Geochemistry of ODP Hole 183-1137A basalts

The Kerguelen Plateau and Broken Ridge in the southern Indian Ocean together represent one of the most voluminous large igneous provinces (LIPs) ever emplaced on Earth. A scientific objective of Ocean Drilling Program (ODP) Leg 183 was to constrain the post-melting magma evolution of Kerguelen Plateau magmas. In an effort to better understand this evolution, isotopic and trace element analysis of individual plagioclase crystals hosted within two Kerguelen Plateau basalts recovered from Elan Bank were undertaken. Previous whole-rock studies established that the two host basalts investigated in this study are samples of crustally contaminated (lower group) and relatively uncontaminated (upper group) basalt. Plagioclase phenocrysts from the uncontaminated basalt are dominantly normal zoned and exhibit a 87Sr/86SrI range of 0.704845-0.704985, which overlaps uncontaminated group whole-rock values previously reported. Plagioclase crystals from the contaminated basalt are dominantly reverse zoned and exhibit a 87Sr/86SrI range of 0.705510-0.705735, which all lie within contaminated group whole-rock values previously reported. There are no systematic within crystal core to rim variations in 87Sr/86SrI from either group, with the exception that contaminated group crystal rims have overall less radiogenic 87Sr/86SrI than other zones. These observations indicate that crustal assimilation occurred before the formation of Unit 10 plagioclase phenocrysts, which is supported by parent magma trace element abundance data inverted using carefully calculated partition coefficients. Trace element diffusion modeling indicates that the upper group basalt (Unit 4) experienced a more vigorous eruptive flux than the lower group basalt (Unit 10). We suggest that plagioclase phenocrysts in both the upper and lower group basalts originated from the shallowest section of what was likely a complex magma chamber system. We contend that the magmatic system contained regions of extensive plagioclase-dominated crystal mush. Crustal assimilation was not a significant ongoing process in this portion of the Elan Bank magmatic system. Both basalts exhibit compelling evidence for remobilization and partial resorption of crystalline debris (e.g., reverse zoned crystals, glomerocrysts). We suggest Unit 4 and 10 magmas ascended different sections of the Elan Bank magma system, where the Unit 10 magmas ascended a section of the magma system that penetrated a stranded fragment of continental crust.

Element ratio (Sr/Ca, Ba/Ca, B/Ca, and Mg/Ca) profiles throughout the larval life stage of Mytilus edulis, 2011

Rising anthropogenic CO2 in the surface ocean has raised serious concerns for the ability of calcifying organisms to secrete their shells and skeletons. Previous mollusc carbonate perturbation experiments report deleterious effects at lowered pH (7.8-7.4 pH units), including reduced shell length and thickness and deformed shell morphology. It is not clear whether the reduced shell growth results from a decrease in calcification rate due to lowered aragonite saturation or from an indirect effect on mollusc metabolism. We take a novel approach to discerning between these two processes by examining the impact of lowered pH on the 'vital-effect' associated with element ratios. Reported herein are the first element ratio (Sr/Ca, Ba/Ca, B/Ca, Mg/Ca and Mn/Ca) profiles throughout the larval life stage of Mytilus edulis. Element ratio data for individuals reared in ambient conditions provide new insights into biomineralization during larval development. Sr/Ca ratios are consistent with Sr incorporation in the mineral phase. Mg and Mn are likely hosted in an organic phase. The Ba partition coefficient of early larval shells is one of the highest reported in biogenic aragonite. The reason for the high Ba concentrations is unknown, but may reflect the assimilation of Ba from food and/or Ba concentration in an organic or amorphous carbonate phase. There is no observable difference in the way the studied elements are incorporated into the shells of individuals reared in ambient and lowered pH conditions. The reduced growth rate at lower pH may be a consequence of a disruption to the larval mollusc metabolism.

Seawater carbonate chemistry and boron incorporation of planktic foraminifer Orbulina universa during experiments, 2011

Culture experiments with living planktic foraminifers reveal that the ratio of boron to calcium (B/Ca) in Orbulina universa increases from 56 to 92 µmol mol-1 when pH is raised from 7.61 +/- 0.02 to 8.67 +/- 0.03 (total scale). Across this pH range, the abundances of carbonate, bicarbonate, and borate ions also change (+ 530, - 500, and + 170 µmol kg-1, respectively). Thus specific carbonate system control(s) on B/Ca remain unclear, complicating interpretation of paleorecords. B/Ca in cultured O. universa also increases with salinity (55-72 µmol mol-1 from 29.9-35.4 per mil) and seawater boron concentration (62-899 µmol mol-1 from 4-40 ppm B), suggesting that these parameters may need to be taken into account for paleorecords spanning large salinity changes (~ 2 per mil) and for samples grown in seawater whose boron concentration ([B]SW) differs from modern by more than 0.25 ppm. While our results are consistent with the predominant incorporation of the charged borate species B(OH)4 into foraminiferal calcite, the behavior of the partition coefficient KD (defined as [B/Ca]calcite/B(OH)4/HCO3seawater) cannot be explained by borate incorporation alone, and suggests the involvement of other pH-sensitive ions such as CO3 For a given increase in seawater B(OH)4, the corresponding increase in B/Ca is stronger when B(OH)4 is raised by increasing [B]SW than when it is raised by increasing pH. These results suggest that B incorporation controls should be reconsidered. Additional insight is gained from laser-ablation ICP-MS profiles, which reveal variable B/Ca distributions within individual shells.

(Table 2) 230Th, 230Th xs and 232Th concentrations in dissolved, particulate and total (dissolved+small particles) for all KEOPS stations, Marion Dufresne cruise MD145

In the context of the KErguelen Ocean and Plateau compared Study (KEOPS, 19 January-13 February 2005), particle dynamics were investigated using thorium isotope measurements over and off the Kerguelen plateau. Dissolved and particulate 230Th and 232Th samples were collected at nine stations. Dissolved excess 230Th concentrations (230Thxs) vary from 0.5 to 20.8 fg/kg and particulate 230Thxs concentrations from 0.1 to 10.0 fg/kg. Dissolved and particulate 232Th concentration ranges are 16.8-450.2 pg/kg and 3.8-502.8 pg/kg, respectively. The 230Thxs concentrations increase linearly with depth down to the bottom at most of the plateau stations and down to 1000 m at the off-plateau stations. This linear trend is observed down to the bottom (1550 m) at Kerfix, the open-ocean "upstream" station located west of the Kerguelen plateau. A simple reversible scavenging model applied to these data allowed the estimation of adsorption rate constant (k1~=0.2-0.8 per year), desorption rate constant (k-1~=1-8 per year) and partition coefficients (average K=0.16±0.07). Calculated particle settling velocities S deduced from this simple model are ca. 500 m/year at most of the plateau stations and 800 m/year at all the off-plateau stations. The plateau settling velocities are relatively low for such a productive site, compared to the surrounding HNLC areas. The difference might reflect the fact that lateral advection is neglected in this model. Taking this advection into account allows the reconstruction of the observed 230Thxs linear distributions, but only if faster settling velocities are considered. This implies that the 1D model strongly underestimates the settling velocity of the particles. In the deep layers, the occurrence of intense boundary scavenging along the escarpment due to bottom sediment re-suspension and interaction with a nepheloid layer, yielding a removal of ?50% of the Th stock along the northwestward transect, is suggested.

Grain properties of rock fragments from shelf bottom sediments of the Sea of Okhotsk

Grain size, shape and roundness of rock fragments, texture, composition of bottom sediments from the Sea of Okhotsk are under study. These data are compared with parameters of modern lithodynamic conditions of the sea and genetic types of deposits are identified. These criteria are used for partition of Holocene and Upper Pleistocene sediment series and for identifying conditions of their formation. Dependence of structure of different genetic types of deposits on intensity of hydrodynamic processes, of terrigenous contribution, and on direction consedimentational tectonic movements is under consideration.

Chemical analyses and results of sediments from different DSDP Holes from the North Atlantic

Chemical analyses of North Atlantic D.S.D.P. (Deep Sea Drilling Project) sediments indicate that basal sediments generally contain higher concentrations of Fe, Mn, Mg, Pb, and Ni, and similar or lower concentrations of Ti, Al, Cr, Cu, Zn, and Li than the material overlying them. Partition studies on selected samples indicate that the enriched metals in the basal sediments are usually held in a fashion similar to that in basal sediments from the Pacific, other D.S.D.P. sediments, and modern North Atlantic ridge and non-ridge material. Although, on average, chemical differences between basal sediments of varying ages are apparent, normalization of the data indicates that the processes leading to metal enrichment on the crest of the Mid-Atlantic Ridge appear to have been approximately constant in intensity since Cretaceous times. In addition, the bulk composition of detrital sediments also appears to have been relatively constant over the same time period. Paleocene sediments from site 118 are, however, an exception to this rule, there apparently having been an increased detrital influx during this period. The bulk geochemistry, partitioning patterns, and mineralogy of sediments from D.S.D.P. 9A indicates that post-depositional migration of such elements as Mn, Ni, Cu, Zn, and Pb may have occurred. The basement encountered at the base of site 138 is thought to be a basaltic sill, but the overlying basal sediments are geochemically similar to other metalliferous basal sediments from the North Atlantic. These results, as well as those from site 114 where true oceanic basement was encountered, but where there was an estimated 7 m.y. hiatus between basaltic extrusion and basal sediment deposition, indicate that ridge-crest sediments are not necessarily deposited during active volcanism but can be formed after the volcanism has ceased. The predominant processes for metal enrichment in these deposits and those formed in association with other submarine volcanic features is a combination of shallow hydrothermal activity, submarine weathering of basalt, and the formation of ferromanganese oxides which can scavenge metals from seawater. In addition, it seems as though the formation of submarine metalliferous sediments is not restricted to active-ridge areas.

(Table 1) Elemental composition of benthic foraminifera from South Atlantic core top samples

The ocean plays a major role in the global carbon cycle, and attempts to reconstruct past changes in the marine carbonate system are increasing. The speciation of dissolved uranium is sensitive to variations in carbonate system parameters, and previous studies have shown that this is recorded in the uranium-to-calcium ratio (U/Ca) of the calcite shells of planktonic foraminifera. Here we test whether U/Ca ratios of deep-sea benthic foraminifera are equally suited as an indicator of the carbonate system. We compare U/Ca in two common benthic foraminifer species (Planulina wuellerstorfi and Cibicidoides mundulus) from South Atlantic core top samples with the calcite saturation state (Delta [CO3**2-] = [CO3**2-]in situ - [CO3**2-]sat) of the ambient seawater and find significant negative correlations for both species. Compared with planktonic foraminifera, the sensitivity of U/Ca in benthic foraminifera to changes in Delta [CO3**2-] is about 1 order of magnitude higher. Although Delta [CO3**2-] exerts the dominant control on the average foraminiferal U/Ca, the intertest and intratest variability indicates the presence of additional factors forcing U/Ca.

Influence of temperature and CO2 on the strontium and magnesium composition of coccolithophore calcite

Marine calcareous sediments provide a fundamental basis for palaeoceanographic studies aiming to reconstruct past oceanic conditions and understand key biogeochemical element cycles. Calcifying unicellular phytoplankton (coccolithophores) are a major contributor to both carbon and calcium cycling by photosynthesis and the production of calcite (coccoliths) in the euphotic zone, and the subsequent long-term deposition and burial into marine sediments. Here we present data from controlled laboratory experiments on four coccolithophore species and elucidate the relation between the divalent cation (Sr, Mg and Ca) partitioning in coccoliths and cellular physiology (growth, calcification and photosynthesis). Coccolithophores were cultured under different seawater temperature and carbonate chemistry conditions. The partition coefficient of strontium (DSr) was positively correlated with both carbon dioxide (pCO2) and temperature but displayed no coherent relation to particulate organic and inorganic carbon production rates. Furthermore, DSr correlated positively with cellular growth rates when driven by temperature but no correlation was present when changes in growth rates were pCO2-induced. Our results demonstrate the complex interaction between environmental forcing and physiological control on the strontium partitioning in coccolithophore calcite and challenge interpretations of the coccolith Sr / Ca ratio from high-pCO2 environments (e.g. Palaeocene-Eocene thermal maximum). The partition coefficient of magnesium (DMg) displayed species-specific differences and elevated values under nutrient limitation. No conclusive correlation between coccolith DMg and temperature was observed but pCO2 induced a rising trend in coccolith DMg. Interestingly, the best correlation was found between coccolith DMg and chlorophyll a production, suggesting that chlorophyll a and calcite associated Mg originate from the same intracellular pool. These and previous findings indicate that Mg is transported into the cell and to the site of calcification via different pathways than Ca and Sr. Consequently, the coccolith Mg / Ca ratio should be decoupled from the seawater Mg / Ca ratio. This study gives an extended insight into the driving factors influencing the coccolith Mg / Ca ratio and should be considered for future palaeoproxy calibrations.

Sources and seasonality of polycyclic aromatic hydrocarbons transported to Alert, Canadian Arctic

A probabilistic function (integrated source contribution function, ISCF) based on backward air mass trajectory calculation was developed to track sources and atmospheric pathways of polycyclic aromatic hydrocarbons (PAHs) to the Canadian High Arctic station of Alert. In addition to the movement of air masses, the emission intensities at the sources and the major processes of partition, indirect photolysis, and deposition occurring on the way to the Arctic were incorporated into the ISCF. The predicted temporal trend of PAHs at Alert was validated by measured PAH concentrations throughout 2004. The PAH levels in the summer are orders of magnitude lower than those in the winter and spring when long-range atmospheric transport events occur more frequently. PAHs observed at Alert are mostly from East Asia (including Russia Far East), North Europe (including European Russia), and North America. These sources account for 25, 45, and 27% of PAHs atmospheric level at Alert, respectively. Source regions and transport pathways contributing to the PAHs contamination in the Canadian High Arctic vary seasonally. In the winter, Russia and Europe are the major sources. PAHs from these sources travel eastward and turn to the north at approximately 120°E before reaching Alert, in conjunction with the well- known Arctic haze events. In the spring, PAHs from Russia and Europe first migrate to the west and then turn to the north at 60°W toward Alert. The majority of PAHs in the summer are from northern Canada where they are carried to Alert via low- level transport pathways. In the fall, 70% of PAHs arriving at Alert are delivered from North American sources.

Gasterosteus aculeatus egg traits and fish lengths vs. experiment setup

1) Our study addresses the role of non-genetic and genetic inheritance in shaping the adaptive potential of populations under a warming ocean scenario. We used a combined experimental approach (transgenerational plasticity and quantitative genetics) to partition the relative contribution of maternal vs. paternal (additive genetic) effects to offspring body size (a key component of fitness), and investigated a potential physiological mechanism (mitochondrial respiration capacities) underlying whole organism growth/size responses. 2) In very early stages of growth (up to 30 days), offspring body size of marine sticklebacks benefited from maternal transgenerational plasticity (TGP): offspring of mothers acclimated to17°C were larger when reared at 17°C, and offspring of mothers acclimated to 21°C were larger when reared at 21°C. The benefits of maternal TGP on body size were stronger and persisted longer (up to 60 days) for offspring reared in the warmer (21°C) environment, suggesting that maternal effects will be highly relevant for climate change scenarios in this system. 3) Mitochondrial respiration capacities measured on mature offspring (F1 adults) matched the pattern of TGP for juvenile body size, providing an intuitive mechanistic basis for the maternal acclimation persisting into adulthood. Size differences between temperatures seen at early growth stages remained in the F1 adults, linking offspring body size to maternal inheritance of mitochondria. 4) Lower maternal variance components in the warmer environment were mostly driven by mothers acclimated to ambient (colder) conditions, further supporting our tenet that maternal effects were stronger at elevated temperature. Importantly, all parent-offspring temperature combination groups showed genotype x environment (GxE) interactions, suggesting that reaction norms have the potential to evolve. 5) To summarise, transgenerational plasticity and genotype x environment interactions work in concert to mediate impacts of ocean warming on metabolic capacity and early growth of marine sticklebacks. TGP can buffer short-term detrimental effects of climate warming and may buy time for genetic adaptation to catch up, therefore markedly contributing to the evolutionary potential and persistence of populations under climate change.

(Table A1) CaCO3 contents and Sr/Ca ratios in ODP Leg 130, 138 and 154

Strontium/calcium (Sr/Ca) ratios in bulk and foraminiferal calcite have been used to constrain the history of Sr/Ca in the oceans and to evaluate calcite diagenetic alteration. However bulk Sr/Ca records also may be influenced by differences in Sr uptake and/or in the diagenetic susceptibility of different calcium carbonate sedimentary components. We present data on the sediment size fraction and calcium carbonate distribution in bulk samples, Sr/Ca in a range of sedimentary size components, and Sr/Ca in bulk sediments. Ocean Drilling Program samples from sites on Ontong Java Plateau and Ceara Rise (in the western equatorial Pacific and Atlantic, respectively) and from sites in the eastern equatorial Pacific were selected to represent progressive stages in the diagenetic pathway from the sea floor through a range of burial depths equivalent to sediment ages of ~5.6, ~9.4, and ~37.1 Ma. Samples were subdivided by size to produce a unique data set of size-specific Sr/Ca ratios. Fine fraction (<45 ?m) Sr/Ca ratios are higher than those of all corresponding coarse fractions, indicating that fine nannofossil-dominated calcite has a Sr partition coefficient 1.3-1.5 times greater than that of coarse foraminifera-dominated calcite. Thus, absolute values of bulk Sr/Ca in contemporaneous samples reflect, in part, the ratio of fine to coarse calcite sedimentary components. Sr/Ca values in fine and coarse components also behave differently in their response to pre-burial dissolution and to recrystallization at depth. Coarse size components are sensitive to bottom water carbonate ion undersaturation, and they lose original Sr/Ca differences among contemporary samples over not, vert, similar10 my. In contrast, fine components recrystallize faster in more deeply buried samples. Interpretation of the historical Sr/Ca record is complicated by post-depositional diagenetic artifacts, and thus our data do not provide clear evidence of specific temporal changes in oceanic Sr/Ca ratios over the past 10 million years. This paper represents the first systematic attempt to examine trends in calcite Sr/Ca as a function of sediment size fraction and age.