Chemical measurements from the EPICA Dome C core

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.

Data from the EPICA Dome C ice core EDC

The Antarctic Vostok ice core provided compelling evidence of the nature of climate, and of climate feedbacks, over the past 420,000 years. Marine records suggest that the amplitude of climate variability was smaller before that time, but such records are often poorly resolved. Moreover, it is not possible to infer the abundance of greenhouse gases in the atmosphere from marine records. Here we report the recovery of a deep ice core from Dome C, Antarctica, that provides a climate record for the past 740,000 years. For the four most recent glacial cycles, the data agree well with the record from Vostok. The earlier period, between 740,000 and 430,000 years ago, was characterized by less pronounced warmth in interglacial periods in Antarctica, but a higher proportion of each cycle was spent in the warm mode. The transition from glacial to interglacial conditions about 430,000 years ago (Termination V) resembles the transition into the present interglacial period in terms of the magnitude of change in temperatures and greenhouse gases, but there are significant differences in the patterns of change. The interglacial stage following Termination V was exceptionally long - 28,000 years compared to, for example, the 12,000 years recorded so far in the present interglacial period. Given the similarities between this earlier warm period and today, our results may imply that without human intervention, a climate similar to the present one would extend well into the future.

Stable isotope record of sediment cores from the North Atlantic

Abrupt and short climate changes, such as the Younger Dryas, punctuated the last glacial-to-interglacial transition (Ruddiman and McIntyre, 1981 doi:10.1016/0031-0182(81)90097-3; Duplessy et al., 1981 doi:10.1016/0031-0182(81)90096-1; Oeschger et al. 1984; Broecker et al., 1985 doi:10.1038/315021a0). Broecker et al. (1988 doi:10.1029/PA003i001p00001) proposed that these may have been caused by an interruption of thermohaline circulation as inputs of glacial meltwater freshened the surface waters of the North Atlantic. The finding (Fairbanks, 1989 doi:10.1038/342637a0) that meltwater discharge was minimal during the Younger Dryas, however, led to the suggestion that the surface-water salinity drop might have been caused instead by changes in the freshwater budget (the difference between precipitation and evaporation), accompanied by a reduction in poleward advection of saline subtropical water. Here we use micropalaeontological and stable-isotope records from foraminifera in two cores from the North Atlantic to generate two continuous, high-resolution records of sea surface temperature and salinity changes over the past 18,000 years. Despite the injection of glacial meltwater during warm episodes, we find that sea surface salinity and temperature remain positively correlated during deglaciation. Cold, low-salinity events occurred during the early stages of deglaciation (14,500-13,000 years ago) and the Younger Dryas, but the minor injections of meltwater at high latitudes during these events are insufficient to account for the observed salinity changes. We conclude that an additional feedback from changes in the hydrological cycle and in advection was necessary to trigger changes in thermohaline circulation and thus in climate. This feedback did not act when the meltwater injection occurred at low latitude.

Sea surface temperature reconstruction based on dinoflagellates from the North Atlantic

The application of quantitative and semiquantitative methods to assemblage data from dinoflagellate cysts shows potential for interpreting past environments, both in terms of paleotemperature estimates and in recognizing water masses and circulation patterns. Estimates of winter sea-surface temperature (WSST) were produced by using the Impagidinium Index (II) method, and by applying a winter-temperature transfer function (TFw). Estimates of summer sea-surface temperature (SSST) were produced by using a summer-temperature transfer function (TFs), two methods based on a temperature-distribution chart (ACT and ACTpo), and a method based on the ratio of gonyaulacoid:protoperidinioid specimens (G:P). WSST estimates from the II and TFw methods are in close agreement except where Impagidinium species are sparse. SSST estimates from TFs are more variable. The value of the G:P ratio for the Pliocene data in this paper is limited by the apparent sparsity of protoperidinioids, which results in monotonous SSST estimates of 14-26°C. The ACT methods show two biases for the Pliocene data set: taxonomic substitution may force 'matches' yielding incorrect temperature estimates, and the method is highly sensitive to the end-points of species distributions. Dinocyst assemblage data were applied to reconstruct Pliocene sea-surface temperatures between 3.5-2.5 Ma from DSDP Hole 552A, and ODP Holes 646B and 642B, which are presently located beneath cold and cool-temperate waters north of 56°N. Our initial results suggest that at 3.0 Ma, WSSTs were a few degrees C warmer than the present and that there was a somewhat reduced north-south temperature gradient. For all three sites, it is likely that SSSTs were also warmer, but by an unknown, perhaps large, amount. Past oceanic circulation in the North Atlantic was probably different from the present.

Chronology and stable carbon isotopic ratios of sediments from the Western Pacific Warm Pool region

Instrumental data suggest that major shifts in tropical Pacific atmospheric dynamics and hydrology have occurred within the past century, potentially in response to anthropogenic warming. To better understand these trends, we use the hydrogen isotopic ratios of terrestrial higher plant leaf waxes (DDwax) in marine sediments from southwest Sulawesi, Indonesia, to compile a detailed reconstruction of central Indo-Pacific Warm Pool (IPWP) hydrologic variability spanning most of the last two millennia. Our paleodata are highly correlated with a monsoon reconstruction from Southeast Asia, indicating that intervals of strong East Asian summer monsoon (EASM) activity are associated with a weaker Indonesian monsoon (IM). Furthermore, the centennial-scale oscillations in our data follow known changes in Northern Hemisphere climate (e.g., the Little Ice Age and Medieval Warm Period) implying a dynamic link between Northern Hemisphere temperatures and IPWP hydrology. The inverse relationship between the EASM and IM suggests that migrations of the Intertropical Convergence Zone and associated changes in monsoon strength caused synoptic hydrologic shifts in the IPWP throughout most of the past two millennia.

Composition of dikes and lavas from the Pito Deep Rift

The northwest trending walls of the Pito Deep Rift (PDR), a tectonic window in the southeast Pacific, expose in situ oceanic crust generated ?3 Ma at the superfast spreading southern East Pacific Rise (SEPR). Whole rock analyses were performed on over 200 samples of dikes and lavas recovered from two ~8 km**2 study areas. Most of the PDR samples are incompatible-element-depleted normal mid-ocean ridge basalts (NMORB; (La/Sm)N < 1.0) that show typical tholeiitic fractionation trends. Correlated variations in Pb isotope ratios, rare earth element patterns, and ratios of incompatible elements (e.g., (Ce/Yb)N) are best explained by mixing curves between two enriched and one depleted mantle sources. Pb isotope compositions of most PDR NMORB are offset from SEPR data toward higher values of 207Pb/204Pb, suggesting that an enriched component of the mantle was present in this region in the past ?3 Ma but is not evident today. Overall, the PDR crust is highly variable in composition over long and short spatial scales, demonstrating that chemically distinct lavas and dikes can be emplaced within the same segment over short timescales. However, the limited spatial distribution of high 206Pb/204Pb samples and the occurrence of relatively homogeneous MgO compositions (ranging <2.5 wt %) within a few of the individual dive transects (over distances of ~1 km) suggests that the mantle source composition evolved and magmatic temperatures persisted over timescales of tens of thousands of years. The high degree of chemical variability between pairs of adjacent dikes is interpreted as evidence for along-axis transport of magma from chemically distinct portions of the melt lens. Our findings suggest that lateral dike propagation occurs to a significant degree at superfast spreading centers.

Os and Re concentrations and Os isotope ratios for DSDP and ODP metalliferous sediments from the Pacific Ocean (Table 1)

We report new 187Os/186Os data and Re and Os concentrations in metalliferous sediments from the Pacific to construct a composite Os isotope seawater evolution curve over the past 80 m.y. Analyses of four samples of upper Cretaceous age yield 187Os/186Os values of between 3 and 6.5 and 187Re/186Os values below 55. Mass balance calculations indicate that the pronounced minimum of about 2 in the Os isotope ratio of seawater at the K-T boundary probably reflects the enormous input of cosmogenic material into the oceans by the K-T impactor(s). Following a rapid recovery to 187Os/186Os of 3.5 at 63 Ma, data for the early and middle part of the Cenozoic show an increase in 187Os/186Os to about 6 at 15 Ma. Variations in the isotopic composition of leachable Os from slowly accumulating metalliferous sediments show large fluctuations over short time spans. In contrast, analyses of rapidly accumulating metalliferous carbonates do not exhibit the large oscillations observed in the pelagic clay leach data. These results together with sediment leaching experiments indicate that dissolution of non-hydrogenous Os can occur during the hydrogen peroxide leach and demonstrate that Os data from pelagic clay leachates do not always reflect the Os isotopic composition of seawater. New data for the late Cenozoic further substantiate the rapid increase in the 187Os/186Os of seawater during the past 15 Ma. We interpret the correlation between the marine Sr and Os isotope records during this time period as evidence that weathering within the drainage basin of the Ganges-Brahmaputra river system is responsible for driving seawater Sr and Os toward more radiogenic isotopic compositions. The positive correlation between 87Sr/86Sr and U concentration, the covariation of U and Re concentrations, and the high dissolved Re, U and Sr concentrations found in the Ganges-Brahmaputra river waters supports this interpretation. Accelerating uplift of many orogens worldwide over the past 15 Ma, especially during the last 5 Ma, could have contributed to the rapid increase in 187Os/186Os from 6 to 8.5 over the past 15 Ma. Prior to 15 Ma the marine Sr and Os record are not tightly coupled. The heterogeneous distribution of different lithologies within eroding terrains may play an important role in decoupling the supplies of radiogenic Os and Sr to the oceans and account for the periods of decoupling of the marine Sr and Os isotope records.

Agricultural pesticide in sediment cores from the Lac de Saint-André, France

Agricultural pesticide use has increased worldwide during the last several decades, but the long-term fate, storage, and transfer dynamics of pesticides in a changing environment are poorly understood. Many pesticides have been progressively banned, but in numerous cases, these molecules are stable and may persist in soils, sediments, and ice. Many studies have addressed the question of their possible remobilization as a result of global change. In this article, we present a retro-observation approach based on lake sediment records to monitor micropollutants and to evaluate the long-term succession and diffuse transfer of herbicides, fungicides, and insecticide treatments in a vineyard catchment in France. The sediment allows for a reliable reconstruction of past pesticide use through time, validated by the historical introduction, use, and banning of these organic and inorganic pesticides in local vineyards. Our results also revealed how changes in these practices affect storage conditions and, consequently, the pesticides' transfer dynamics. For example, the use of postemergence herbicides (glyphosate), which induce an increase in soil erosion, led to a release of a banned remnant pesticide (dichlorodiphenyltrichloroethane, DDT), which had been previously stored in vineyard soil, back into the environment. Management strategies of ecotoxicological risk would be well served by recognition of the diversity of compounds stored in various environmental sinks, such as agriculture soil, and their capability to become sources when environmental conditions change.

Mg/Ca and stable oxygen measurement of the past 27 Ma of ODP Hole 120-747A

We explore the applicability of paired Mg/Ca and 18O/16O measurements on benthic foraminifera from Southern Ocean site 747 to paleoceanographic reconstructions on pre-Pleistocene timescales. We focus on the late Oligocene through Pleistocene (27-0 Ma) history of paleotemperatures and the evolution of the d18O values of seawater (d18Osw) at a temporal resolution of ~100-200 kyr. Absolute paleotemperature estimates depend on assumptions of how Mg/Ca ratios of seawater have changed over the past 27 Myr, but relative changes that occur on geologically brief timescales are robust. Results indicate that at the Oligocene to Miocene boundary (23.8 Ma), temperatures lag the increase in global ice-volume deduced from benthic foraminiferal d18O values, but the smaller-scale Miocene glaciations are accompanied by ocean cooling of -1°C. During the mid-Miocene phase of Antarctic ice sheet growth (~15-13 Ma), water temperatures cool by ~3°C. Unlike the benthic foraminiferal d18O values, which remain relatively constant thereafter, temperatures vary (by 3°C) and reach maxima at ~12 and ~8.5 Ma. The onset of significant Northern Hemisphere glaciation during the late Pliocene is synchronous with an ~4°C cooling at site 747. A comparison of our d18Osw curve to the Haq et al. (1987, doi:10.1126/science.235.4793.1156 ) sea level curve yields excellent agreement between sequence boundaries and times of increasing seawater 18O/16O ratios. At ~12-11 Ma in particular, when benthic foraminiferal d18O values do not support a further increase in ice volume, the d18Osw curve comes to a maximum that corresponds to a major mid-Miocene sea level regression. The agreement between the character of our Mg/Ca-based d18Osw curve and sequence stratigraphy demonstrates that benthic foramaniferal Mg/Ca ratios can be used to trace the d18Osw on pre-Pleistocene timescales despite a number of uncertainties related to poorly constrained temperature calibrations and paleoseawater Mg/Ca ratios. The Mg/Ca record also highlights that deep ocean temperatures can vary independently and unexpectedly from ice volume changes, which can lead to misinterpretations of the d18O record.

Holocene corals from the South China Sea

The South China Sea (SCS) is well connected with the western Pacific and influenced by the East Asian monsoon. We have examined temporal variations in radiocarbon marine reservoir ages (R) and regional marine reservoir corrections (DeltaR) of the SCS during the Holocene using paired measurements of AMS 14C and TIMS 230Th on 20 pristine corals. The results show large fluctuations in both R and DeltaR values over the past 7500 years (yrs) with two distinct plateaus during 7.5-5.6 and 3.5-2.5 thousand calendar years before present (cal ka BP). The respective weighted mean DeltaR values of these plateaus are 151 ± 85 and 89 ± 59 yrs, which are significantly higher than its modern value of -23 ± 52 yrs. This suggests that using a constant modern DeltaR value to calibrate 14C dates of the SCS marine samples will introduce additional errors to the calibrated ages. Our results provide the first database for the Holocene R and DeltaR values of the SCS for improved radiocarbon calibration of marine samples. We interpret the two DeltaR plateaus as being related to two intervals with weakened El Niño - Southern Oscillation (ENSO) and intensified East Asian summer monsoon (EASM). This is because the 14C content of the SCS surface water is controlled by both the 14C concentration of the Pacific North Equatorial Current (NEC) which is in turn influenced by ENSO-induced upwelling along the Pacific equator and vertical upwelling within the SCS as a result of moisture transportation to midlatitude region to supply the EASM rainfall.

Carbonate system of surface sediments from the South Pacific

B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].

Lithogenic sediment deposition of 7 sediment cores from the Pacific Southern Ocean

Dust deposition in the Southern Ocean constitutes a critical modulator of past global climate variability, but how it has varied temporally and geographically is underdetermined. Here, we present data sets of glacial-interglacial dust-supply cycles from the largest Southern Ocean sector, the polar South Pacific, indicating three times higher dust deposition during glacial periods than during interglacials for the past million years. Although the most likely dust source for the South Pacific is Australia and New Zealand, the glacial-interglacial pattern and timing of lithogenic sediment deposition is similar to dust records from Antarctica and the South Atlantic dominated by Patagonian sources. These similarities imply large-scale common climate forcings such as latitudinal shifts of the southern westerlies and regionally enhanced glaciogenic dust mobilization in New Zealand and Patagonia.

Magnetic susceptibility of deep-sea cores from the Scotia Sea

We studied two deep-sea cores from the Scotia Sea to reconstruct past atmospheric circulation in the southern hemisphere and to resolve a long-standing debate on the interpretation of magnetic susceptibility (MS) records in Southern Ocean (SO) sediment. High-sedimentation sites MD07-3134 (0.2 - 1.2 m/kyr) and MD07-3133 (0.3 - 2 m/kyr) cover the last 92.5 kyr and 36 kyr, respectively. Both exhibit a one-to-one coupling of the MS and Ca2+ signal to the non-sea salt (nss) Ca2+ signal of the EDML ice core, clearly identifying atmospheric circulation as means of distribution. Comparison of additional proxies also excludes major influence by volcanic sources, sea-ice, icebergs, or oceanic current transport. The close resemblance of the dust proxies over the last glacial cycle, in turn, allows for the establishment of an age model of unprecedented resolution and precision for SO deep-sea sediment because atmospheric transport involves no major leads or lags. This is of particular importance because MS is routinely measured on deep-sea cores in the SO but the sediments usually lack biogenic carbonate and therefore had only limited stratigraphic control so far. Southern South America (SSA) is the likely source of eolian material because Site MD07-3133, located closer to the continent, has slightly higher MS values than Site MD07-3134, and also the MS record of Patagonian Site SALSA shows comparable variability. Patagonia was the dust source for both the Scotia Sea and East Antarctica. Dust fluxes were several times higher during glacial times, when atmospheric circulation was either stronger or shifted in latitude, sea level was lowered, shelf surfaces were exposed, and environmental conditions in SSA were dominated by glaciers and extended outwash plains. Hence, MS records of SO deep-sea sediment are reliable tracers of atmospheric circulation, allowing for chronologically-constrained reconstructions of the circum Antarctic paleoclimate history.

Compilation of quality controlled nutrient profiles from the Mediterranean Sea

In the last decades, a striking amount of hydrographic data, covering the most part of Mediterranean basin, have been generated by the efforts made to characterize the oceanography and ecology of the basin. On the other side, the improvement in technologies, and the consequent perfecting of sampling and analytical techniques, provided data even more reliable than in the past. Nutrient data enter fully in this context, but suffer of the fact of having been produced by a large number of uncoordinated research programs and of being often deficient in quality control, with data bases lacking of intercalibration. In this study we present a computational procedure based on robust statistical parameters and on the physical dynamic properties of the Mediterranean sea and its morphological characteristics, to partially overcome the above limits in the existing data sets. Through a data pre filtering based on the outlier analysis, and thanks to the subsequent shape analysis, the procedure identifies the inconsistent data and for each basin area identifies a characteristic set of shapes (vertical profiles). Rejecting all the profiles that do not follow any of the spotted shapes, the procedure identifies all the reliable profiles and allows us to obtain a data set that can be considered more internally consistent than the existing ones.

Geochemical data and magnetic measurements of IODP Expedition 308, Hole U1319A from the Gulf of Mexico

A 160 m mostly turbiditic late Pleistocene sediment sequence (IODP Expedition 308, Hole U1319A) from the Brazos-Trinity intraslope basin system off Texas was investigated with paleo- and rock magnetic methods. Numerous layers depleted in iron oxides and enriched by the ferrimagnetic iron-sulfide mineral greigite (Fe3S4) were detected by diagnostic magnetic properties. From the distribution of these layers, their stratigraphic context and the present geochemical zonation, we develop two conceptual reaction models of greigite formation in non-steady depositional environments. The "sulfidization model" predicts single or twin greigite layers by incomplete transformation of iron monosulfides with polysulfides around the sulfate methane transition (SMT). The "oxidation model" explains greigite formation by partial oxidation of iron monosulfides near the iron redox boundary during periods of downward shifting oxidation fronts. The stratigraphic record provides evidence that both these greigite formation processes act here at typical depths of about 12-14 mbsf and 3-4 mbsf. Numerous "fossil" greigite layers most likely preserved by rapid upward shifts of the redox zonation denote past SMT and sea floor positions characterized by stagnant hemipelagic sedimentation conditions. Six diagenetic stages from a pristine magnetite-dominated to a fully greigite-dominated magnetic mineralogy were differentiated by combination of various hysteresis and remanence parameters.