Isotope characterisation of Villars Cave stalagmites

We present a new mid-latitude speleothem record of millennial-scale climatic variability during OIS3 from the Villars Cave that, combined with former published contemporaneous samples from the same cave, gives a coherent image of the climate variability in SW-France between ~55 ka and ~30 ka. The 0.82 m long stalagmite Vil-stm27 was dated with 26 TIMS U-Th analyses and its growth curve displays variations that are linked with the stable isotopes, both controlled by the climatic conditions. It consists in a higher resolved replicate of the previously published Vil-stm9 and Vil-stm14 stalagmites where Dansgaard-Oeschger (DO) events have been observed. The good consistency between these three stalagmites and the comparison with other palaoeclimatic reconstructions, especially high resolution pollen records (ODP 976 from the Alboran Sea, Monticchio Lake record from southern Italy) and the nearby MD04-2845 Atlantic Ocean record, permits to draw a specific climatic pattern in SW-France during the OIS3 and to see regional differences between these sites. Main features of this period are: 1) warm events corresponding to Greenland Interstadials (GIS) that are characterized by low speleothem d13C, high temperate pollen percentages, warm temperatures and high humidity; among these events, GIS#12 is the most pronounced one at Villars characterized by an abrupt onset at ~46.6 ka and a duration of about 2.5 ka. The other well individualized warm event coincides with GIS#8 which is however much less pronounced and occurred during a cooler period as shown by a lower growth rate and a higher d13C; 2) cold events corresponding to Greenland Stadials (GS) that are clearly characterized by high speleothem d13C, low temperate pollen abundance, low temperature and enhanced dryness, particularly well expressed during GS coinciding with Heinrich events H5 and H4. The main feature of the Villars record is a general cooling trend between the DO#12 event ~45.5 ka and the synchronous stop of the three stalagmites at ~30 ka ±1, with a first well marked climatic threshold at ~41 ka after which the growth rate and the diameter of all stalagmites slows down significantly. This climatic evolution differs from that shown at southern Mediterranean sites where this trend is not observed. The ~30 ka age marks the second climatic threshold after which low temperatures and low rainfalls prevent speleothem growth in the Villars area until the Lateglacial warming that occurred at ~16.5 ± 0.5 ka. This 15 ka long hiatus, as the older Villars growth hiatus that occurred between 67.4 and 61 ka, are linked to low sea levels, reduced ocean circulation and a southward shift of the Polar Front that likely provoked local permafrost formation. These cold periods coincide with both low summer 65°N insolation, low atmospheric CO2 concentration and large ice sheets development (especially the Fennoscandian).

U and Th concentrations and isotope ratios of samples from ODP Leg 166

Constraining the history of seawater (234U/238U) is important because this ratio is used to assess the validity of U/Th ages, and because it provides information about the past rate of physical weathering on the continents. This study makes use of U-rich slope sediments from the Bahamas in an attempt to reconstruct seawater (234U/238U) for the last 800 kyr. For the last 360 kyr, U/Th dating of these sediments provides ages and initial (234U/238U) values. Sixty-seven samples, largely from marine highstands, have initial (234U/238U) which scatter somewhat about the modern seawater value (~1.145) but neither this scatter nor the average value increases with age of sample. These data contrast with published coral data and suggest that seawater (234U/238U) has remained within 15? of the modern value for the last 360 kyr. This confirms the rejection of coral U/Th ages where the initial (234U/238U) is significantly different from modern seawater. Data from older highstands, dated with delta18O stratigraphy or by the presence of the Brunhes/Matuyama (B/M) reversal at 780 kyr, allow seawater (234U/238U) to be assessed prior to the range of the 230Th chronometer. Unfortunately, diagenetic scatter in the data between the B/M reversal and 360 kyr is rather large, probably relating to low U concentrations for these samples. But there is no indication of a trend in seawater (234U/238U) with age. High U samples from close to the B/M reversal show less diagenetic scatter and an initial (234U/238U) that averages 1.102. This lower value can be explained by lower seawater (234U/238U) at the time of the B/M reversal, or by progressive loss of 234U from the sediment by alpha-recoil. A simple box model is presented to illustrate the response of seawater (234U/238U) to variations in riverine input, such as might be caused by changes in continental weathering. Comparison of the Bahamas (234U/238U) data with model results indicates that riverine (234U/238U) has not varied by more than 65? for any 100 kyr period during the last 360 kyr. It also indicates that the ratio of physical to chemical weathering on the continents has not been higher than at present for any extended period during the last 800 kyr.

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.

Neodymium isotope signature of Holocene corals

The neodymium isotopic composition of marine precipitates is increasingly recognized as a powerful tool for identifying changes in ocean circulation and mixing on million year to millennial timescales. Unlike nutrient proxies such as ?13C or Cd/Ca, Nd isotopes are not thought to be altered in any significant way by biological processes, and thus they can serve as a quasi-conservative water mass tracer. However, the application of Nd isotopes in understanding the role of thermohaline circulation in rapid climate change is currently hindered by the lack of direct constraints on the signature of the North Atlantic end-member through time. Here we present the first results of Nd isotopes measured in U-Th-dated deep-sea corals from the New England seamounts in the northwest Atlantic Ocean. Our data are consistent with the conclusion that the Nd isotopic composition of North Atlantic deep and intermediate water has remained nearly constant through the last glacial cycle. The results address long-standing concerns that there may have been significant changes in the Nd isotopic composition of the North Atlantic end-member during this interval and substantiate the applicability of this novel tracer on millennial timescales for paleoceanography research.

Element and isotope composition of selected volcanics from the Bicol arc, Philippines

Pliocene to recent volcanic rocks from the Bulusan volcanic complex in the southern part of the Bicol arc (Philippines) exhibit a wide compositional range (medium- to high-K basaltic-andesites, andesites and a dacite/rhyolite suite), but are characterised by large ion lithophile element enrichments and HFS element depletions typical of subduction-related rocks. Field, petrographic and geochemical data indicate that the more silicic syn- and post-caldera magmas have been influenced by intracrustal processes such as magma mixing and fractional crystallisation. However, the available data indicate that the Bicol rocks as a group exhibit relatively lower and less variable 87Sr/86Sr ratios (0.7036-0.7039) compared with many of the other subduction-related volcanics from the Philippine archipelago. The Pb isotope ratios of the Bicol volcanics appear to be unlike those of other Philippine arc segments. They typically plot within and below the data field for the Philippine Sea Basin on 207Pb/204Pb versus 206Pb/204Pb and 208Pb/204Pb versus 206Pb/204Pb diagrams, implying a pre-subduction mantle wedge similar to that sampled by the Palau Kyushu Ridge, east of the Philippine Trench. 143Nd/144Nd ratios are moderately variable (0.51285-0.51300). Low silica (<55 wt%) samples that have lower 143Nd/144Nd tend to have high Th/Nd, high Th/Nb, and moderately low Ce/Ce* ratios. Unlike some other arc segments in the Philippines (e.g. the Babuyan-Taiwan segment), there is little evidence for the involvement of subducted terrigenous sediment. Instead, the moderately low 143Nd/144Nd ratios in some of the Bicol volcanics may result from subduction of pelagic sediment (low Ce/Ce*, high Th/Nd, and high Th/Nb) and its incorporation into the mantle wedge via a slabderived partial melt.

Uranium contents and isotope ratios of uranium and strontium in sediments, leachates and pore fluids from ODP Hole 162-984A

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%). The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by a-recoil injection of 234Th. The fraction of 238U decays that result in a-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 0.0000004 to 0.000002 1/yr. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 1000 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials. The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ~ 0.1 1/age for ages spanning 1000 to 500,000,000 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.