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.

Isotope characterization and estimated temperature of formation of calcite veins in ODP Sites 124-768 and 124-770 (Table 1)

Secondary carbonate minerals were recovered within the basalts at both ODP Sites 768 and 770 in the Sulu and Celebes seas. Petrographic and X-ray diffraction analyses indicate that the carbonates are calcites. Other alteration products recognized in the thin sections are smectites, iron oxides, and gypsum. The 13C values of carbonates from both sites range from 1.6 per mil to 2.3 per mil, which are indicative of inorganic carbonate formation with no contributions from 13C-depleted sources such as oxidized organic carbon or methane. The oxygen isotopes at Site 770 range from 30.8 per mil to 31.6 per mil, which indicates a pervasive circulation of cold seawater (9° to 12°C) during alteration of the Celebes Sea basalts. In contrast, carbonates associated with Site 768 basalts have less positive d18O values (21.0 per mil to 27.3 per mil). A lighter 18O isotopic signature indicates the formation of secondary calcite at either higher temperatures or in a system closed to seawater. The rapidly deposited pyroclastic flows at Site 768 would have limited water access to the crust very soon after its formation, which leads us to speculate that the carbonates in the Sulu Sea basalts were formed by isotopically modified fluids resulting from basalt alteration in a closed system.

Pliocene-Pleistocene stable isotope record of ODP Site 107-653

Planktonic foraminiferal oxygen and carbon isotope analyses from Tyrrhenian Sea Ocean Drilling Program (ODP) Site 653 provide a continuous record of the Pliocene-Pleistocene paleoceanographic history of the Mediterranean. Long-term trends in oxygen isotopes primarily reflect changes in global climatic conditions, with a more local or regional signal superimposed on this record. For example, significant enrichments in 18O due to decreases in surface water temperature and/or increases in continental ice volume occurred at 3.1, 2.7, 2.1, 1.6, and 0.4 Ma. In contrast to most open-ocean results, the early Pliocene 6lsO record of Site 653 exhibits high-amplitude fluctuations indicative of very unstable climatic conditions in this region. Another unique aspect of this Mediterranean d18Orecord is the pronounced cooling at the Pliocene/Pleistocene boundary. The carbon isotope record for Site 653 also exhibits high-amplitude variability throughout the Pliocene-Pleistocene. This variability most probably reflects changes in the carbon isotopic composition of the source of Mediterranean surface waters.

Pleistocene-Pliocene strontium-isotope ratios of ODP Site 107-653 (Table 1)

Strontium isotopic determinations were made on samples from the Pliocene-Pleistocene sequence recovered at ODP Hole 653A, the proposed "deep-sea type section" for the Mediterranean region. Biostratigraphic correlations can be combined with the patterns of variations in the 87Sr/86Sr values to delineate the following: (1) the earliest Pliocene (MP11 to basal MP12 zones) is distinguished by fluctuations in the ratio, probably related to the unstable paleoceanographic conditions following the Zanclean flooding and initial in-filling of the Mediterranean after the Messinian desiccation, (2) during most of the Pliocene between approximately 4.5 and 2.4 Ma (MP12 to MP15 zones) the 87Sr/86Sr values remain relatively constant, producing a plateau in the strontium isotope-depth curve for this period, and (3) beginning at approximately 2.4 Ma (across the MP15/MP16 boundary) and continuing into the latest Pleistocene, the 7Sr/86Sr values increase significantly but show fluctuations that have both positive and negative slopes. The presence of a plateau in the curve generated for the Mediterranean type section duplicates in greater detail the late Neogene results reported by DePaolo (1986, doi:10.1130/0091-7613(1986)14<103:DROTNS>2.0.CO;2). The virtual lack of change in the ratio between 4.5 and 2.4 Ma essentially eliminates strontium isotopes as a high-resolution correlation method for this period. The fluctuations in the ratio beginning at 2.4 Ma may be a reflection of major climatic changes occurring in the latest Pliocene-Pleistocene. The relationship between glacial-interglacial cycles and seawater 87Sr/86Sr values suggested by DePaolo (1986) and Capo and DePaolo (1987) is uncertain but should be tested as significant increases and decreases in 87Sr/86Sr of seawater have apparently occurred since 2.4 Ma.

Helium isotope ratios and pore gases in deep-sea sediments of the Japan Sea

We have measured the 3He/4He and 4He/20Ne ratios and chemical compositions of gases exsolved from deep-sea sediments at two sites (798 and 799) in the Japan Sea. The 3He/4He and 4He/20Ne ratios vary from 0.642 Ratm (where Ratm is the atmospheric 3He/4He ratio of 1.393*10**-6) to 0.840 Ratm, and from 0.41 to 4.5, respectively. Helium in the samples can be explained by the mixing between atmospheric helium dissolved in bottom water of the Japan Sea and crustal helium in the sediment. The sedimentary helium is enriched in mantle-derived 3He compared with those from the Japan Trench and the Nankai Trough. This suggests that the basement of the Japan Sea has relatively large remnants of mantle-derived helium compared with that of the Pacific. Major chemical compositions of the samples are methane and nitrogen. There is a positive correlation between methane content and helium content corrected for air component. Based on the 3He/4He-Sum C/3He diagram, the major part of methane can be attributed to crustal and/or organic origin.

(Table T1) Stable carbon and oxygen isotope ratios of benthic foraminifera in the Late Pliocene-Pleistocene section of ODP Site 181-1123 in the Southwest Pacific

Stable isotope records were generated for a late Pliocene-early Pleistocene interval from Ocean Drilling Program (ODP) Site 1123 in the southwest Pacific (41°47 S, 171°30 W; 3290 m water depth). Based on these data, new revisions were made to the shipboard splice and composite section. The isotope records will be used to evaluate the influence of North Atlantic and Southern Ocean deepwater masses on water entering the Pacific in the Deep Western Boundary Current. Three holes were cored at Site 1123, yielding a complete composite section over approximately the last 4.7 m.y. A representative spliced record ("the splice") was developed aboard ship based on magnetic susceptibility, gamma ray attenuation bulk density, and percent reflectance data from the three adjacent holes (Carter, McCave, Richter, Carter, et al., 1999, doi:10.2973/odp.proc.ir.181.2000). No gaps in the sedimentary record were detected for the multiple-cored section of Site 1123. In addition to the isotope data, postcruise revisions to the splice and composite section based on stable isotope data are described here.

Micropaleontology and stable isotope record of ODP Hole 178-1098C

Detailed study of four Holocene sediment intervals from Ocean Drilling Program Site 1098 (Palmer Deep, Antarctic Peninsula) reveals that in situ dissolution of calcareous foraminifers in the core repository has significantly altered and in some cases eliminated calcareous foraminifers. Despite dissolution, the foraminifer and supporting diatom data show that the most open-ocean and reduced sea-ice conditions occurred in the early Holocene. The influence of Circumpolar Deep Water was greatest during the early Holocene but continued to be important throughout the Holocene. An increase in sea-ice proximal diatoms at 3500 cal. BP documents an expansion in the amount of persistent sea ice. The inferred increase in sea ice corresponds with an overall increase in magnetic susceptibility values. Benthic foraminifers are present in all samples from the Palmer Deep, including the middle Holocene pervasively laminated sediments with low magnetic susceptibility values. The consistent presence of mobile epifaunal benthic foraminifers in the laminated sediments demonstrates that the laminations do not represent anoxic conditions. The uniform composition of the agglutinated foraminifer fauna throughout the late Holocene suggests that the Palmer Deep did not experience bottom-water-mass changes associated with the alternating deposition of bioturbated or laminated sediments.

Stable carbon and oxygen isotope ratios of bulk sediment from DSDP Hole 62-463 (Appendix A)

In order to elucidate early Aptian marine paleotemperature evolution across the period of enhanced organic carbon (Corg)-burial [Oceanic Anoxic Event (OAE) 1a], stable isotope analyses were performed on pelagic limestones at Deep Sea Drilling Project Site 463, central Pacific Ocean. The delta18O data exhibit a distinct anomaly by ~-2? spanning the OAE 1a interval (i.e., a ~6 m-thick, phytoplanktonic Corg-rich unit constrained by magneto-, bio- and delta13C stratigraphy). Elucidation of paleotemperature significance of the delta18O shift is made by taking account of recent Sr/Ca evidence at the same section, which revealed that geochemical signals in carbonate-poor lithologies are relatively unaltered against burial diagenesis. By discriminating delta18O values from carbonate-poor samples (CaCO3 contents=5-30 wt.%), it appears that an abrupt rise in seasurface temperatures (SSTs) by 8 °C (=-1.7? shift in delta18O) occurred immediately before OAE 1a, whereas a cooling mode likely prevailed during the peak Corg-burial. In terms of its stratigraphic relationship as to the Corg-rich interval and to a pronounced negative delta13C excursion, as well as its timescale, the observed SST rise resembles those associated with the Paleocene-Eocene thermal maximum and, more strikingly, Jurassic Toarcian OAE. This observation is consistent with the hypothesis that these paleoenvironmental events were driven by a common causal mechanism, which was likely initiated by the greenhouse effect via massive release of CH4 or CO2 from the isotopically-light carbon reservoir and terminated by a negative productivity feedback.

Pliocene-Pleistocene carbon isotope record of foraminifera from DSDP Site 89-586

Oceanographic changes in the western equatorial Pacific during the past 6 m.y. are inferred from carbon isotopic analyses of planktonic and benthic foraminifers from Ontong Java Plateau (DSDP Site 586). Sample spacing is 1.5 m (ca. 35,000-75,000 yr). An overall trend of d13C toward lighter values is evident for the last 5 m.y. in all four foraminiferal taxa analyzed (G. sacculifer, Pulleniatina, P. wuellerstorfi, and O. umbonatus). This trend is interpreted as an enrichment of the global ocean with 12C, because of the addition of carbon from organic carbon reservoirs (or lack of removal of carbon to such reservoirs), as a consequence of an overall drop in sea level. Differences between shallow- and deep-water d13C decrease slightly during this time interval, suggesting a moderate drop in productivity. This drop is not sufficient to explain the drop in sedimentation rate, however, much of which apparently must be ascribed to winnowing effects. A marked convergence in the d13C values of planktonic taxa exists within the last 2 m.y. We propose that this convergence indicates nutrient depletion in thermocline waters, caused by the vigorous removal of phosphate in marginal upwelling regions, or by the stripping of intermediate waters in their source regions. No large shifts are seen in the carbon isotope record of the last 6 m.y., in contrast to the oxygen isotope record. Some indication of cyclicity is present, with a period between 0.5 and 1.0 m.y. (especially in the earlier portion of the record).

(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.

Nd, Pb and Sr isotopes in sediment cores from the Gulf of Cadiz and the Portuguese margin

Mediterranean Outflow Water (MOW) is characterised by higher temperatures and salinities than other ambient water masses. MOW spreads at water depths between 500 and 1500 m in the eastern North Atlantic and has been a source of salinity for the Atlantic Meridional Overturning Circulation in the North Atlantic. We used high-resolution Nd and Pb isotope records of past ambient seawater obtained from authigenic ferromanganese coatings of sediments in three gravity cores at 577, 1745 and 1974 m water depth in the Gulf of Cadiz and along the Portuguese margin complemented by a selection of surface sediments to reconstruct the extent and pathways of MOWover the past 23 000 years. The surface and downcore Nd isotope data from all water depths exhibit only a very small variability close to the present day composition of MOW but do not reflect the present day Nd isotopic stratification of the water column as determined from a nearby open ocean hydrographic station. In contrast, the Pb isotope records show significant and systematic variations, which provide evidence for a significantly different pattern of the MOW pathways between 20 000 and 12 000 years ago compared with the subsequent period of time.

Radiogenic isotope record of Arctic Ocean circulation and weathering inputs of the past 15 million years

Lead (Pb), neodymium (Nd), and strontium (Sr) isotopic analyses were carried out on sediment leachates (reflecting the isotope composition of past seawater) and digests of the bulk residues (reflecting detrital continental inputs) of Integrated Ocean Drilling Program (IODP) Leg 302 and core PS2185 from the Lomonosov Ridge (Arctic Ocean). Our records are interpreted to reflect changes in continental erosion and oceanic circulation, driven predominantly by tectonic forcing on million-year timescales in the older (pre-2 Ma) part of the record and by climatic forcing of weathering and erosion of the Eurasian continental margin on thousand-year timescales in the younger (post-2 Ma) part. These data, covering the past ~15 Ma, show that continental inputs to the central Arctic Ocean have been more closely linked to glacial and hydrological processes occurring on the Eurasian margin than on continental North America and Greenland. The constancy of the detrital input signatures supports the early existence of an Arctic sea ice cover, whereas the major initiation of Northern Hemisphere glaciation at 2.7 Ma appears to have had little impact on the weathering regime of the Eurasian continental margin.

Nd, Sr and Pb isotopes and clay minerals in sediment cores from the Gulf of Cadiz and the Portuguese margin

The assemblages of marine sediments on the SW Iberian shelf have been controlled by contributions from distinct sources, which have varied in response to environmental changes since the Last Glacial Maximum (LGM). The rapid, decadal scale Mediterranean overturning circulation permits mixing of suspended particles from the entire Mediterranean Sea. They are entrained into the suspended particulate matter (SPM) carried by Mediterranean Outflow Water (MOW), which enters the eastern North Atlantic through the Strait of Gibraltar and spreads at intermediate depths in the Gulf of Cadiz and along the Portuguese continental margin. Other major sediment sources that have contributed to the characteristics and budget of SPM along the flow path of MOW on the SW Iberian shelf are North African dust and river-transported particles from the Iberian Peninsula. To reconstruct climate- and circulation-driven changes in the supply of sediments over the past ~23000 cal yr B.P., radiogenic Nd, Sr and Pb isotope records of the clay-size sediment fraction were obtained from one gravity core in the Gulf of Cadiz (577 m water depth) and from two gravity cores on the Portuguese shelf (1745 m, 1974 m water depth). These records are supplemented by time series analyses of clay mineral abundances from the same set of samples. Contrary to expectations, the transition from the LGM to the Holocene was not accompanied by strong changes in sediment provenance or transport, whereas Heinrich Event 1 (H1) and the African Humid Period (AHP) were marked by significantly different isotopic signatures reflecting changes in source contributions caused by supply of ice rafted material originating from the North American craton during H1 and diminished supply of Saharan dust during the AHP. The data also reveal that the timing of variations in the clay mineral abundances was decoupled from that of the radiogenic isotope signatures.

Holocene Mg/Ca, alkenones, and light stable isotope measurements on the outer North Iceland shelf, sediment core MD99-2269

We present new Holocene century to millennial-scale proxies for the well-dated piston core MD99-2269 from Húnaflóadjúp on the North Iceland Shelf. The core is located in 365 mwd and lies close to the fluctuating boundary between Atlantic and Arctic/Polar waters. The proxies are: alkenone-based SST°C, and Mg/Ca SST°C estimates and stable d13C and d18O values on planktonic and benthic foraminifera. The data were converted to 60 yr equi-spaced time-series. Significant trends in the data were extracted using Singular Spectrum Analysis and these accounted for between 50% and 70% of the variance. A comparison between these data with previously published climate proxies from MD99-2269 was carried out on a data set which consisted of 14-variable data set covering the interval 400-9200 cal yr BP at 100 yr time steps. This analysis indicated that the 1st two PC axes accounted for 57% of the variability with high loadings clustering primarily into "nutrient" and "temperature" proxies. Clustering on the 100 yr time-series indicated major changes in environment at ~6350 and ~3450 cal yr BP, which define early, mid- and late Holocene climatic intervals. We argue that a pervasive freshwater cap during the early Holocene resulted in warm SST°s, a stratified water column, and a depleted nutrient supply. The loss of the freshwater layer in the mid-Holocene resulted in high carbonate production, and the late Holocene/neoglacial interval was marked by significantly more variable sea surface conditions.

Mg/Ca and Sr/Ca ratios of planktonic foraminifera from North Atlantic surface sediments

Reliable temperature estimates from both surface and subsurface ocean waters are needed to reconstruct past upper water column temperature gradients and past oceanic heat content. This work examines the relationships between trace element ratios in fossil shells and seawater temperature for surface-dwelling foraminifera species, Globigerinoides ruber (white) and Globigerina bulloides, and deep-dwelling species, Globorotalia inflata, Globorotalia truncatulinoides (dextral and sinistral) and Pulleniatina obliquiloculata. Mg/Ca and Sr/Ca ratios in shells picked in 29 modern core tops from the North Atlantic Ocean are calibrated using calculated isotopic temperatures. Mg/Ca ratios on G. ruber and G. bulloides agree with published data and relationships. For deep-dwelling species, Mg/Ca calibration follows the equation Mg/Ca = 0.78 (±0.04) * exp (0.051 (±0.003) * T) with a significant correlation coefficient of R**2 = 0.74. Moreover, there is no significant difference between the different deep-dwellers analyzed. For the Sr/Ca ratio, the surface dwellers and P. obliquiloculata do not record any temperature dependence. For the Globorotalia species, the thermo dependence of Sr/Ca ratio can be described by a single linear relationship: Sr/Ca = (0.0182 (±0.001) * T) + 1.097 (±0.018), R**2 = 0.85. Temperature estimates with a 1 sigma error of ±2.0°C and ±1.3°C can be derived from the Mg/Ca and Sr/Ca ratios, respectively, as long as the Sr geochemistry in the ocean has been constant through time.