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Coccoliths comprise a major fraction of the global carbonate sink. Therefore, changes in coccolithophores' Ca isotopic fractionation could affect seawater Ca isotopic composition, affecting interpretations of the global Ca cycle and related changes in seawater chemistry and climate. Despite this, a quantitative interpretation of coccolith Ca isotopic fractionation and a clear understanding of the mechanisms driving it are not yet available. Here, we address this gap in knowledge by developing a simple model (CaSri–Co) to track coccolith Ca isotopic fractionation during cellular Ca uptake and allocation to calcification. We then apply it to published and new δ44/40Ca and Sr/Ca data of cultured coccolithophores of the species Emiliania huxleyi and Gephyrocapsa oceanica. We identify changes in calcification rates, Ca retention efficiency and solvation–desolvation rates as major drivers of the Ca isotopic fractionation and Sr/Ca variations observed in cultures. Higher calcification rates, higher Ca retention efficiencies and lower solvation–desolvation rates increase both coccolith Ca isotopic fractionation and Sr/Ca. Coccolith Ca isotopic fractionation is most sensitive to changes in solvation–desolvation rates. Changes in Ca retention efficiency may be a major driver of coccolith Sr/Ca variations in cultures. We suggest that substantial changes in the water structure strength caused by past changes in temperature could have induced significant changes in coccolithophores' Ca isotopic fractionation, potentially having some influence on seawater Ca isotopic composition. We also suggest a potential effect on Ca isotopic fractionation via modification of the solvation environment through cellular exudates, a hypothesis that remains to be tested.

Highlights • δ44Ca was measured in bulk carbonate and barite at two sites over the PETM. • Diagenetic effects on δ44Ca are observed associated with ocean acidification. • Multiple sites and proxy archives necessary to reconstruct the past accurately. Abstract Carbonates are used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales. However, these archives are susceptible to diagenetic alteration via dissolution, recrystallization and secondary precipitation, particularly during ocean acidification events when intense dissolution can occur. Despite the possible effects of diagenesis on proxy fidelity, the impacts of diagenesis on the calcium isotopic composition (δ44Ca) of carbonates are unclear. To shed light on this issue, bulk carbonate δ44Ca was measured at high resolution in two Pacific deep sea sediment cores (ODP Sites 1212 and 1221) with considerably different dissolution histories over the Paleocene–Eocene Thermal Maximum (PETM, ∼55 Ma∼55 Ma). The δ44Ca of marine barite was also measured at the deeper Site 1221, which experienced severe carbonate dissolution during the PETM. Large variations (∼0.8‰∼0.8‰) in bulk carbonate δ44Ca occur in the deeper of the two sites at depths corresponding to the peak carbon isotope excursion, which correlate with a large drop in carbonate weight percent. Such an effect is not observed in either the 1221 barite record or the bulk carbonate record at the shallower Site 1212, which is also less affected by dissolution. We contend that ocean chemical changes associated with abrupt and massive carbon release into the ocean–atmosphere system and subsequent ocean acidification at the PETM affected the bulk carbonate δ44Ca record via diagenesis in the sedimentary column. Such effects are considerable, and need to be taken into account when interpreting Ca isotope data and, potentially, other geochemical proxies over extreme climatic events that drive sediment dissolution.

Chemical (Sr, Mg) and isotopic (δ18O, 87Sr/86Sr) compositions of calcium carbonate veins (CCV) in the oceanic basement were determined to reconstruct changes in Sr/Ca and Mg/Ca of seawater in the Cenozoic. We examined CCV from 10 basement drill sites in the Atlantic and Pacific, ranging in age between 165 and 2.3 Ma. Six of these sites are from cold ridge flanks in basement

Mg/Ca and Sr/Ca ratios were determined on a single species of planktonic foraminiferan, Globigerinoides ruber (white), collected from the Gulf of Eilat and cultured in seawater at five different salinities (32 to 44), five temperatures (18 to 30 °C) and four pH values (7.9 to 8.4). The Mg/Ca-temperature calibration of cultured G. ruber (with an exponential slope of 8 ± 3%/°C) agrees well with previously published calibrations from core-tops and sediment traps. However, the dependence of Mg/Ca on salinity (with an exponential slope of 5 ± 3%/psu) is also significant and should be included in the calibration equation. With this purpose, we calculated a calibration equation for G. ruber dependent on both temperature and salinity within the 95% confidence limits: Mg/Ca(mmol/mol)=exp[0.06(±0.02)*S(psu)+0.08(±0.02)*T(°C)−2.8(±1.0)],R2=0.95 The influence of pH on Mg/Ca ratios is negligible at ambient seawater pH (8.1 to 8.3). However, we observe a dominating pH control on shell Mg/Ca when the pH of seawater is lower than 8.0. Sr/Ca in G. ruber shows a significant positive correlation with average growth rate. Presumably, part of the variability in shell Sr/Ca in the geological record is linked to changes in growth rates of foraminifera as a response to changing environmental conditions.

We investigated the controls of hydrography and of scavenging on the distribution of the particle reactive radionuclides 231Pa and 230Th in the water column and in surface sediments off Southwest Africa (Angola and Cape basins). Based on a vertical section of total 230Thex concentrations in the water column we show that small differences in the salinity between the North Atlantic Deep Water (NADW) in the Angola Basin and the NADW in the Cape Basin as well as the advection of NADW associated with the Namib Col Current are reflected in total 230Thex concentrations. These variable total concentrations are believed to reflect the flow path and mixing history of NADW with the NADW in the Angola Basin being relatively older and 230Th enriched compared to the NADW in the Cape Basin. In the area investigated we found high 231Paex/230Thex ratios (231Paex/230Thex > 0.093) in surface sediments at the continental margin and lower ones (231Paex/230Thex < 0.093) in the open ocean. Such a distribution is normally interpreted to result from high particle flux at ocean margins (boundary scavenging). However, the lack of any significant depletion of dissolved 230Th and 231Pa in the water column does not indicate extensive scavenging at the continental margin. High 231Paex/230Thex ratios are constrained to shallow waters depths (< 2000 m) only and coincide with low fractionation between 231Pa and 230Th indicating that preferential scavenging of 231Pa on opal may have caused high 231Paex/230Thex ratios in the sediments. The observed close negative correlation (r2 = 0.82) between 231Paex/230Thex ratios in sediments and water depths is believed to reflect changes in the particle composition, i.e. a decrease in opal content with water depth. In the Angola and Cape basins the total 231Paex concentrations in NADW were the highest observed so far in the Atlantic Ocean, and they are attributed to the meridional export of 231Pa from the North Atlantic. This caused the average dissolved 231Pa/230Th in the Southeast Atlantic to be about a factor 2 higher when compared to the North Atlantic (Labrador Sea). These differences in the dissolved 231Pa/230Th were not reflected in 231Pa/230Th ratios of surface sediments because the fractionation is lower in the Labrador Sea compared to the Southeast Atlantic, i.e. fractionation counteracts changes in the dissolved 231Pa/230Th. This suggests that fractionation is more important for the determination of 231Paex/230Thex ratios in sediments than the meridional export of 231Pa from the North Atlantic.

For paleoceanographic studies, it is important to understand the processes that influence the calcium (Ca) isotopic composition of foraminiferal calcite tests preserved in the sediment record. Seven species of planktonic foraminifera from coretop sediments collectively exhibited a Ca temperature dependent fractionation of 0.013‰per °C. Thisisin agreement with previously published estimatesformostspecies ofplanktonic foraminifera as well asbiogenicandinorganiccalciteandaragonite.Fourspeciesofplanktonicforaminiferacollectedfromasedimenttrapshowedaconsiderableamountof scatterandnoconsistenttemperaturedependentfractionation.Analyzedsizefractionsofcoretopsamplesshownosignificantrelationshipwith δ 44/40 Ca. However, preliminary results suggest that the symbiotic and spinose foraminifera Globigerinoides sacculifer might exhibit a relationship between test size and δ 44/40 Ca. A one-box model in which Ca isotopes are allowed to fractionate by Rayleigh distillation from a biomineralization reservoir (internal pool) was used to constrain the isotopic composition of the original biomineralization Ca reservoir, assuming around 85% of the Ca reservoir is precipitatedandthefractionationfactorduringprecipitationis0.9985+0.00002(T°C).ToexplaintheforaminiferalCaisotopedata,thismodelindicates

The Ifaty coral record from off SW Madagascar provide a 336-year coral oxygen isotope record that is used to investigate the natural variability of the western Indian Ocean subtropical SST dipole and ENSO. The coral oxygen isotope record primarily reflects past sea-surface temperature (SST) variability on seasonal to multidecadal scales. To validate the SST reconstructions derived from oxygen isotopes, Sr/Ca ratios were obtained for selected time windows (1973–1995, 1863–1910, 1784–1809, 1688–1710). The period 1675–1760 was found to be the coolest period of the entire record with anomalies of 0.3–0.5 °C that includes the Late Maunder Minimum (1675–1710). The warmest periods, as indicated by our data, occur between 1880 and 1900 and the upper part of the Ifaty record (1973–1995). We generated a time series of coral δ18O for different seasons of the year to investigate austral winter and summer SST variability that influences rainfall intensity over southern Africa. Winter coral δ18O is coherent with winter SST on decadal and multidecadal time scales between 1854 and 1995. We suggest that the Ifaty winter time series provides a record of winter SST variability over the Mozambique Channel/Agulhas Current region over 336 years. Strong Indian Ocean subtropical dipole events, occurring during austral summer, are displayed in the Ifaty record. The austral summer coral δ18O is coherent and in phase with ENSO indices on interannual time scales (2–4 years) between 1880–1920, 1930–1940 and after 1970. Our data indicate that the impact of ENSO on SW Indian Ocean SST and atmospheric circulation was also strong between 1680–1720 and 1760–1790, in agreement with other studies. We show evidence that these variations are caused by changes in the regional hydrologic balance. The results demonstrate that the impact of ENSO cycles in the region of the SW Indian Ocean has changed significantly since 1970 and relate to a warming of southwestern Indian Ocean surface waters altering the spatial signature of ENSO.

The internal microstructure of a ferromanganese nodule (#2392, from 154°37.52′W, 9°37.56′N, at water depth 5194 m) was examined in detail on polished sections, and radiometrically dated (230Thex/232Th) along a high-resolution (0.1 mm) depth profile (0–1.3 mm), spanning approximately 271 ka. The fabric shows typical stromatolithic structure and exhibits four orders of basic cyclic growth pattern, namely laminae bands, laminae zones, laminae groups and laminae pairs having average thicknesses of 402–454, 185–206, 58–67 and 15–18 μm, respectively. A profile from the depth of 200–2661 μm was selected to obtain the geochemical series using line-scanning electron microprobe analyses, which provide a record of paleoceanographic oscillations during the growth period. Power spectral analysis of the geochemical series for Al, Mn, Fe and Fe/Mn from the depth of 200–1220 μm, where no obvious discontinuity could be observed, display conspicuous cyclicities. The cycles of laminae zones, laminae groups and laminae pairs are reflected in the spectral patterns as well. The significant spectral peaks are located at 186, 108, 66 μm. Together with the cycle of laminae bands, the ratios of these cyclicities are close to those of Milankovitch orbital cycles. Through tuning to orbital cycles, a net growth rate of 4.5 mm/Ma is derived for the profile, which is in perfect agreement with the growth rate of 4.6 mm/Ma determined by 230Thex/232Th dating. Therefore, the rhythmic growth of ferromanganese nodules appears definitely associated with Milankovitch cycles, and the growth cyclicities may offer a new tool for estimating growth rates of ferromanganese nodules and paleoenvironmental reconstruction at substage resolution when supported by radiometric dating.

Boron contents and boron, carbon and oxygen stable isotopes were determined for authigenic carbonates recovered from Ocean Drilling Program Leg 146, Oregon margin. Carbonate precipitates are the most widespread authigenic phase in the shallow accretionary wedge and carry chemical information about long-term variations in pore fluid origin and flow paths in the Cascadia subduction zone. Drilling the first ridge (toe area including the frontal thrust) and the second ridge (or Hydrate Ridge) of the prism demonstrated different fluid regimes, with higher B contents in the authigenic precipitates at the toe. The δ11B of 18 authigenic precipitates analysed ranges from 13.9‰ to as high as 39.8‰, extending the upper range of previously reported carbonate δ11B values considerably. When related to the δ11B ratio of their parent solutions, these data are characteristic of fluid-related processes in accretionary prisms. Together with δ13C and δ18O, δ11B ratios of the carbonate concretions, nodules and crusts allow one to distinguish between precipitation influenced by (i) seawater, (ii) fluid reservoirs at different depth levels within the accretionary prism and (iii) cage water from dissociated gas hydrates, the latter possibly indicating a fluctuation of the bottom simulating reflector during most recent Earth’s history. From this first systematic boron study on authigenic precipitates from an accretionary prism it is suggested that B contents of such carbonate crusts and concretions exceed those reported for other marine carbonates. Given the abundance of such precipitates at convergent margins, they represent a significant B sink in geochemical cycling. Isotopic compositions of the parent fluids to the carbonates mirror B chemistry of modern pore waters from convergent margins. The precipitates carry information of different subduction-related fluid processes over a certain period of time, and hence are a crucial tracer in the investigation of palaeo-fluid flow.

High resolution 230Thex and 10Be and biogenic barium profiles were measured at three sediment gravity cores (length 605–850 cm) from the Weddell Sea continental margin. Applying the 230Thex dating method, average sedimentation rates of 3 cm/kyr for the two cores from the South Orkney Slope and of 2.4 cm/kyr for the core from the eastern Weddell Sea were determined and compared to δ18O and lithostratigraphic results. Strong variations in the radionuclide concentrations in the sediments resembling the glacial/interglacial pattern of the δ18O stratigraphy and the 10Be stratigraphy of high northern latitudes were used for establishing a chronostratigraphy. Biogenic Ba shows a pattern similar to the radionuclide profiles, suggesting that both records were influenced by increased paleoproductivity at the beginning of the interglacials. However, 230Thex0 fluxes (0 stands for initial) exceeding production by up to a factor of 4 suggest that sediment redistribution processes, linked to variations in bottom water current velocity, played the major role in controlling the radionuclide and biogenic barium deposition during isotope stages 5e and 1. The correction for sediment focusing makes the ‘true’ vertical paleoproductivity rates, deduced from the fluxes of proxy tracers like biogenic barium, much lower than previously estimated. Very low 230Thex0 concentrations and fluxes during isotope stage 6 were probably caused by rapid deposition of older, resedimented material, delivered to the Weddell Sea continental slopes by the grounded ice shelves and contemporaneous erosion of particles originating from the water column.

To investigate the growth rates and absolute time stratigraphy of marine hydrogenetic ferromanganese encrustations, we performed 10Be profiling and ‘Co chronometry’ of crustal layers, as well as 87Sr86Sr and δ18O analysis of phosphatised limestone (francolite) within a ∼ 9.5 cm thick ferromanganese crust from Schumann Seamount in the Hawaiian Archipelago. Together with microfossil stratigraphy, our results indicate that some seamount crusts greatly exceed the commonly accepted Miocene maximum age, in this case probably approaching the Cretaceous age of the seamount. In addition to the unconformity at the crust-substrate boundary, at least eight major disconformities are indicated in the Schumann Seamount crust which probably represent depositional hiatuses or episodes of crust erosion. Three of the six upper disconformities can be placed at the Plio-Pleistocene, Middle Miocene and Paleocene-Eocene based on 10Be, microfossil and Co chronometer evidence. 87Sr86Sr and δ18O values of purified francolite from an inclusion-rich layer between the depths of 44 and 49 mm suggest apparent ages that approach those of Eocene-Late Paleocene microfossils reported in overlying layers, whereas francolite vein infillings in the lower part of the crust and in the basaltic substrate yield values that, if interpreted as ages of phosphatization, suggest a minimum Oligocene age. Paleotracking suggests the phosphogenesis observed here and on other Central Pacific seamounts could not have resulted from upwelling enhanced productivity associated with equatorial divergence if the Oligocene and Middle Miocene isotopic ages reported here and elsewhere are correct; however, a maximum Late Paleocene age for the phosphogenesis, consistent with the stratigraphy, would place these seamounts within 10°N of the equator. Paleotracking also suggests northeast tradewind transport of aluminosilicates in the Cenozoic, in agreement with other evidence for the antiquity of this ferromanganese crust.

The Houtman Abrolhos Islands, situated at the western passive margin of the Australian continent, consist of a series of shelf-edge coral reefs. The central platforms of the reefs are Late Pleistocene in age and are generally some 3–5 m above present sea level. The uppermost part of the Last Interglacial reefs normally has an upward-shallowing sequence, consisting of coral framestone, coralline algal bindstone and skeletal grainstone to rudstone. This sequence represents deposition in water depths of less than 2 m, and provides a good indicator of sea level. High-precision mass-spectrometric dates of corals from the Abrolhos reefs, including dates obtained from drill cores, arological, isotopic and stratigraphic criteria are established for the selection of suitable samples for dating and for assessing the reliability of dates. Using the screened dates and the stratigraphic evidence, the timing and character of the sea level variations of the Last Interglacial in the Abrolhos region are examined. The data show that sea level of the Last Interglacial in the Abrolhos was 4 m below its present height by ca. 134 ka BP and probably reached about 2 m above present height at ca. 133 ka BP. The exact time at which sea level reached its peak (6 m above present sea level) cannot be determined from our data. But it is clear that the sea level high stand of the Last Interglacial lasted until ca. 116 ka BP and that for much of the Last Interglacial sea level at the Abrolhos was at a height of about 4 m above its present level.

U/Th (TIMS) and ^(14)C (AMS) measurements are presented from two coral cores from the Easter group of the Houtman Abrolhos Islands between 28°S and 29°S on the western continental margin of Australia. The U/Th measurements on the Morley core from Morley Island cover a depth interval from 0.2 m above present sea level to 24.4 m below present sea level and comprise eleven samples. The ages vary between 6320 ± 50 a, at 0.2 m above sea level, and 9809 ± 95 a, at 24.4 m below sea level (all errors are 2σ). The mean growth rate is 7.1 ± 0.9 m/ka. The ^(14)C dates of selected Morley core corals show that the ^(14)C ages are ∼ 1000 a younger than their corresponding U/Th ages, which agrees with previous results. The main purpose of our ^(14)C measurements is to be able to compare them precisely with other coral cores where no U/Th measurements are available. The U/Th measurements of the Suomi core from Suomi Island cover a depth interval from 0.05 m to 14.2 m below present sea level and consist of four samples. The ages vary between 4671 ± 40 a, at 0.05 m below sea level, and 7102 ± 82 a, at 14.2 m below sea level, with a mean growth rate of 5.8 ± 0.2 m/ka. The growth history of both cores is explained by a simple model in which the growth rates of the Morley core can be interpreted as reflecting local rates of sea level rise, whereas the Suomi core is interpreted as reflecting lateral growth during the past ∼ 6000 a. Our results indicate that sea level relative to the western margins of the Australian continent was about 24 m lower than present at about 9800 a B.P. (^(14)C gives a date of 8500 a B.P.). Sea level then rose and reached a highstand, slightly higher than the present position at about 6300 a B.P (14C date: 5500 a). This highstand declined but was still higher than present at 4600 a B.P. This is in agreement with previous observations along the Australian coastal margins and with observations from the Huon peninsula (Papua New Guinea). Our results are very similar to theoretical numerical models, which take into consideration water loading and isostatic compensation and viscous mantle flow. In contrast, coral cores from Barbados show that corals with a ^(14)C age of ∼ 5500 a B.P. are some ∼ 10 m b.p.s.l. We interpret the difference between the Barbados core and the Morley core as resulting from additional “flooding” of Barbados by water redistribution, due to changes in the Earth's geoid but not reflecting global sea level rise or major addition of melt waters over the past ∼ 6000 a. The difference in the geoid at Barbados between ∼ 6000 a B.P. and the present will require a refinement in the geophysical models. Precise ^(230)Th (TIMS) measurements on continental coasts will be required to provide an adequate data base for modelling deformation, flow of mantle material and sea-level height.

The concentration of 230 Th in Mn crust VA13-2 (146°W, 9°25′S, 4830 m) from the Pacific Ocean was measured with high depth resolution (0.02 mm) to a depth of 1.4 mm corresponding to an age of ∼226 ka B.P. The mean growth rate estimated from these results is 6.2 ± 0.4 mm/Ma. However, the exponential curve obtained shows two drastic events in the 230 Th concentration record with durations of 41 ± 4 ka and 37 ± 6 ka which are interpreted as growth standstills. The decay-corrected 230 Th concentration is inversely correlated with those of Mn, Fe and Co indicating that the 230 Th flux into the crust has been constant throughout time and that the observed fluctuations in 230 Th are due to dilution by the main components. By applying a constant 230 Th flux model, high-resolution growth rates were derived from every sample investigated. A detailed comparison of the growth pattern with the SPECMAP time table reveals that the VA13-2 growth rates tend to be higher during interglacial than during glacial periods. In particular, the observed growth standstills are associated with glacial stages 6 and 8. Further investigation of Mn crust 72 DK 9 taken from shallower water (170°35′W, 20°13′N, 1550 m) tend to confirm that there is a link between the growth rates of hydrogenetic crusts and the climate of the Late Quaternary.