(Table 3) Li concentrations and isotopic compositions in foraminiferal shells, carbonate sediments, and associated pore waters from ODP Sites 131-806 and 138-851

An improved procedure for lithium isotope analysis using Li3PO4 as the ion source has been investigated for application to geological samples. The 7Li/6Li ratio is measured using double rhenium filament thermal ionization mass spectrometry in which isotopic fractionation is minimized at high temperatures. The method produces a stable, high intensity Li+ ion beam that allows measurement of nanogram quantities of lithium. This results in a reduction in sample size of up to 1000 times relative to that required for the established Li2BO2+ method while maintaining a comparable precision of better than 1? (1 sigma). Replicate analyses of the NBS L-SVEC Li2CO3 standard yielded a mean value of 12.1047+/-0.0043 (n=21), which is close to the reported absolute value of 12.02+/-0.03. Intercalibration with a wide range of geological samples shows excellent agreement between the Li3PO4 and Li2BO2+ techniques. Replicate analyses of seawater and a fresh submarine basalt display high precision results that agree with previous measurements. Taking advantage of the high ionization efficiency of the phosphate ion source, we have made the first measurements of the lithium concentration (by isotope dilution) and isotopic composition of calcareous foraminiferal tests and other marine carbonates. Preliminary results indicate that substantial lithium exchange occurs between carbonate sediments and their interstitial waters. In addition, a possible link between lithium paleoceanography and paleoclimate during the last 1000 ky may be derived from planktonic foraminiferal tests. This highly sensitive technique can be applied in the examination of low lithium reservoirs and thereby provide insight into some fundamental aspects of lithium geochemistry.

Temperature modulates coccolithophorid sensitivity of growth, photosynthesis and calcification to increasing seawater pCO2

Increasing atmospheric CO2 concentrations are expected to impact pelagic ecosystem functioning in the near future by driving ocean warming and acidification. While numerous studies have investigated impacts of rising temperature and seawater acidification on planktonic organisms separately, little is presently known on their combined effects. To test for possible synergistic effects we exposed two coccolithophore species, Emiliania huxleyi and Gephyrocapsa oceanica, to a CO2 gradient ranging from ~0.5-250 µmol/kg (i.e. ~20-6000 µatm pCO2) at three different temperatures (i.e. 10, 15, 20°C for E. huxleyi and 15, 20, 25°C for G. oceanica). Both species showed CO2-dependent optimum-curve responses for growth, photosynthesis and calcification rates at all temperatures. Increased temperature generally enhanced growth and production rates and modified sensitivities of metabolic processes to increasing CO2. CO2 optimum concentrations for growth, calcification, and organic carbon fixation rates were only marginally influenced from low to intermediate temperatures. However, there was a clear optimum shift towards higher CO2 concentrations from intermediate to high temperatures in both species. Our results demonstrate that the CO2 concentration where optimum growth, calcification and carbon fixation rates occur is modulated by temperature. Thus, the response of a coccolithophore strain to ocean acidification at a given temperature can be negative, neutral or positive depending on that strain's temperature optimum. This emphasizes that the cellular responses of coccolithophores to ocean acidification can only be judged accurately when interpreted in the proper eco-physiological context of a given strain or species. Addressing the synergistic effects of changing carbonate chemistry and temperature is an essential step when assessing the success of coccolithophores in the future ocean.

Experiment: Combined effects of CO2, temperature, irradiance and time on the physiological performance of Chondrus crispus (Rhodophyta)

In natural environments, marine biotas are exposed to a variety of simultaneously acting abiotic factors. Among these, temperature, irradiance and CO2 availability are major factors influencing the physiological performance of marine macroalgae. To test whether elevated levels of CO2 may remediate the otherwise reduced performance of uncalcified seaweeds under the influence of other stressful abiotic factors, we performed multifactorial experiments with the red alga Chondrus crispus from Helgoland (North Sea) with two levels of CO2, temperature and irradiance: low and high pCO2 levels were tested in combination with either (1) optimal and low irradiances or (2) optimal and sub-lethal high temperatures for growth. Performance of C. crispus was evaluated as biomass increase and relative growth rates (RGR), gross photosynthesis and pigment content. Acclimations of growth and photosynthesis were measured after 4 and 8 days. Acclimation time was crucial for elucidating single or combined CO2 effects on growth and photosynthesis. Signifi- cant CO2 effects became evident only in combination with either elevated temperature or reduced irradiance. Growth and photosynthesis had divergent patterns: RGR and biomass significantly increased only under a combination of high pCO2 and elevated temperature; gross photosynthesis was significantly reduced under high pCO2 conditions at low irradiance. Pigment content varied in response to irradiance and temperature, but was independent of pCO2.

Being young in a changing world: how temperature and salinity changes interactively modify the performance of larval stages of the barnacle Amphibalanus improvisus

The fate of key species, such as the barnacle Amphibalanus improvisus, in the course of global change is of particular interest since any change in their abundance and/or performance may entail community-wide effects. In the fluctuating Western Baltic, species typically experience a broad range of environmental conditions, which may preselect them to better cope with climate change. In this study, we examined the sensitivity of two crucial ontogenetic phases (naupliar, cypris) of the barnacle toward a range of temperature (12, 20, and 28°C) and salinity (5, 15, and 30 psu) combinations. Under all salinity treatments, nauplii developed faster at intermediate and high temperatures. Cyprid metamorphosis success, in contrast, was interactively impacted by temperature and salinity. Survival of nauplii decreased with increasing salinity under all temperature treatments. Highest settlement rates occurred at the intermediate temperature and salinity combination, i.e., 20°C and 15 psu. Settlement success of "naive" cyprids, i.e., when nauplii were raised in the absence of stress (20°C/15 psu), was less impacted by stressful temperature/salinity combinations than that of cyprids with a stress history. Here, settlement success was highest at 30 psu particularly at low and high temperatures. Surprisingly, larval survival was not highest under the conditions typical for the Kiel Fjord at the season of peak settlement (20°C/15 psu). The proportion of nauplii that ultimately transformed to attached juveniles was, however, highest under these "home" conditions. Overall, only particularly stressful combinations of temperature and salinity substantially reduced larval performance and development. Given more time for adaptation, the relatively smooth climate shifts predicted will probably not dramatically affect this species.

(Table 1) Sulfur isotopes and description of anhydrite in DSDP Holes 70-504B and 83-504B

Anhydrite occurs in veins in hydrothermally altered basalts recovered from Hole 504B during Leg 83 of the Deep Sea Drilling Project. Sulfur isotopic data indicate that the anhydrites formed from fluids with sulfur isotopic compositions similar to seawater sulfate. Anhydrite probably formed as a pulse of relatively unreacted seawater was heated when it entered a relatively hot hydrothermal system containing evolved fluids. Reheating and continued evolution of the system followed anhydrite deposition. Preservation of anhydrite in Hole 504B was probably favored by the high temperatures and by the low permeability that resulted from the sealing of cracks with secondary minerals. Evidence also indicates that anhydrite was partly replaced by laumontite and prehnite at relatively high temperatures, and possibly by calcite at lower temperatures.

Thallium concentrations and isotope composition of MORB glasses and altered oceani crust from DSDP/ODP Hole 504B and DSDP Hole 52-417D

Hydrothermal fluids expelled from the seafloor at high and low temperatures play pivotal roles in controlling seawater chemistry. However, the magnitude of the high temperature water flux of mid-ocean ridge axes remains widely disputed and the volume of low temperature vent fluids at ridge flanks is virtually unconstrained. Here, we determine both high and low temperature hydrothermal fluid fluxes using the chemical and isotopic mass balance of the element thallium (Tl) in the ocean crust. Thallium is a unique tracer of ocean floor hydrothermal exchange because of its contrasting behavior during seafloor alteration at low and high temperatures and the distinctive isotopic signatures of fresh and altered MORB and seawater. The calculated high temperature hydrothermal water flux is (0.17-2.93)*10**13 kg/yr with a best estimate of 0.72*10**13 kg/yr. This result suggests that only about 5 to 80% of the heat available at mid-ocean ridge axes from the crystallization and cooling of the freshly formed ocean crust, is released by high temperature black smoker fluids.The residual thermal energy ismost likely lost via conduction and/or through the circulation of intermediate temperature hydrothermal fluids that do not alter the chemical budgets of Tl in the ocean crust. The Tl-based calculations indicate that the low temperature hydrothermal water flux at ridge flanks is (0.2-5.4)*10**17 kg/yr. This implies that the fluids have an average temperature anomaly of only about 0.1 to 3.6 °C relative to ambient seawater. If these low temperatures are correct then both Sr and Mg are expected to be relatively unreactive in ridge-flank hydrothermal systems and this may explain why the extent of basalt alteration that is observed for altered ocean crust appears insufficient to balance the oceanic budgets of 87Sr/86Sr and Mg.

Physiological energetics of the thick shell mussel Mytilus coruscus exposed to seawater acidification and thermal stress

Anthropogenic CO2 emissions have caused seawater temperature elevation and ocean acidification. In view of both phenomena are occurring simultaneously, their combined effects on marine species must be experimentally evaluated. The purpose of this study was to estimate the combined effects of seawater acidification and temperature increase on the energy budget of the thick shell mussel Mytilus coruscus. Juvenile mussels were exposed to six combined treatments with three pH levels (8.1, 7.7 and 7.3) * two temperatures (25 °C and 30 °C) for 14 d. We found that clearance rates (CRs), food absorption efficiencies (AEs), respiration rates (RRs), ammonium excretion rates (ER), scope for growth (SFG) and O:N ratios were significantly reduced by elevated temperature sometimes during the whole experiments. Low pH showed significant negative effects on RR and ER, and significantly increased O:N ratios, but showed almost no effects on CR, AE and SFG of M. coruscus. Nevertheless, their interactive effects were observed in RR, ER and O:N ratios. PCA revealed positive relationships among most physiological indicators, especially between SFG and CR under normal temperatures compared to high temperatures. PCA also showed that the high RR was closely correlated to an increasing ER with increasing pH levels. These results suggest that physiological energetics of juvenile M. coruscus are able to acclimate to CO2 acidification with a little physiological effect, but not increased temperatures. Therefore, the negative effects of a temperature increase could potentially impact the ecophysiological responses of M. coruscus and have significant ecological consequences, mainly in those habitats where this species is dominant in terms of abundance and biomass.

Planktic foraminiferal and sea surface temperature record during the last 1 Myr across the Subtropical Front, Southwest Pacific

Planktic foraminiferal faunas and modern analogue technique estimates of sea surface temperature (SST) for the last 1 million years (Myr) are compared between core sites to the north (ODP 1125, 178 faunas) and south (DSDP 594, 374 faunas) of the present location of the Subtropical Front (STF), east of New Zealand. Faunas beneath cool subtropical water (STW) north of the STF are dominated by dextral Neogloboquadrina pachyderma, Globorotalia inflata, and Globigerina bulloides, whereas faunas to the south are strongly dominated by sinistral N. pachyderma (80-95% in glacials), with increased G. bulloides (20-50%) and dextral N. pachyderma (15-50%) in interglacials (beneath Subantarctic Water, or SAW). Canonical correspondence analysis indicates that at both sites, SST and related factors were the most important environmental influences on faunal composition. Greater climate-related faunal fluctuations occur in the south. Significant faunal changes occur through time at both sites, particularly towards the end of the mid-Pleistocene climate transition, MIS18-15 (e.g., decline of Globorotalia crassula in STW, disappearance of Globorotalia puncticulata in SAW), and during MIS8-5. Interglacial SST estimates in the north are similar to the present day throughout the last 1 Myr. To the south, interglacial SSTs are more variable with peaks 4-7 °C cooler than present through much of the early and middle Pleistocene, but in MIS11, MIS5.5, and early MIS1, peaks are estimated to have been 2-4 °C warmer than present. These high temperatures are attributed to southward spread of the STF across the submarine Chatham Rise, along which the STF appears to have been dynamically positioned throughout most of the last 1 Myr. For much of the last 1 Myr, glacial SST estimates in the north were only 1-2 °C cooler than the present interglacial, except in MIS16, MIS8, MIS6, and MIS4-2 when estimates are 4-7 °C cooler. These cooler temperatures are attributed to jetting of SAW through the Mernoo Saddle (across the Chatham Rise) and/or waning of the STW current. To the south, glacial SST estimates were consistently 10-11 °C cooler than present, similar to temperatures and faunas currently found in the vicinity of the Polar Front. One interpretation is that these cold temperatures reflect thermocline changes and increased Circumpolar Surface Water spinning off the Subantarctic Front as an enhanced Bounty Gyre along the south side of the Chatham Rise. For most of the last 1 Myr, the temperature gradient across the STF has been considerably greater than the present 4 °C. During glacial episodes, the STF in this region did not migrate northwards, but instead there was an intensification of the temperature gradient across it (interglacials 4-11 °C; glacials 8-14 °C).

(Table 2) Major and trace elements in black smoker particulates

We present geochemical data of black smoker particulates filtered from hydrothermal fluids with seawater-dilutions ranging from 0-99%. Results indicate the dominance of sulphide minerals (Fe, Cu, and Zn sulphides) in all samples taken at different hydrothermal sites on the Mid-Atlantic Ridge. Pronounced differences in the geochemistry of the particles between Logatchev I and 5°S hydrothermal fields could be attributed to differences in fluid chemistry. Lower metal/sulphur ratios (Me/H2S < 1) compared to Logatchev I result in a larger amount of particles precipitated per liter fluid and the occurrence of elemental sulphur at 5°S, while at Logatchev I Fe oxides occur in larger amounts. Systematic trends with dilution degree of the fluid include the precipitation of large amounts of Cu sulphides at a low dilution and a pronounced drop with increasing dilution. Moreover, Fe (sulphides or oxides) precipitation increases with dilution of the vent fluid by seawater. Geochemical reaction path modeling of hydrothermal fluid-seawater mixing and conductive cooling indicates that Cu sulphide formation at Logatchev I and 5°S mainly occurs at high temperatures and low dilution of the hydrothermal fluid by seawater. Iron precipitation is enhanced at higher fluid dilution, and the different amounts of minerals forming at 5°S and Logatchev I are thermodynamically controlled. Larger total amounts of minerals and larger amounts of sulphide precipitate during the mixing path when compared to the cooling path. Differences between model and field observations do occur and are attributable to closed system modeling, to kinetic influences and possibly to organic constituents of the hydrothermal fluids not accounted for by the model.

Seawater carbonate chemistry and biological processes duirng experiments with bryozoan Myriapora truncata, 2010

There are serious concerns that ocean acidification will combine with the effects of global warming to cause major shifts in marine ecosystems, but there is a lack of field data on the combined ecological effects of these changes due to the difficulty of creating large-scale, long-term exposures to elevated CO2 and temperature. Here we report the first coastal transplant experiment designed to investigate the effects of naturally acidified seawater on the rates of net calcification and dissolution of the branched calcitic bryozoan Myriapora truncata (Pallas, 1766). Colonies were transplanted to normal (pH 8.1), high (mean pH 7.66, minimum value 7.33) and extremely high CO2 conditions (mean pH 7.43, minimum value 6.83) at gas vents off Ischia Island (Tyrrhenian Sea, Italy). The net calcification rates of live colonies and the dissolution rates of dead colonies were estimated by weighing after 45 days (May-June 2008) and after 128 days (July-October) to examine the hypothesis that high CO2 levels affect bryozoan growth and survival differently during moderate and warm water conditions. In the first observation period, seawater temperatures ranged from 19 to 24 °C; dead M. truncata colonies dissolved at high CO2 levels (pH 7.66), whereas live specimens maintained the same net calcification rate as those growing at normal pH. In extremely high CO2 conditions (mean pH 7.43), the live bryozoans calcified significantly less than those at normal pH. Therefore, established colonies of M. truncata seem well able to withstand the levels of ocean acidification predicted in the next 200 years, possibly because the soft tissues protect the skeleton from an external decrease in pH. However, during the second period of observation a prolonged period of high seawater temperatures (25-28 °C) halted calcification both in controls and at high CO2, and all transplants died when high temperatures were combined with extremely high CO2 levels. Clearly, attempts to predict the future response of organisms to ocean acidification need to consider the effects of concurrent changes such as the Mediterranean trend for increased summer temperatures in surface waters. Although M. truncata was resilient to short-term exposure to high levels of ocean acidification at normal temperatures, our field transplants showed that its ability to calcify at higher temperatures was compromised, adding it to the growing list of species now potentially threatened by global warming.

(Supplement Table1) Abundances of major elements from KH93-3_DR10 at the Southwest Indian Ridge near the Rodriguez Triple Junction

Petrographic and geochemical analyses of basaltic rocks dredged from the first segment of the Southwest Indian Ridge near the Rodriguez Triple Junction have been completed in order to investigate water-rock interaction processes during mid-ocean ridge (MOR) hydrothermal alteration in the Indian Ocean. In the study area, we have successfully recovered a serial section of upper oceanic crust exposed along a steep rift valley wall which was uplifted and emplaced along a low angle normal fault. On the basis of microscopic observation, dredged samples are classified into three types: fresh lavas, low-temperature altered rocks, and high-temperature altered rocks. The fresh lavas have essentially the same chemical composition as typical N-MORB, although LILE and Nb are slightly enriched and depleted, respectively. Low temperature alteration brought about the enrichment of K2O, Rb, and U due to the presence of K-rich celadonite and U-adsorption onto Fe-oxyhydroxide and clay minerals. On the other hand, chloritization, albitization, and addition of base metals by high temperature hydrothermal alteration result in enrichments of MnO, MgO, Na2O, Cu, and Zn and depletions of CaO, K2O, Cr, Co, Ni, Rb, Sr, and Ba. In addition, U-enrichment is also observable in the high temperature altered rocks probably due to the decrease of uranite solubility in the reducing high-temperature hydrothermal solution. These petrological and geochemical features are comparable to those of the volcanic zone to transition zone rocks in the DSDP/ODP Hole 504B, indicating that our samples were recovered from the upper ~1000 m section of the oceanic crust. Only the alteration minerals related to off-axis alteration are absent in our samples dredged from near the spreading axis. The similarity of alteration between our samples from the Indian Ocean and the Hole 504B rocks from the Pacific Ocean suggests that MOR hydrothermal systems are probably similar across all world oceans.

Coral and mollusc resistance to ocean acidification adversely affected by warming, 2011

Increasing atmospheric carbon dioxide (CO2) concentrations are expectedto decrease surface ocean pH by 0.3-0.5 units by 2100, lowering the carbonate ion concentration of surfacewaters. This rapid acidification is predicted to dramatically decrease calcification in many marine organisms. Reduced skeletal growth under increased CO2 levels has already been shown for corals, molluscs and many other marine organisms. The impact of acidification on the ability of individual species to calcify has remained elusive, however, as measuring net calcification fails to disentangle the relative contributions of gross calcification and dissolution rates on growth. Here, we show that corals and molluscs transplanted along gradients of carbonate saturation state at Mediterranean CO2 vents are able to calcify and grow at even faster than normal rates when exposed to the high CO2 levels projected for the next 300 years. Calcifiers remain at risk, however, owing to the dissolution of exposed shells and skeletons that occurs as pH levels fall. Our results show that tissues and external organic layers play a major role in protecting shells and skeletons from corrosive sea water, limiting dissolution and allowing organisms to calcify. Our combined field and laboratory results demonstrate that the adverse effects of global warming are exacerbated when high temperatures coincide with acidification.

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.

Magnetic properties and heavy metals at DSDP Hole 83-504B

We report measurements of magnetic intensity, inclination, initial susceptibility, Koenigsberger's ratio, saturation magnetization, and Curie temperatures of 68 basalt samples from the Leg 83 section of Hole 504B. As in the upper part of the hole, reversely magnetized units predominate. Intensities of natural remanent magnetization vary widely, but the range of variation is an order of magnitude less than in the upper part of the hole. This and the other properties measured indicate that the magnetic characteristics of basalts from Hole 504B have been strongly affected by hydrothermal alteration, particularly in the deeper, Leg 83 section. The alteration states of the magnetic samples were studies using Xray diffraction, electron microprobe, X-ray fluorescence, and ion coupled plasma. Our results suggest three alteration zones in Hole 504B: a low-temperature zone (274.5-890 m) and two high-temperature zones (890-1050 m and 1050- 1350 m), differing in the number of veins observed in the samples and presumably differing in the volumes of hydrothermal fluids which reacted with the basalts.