Description: 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.

Description: 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.

Description: 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.

Description: The weathering of silicate minerals exposed on the continents is the largest sink of atmospheric CO2 on time scales of millions of years. The rate of this process is positively correlated with global mean temperature and atmospheric CO2 concentration, resulting in a negative feedback that stabilizes Earths’ climate (Berner, 2004). Detrital silicates derived from the physical denudation of the continents are a major component of marine sediments (Li and Schoonmaker, 2003). However, their geochemical behaviour is poorly understood and they are considered to be unimportant to the long-term carbon cycle. We show that in organic matter-rich sediments of the Sea of Okhotsk detrital silicates undergo intense weathering. This process is likely favoured by microbial activity, which lowers pore water pH and releases dissolved humic substances, and by the freshness of detrital silicates which originate from the cold, poorly weathered Amur River basin. Numerical simulations of early diagenesis show that submarine weathering rates in our study area are comparable to average continental weathering rates (Gaillardet et al., 1999). Furthermore, silicate weathering seems to be widespread in organic matter-rich sediments of continental margins, suggesting the existence of a significant CO2 sink there. These findings imply a greater efficiency of the silicate weathering engine also at low surface temperatures, resulting in a weakening of the negative feedback between pCO2, climate evolution and silicate weathering.

Description: All four naturally occurring radium isotopes (223Ra, 224Ra, 226Ra, 228Ra) and 222Rn in the groundwater affected Eckernförder Bay (EB) of the Baltic Sea (Germany) were measured using alpha-spectrometry and liquid scintillation (LS) counting. The applied analytical methods are optimally adapted for extensive field surveillance of short-lived radiotracers. Dispersive physical mixing acting over time scales on the order of days is responsible for the distribution of 223Ra, 224Ra and 222Rn in EB. The distribution of these natural tracers is controlled by the strength of the sedimentary source, the influence of direct groundwater input, the dispersive mixing coefficient in the water column and their radioactive decay. Using a simple one-dimensional transport model, the distribution of 224Ra near the sea floor can be described with a horizontal dispersivity in the range between 100 to 5×101 m2 s−1. From the inventory of 222Rn (72.4±7.4 Bq m−2) in the EB, the groundwater discharge rate is estimated to be 〈1.7 m3 s−1. In order to balance the inventory of 223Ra (0.52±0.22 Bq m−2) and 224Ra (6.46±2.6 B qm−2) a source other than groundwater seepage has to be responsible for almost all of the 224Ra and 223Ra inventory of the EB. Diffusion from sediments seems to be the major source for short-lived Ra isotopes in the lower water column of EB.

Description: During ODP Leg 193, 4 sites were drilled in the active PACMANUS hydrothermal field on the crest of the felsic Pual Ridge to examine the vertical and lateral variations in mineralization and alteration patterns. We present new data on clay mineral assemblages, clay and whole rock chemistry and clay mineral strontium and oxygen isotopic compositions of altered rocks from a site of diffuse low-temperature venting (Snowcap, Site 1188) and a site of high-temperature venting (Roman Ruins, Site 1189) in order to investigate the water-rock reactions and associated elemental exchanges. The volcanic succession at Snowcap has been hydrothermally altered, producing five alteration zones: (1) chlorite +/- illite-cristobalite-plagioclase alteration apparently overprinted locally by pyrophyllite bleaching at temperatures of 260-310degreesC; (2) chlorite +/- mixed-layer clay alteration at temperatures of 230degreesC; (3) chlorite and illite alteration; (4) illite and chlorite +/- illite mixed-layer alteration at temperatures of 250-260degreesC; and (5) illite +/- chlorite alteration at 290-300degreesC. Felsic rocks recovered from two holes (1189A and 1189B) at Roman Ruins, although very close together, show differing alteration features. Hole 1189A is characterized by a uniform chlorite-illite alteration formed at similar to250degreesC, overprinted by quartz veining at 350degreesC. In contrast, four alteration zones occur in Hole 1189B: (1) illite chlorite alteration formed at similar to300degreesC; (2) chlorite +/- illite alteration at 235degreesC; (3) chlorite illite and. mixed layer clay alteration; and (4) chlorite illite alteration at 220degreesC. Mass balance calculations indicate that the chloritization, illitization and bleaching (silica-pyrophyllite assemblages) alteration stages are accompanied by different chemical changes relative to a calculated pristine precursor lava. The element Cr appears to have a general enrichment in the altered samples from PACMANUS. The clay concentrate data show that Cr and Cu are predominantly present in the pyrophyllites. Illite shows a significant enrichment for Cs and Cu relative to the bulk altered samples. Considerations of mineral stability allow us to place some constraints on fluid chemistry. Hydrothermal fluid pH for the chloritization and illitization was neutral to slightly acidic and relatively acidic for the pyrophyllite alteration. In general the fluids, especially from Roman Ruins and at intermediate depths below Snowcap, show only a small proportion of seawater mixing (〈10%). Fluids in shallow and deep parts of the Snowcap holes, in contrast, show stronger seawater influence. Copyright (C) 2004 Elsevier Ltd.

Description: ODP Leg 204, which drilled at Hydrate Ridge, provides unique insights into the fluid regime of an accretionary complex and delineates specific sub-seafloor pathways for fluid transport. Compaction and dewatering due to smectite–illite transition increase with distance from the toe of the accretionary prism and bring up fluids from deep within the accretionary complex to sampled depths (≤ 600 mbsf). These fluids have a distinctly non-radiogenic strontium isotope signature indicating reaction with the oceanic basement. Boron isotopes are also consistent with a deep fluid source that has been modified by desorption of heavy boron as clay minerals change from smectite to illite. One of three major horizons serves as conduit for the transport of mainly fluid. Our results enable us to evaluate fluid migration pathways that play important roles on massive gas hydrate accumulations and seepage of methane-rich fluids on southern Hydrate Ridge.

Description: 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.

Description: Exploring the potentials of new methods in palaeothermometry is essential to improve our understanding of past climate change. Here, we present a refinement of the published δ44/40Ca-temperature calibration investigating modern specimens of planktonic foraminifera Globigerinoides sacculifer and apply this to sea surface temperature (SST) reconstructions over the last two glacial–interglacial cycles. Reproduced measurements of modern G. sacculifer collected from surface waters describe a linear relationship for the investigated temperature range (19.0–28.5 °C): δ44/40Ca [‰] = 0.22 (±0.05)∗SST [°C] −4.88. Thus a change of δ44/40Ca[‰] of 0.22 (±0.05) corresponds to a relative change of 1 °C. The refined δ44/40Camodern-calibration allows the determination of both relative temperature changes and absolute temperatures in the past. This δ44/40Camodern-calibration for G. sacculifer has been applied to the tropical East Atlantic sediment core GeoB1112 for which other SST proxy data are available. Comparison of the different data sets gives no indication for significant secondary overprinting of the δ44/40Ca signal. Long-term trends in reconstructed SST correlate strongly with temperature records derived from oxygen isotopes and Mg/Ca ratios supporting the methods validity. The observed change of SST of approximately 3 °C at the Holocene-last glacial maximum transition reveals additional evidence for the important role of the tropical Atlantic in triggering global climate change, based on a new independent palaeothermometer.

Description: The accurate dating of fossil coral reefs is of prime importance in determining the timing of deglaciation events and thus understanding the mechanisms driving glacial–interglacial cycles. So far, the most useful coral reef records of past sea level changes are those related to the last deglaciation and the Last Interglacial period. U/Th ages for older isotopic stages are more limited, due to the scarcity of datable material, reflecting diagenetic alteration. Most data are from emergent parts of reefs and reef terraces in active subduction zones where relative sea level records may be biased by variations in rates of tectonic uplift. New constraints on sea level changes over the past 300 000 yr are based on high-precision U-series age measurements of successive reef units on Mururoa. These have been cored in four continuous 300-m-long drill holes with seaward inclinations of 30 to 45° on the northeastern rim of the atoll. Past sea level positions have been calculated from the radiometric ages of corals by correcting the present depth of subsurface horizons both for thermal subsidence and for depositional palaeodepth. The location of this atoll at a considerable distance from former ice sheets (‘far field’) minimises the influence of glacio–isostatic rebound. Prominent units formed during four periods of relative sea level highstands, including the Holocene and stages 5 (∼125 ka), 7 (∼212 ka) and 9 (∼332 ka). These are primarily composed of coralgal frameworks that grew in very shallow water. Three periods of relative low stand correspond to stages 2 (∼17–23 ka), 4 (∼60 ka) and 8 (∼270 ka) during which small reefs developed in association with large bioclastic accumulations. Good agreement with the timing of sea level changes based on oxygen isotope measurements in deep-sea cores is noted for most of the dated reef units. We report here the first accurate coral record of the Last Glacial Maximum in the Pacific, 135–143 m below the present sea surface, suggesting that sea level may have been lower than expected during this period.