(Table 3) Relative depth and age, CaCO3, d18O, d13C and Sr/Ca analysis from ODP Leg 130, 154 and 138

Interpretations of calcite strontium/calcium records in terms of ocean history and calcite diagenesis require distinguishing the effects on deep-sea calcite sediments of changes in ocean chemistry, of different mixes of calcite-depositing organisms as sediment contributors through time and space, and of the loss of Sr during diagenetic calcite recrystallization. In this paper Sr/Ca and d18O values of bulk calcium carbonate sediments are used to estimate the relative extent of calcite recrystallization in samples from four time points (core tops, 5.6, 9.4, and 37.1 Ma) at eight Ocean Drilling Program sites in the equatorial Atlantic (Ceara Rise) and equatorial Pacific (Ontong Java Plateau and two eastern equatorial Pacific sites). The possibility that site-to-site differences in calcite Sr/Ca at a given time point originated from temporal variations in ocean chemistry was eliminated by careful age control of samples for each time point, with sample ages differing by less than the oceanic residence times of Sr and Ca. The Sr/Ca and d18O values of 5.6- and 9.4-Ma samples from the less-carbonate-rich eastern equatorial Pacific sites and Ceara Rise Site 929 appear to be less diagenetically altered than the Sr/Ca and d18O values of contemporaneous samples from the more carbonate-rich sites. It is evident from these data that both Sr/Ca and d18O in bulk calcite have been diagenetically altered in some samples 5.6 Ma and older. These data indicate that noncarbonate sedimentary components, like clay and biogenic silica, have partially suppressed recrystallization at the lower carbonate sites. Sr/Ca data from the less altered, carbonate-poor sites indicate higher oceanic Sr/Ca relative to today at 5.6 and 9.4 Ma.

(Table 1) TOC, d13C, and preservation factors of turbidite sediments

In ocean margin sediments both marine and terrestrial organic matter (OM) are buried but the factors governing their relative preservation and degradation are not well understood. In this study, we analysed the degree of preservation of marine isoprenoidal and soil-derived branched glycerol dialkyl glycerol tetraethers (GDGTs) upon long-term oxygen exposure in OM-rich turbidites from the Madeira Abyssal Plain by analyzing GDGT concentrations across oxidation fronts. Relative to the anoxic part of the turbidites ca. 7-20% of the soil-derived branched GDGTs were preserved in the oxidized part while only 0.2-3% of the marine isoprenoid GDGT crenarchaeol was preserved. Due to these different preservation factors the Branched Isoprenoid Tetraether (BIT) index, a ratio between crenarchaeol and the major branched GDGTs that is used as a tracer for soil-derived organic matter, substantially increases from 0.02 to 0.4. Split Flow Thin Cell (SPLITT) separation of turbidite sediments showed that the enhanced preservation of soil-derived carbon was a general phenomenon across the fine particle size ranges (<38 ?m). Calculations reveal that, despite their relatively similar chemical structures, degradation rates of crenarchaeol are 2-fold higher than those of soil-derived branched GDGTs, suggesting preferential soil OM preservation possibly due to matrix protection.

Seawater carbonate chemistry and biological processes during experiments with four species of marine diatoms

The effect of pCO2 on carbon acquisition and intracellular assimilation was investigated in the three bloom-forming diatom species, Eucampia zodiacus (Ehrenberg), Skeletonema costatum (Greville) Cleve, Thalassionema nitzschioides (Grunow) Mereschkowsky and the non-bloom-forming Thalassiosira pseudonana (Hust.) Hasle and Heimdal. In vivo activities of carbonic anhydrase (CA), photosynthetic O2 evolution, CO2 and HCO3? uptake rates were measured by membrane-inlet mass spectrometry (MIMS) in cells acclimated to pCO2 levels of 370 and 800 ?atm. To investigate whether the cells operate a C4-like pathway, activities of ribulose-1,5-bisphosphate carboxylase (RubisCO) and phosphoenolpyruvate carboxylase (PEPC) were measured at the mentioned pCO2 levels and a lower pCO2 level of 50 ?atm. In the bloom-forming species, extracellular CA activities strongly increased with decreasing CO2 supply while constantly low activities were obtained for T. pseudonana. Half-saturation concentrations (K1/2) for photosynthetic O2 evolution decreased with decreasing CO2 supply in the two bloom-forming species S. costatum and T. nitzschioides, but not in T. pseudonana and E. zodiacus. With the exception of S. costatum, maximum rates (Vmax) of photosynthesis remained constant in all investigated diatom species. Independent of the pCO2 level, PEPC activities were significantly lower than those for RubisCO, averaging generally less than 3%. All examined diatom species operate highly efficient CCMs under ambient and high pCO2, but differ strongly in the degree of regulation of individual components of the CCM such as Ci uptake kinetics and extracellular CA activities. The present data do not suggest C4 metabolism in the investigated species.

Seawater carbonate chemistry, calcification and dissolution response, and skeletal mineralogy of benthic orhanisms during experiments, 2011

Increasing atmospheric pCO2 reduces the saturation state of seawater with respect to the aragonite, high-Mg calcite (Mg/Ca > 0.04), and low-Mg calcite (Mg/Ca < 0.04) minerals from which marine calcifiers build their shells and skeletons. Notably, these polymorphs of CaCO3 have different solubilities in seawater: aragonite is more soluble than pure calcite, and the solubility of calcite increases with its Mg-content. Although much recent progress has been made investigating the effects of CO2-induced ocean acidification on rates of biological calcification, considerable uncertainties remain regarding impacts on shell/skeletal polymorph mineralogy. To investigate this subject, eighteen species of marine calcifiers were reared for 60-days in seawater bubbled with air-CO2 mixtures of 409 ± 6, 606 ± 7, 903 ± 12, and 2856 ± 54 ppm pCO2, yielding aragonite saturation states of 2.5 ± 0.4, 2.0 ± 0.4, 1.5 ± 0.3, and 0.7 ± 0.2. Calcite/aragonite ratios within bimineralic calcifiers increased with increasing pCO2, but were invariant within monomineralic calcifiers. Calcite Mg/Ca ratios (Mg/CaC) also varied with atmospheric pCO2 for two of the five high-Mg-calcite-producing organisms, but not for the low-Mg-calcite-producing organisms. These results suggest that shell/skeletal mineralogy within some-but not all-marine calcifiers will change as atmospheric pCO2 continues rising as a result of fossil fuel combustion and deforestation. Paleoceanographic reconstructions of seawater Mg/Ca, temperature, and salinity from the Mg/CaC of well-preserved calcitic marine fossils may also be improved by accounting for the effects of paleo-atmospheric pCO2 on skeletal Mg-fractionation.

Element abundances, loss on ignition, total analyzed abundances, CIA values, and Al-oxide/Ti-oxide ratios of sediment core CRP-2A (Table1)

The CRP-2/2A core, drilled in western McMurdo Sound in October and November 1998, penetrated 624 m of Quaternary. Pliocene, lower Miocene, and Oligocene glacigenic sediments. The palaeoclimatic record of CRP-2/2A is examined using major element analyses of bulk core samples of fine grained sediments (mudstones and siltstones) and the Chemical Index of Alteration (CIA) of Nesbitt & Young (1982). The CIA is calculated from the relative abundances of AI, K, Ca, and Na oxides, and its magnitude increases as the effects of chemical weathering increase. However, changes in sediment provenance can also affect the CIA, and provenance changes are recorded by shifts in the Al2O3/TiO2 ratios and the Nb contents of these CRP-2/2A mudstones. Relatively low CIA values (40-50) occur throughout the CRP-2/2A sequence, whereas the Al2O3/TiO2 ratio decreases upsection. The major provenance change is an abrupt onset of McMurdo Volcanic Group detritus at ~300 mbsf and is best characterized by a rapid increase in Nb content in the sediments. This provenance shift is not evident in the CIA record, suggesting that a contribution from the Ferrar Dolerite to the older sediments was replaced by an input of McMurdo Volcanic Group material in the younger sediments. If this is true, then the relatively uniform CIA values indicate relatively consistent palaeoweathering intensities throughout the Oligocene and early Miocene in the areas that supplied sediment to CRP-2/2A.

Major ion chemistry of snow cores along a transect in central Dronning Maud Land, Antarctica

Among the large variety of particulates in the atmosphere, calcic mineral dust particles have highly reactive surfaces that undergo heterogeneous reactions with nitrogen oxides contiguously. The association between Ca2+, an important proxy indicator of mineral dust and NO3-, a dominant anion in the Antarctic snow pack was analysed. A total of 41 snow cores (~ 1 m each) that represent snow deposited during 2008-2009 were studied along coastal-inland transects from two different regions - the Princess Elizabeth Land (PEL) and central Dronning Maud Land (cDML) in East Antarctica. Correlation statistics showed a strong association (at 99 % significance level) between NO3- and Ca2+ at the near-coastal sections of both PEL (r = 0.72) and cDML (r = 0.76) transects. Similarly, a strong association between these ions was also observed in snow deposits at the inland sections of PEL (r = 0.8) and cDML (r = 0.85). Such systematic associations between Ca2+ and NO3- is attributed to the interaction between calcic mineral dust and nitrogen oxides in the atmosphere, leading to the possible formation of calcium nitrate (Ca(NO3)2). Forward and back trajectory analyses using HYSPLIT model v. 4 revealed that Southern South America (SSA) was an important dust emitting source to the study region, aided by the westerlies. Particle size distribution showed that over 90 % of the dust was in the range < 4 µm, indicating that these dust particles reached the Antarctic region via long range transport from the SSA region. We propose that the association between Ca2+ and NO3- occurs during the long range transport due to the formation of Ca(NO3)2. The Ca(NO3)2 thus formed in the atmosphere undergo deposition over Antarctica under the influence of anticyclonic polar easterlies. However, influence of local dust sources from the nunataks in cDML evidently mask such association in the mountainous region. The study indicates that the input of dust-bound NO3- may contribute a significant fraction of the total NO3- deposited in Antarctic snow.

Impact of ocean acidification and warming on the larval development of the spider crab Hyas araneus from different latitudes (54° vs 79°N), 2010

The combined impacts of future scenarios of ocean acidification and global warming on the larvae of a cold-eurythermal spider crab, Hyas araneus L., were investigated in one of its southernmost populations (living around Helgoland, southern North Sea, 54°N) and one of the northernmost populations (Svalbard, North Atlantic, 79°N). Larvae were exposed at temperatures of 3, 9 and 15°C to present day normocapnia (380 ppm CO2) and to CO2 conditions expected for the near or medium-term future (710 ppm by 2100 and 3000 ppm CO2 by 2300 and beyond). Larval development time and biochemical composition were studied in the larval stages Zoea I, II, and Megalopa. Permanent differences in instar duration between both populations were detected in all stages, likely as a result of evolutionary temperature adaptation. With the exception of Zoea II at 3°C and under all CO2 conditions, development in all instars from Svalbard was delayed compared to those from Helgoland, under all conditions. Most prominently, development was much longer and fewer specimens morphosed to the first crab instar in the Megalopa from Svalbard than from Helgoland. Enhanced CO2 levels (710 and particularly 3000 ppm), caused extended duration of larval development and reduced larval growth (measured as dry mass) and fitness (decreasing C/N ratio, a proxy of the lipid content). Such effects were strongest in the zoeal stages in Svalbard larvae, and during the Megalopa instar in Helgoland larvae.

Seawater carbonate chemistry, Mg/Ca, Sr/Ca, oxygen production and calcification rate during experiments with coral Pocillopora damicornis, 2011

The Sr/Ca of aragonitic coral skeletons is a commonly used palaeothermometer. However skeletal Sr/Ca is typically dominated by weekly-monthly oscillations which do not reflect temperature or seawater composition and the origins of which are currently unknown. To test the impact of transcellular Ca2+ transport processes on skeletal Sr/Ca, colonies of the branching coral, Pocillopora damicornis, were cultured in the presence of inhibitors of Ca-ATPase (ruthenium red) and Ca channels (verapamil hydrochloride). The photosynthesis, respiration and calcification rates of the colonies were monitored throughout the experiment. The skeleton deposited in the presence of the inhibitors was identified (by 42Ca spike) and analysed for Sr/Ca and Mg/Ca by secondary ion mass spectrometry. The Sr/Ca of the aragonite deposited in the presence of either of the inhibitors was not significantly different from that of the solvent (dimethyl sulfoxide) control, although the coral calcification rate was reduced by up to 66% and 73% in the ruthenium red and verapamil treatments, respectively. The typical precision (95% confidence limits) of mean Sr/Ca determinations within any treatment was <±1% and differences in skeletal Sr/Ca between treatments were correspondingly small. Either Ca-ATPase and Ca channels transport Sr2+ and Ca2+ in virtually the same ratio in which they are present in seawater or transcellular processes contribute little Ca2+ to the skeleton and most Ca is derived from seawater transported directly to the calcification site. Variations in the activities of Ca-ATPase and Ca-channels are not responsible for the weekly-monthly Sr/Ca oscillations observed in skeletal chronologies, assuming that the specificities of Ca transcellular transport processes are similar between coral genera.

(Table 1) Radiocarbon ages of samples taken from five sites in north-eastern European Russia

Aim: Concepts about patterns and rates of post-glacial tree population migration are changing as a result of the increasing amount of palaeobotanical information being provided by macroscopic plant remains. Here we combine macrofossil, pollen and stomata records from five sites in north-eastern European Russia and summarize the results for the late-glacial-early Holocene transition. The late-glacial-early Holocene transition encompasses the first indications of trees (tree-type Betula, Picea abies, Abies sibirica and Larix sibirica) and subsequent forest development. Considerable time-lags between the first macrobotanical and/or stomata finds of spruce (Picea abies) and the establishment of a closed forest are reconsidered. Location: Pechora basin, north-eastern European Russia. Methods: We used plant macrofossil, stomata, pollen and radiocarbon analyses to reconstruct late-glacial and early Holocene tree establishment and forest development. The data were derived from lake sediment and peat archives. Results: Palaeobotanical data reveal an early Holocene presence (11,500-10,000 cal. yr bp) of arboreal taxa at all five sites. One site presently located in the northernmost taiga zone, shows the presence of spruce and reproducing tree birch during the late-glacial. Given the current view of post-glacial population dynamics and migration rates, it seems likely that the source area of these early tree populations in north-eastern European Russia was not located in southern Europe but that these populations had local origins. Results thus support the emerging view that the first post-glacial population expansions in non-glaciated regions at high latitudes do not reflect migration from the south but were a result of an increase in the size and density of small persisting outlying tree populations. Main conclusions: Results suggest that the area east of the margin of the Scandinavian ice sheet to the Ural Mountains had isolated patches of trees during the late-glacial and early Holocene and that these small populations acted as initial nuclei for population expansion and forest development in the early Holocene.

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.

Stable isotope ratios from foraminfera in Kara Sea sediments

Ostracods secrete their valve calcite within a few hours or days, therefore, its isotopic composition records ambient environmental conditions of only a short time span. Hydrographic changes between the calcification of individuals lead to a corresponding range (max.-min.) in the isotope values when measuring several (>=5) single valves from a specific sediment sample. Analyses of living (stained) ostracods from the Kara Sea sediment surface revealed high ranges of >2per mil of d18O and d13C at low absolute levels (d18O: <3per mil, d13C: <-3per mil) near the river estuaries of Ob and Yenisei and low ranges of not, vert, similar1per mil at higher absolute levels (d18O: 2-5.4per mil, d13C: -3 per mil to -1.5per mil) on the shelf and in submarine paleo-river channels. Comparison with a hydrographic data base and isotope measurements of bottom water samples shows that the average and the span of the ostracod-based isotope ranges closely mirror the long-term means and variabilities (standard deviation) of bottom water temperature and salinity. The bottom hydrography in the southern part of the Kara Sea shows strong response to the river discharge and its extreme seasonal and interannual variability. Less variable hydrographic conditions are indicative for deeper shelf areas to the north, but also for areas near the river estuaries along submarine paleo-river channels, which act as corridors for southward flowing cold and saline bottom water. Isotope analyses on up to five single ostracod valves per sample in the lower section (8-7 cal. ka BP) of a sediment core north of Yenisei estuary revealed d18O and d13C values which on average are lower by 0.6? in both, d18O and d13C, than in the upper core section (<5 cal. ka BP). The isotope shifts illustrate the decreasing influence of isotopically light river water at the bottom as a result of the southward retreat of the Yenisei river mouth from the coring site due to global sea level rise. However, the ranges (max.-min.) in the single-valve d18O and d13C data of the individual core samples are similar in the upper and in the lower core section, although a higher hydrographic variability is expected prior to 7 cal. ka BP due to river proximity. This lack of variability indicates the southward flow of cold, saline water along a submarine paleo-river channel, formerly existing at the core location. Despite shallowing of the site due to sediment filling of the channel and isostatic uplift of the area, the hydrographic variability at the core location remained low during the Late Holocene, because the shallowing proceeded synchronously with the retreat of the river mouth due to the global sea level rise

Sea surafe temperture calculation for the Arabian Sea

Sea surface temperature (SST) and seawater d18O (d18Ow) were reconstructed in a suite of sediment cores from throughout the Arabian Sea for four distinct time intervals (0 ka, 8 ka, 15 ka, and 20 ka) with the aim of understanding the history of the Indian Monsoon and the climate of the Arabian Sea region. This was accomplished through the use of paired Mg/Ca and d18O measurements of the planktonic foraminifer Globigerinoides ruber. By analyzing basin-wide changes and changes in cross-basinal gradients, we assess both monsoonal and regional-scale climate changes. SST was colder than present for the majority of sites within all three paleotime slices. Furthermore, both the Indian Monsoon and the regional Arabian Sea mean climate have varied substantially over the past 20 kyr. The 20 ka and 15 ka time slices exhibit average negative temperature anomalies of 2.5°-3.5°C attributable, in part, to the influences of glacial atmospheric CO2 concentrations and large continental ice sheets. The elimination of the cross-basinal SST gradient during these two time slices likely reflects a decrease in summer monsoon and an increase in winter monsoon strength. Changes in d18Ow that are smaller than the d18O signal due to global ice volume reflect decreased evaporation and increased winter monsoon mixing. SSTs throughout the Arabian Sea were still cooler than present by an average of 1.4°C in the 8 ka time slice. These cool SSTs, along with lower d18Ow throughout the basin, are attributed to stronger than modern summer and winter monsoons and increased runoff and precipitation. The results of this study underscore the importance of taking a spatial approach to the reconstruction of processes such as monsoon upwelling.

Interstitial water chemistry, Deep Sea Drilling Project, Leg 96

On Leg 96 of the Deep Sea Drilling Project (DSDP), holes were drilled in Orca and Pigmy basins on the northern Gulf of Mexico continental slope and on the Mississippi Fan. The holes on the fan encountered interbedded sand, silt, and mud deposited extremely rapidly, most during late Wisconsin glacial time. Pore-water chemistry in these holes is variable, but does not follow lithologic changes in any simple way. Both Ca and SO4 are enriched in the pore water of many samples from the fan. Two sites drilled in the prominent central channel of the middle fan show rapid SO4 reduction with depth, whereas two nearby sites in overbank deposits show no sulfate reduction for 300 m. Calcium concentration decreases as SO4 is depleted and Li follows the same pattern. Strontium, which like Li, is enriched in samples enriched in Ca, does not decrease with SO4 and Ca. Potassium in the pore water decreases with depth at almost all sites. Sulfate reduction was active at the two basin sites and, as on the fan, this resulted in calcium carbonate precipitation and a lowering of pore water Ca, Mg, and Li. The Orca Basin site was drilled through a brine pool of 258? salinity. Pore-water salinity decreases smoothly with depth to 50 m and remains well above normal seawater values to the bottom of the hole at about 90 m. This suggests constant sedimentation under anoxic hypersaline conditions for at least the last 50,000 yr.

Diagenetic dolomite formation in Quaternary anoxic diatomaceous muds at DSDP Leg 64 Holes

During drilling in the Gulf of California, diagenetic carbonate rocks were recovered at 7 out of 8 sites. These are primarily dolomites which record 13C isotopic evidence of the incorporation of carbon derived from the decomposition of organic matter. In Hole 479, drilled to a sub-bottom depth of 440 meters on the Guaymas Slope, under a fertile upwelling belt, we recognized an excellent example of deep sea dolomitization in progress. This Quaternary section of organic-carbon- rich, low-carbonate, hemipelagic diatomaceous oozes contains numerous fine-grained, decimeter-thin, episodic beds of dolomite, which show sedimentologic, geochemical, and isotopic evidence of accretion by precipitation below 40 meters sub-bottom in zones of high alkalinity and low sulfate. The beds preserve original sedimentary structures. Carbon-13 varies from +3 to +14 per mil, indicating biogenic CO2 reservoirs related to active methanogenesis. In single beds, 18O values range outwardly from +5 to -7 per mil, reflecting increasing temperature with progressive accretion of dolomite with depth; the values parallel progressive trends in lithification, texture, mineralogy, and fossil preservation. We estimate slow accretion rates on the order of 0.1-0.7 mm/10**3 yr. with burial. Dolomitization does not proceed merely at the expense of nearby nannofossils. Ca and Mg ions must be derived from interstitial waters. The episodic appearance of beds in the sequence seems partly a reflection of latent climate signals. This process of deep sea dolomitization carries implications for hydrocarbon migration, as well as an interpretation of the presence of dolomite in other modern and ancient pelagic to hemipelagic sediment sequences.