Sr/Ca ratios of Cenozoic benthic foraminifera

A Cenozoic multi-species record of benthic foraminiferal calcite Sr/Ca has been produced and is corrected for interspecific offsets (typically less than 0.3 mmol/mol) and for the linear relationship between decreasing benthic foraminiferal Sr/Ca and increasing water depth. The water depth correction, determined from Holocene, Late Glacial Maximum and Eocene paleowater-depth transects, is ~0.1 mmol/mol/km. The corrected Cenozoic benthic foraminiferal Sr/Ca record ranges from 1.2 to 2.0 mmol/mol, and has been interpreted in terms of long-term changes in seawater Sr/Ca, enabling issues related to higher-resolution variability in Sr/Ca to be ignored. We estimate that seawater Sr/Ca was ~1.5 times modern values in the late Cretaceous, but declined rapidly into the Paleogene. Following a minimum in the Eocene, seawater Sr/Ca increased gradually through to the present day with a minimum superimposed on this trend centered in the late Miocene. By assuming scenarios for changing seawater calcium concentration, and using published carbonate accumulation rate data combined with suitable values for Sr partition coefficients into carbonates, the seawater Sr/Ca record is used to estimate global average river Sr fluxes. These fluxes are used in conjunction with the seawater strontium isotope curve and estimates of hydrothermal activity/tectonic outgassing to calculate changes in global average river 87Sr/86Sr through the Cenozoic. The absolute magnitude of Sr fluxes and isotopic compositions calculated in this way are subject to relatively large uncertainties. Nevertheless, our results suggest that river Sr flux increased from 35 Ma to the present day (roughly two-fold) accompanied by an overall increase in 87Sr/86Sr (by ~0 to 0.001). Between 75 and 35 Ma, river 87Sr/86Sr also increased (by ~0.001 to 0.002) but was accompanied by a decrease (two- to three-fold) in river Sr flux.

Delta 66Zn ratios and age of carbonates from ODP Site 138-849 (Table 1)

The carbonate fraction of sediment core ODP 849, leg 138, located in the eastern equatorial Pacific, mostly consisting of coccoliths, was separated and analyzed for its Zn isotopic composition. The overall variation in Zn isotopic composition, as determined by multiple-collector, magnetic-sector, inductively coupled plasma mass spectrometry, was found to be on the order of 1? (expressed in delta66Zn, where deltaxZn=[(xZn/64Zn)sample/(xZn/64Zn)standard -1]*10**3 and x=66, 67 or 68) over the last 175 ka. The analytical precision was 0.04 per mil and the overall reproducibility was usually better than 0.07 per mil. The Zn isotopic composition signal exhibits several marked peaks and a high-frequency variability. A periodogram of the delta66Zn signal showed two periodicities of 35.2 and 21.2 ka. We suggest that the latter is caused by the precession of the Earth's axis of rotation. The periodogram exhibits a minimum at 41.1 ka, thus showing that the Zn isotopic composition is independent of the obliquity in the eastern equatorial Pacific. The range of delta66Zn values observed for the carbonate fraction of ODP 849 overlaps with the range observed for Fe-Mn nodules in the world's oceans, which suggests that seawater/carbonate Zn isotope fractionation is weak. We therefore assume that most of the Zn isotope variability is a result of the selective entrainment of the light isotopes by organic matter in the surface ocean. The ODP 849 delta66Zn record seems to follow the changes in the insolation cycles. Changes in the late summer/fall equatorial insolation modulate the intensity of the equatorial upwelling, hence the mixing between deep and surface waters. We propose that during decreased summer/fall equatorial insolation, when a steep thermocline can develop (El Niño-like conditions), the surface waters cannot be replenished by deep waters and become depleted in the lighter Zn isotopes by biological activity, thus resulting in the progressive increase of the delta66Zn values of the carbonate shells presumably in equilibrium with surface seawater.

Enzyme activity and liver tissue PCB concentrations of chicks of northern fulmars (F. glacialis) and black-legged kittiwakes (R. tridactyla) from Kongsfjorden

Arctic seabirds are exposed to a wide range of halogenated organic contaminants (HOCs). Exposure occurs mainly through food intake, and many pollutants accumulate in lipid-rich tissues. Little is known about how HOCs are biotransformed in arctic seabirds. In this study, we characterized biotransformation enzymes in chicks of northern fulmars (Fulmarus glacialis) and black-legged kittiwakes (Rissa tridactyla) from Kongsfjorden (Svalbard, Norway). Phase I and II enzymes were analyzed at the transcriptional, translational and activity levels. For gene expression patterns, quantitative polymerase chain reactions (qPCR), using gene-sequence primers, were performed. Protein levels were analyzed using immunochemical assays of western blot with commercially available antibodies. Liver samples were analyzed for phase I and II enzyme activities using a variety of substrates including ethoxyresorufin (cytochrome (CYP)1A1/1A2), pentoxyresorufin (CYP2B), methoxyresorufin (CYP1A), benzyloxyresorufin (CYP3A), testosterone (CYP3A/CYP2B), 1-chloro-2,4-nitrobenzene (CDNB) (glutathione S-transferase (GST)) and 4-nitrophenol (uridine diphosphate glucuronyltransferase (UDPGT)). In addition, the hydroxylated (OH-) polychlorinated biphenyls (PCBs) were analyzed in the blood, liver and brain tissue, whereas the methylsulfone (MeSO2-) PCBs were analyzed in liver tissue. Results indicated the presence of phase I (CYP1A4/CYP1A5, CYP2B, and CYP3A) and phase II (GST and UDPGT) enzymes at the activity, protein and/or mRNA level in both species. Northern fulmar chicks had higher enzyme activity than black-legged kittiwake chicks. This in combination with the higher XOH-PCB to parent PCB ratios suggests that northern fulmar chicks have a different biotransformation capacity than black-legged kittiwake chicks.

Uranium concentrations and isotope ratios Bahamas seawater and ODP holes pore-water

The geometry, timing, and rate of fluid-flow through carbonate margins and platforms is not well constrained. In this study, we use U concentrations and isotope ratios measured on small volumes of pore-water from Bahamas slope sediment, coupled with existing chlorinity data, to place constraints on the fluid-flow in this region and, by implication, other carbonate platforms. These data also allow an assessment of the behaviour of U isotopes in an unusually well constrained water-rock system. We report pore-water U concentrations which are controlled by dissolution of high-U organic material at shallow depths in the sediment and by reduction of U to its insoluble 4+ state at greater depths. The dominant process influencing pore-water (234U/238U) is alpha recoil. In Holocene sediments, the increase of pore-water (234U/238U) due to recoil provides an estimate of the horizontal flow rate of 11 cm/year, but with considerable uncertainty. At depths in the sediment where conditions are reducing, features in the U concentration and (234U/238U) profiles are offset from one another which constrains the effective diffusivity for U in these sediments to be c. 1-2 * 10**-8 cm**2/s. At depths between the Holocene and these reducing sediments, pore-water (234U/238U) values are unusually low due to a recent increase in the dissolution rate of grain surfaces. This suggests a strengthening of fluid flow, probably due to the flooding of the banks at the last deglaciation and the re-initiation of thermally-driven venting of fluid on the bank top and accompanying recharge on the slopes. Interpretation of existing chlorinity data, in the light of this change in flow rate, constrain the recent horizontal flow rate to be 10.6 ( 3.4) cm/year. Estimates of flow rate from (234U/238U) and Cl[-] are therefore in agreement and suggest flow rates close to those predicted by thermally-driven models of fluid flow. This agreement supports the idea that flow within the Bahamas Banks is mostly thermally driven and suggests that flow rates on the order of 10 cm/year are typical for carbonate platforms where such flow occurs.

Ages and stable isotope ratios from speleothem calcite from Cold Water Cave, Iowa

High-precision uranium-thorium mass spectrometric chronology and 18O-13C isotopic analysis of speleothem calcite from Cold Water Cave in northeast Iowa have been used to chart mid-Holocene climate change. Significant shifts in d18O and d13C isotopic values coincide with well-documented Holocene vegetation changes. Temperature estimates based on 18O/16O ratios suggest that the climate warmed rapidly by about 3°C at 5900 years before present and then cooled by 4°C at 3600 years before present. Initiation of a gradual increase in ?d13C at 5900 years before present suggests that turnover of the forest soil biomass was slow and that equilibrium with prairie vegetation was not attained by 3600 years before present.

Geochemistry, isotopic ratios, granulometry and Uk'37 derived SST of cores obtained during Poseidon cruise POS287, off Portugal

Continental and marine conditions during the last millennium off Porto, Portugal (the southern pole of the North Atlantic Oscillation, NAO), are reconstructed from a sediment archive through a high-resolution multiproxy study and instrumental evidence. Results show multidecadal variability and sea surface temperatures (SSTs) that correlate well with previously published land and sea-based Northern Hemisphere temperature records, and appear to be responding to long-term solar insolation variability. Precipitation was negatively correlated with the NAO, whereas strong flooding events occurred at times of marked climate cooling (AD 1100-1150 and 1400-1470) and transitions in solar activity. AD 1850 marks a major shift in the phytoplankton community associated with a decoupling of d18O records of 3 planktonic foraminifera species. These changes are interpreted as a response to a reduction in the summer and/or annual upwelling and more frequent fall-winter upwelling-like events. This shift's coincidence with a decrease in SST and the increase in coherence between our data and the Atlantic Multidecadal Oscillation (AMO) confirms the connection of the upwelling variability to the North Atlantic Ocean's surface and thermohaline circulation on a decadal scale. The disappearance of this agreement between the AMO and our records beyond AD 1850 and its coincidence with the beginning of the recent rise in atmospheric CO2 supports the hypothesis of a strong anthropogenic effect on the last ~150 yr of the climate record. Furthermore, it raises an important question of the use of instrumental records as the sole calibration data set for climate reconstructions, as these may not provide the best analogue for climate beyond AD 1730.

Compilation of 231Protactinium/230 Thorium excess ratios in various surface sediment samples from the South Atlantic

In large areas of the world's oceans, there is a relationship between the mass flux of particulate matter and the unsupported 231Pa/230Th (xs231Pa/xs230Th) activity ratio of recent sediments. This observation forms the basis for using the xs231Pa/xs230Th ratio as a proxy for past changes in export productivity. However, a simple relationship between xs231Pa/xs 230Th ratio and particle flux requires that the water residence time in an ocean basin is far in excess of the scavenging residence time of 231Pa, and that the composition of sinking particles maintains a strong preference for the adsorption of 230Th over 231Pa with a constant 230Th/231Pa fractionation factor (F). The best correlation between xs231Pa/xs230Th ratio and mass flux is found in the Pacific Ocean. In the Atlantic, the contrast in the xs231Pa/xs230Th ratios between open ocean (low flux regions) and ocean margins (high flux regions) is much less pronounced due to the shorter residence time of deep water, resulting in less effective boundary scavenging of 231Pa. In the Southern Ocean, south of the Polar Front, there is no more a simple relationship between xs231Pa/xs230Th and particle flux. This is a result of a southward decrease in F, probably reflecting the increased opal content of sinking particles. Opal does not fractionate 231Pa and 230Th significantly. This lack of fractionation results in high xs231Pa/xs230Th ratios in opal-dominated regions, even in areas of very low particle fluxes such as the Weddell Sea. The xs231Pa/xs230Th ratio can therefore only be used as a paleoproductivity proxy if, in the time interval of interest, changes in the basin ventilation rate and differential scavenging of both radionuclides due to changes in the chemical composition of particulate matter can be excluded.

Stable isotope record and trace element ratios of Eocene and Oligocene foraminifers from ODP Site 120-748

Stable carbon and oxygen isotope analyses were conducted on well-preserved planktonic and benthic foraminifers from a continuous middle Eocene to Oligocene sequence at Ocean Drilling Program (ODP) Site 748 on the Kerguelen Plateau. Benthic foraminifer d18O values show a 1.0 per mil increase through the middle and upper Eocene, followed by a rapid 1.2 per mil increase in the lowermost Oligocene (35.5 Ma). Surface-dwelling planktonic foraminifer d18O values increase in the lowermost Oligocene, but only by 0.6 per mil whereas intermediate-depth planktonic foraminifers show an increase of about l.0 per mil. Benthic foraminifer d13C values increase by 0.9 per mil in the lowermost Oligocene at precisely the same time as the large d18O increase, whereas planktonic foraminifer d13C values show little or no change. Site 748 oxygen isotope and paleontological records suggest that southern Indian Ocean surface and intermediate waters underwent significant cooling from the early to late Eocene. The rapid 1.2 per mil oxygen isotope increase recorded by benthic foraminifers just above the Eocene/Oligocene boundary represents the ubiquitous early Oligocene d18O event. The shift here is unique, however, as it coincided with the sudden appearance of ice-rafted debris (IRD), providing the first direct link between Antarctic glacial activity and the earliest Oligocene d18O increase. The d18O increase caused by the ice-volume change in the early Oligocene is constrained by (1) related changes in the planktonic to benthic foraminifer d18O gradient at Site 748 and (2) comparisons of late Eocene and early Oligocene planktonic foraminifer d18Ovalues from various latitudes. Both of these records indicate that 0.3 per mil to 0.4 per mil of the early Oligocene d18O increase was ice-volume related.

Strontium isotope ratios of middle Eocene to Oligocene sediments from Maud Rise, Antarctica

A 87Sr/86Sr isotope curve of the middle Eocene to Oligocene was produced from analysis of foraminifera in Ocean Drilling Program Hole 689B, Maud Rise, near the coast of Antarctica. Sediments from the hole are well preserved with no evidence of diagenetic alteration. The sequence is nearly complete from 46.3 to 24.8 Ma, with an average sampling interval of 166 kyr. Excellent magnetostratigraphy in Hole 689B allows calibration to the geomagnetic polarity time scale of Cande and Kent (1992). Marine strontium isotopic ratios were nearly stable from 46.3 to 35.5 Ma, averaging near 0.70773, after which they began to increase. A slow increase began after 40.4 Ma, rising at a rate of only about 8*10**-6/m.y. from base values of 0.707707. From 35.5 Ma to 24.8 Ma the average slope increased to 40*10**-6/m.y. The slope remained constant at least until 24.8 Ma, when the record becomes discontinuous owing to unconformities. We evaluate several possible controls on the marine strontium isotope curve that could have led to the observed growth in 87Sr/86Sr ratios near the Eocene/Oligocene boundary. Three mechanisms are considered, including the onset of Antarctic glaciation, increased mountain building in the Himalayan-Tibetan region, and decreased hydrothermal activity. None of the mechanisms alone seems to adequately explain the increased 87Sr/86Sr ratios during the Oligocene. Glaciation as a weathering agent was too episodic and probably began too late to explain the upturn in marine 87Sr/86Sr ratios. There is evidence that uplift in the Himalayan-Tibetan region began in the Miocene, much too late to control Oligocene strontium isotope ratios. Lastly, hydrothermal flux changes since the Eocene were apparently not great enough alone to account for the rise in marine 87Sr/86Sr ratios. We suggest that a combination of causes, such as decreased hydrothermal activity perhaps followed by increased glaciation and mountain building, might best explain the growth of the marine 87Sr/86Sr curve during the Oligocene.

Rare-earth elements and isotope ratios at DSDP Leg 82 Holes

We report 48 analyses of rare-earth elements (REE) and 15 143Nd/144Nd and 87Sr/86Sr analyses for basalts from the eight holes drilled during Leg 82. Discrete and distinct REE patterns and 143Nd/144Nd ratios characterize the eight holes, with little variation observed downhole except in Holes 561 and 558, thus suggesting dominantly long-term temporal and large-scale spatial variations in the mantle source of these basalts beneath the Mid-Atlantic Ridge over the last 35 Ma of its spreading activity. There is a good inverse correlation between 143Nd/144Nd and (La/Sm)EF with one exception in Hole 558 (approximately 35 Ma), the latter suggesting a recent (35 Ma) light REE depletion event, perhaps caused by dynamic or fractional melting. Short-term temporal and small-scale spatial mantle source variability is also evident in Hole 561 (approximately 18 Ma), which has rapid fluctuations in REE patterns and 143Nd/144Nd ratios (suggesting rapid transfer of magma from the time of melting) and is evidence contrary to the presence of a well-mixed magma chamber at this particular site and time. The mantle source variations noted can be interpreted within two extreme models. The first model invokes a convecting mantle depleted in large ion lithophile elements (LILE) and containing lumps (or veins) of LILE-enriched material of various shapes and sizes, passively and randomly distributed throughout. A second more restrictive model considers the interaction of fixed mantle plumes and the LILE-depleted asthenosphere flowing towards a migrating Mid- Atlantic Ridge (MAR) axis. With the exception of Hole 558 and the uncertainties of reconstructions of absolute plate movements in the region, the observed variations can be explained by two hot spots; the nearly ridge-centered Azores hot spot (plume) and another hot spot located beneath the African plate that may be affecting the source of basalts currently erupting at the MAR axis at 35°N and which, in the past, would have produced the New England chain of seamounts on the North American plate and (later) the Atlantis-Great Meteor chain on the African plate. Basalts erupted south of the Hayes Fracture Zone have not been affected by either of these two hot spots over the last 35 Ma and appear to have been continuously derived from the LILE-depleted source. Subaxial flow downridge from the Azores plume appears to have started 9 Ma, on the basis of the southward converging V-shaped time-transgressive ridges branching from the Pico and Corves Island, or not earlier than 16 Ma, on the basis of the geochemical results. Variations within Hole 558 remains unexplained by the latter model, unless we hypothesize a third hot spot.

137Cs and 90Sr depositions, and 137Cs/90Sr ratios of samples from the Kraton-3 underground nuclear explosion site, Russia

Strontium-90 activity concentrations in surface soils and areal deposition densities have been studied at a site contaminated by an accidental release to atmosphere from the underground nuclear explosion 'Kraton-3' conducted near the Polar Circle (65.9°N, 112.3°E) within the territory of the former USSR in 1978. In 2001-2002, the ground surface contamination at 14 plots studied ranged from 20 to 15000 kBq/m**2, which significantly exceeds the value of 0.44 kBq/m**2 deduced for three background plots. The zone with substantial radiostrontium contamination extends, at least, 2.5 km in a north-easterly direction from the borehole. The average 137Cs/90Sr ratio in the ground contamination originated from the 'Kraton-3' fallout was estimated to be 0.55, which is significantly different from the ratio of 2.05 evaluated for background plots contaminated mostly from global fallout. Although vertical migration of 90Sr in all undisturbed soil profiles studied is more rapid than that for 137Cs, the depth of percolation of both radionuclides into the ground is mostly limited to the top 10-20 cm, which may be explained, primarily, by permafrost conditions. The horizontal migration rate of radiostrontium in the aqueous phase exceeds the radiocaesium migration rate by many times. This phenomenon seems to be a reason for the significant enrichment of the soil surface layers by radiostrontium at some sites, with variations occurring in accordance with small-scale irregularities of landscape.

Geochemistry and isotopic ratios of boninites and related rocks of the Izu-Bonin Forearc

Twenty-six samples representing the wide range of lithologies (low- and intermediate-Ca boninites and bronzite andesites, high-Ca boninites, basaltic andesites-rhyolites) drilled during Leg 125 at Sites 782 and 786 on the Izu-Bonin outer-arc high have been analyzed for Sr, Nd, and Pb isotopes. Nd-Sr isotope covariations show that most samples follow a trend parallel to a line from Pacific MORB mantle (PMM) to Pacific Volcanogenic sediment (PVS) but displaced slightly toward more radiogenic Sr. Pb isotope covariations show that all the Eocene-Oligocene samples plot along the Northern Hemisphere Reference Line, indicating little or no Pb derived from subducted pelagic sediment in their source. Two young basaltic andesite clasts within sediment do have a pelagic sediment signature but this may have been gained by alteration rather than subduction. In all isotopic projections, the samples form consistent groupings: the tholeiites from Site 782 and Hole 786A plot closest to PMM, the boninites and related rocks from Sites 786B plot closest to PVS, and the boninite lavas from Hole 786A and late boninitic dikes from Hole 786B occupy an intermediate position. Isotope-trace element covariations indicate that these isotopic variations can be explained by a three-component mixing model. One component (A) has the isotopic signature of PMM but is depleted in the more incompatible elements. It is interpreted as representing suboceanic mantle lithosphere. A second component (B) is relatively radiogenic (epsilon-Nd = ca 4-6; 206Pb/204Pb = ca 19.0-19.3; epsilon-Sr = ca -10 to -6)). Its trace element pattern has, among other characteristics, a high Zr/Sm ratio, which distinguishes it from the ìnormalî fluid components associated with subduction and hotspot activity. There are insufficient data at present to tie down its origin: probably it was either derived from subducted lithosphere or volcanogenic sediment fused in amphibolite facies; or it represents an asthenospheric melt component that has been fractionated by interaction with amphibole-bearing mantle. The third component (C) is characterized by high contents of Sr and high epsilon-Sr values and is interpreted as a subducted fluid component. The mixing line on a diagram of Zr/Sr against epsilon-Sr suggests that component C may have enriched the lithosphere (component A) before component B. These components may also be present on a regional basis but, if so, may not have had uniform compositions. Only the boninitic series from nearby Chichijima would require an additional, pelagic sediment component. In general, these results are consistent with models of subduction of ridges and young lithosphere during the change from a ridge-transform to subduction geometry at the initiation of subduction in the Western Pacific.

Radionuclide concentrations, ratios, and derived ages of massive sulfides from ODP Leg 139 and Leg 169 sites

Massive sulfide samples from the Bent Hill area were analyzed for 230Th/234U and 231Pa/235U disequilibria. Apparent ages calculated from these ratios are between 8.2 and >300 ka. Concordant ages were found for only three samples that originate near the surface from the clastic sulfide zone and suggest "true" ages of between 8.5 and 16.0 ka (mean of 230Th and 231Pa ages). The uranium vs. depth distribution in the Bent Hill Massive Sulfide deposit suggests an open system for uranium for the deeper part of the deposit, which was probably caused by extensive recrystallization processes inhibiting true age determinations.