the retention time and peak area with standard solutions using ChromGate software. Mannitol was extracted from three subsamples of 10-20 mg powdered alga material (L. hyperborea, L. digitata, S. latissima, F. serratus, F. vesiculosus, F. spiralis, H. elongata, P. canaliculata, A. nodosum, H. siliquosa) and quantified, following the HPLC method described by Karsten et al. (1991). For analyzing carbon and nitrogen contents, dried algal material was ground to powder and three subsamples of 2 mg from each alga thalli were loaded and packed into tin cartridges (6×6×12 mm). The packages were combusted at 950 °C and the absolute contents of C and N were automatically quantified in an elemental analyzer (Elementar Vario EL III, Germany) using acetanilide as standard according to Verardo et al. (1990).

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Hole 69-504B and 70-504B

About 150 basalt samples from Hole 504B, near the Costa Rica Rift were analyzed for sulfur content and sulfur-isotope composition. The basement in Hole 504B can be divided into an upper part, which has oxidative alteration (274.5-550 m below sea floor), and a lower part, which has nonoxidative alteration (550-835 m below sea floor) (the interval from 540 to 585 meters actually is transitional). This division is reflected in both the sulfur content and the sulfurisotope composition. Oxidative alteration of basalts by sea water at low temperatures has resulted in a depletion in sulfur in the upper part of the hole (mostly less than 600 ppm S) as compared to fresh sulfur-saturated oceanic tholeiites (900-1200 ppm S). High amounts of sulfur in the lower part of the hole are a result of precipitation of secondary pyrite under non-oxidative or weakly oxidative conditions from solutions which dissolved igneous sulfides. The average sulfur-isotope composition of the primary igneous sulfides is d34S = -0.01 per mil, which is close to the assumed mantle sulfur composition (d34S = 0 per mil. Pyrite and sulfate sulfur extracted together in a separate preparation step (as "pyrite-sulfate" sulfur) indicate addition of sea-water sulfate to the upper part of the basalts. The d34S of secondary pyrite isolated by hand-picking varies between -8.0 and +5.8 per mil; the "pyrite-sulfate" sulfur (d34S = -4.8 to +10.5 per mil), as well as that of the isolated pyrite, may have originated in the precipitation of pyrite from solutions containing sulfur from the dissolution of igneous sulfides, but addition of sulfur transported by hydrothermal solutions cannot be excluded.

Isotope ratios of smectites, calcites and whole rocks from DSDP Legs 51 and 52, Atlantic Ocean

Delta180 and 87Sr/86Sr isotopic data from smectites, calcites, and whole rocks, together with published isotopic age determinations, alkali element concentration data and petrographic observations suggest a sequential model of ocean floor alteration. The early stage lasts about 3 m.y. and is characterized by palagonite and smectite formation, and solutions with a large basaltic component, increasing with temperature which varies from 15° to 80° C at DSDP site 418A. Most carbonates are deposited after this stage from solutions with a negligible basaltic Sr component and temperatures of 15° to 40° C. Water of seawater Sr and O isotopic composition is shown to percolate to at least 500 m into the basaltic basement. No evidence was found for continuing exchange of strontium or oxygen after 3 m.y.

Biometry, and fatty acid and fatty alcohol composition of the Arctic ctenophore Mertensia ovum from Kongsfjorden

Lipids of the Arctic ctenophore Mertensia ovum, collected from Kongsfjorden (Svalbard) in 2001, were analysed to investigate seasonal variability and fate of dietary lipids. Total lipids, lipid classes and fatty acid and alcohol compositions were determined in animals, which were selected according to age-group and season. Changes in lipids of age-group 0 animals were followed during growth from spring to autumn. Total lipids increased from May to September. Lipids as percentage of dry mass were lowest in August indicating their use for reproduction. Higher values occurred in September, which may be due to lipid storage for overwintering. Wax esters were the major lipid class accounting for about 50% of total lipids in age-group 0 animals from July and August. Phospholipids were the second largest lipid fraction with up to 46% in this age-group. The principal fatty acids of M. ovum from all age-groups were 22:6(n-3), 20:5(n-3) and 16:0. Wax ester fatty alcohols were dominated by 22:1(n-11) and 20:1(n-9) followed by moderate proportions of 16:0. The unique feature of M. ovum lipids was the high amount of free fatty alcohols originating probably from the dietary wax esters. In May, free alcohols exhibited the highest mean proportion with 14.6% in age-group 0 animals. We present the first data describing a detailed free fatty alcohol composition in zooplankton. This composition was very different from the alcohol composition of M. ovum wax esters because of the predominance of the long-chain monounsaturated 22:1 (n-11) alcohol accounting for almost 100% of total free alcohols in some samples. The detailed lipid composition clearly reflected feeding of M. ovum on the herbivorous calanoid species, Calanus glacialis and C. finmarchicus, the abundant members of the zooplankton community in Kongsfjorden. Other copepod species or prey items seem to be less important for M. ovum.

Elemental and isotopic compositions of metalliferous and pelagic sediments from the Galapagos mounds area, data of DSDP Leg 70

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at a subsurface depth of ~2-20 m; Mn-oxide material is limited to the upper 2 m of these mounds. The nontronite forms intervals of up to a few metres thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. The metalliferous phases represent essentially authigenic precipitates, apparently formed in the presence of upwelling basement-derived hydrothermal solutions which dissolved pre-existent pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major-element composition between nontronitic material from varying locations within the mounds; and (2) adjacent granules from a given sample have very similar compositions and are internally homogeneous. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of solution Eh and composition during nontronite formation. The Pb-isotopic composition of the nontronite and Mn-oxide sediments indicates that they were formed from solutions which contained variable proportions of basaltic Pb, introduced into pore waters by basement-derived solutions, and of normal-seawater Pb. However, the Sr-isotopic composition of these sediments is essentially indistinguishable from the value for modern seawater. On the basis of 18O/16O ratios, formation temperatures of ~20-30°C have been estimated for the nontronites. By comparison, temperatures of up to 11.5°C at 9 m depth have been directly measured within the mounds and heat flow data suggest present basement-sediment interface temperatures of 15-25°C.

(Table 1) Strontium concentration and isotope ratios of carbonates from DSDP Holes 69-504B as well as 83-504B and fish debris samples from Indian and Pacific Ocean sediments

Recent revisions of the geological time scale by Kent and Gradstein (in press) suggest that, on the average, Cretaceous magnetic anomalies are approximately 10 m.y. older than in Larson and Hilde's (1975) previous time scale. These revised basement ages change estimates for the duration of alteration in the ocean crust, based on the difference between secondary-mineral isochron ages and magnetic isochron-crustal ages, from 3 to approximately 13 m.y. In addition to the revised time scale, Burke et al.'s (1982) new data on the temporal variation of 87Sr/86Sr in seawater allow a better understanding of the timing of alteration and more realistic determinations of water/rock ratios during seawater-basalt interaction. Carbonates from all DSDP sites which reached Layer 2 of Atlantic crust (Sites 105, 332, 417, and 418) are deposited within 10-15 m.y. of crustal formation from solutions with 87Sr/86Sr ratios identical to unaltered or contemporaneous seawater. Comparisons of the revised seawater curve with the 87Sr/86Sr of basement carbonates is consistent with a duration of approximately 10-15 m.y. for alteration in the ocean crust. Our preliminary Sr and 87Sr/86Sr data for carbonates from Hole 504B, on 5.9-m.y.-old crust south of the Costa Rica Rift, suggest that hydrous solutions from which carbonates precipitated contained substantial amounts of basaltic Sr. For this reason, carbonate 87Sr/86Sr cannot be used to estimate the duration of alteration at this site. A basalt-dominated alteration environment at Hole 504B is consistent with heat-flow evidence which indicates rapid sediment burial of crust at the Costa Rica Rift, sealing it from access by seawater and resulting in unusually low water/rock ratios during alteration.

(Table 1) Stabile isotopes at DSDP Leg 55 Holes

Deep sea drilling on four seamounts in the Emperor Seamount chain revealed that Paleogene shallow-water carbonate sediments of the "bryozoan-algal" facies crown the basalt edifices. According to the biofacies model of Schlanger and Konishi (1966, 1975), this bryozoan- algal assemblage suggests that the seamounts formed in cooler, more northerly waters than those presently occupied by the island of Hawaii; i.e., the paleolatitudes of formation were greater than 20 °N. Moving southward toward the youngest member of the seamount chain, a facies gradient indicative of warmer waters was observed. This gradient is interpreted as a reflection of a northward shift in isotherms during the time span in which the seamounts were progressively formed (Savin et al., 1975). On all seamounts, sedimentation at the drilling sites occurred in a high-energy environment with water depths of approximately 20 meters. Early-stage carbonate diagenesis began in the phreatic zone in the presence of meteoric water, but proceeded after subsidence of the seamounts into intermediate sea waters, where the bulk, stable isotopic composition was determined. The subsidence into intermediate waters was rapid, and permitted establishment of an isotopic equilibrium which, like the facies gradient, reflects the northward shift in isotherms during the Paleogene. Calcite and zeolite cements comprise the later-stage diagenesis, and originated from solutions arising from the hydrolysis of the underlying basalt. In conclusion, the results of this study of the shallow-water carbonate sediments are not inconsistent with a paleolatitude of formation for Suiko Seamount (Site 433) of 26.9 ±3.5 °N, as determined by paleomagnetic measurements (Kono, 1980).

Geochemistry of DSDP Hole 83-504B minerals

Leg 83 of the Deep Sea Drilling Project has deepened Hole 504B to over 1 km into basement, 1350 m below the seafloor (BSF). The hole previously extended through 274.5 m of sediment and 561.5 m of pillow basalts altered at low temperature (< 100°C), to 836 m BSF. Leg 83 drilling penetrated an additional 10 m of pillows, a 209-m transition zone, and 295 m into a sheeted dike complex. Leg 83 basalts (836-1350 m BSF) generally contain superimposed greenschist and zeolite-facies mineral parageneses. Alteration of pillows and dikes from 836 to 898 m BSF occurred under reducing conditions at low water/rock ratios, and at temperatures probably greater than 100°C. Evolution of fluid composition resulted in the formation of (1) clay minerals, followed by (2) zeolites, anhydrite, and calcite. Alteration of basalts in the transition zone and dike sections (898-1350 m BSF) occurred in three basic stages, defined by the opening of fractures and the formation of characteristic secondary minerals. (1) Chlorite, actinolite, pyrite, albite, sphene, and minor quartz formed in veins and host basalts from partially reacted seawater (Mg-bearing, locally metal-and Si-enriched) at temperatures of at least 200-250°C. (2) Quartz, epidote, and sulfides formed in veins at temperatures of up to 380°C, from more evolved (Mg-depleted, metal-, Si-, and 18O-enriched) fluids. (3) The last stage is characterized by zeolite formation: (a) analcite and stilbite formed locally, possibly at temperatures less than 200°C followed by (b) formation of laumontite, heulàndite, scolecite, calcite, and prehnite from solutions depleted in Mg and enriched in Ca and 18O, at temperatures of up to 250°C. The presence of small amounts of anhydrite locally may be due to ingress of relatively unaltered seawater into the system during Stage 3. Alteration was controlled by the permeability of the crust and is characterized by generally incomplete recrystallization and replacement reactions among secondary minerals. Secondary mineralogy in the host basalts is strongly controlled by primary mineralogy. The alteration of Leg 83 basalts can be interpreted in terms of an evolving hydrothermal system, with (a) changes in solution composition because of reaction of seawater fluids with basalts at high temperatures; (b) variations in permeability caused by several stages of sealing and reopening of cracks; and (c) a general cooling of the system, caused either by the cooling of a magma chamber beneath the spreading center and/or the movement of the crust away from the heat source. The relationship of the high-temperature alteration in the transition zone and dike sections to the low-temperature alteration in the overlying pillow section remains uncertain.

Geochemistry of altered smectites

In basalts and volcanogenic sediments from the Indian Ocean, the successive stages of submarine alteration of volcanic rocks and glasses give rise to the incorporation or the relative increase of iron in smectite lattices. During the first stage, the Mg-smectites are the most abundant; they are occasionally associated with Al-smectites. Afterwards, they are gradually replaced by iron-rich smectites. The REE distribution follows the same trend as the mineralogical changes. During the f'trst stage of alteration, REE distribution in clay minerals is the same as in the fresh glasses but, when the iron-rich smectites increase, the Ce has a specific behaviour. The Ce shows a positive anomaly in iron-rich smectites formed early in palagonitized glasses, and a negative one in authigenic smectites formed later from solutions in equilibrium with seawater.

Morphometric measurements throughout ontogeny of selected planktic foraminiferal test species

Development plays an important part in shaping adult morphology and morphological disparity, yet its influence on evolutionary processes is seldom explored because of a lack of preservation of ontogenetic stages in the fossil record. By preserving their entire ontogenetic history within their test, and with the advent of high-resolution imaging techniques, planktic foraminifera allow us to investigate the influence of developmental constraints on disparity. Using Synchrotron radiation X-ray tomographic microscopy (SRXTM), we reconstruct the ontogenetic progression of seven species across several of the major morphotypic groups of planktic foraminifera, including morphotypes of a species exhibiting high phenotypic plasticity and closely related pseudo-cryptic sister-taxa. We show differences in growth patterns between the globigerinid species, which appear more tightly regulated within the framework of isometry from the neanic stage, and the globorotaliid species, whose adult stages present allometric trends. Morphological change through ontogeny results in a change in surface area to volume ratios. Different metabolic processes therefore dominate at different stages of ontogeny, changing the vulnerability of the organism to environmental influences over growth, from factors affecting diffusion rates in the juvenile to those affecting energy supply in the adult. These findings identify some of the parameters within which evolutionary mechanisms have to act.

Effects of ocean acidification on the calcification of otoliths of larval Atlantic cod Gadus morhua

The growth and development of the aragonitic CaCO3 otoliths of teleost fish could be vulnerable to processes resulting from ocean acidification. The potential effects of an increase in atmospheric CO2 on the calcification of the otoliths were investigated by rearing Atlantic cod Gadus morhua L. larvae in 3 pCO2 concentrations-control (370 µatm), medium (1800 µatm) and high (4200 µatm)-from March to May 2010. Increased otolith growth was observed in 7 to 46 d post hatch (dph) cod larvae at elevated pCO2 concentrations. The sagittae and lapilli were usually largest in the high pCO2 treatment followed by the medium and control treatments. The greatest difference in mean otolith surface area (normalized to fish length) was for sagittae at 11 dph, with medium and high treatments being 46 and 43% larger than the control group, respectively. There was no significant pCO2 effect on the shape of the otoliths nor were there any trends in the fluctuating asymmetry, defined as the difference between the right and left sides, in relation to the increase in otolith growth from elevated pCO2.

Growth rates and stable carbon and oxygen isotope record of corals from the Red Sea

Monthly delta18O records of 2 coral colonies (Porites cf. lutea and P. cf. nodifera) from different localities (Aqaba and Eilat) from the northern Gulf of Aqaba, Red Sea, were calibrated with recorded sea surface temperatures (SST) between 1988 and 2000. The results show high correlation coefficients between SST and delta18O. Seasonal variations of coral delta18O in both locations could explain 91% of the recorded SST. Different delta18O/SST relations from both colonies and from the same colonies were obtained, indicating that delta18O from coral skeletons were subject to an extension rate effect. Significant delta18O depletions are associated with high extension rates and higher values with low extension rates. The relation between coral skeletal delta18O and extension rate is not linear and can be described by a simple exponential model. An inverse relationship extends over extension rates from 1 to 5 mm/yr, while for more rapidly growing corals and portions of colonies the relation is constant and the extension rate does not appear to have a significant effect. We recommend that delta18O values be obtained from fast-growing corals or from portions in which the isotopic disequilibrium is fairly constant (extension rate >5 mm/yr). The results show that interspecific differences in corals may produce a significant delta18O profile offset between 2 colonies that is independent of environmental and extension-rate effects. We conclude that the rate of skeletal extension and the species of coral involved have an important influence on coral delta18O and must be considered when using delta18O records for paleoclimatic reconstructions.