Abundances and d13C values of n-alkanes extracted from sediment samples of ODP Hole 116-717C

Siwalik paleosol and Bengal Fan sediment samples were analyzed for the abundance and isotopic composition of n-alkanes in order to test for molecular evidence of the expansion of C4 grasslands on the Indian subcontinent. The carbon isotopic compositions of high-molecular-weight alkanes in both the ancient soils and sediments record a shift from low d13C values (ca. -30 per mil) to higher values (ca. -22 per mil) prior to 6 Ma. This shift is similar in magnitude to that recorded by paleosol carbonate and fossil teeth, and is consistent with a relatively rapid transition from dominantly C3 vegetation to an ecosystem dominated by C4 plants typical of semi-arid grasslands. The n-alkane values from our paleosol samples indicate that the isotopic change began as early as 9 Ma, reflecting either a growing contribution of C4 plants to a dominantly C3 biomass or a decrease in water availability to C3 plants. Molecular and isotopic analyses of other compounds, including n-alcohols and low-molecular weight n-alkanes indicate paleosol organic matter contains contributions from a mixture of sources, including vascular plants, algae and/or cyanobacteria and microorganisms. A range of inputs is likewise reflected in the isotopic composition of the total organic carbon from these samples. In addition, the n-alkanes from two samples show little evidence for pedegenic inputs and we suggest the compounds were derived instead from the paleosol's parent materials. We suggest the record of vegetation in ancient terrestrial ecosystems is better reconstructed using isotopic signatures of molecular markers, rather than bulk organic carbon. This approach provides a means of expanding the spatial and temporal records of C4 plant biomass which will help to resolve possible tectonic, climatic or biological controls on the rise of this important component of the terrestrial biosphere.

Organic geochemistry of sediment samples from Prydz Bay

High molecular weight aliphatic hydrocarbons were extracted from sediments at two sites (741 and 742) drilled during Ocean Drilling Program Leg 119 in Prydz Bay, a major embayment on the continental shelf of East Antarctica. The distributions of n-alkanes and triterpenoid and steroid hydrocarbons suggest that the n-alkanes and steranes are mainly of terrestrial origin and that the hydrocarbons are immature to slightly mature in the Lower Cretaceous sediments and immature to mature in the Tertiary sediments. At Site 741, the Lower Cretaceous depositional sequence, which is generally characterized by immature hydrocarbons, is interrupted by sediment having more mature components, suggesting a change of source during part of Early Cretaceous time. At Site 742, the mature geochemical parameters of a Pliocene sample correlate with results reported elsewhere for Site 739. In all but one of the other Tertiary samples, the geochemical parameters indicate intermediate maturity. The Lower Cretaceous and Pliocene sediments average about 1.9% organic carbon, a value of interest from the point of view of potential sources of petroleum offshore from Antarctica.

Geochemical provenance analysis of fine-grained sediment of sediment core AND1-1

Bulk chemical fine-grained sediment compositions from southern Victoria Land glacimarine sediments provide significant constraints on the reconstruction of sediment provenance models in the McMurdo Sound during Late Cenozoic time. High-resolution (~ 1 ka) geochemical data were obtained with a non-destructive AVAATECH XRF Core Scanner (XRF-CS) on the 1285 m long ANDRILL McMurdo Ice Shelf Project (MIS) sediment core AND-1B. This data set is complemented by high-precision chemical analyses (XRF and ICP-OES) on discrete samples. Statistical analyses reveal three geochemical facies which are interpreted to represent the following sources for the sediments recovered in the AND-1B core: 1) local McMurdo Volcanic Group (MVG) rocks, 2) Transantarctic Mountain rocks west of Ross Island (W TAM), and 3) Transantarctic Mountain rocks from more southerly areas (S TAM). Data indicate in combination with other sediment facies analyses (McKay et al., 2009, doi:10.1130/B26540.1) and provenance scenarios (Talarico and Sandroni, 2009, doi:10.1016/j.gloplacha.2009.04.007) that diamictites at the drill site are largely dominated by local sources (MVG) and are interpreted to indicate cold polar conditions with dry-based ice. MVG is interpreted to indicate cold polar condition with dry-based ice. A mixture of MVG and W TAM is interpreted to represent polar conditions and the S TAM facies is interpreted to represent open-marine conditions. Down-core variations in geochemical facies in the AND-1B core are interpreted to represent five major paleoclimate phases over the past 14 Ma. Cold polar conditions with major MVG influence occur below 1045 mbsf and above 120 mbsf. A section of warmer climate conditions with extensive peaks of S TAM influence characterizes the rest of the core, which is interrupted by a section from 525 to 855 mbsf of alternating influences of MVG and W TAM.

Grain size analyses, Ca/Ti and other selected elemental ratios from XRF core scanning of sediment cores from the Apulian Margin

An extensive, high-resolution, sedimentological-geochemical survey was done using geo-acoustics, XRF-core scans, ICP-AES, AMS 14C-dating and grain size analyses of sediments in 11 cores from the Gulf of Taranto, the southern Adriatic Sea, and the central Ionian Sea spanning the last 16 cal. ka BP. Comparable results were obtained for cores from the Gallipoli Shelf (eastern Gulf of Taranto), and the southern Adriatic Sea suggesting that the dominant provenance of Gallipoli Shelf sediments is from the western Adriatic mud belt. The 210Pb and 14C-dated high-accumulation-rate sediments permit a detailed reconstruction of climate variability over the last 16 cal. ka BP. Although, the Glacial-Interglacial transition is generally dry and stable these conditions are interrupted by two phases of increased detrital input during the Bølling-Allerød and the late Younger Dryas. The event during the Younger Dryas period is characterized by increased sediment inputs from southern Italian sources. This suggests that run-off was higher in southern- compared to northern Italy. At approximately ~ 7 cal. ka BP, increased detrital input from the Adriatic mud belt, related to sea level rise and the onset of deep water formation in the Adriatic Sea, is observed and is coincident with the end of sapropel S1 formation in the southern Adriatic Sea. During the mid-to-late Holocene we observed millennial-scale events of increased detrital input, e.g. during the Roman Humid Period, and of decreased detrital input, e.g., Medieval Warm Period. These dry/wet spells are consistent with variability in the North Atlantic Oscillation (NAO). A negative state of the NAO and thus a more advanced penetration of the westerlies into the central Mediterranean, that result in wet conditions in the research area concord with events of high detrital input e.g., during the Roman Humid Period. In contrast, a positive state of the NAO, resulting in dry conditions in the Mediterranean, dominated during events of rapid climate change such as the Medieval Warm Period and the Bronze Age.

Methanol and ethanol analysis in marine sediment pore water

Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60 nM and 40 nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.

Subdivisions of the sediment column, carbon and calcium carbonate at DSDP Hole 64-480

We analyzed 580 integrated scrape-samples from HPC Site 480 for organic and carbonate carbon. Once precise dating is available, these will provide a high-resolution framework for understanding late Quaternary Oceanographic and climatic fluctuations in this region. Organic carbon ranges mostly within a narrow band of 1.8 to 3.5% C. Calcium carbonate varies from undetectable to over 20%, with an average of only about 5%. Source of carbonate are mostly benthic and planktonic foraminifers, although some sections are dominated by diagenetic carbonate, shelly hash, or nannofossils. Detrital sources are low in carbonate. We divided the sequence into 17 calcium carbonate (CC) zones to separate pulses, low and median values. The CC-Zones show various second-order patterns of cyclicity, asymmetry, and events. Laminated zones have lowest uniform values, but a perfect correlation between carbonate content and homogeneous or laminated facies was not found. Maximum values tend to be located near the transition of these two sediment types, showing that accumulation of carbonate is favored during times of breakdown of stable Oceanographic conditions.

Fatty acid content of POM, sediment, foraminifer and peracarid samples obtained during POLARSTERN cruise ANT-XXIV/2 (PS71)

In order to investigate the diversity of diet composition in macrobenthic peracarid crustaceans from the Antarctic shelf and deep sea, the fatty acid (FA) composition of different species belonging to the orders Isopoda, Amphipoda, Cumacea and Tanaidacea was analysed. Multivariate analyses of the FA composition confirmed general differences between the orders, but also distinct differences within these orders. To gain information on the origin of the FAs found, the potential food sources sediment, POM and foraminiferans were included in the study. Most of the analysed amphipod species displayed high 18:1(n-9)-18:1(n-7) ratios, widely used as an indicator for a carnivorous component in the diet. Cumaceans were characterised by increased phytoplankton FA markers such as 20:5(n-3) (up to 29% of total FAs), suggesting a diet based on phytodetritus. High values of the FA 20:4(n-6) were found in some munnopsid isopods (up to 21% of total FAs) and some tanaidacean species (up to 19% of total FAs). 20:4(n-6) also occurred in high proportions in some foraminiferan samples (up to 21% of total fatty acids), but not in sediment and POM, possibly indicating the ingestion of foraminiferans by some peracarid crustaceans.

Detriral flux of sediment cores in the southeast Indian Ocean

Because of a close relationship between detrital flux variations and magnetic susceptibility (MS) flux (MS cm**3 of bulk sediment multiplied by the linear sedimentation rate) variations in the southeast Indian basin of the southern ocean, MS flux profiles have been used to examine the spatial and temporal detrital flux changes in this basin during the last climatic cycle. Results indicate a general increase in detrital material input during the coldest periods, suggesting a widespread phenomenon, at least on the basin scale. Mineralogical data, geochemical data, and 87Sr/86Sr isotopic ratios have been used to determine the origin and transport mechanisms responsible for increased detrital flux during glacial periods. Mineralogical and geochemical data show that these glacial 'highs' are due to increases in both Kerguelen-Crozet volcanic and Antarctic detrital inputs. The 87Sr/86Sr isotopic composition of the >45-µm fraction indicates that the Kerguelen-Crozet province contributes to at least 50% of the coarse particule input to the west. This contribution decreases eastward to reach less than 10%. These tracers clearly indicate that the Crozet-Kerguelen province was a major source region of detrital in the western part of the basin during glacial times. In contrast, material of Antarctic origin is well represented in the whole basin (fine and coarse fractions). Because of the minor amount of coarse particles in the sediments, volcanic particles from Kerguelen and crustal particles from Antarctica have most probably been transported by the Antarctic bottom water current and/or the Circumpolar deepwater current during glacial periods as is the case today. Nevertheless, the presence of coarse particles even in low amount suggests also a transport by ice rafting (sea-ice and icebergs), originated from both Kerguelen and Antarctic sources. However, the relative importance of both hydrographic and ice-rafting modes of transport cannot be identified accurately with our data. During low sea level stands (glacial maximum periods), increasing instability and erosion of the continental platform and shallow plateaus could have resulted in a more efficient transfer of crustal and volcano-detrital material to the Southeast Indian basin. At the same time, extension of the grounded ice shelves over the continental margins and increase in the erosion rate of the Antarctic ice sheet could have induced a greater input of ice rafted detritus (IRD) to southern ocean basins. Enhancement of the circumpolar deepwater current strength might have also carried a more important flux of detrital material from Kerguelen. However, an increase in the bottom water flow is not necessarily required.

Cenozoic oxygen isotopic values for benthic foraminifera from DSDP and ODP low and high latitude marine sediment cores

The climate during the Cenozoic era changed in several steps from ice-free poles and warm conditions to ice-covered poles and cold conditions. Since the 1950s, a body of information on ice volume and temperature changes has been built up predominantly on the basis of measurements of the oxygen isotopic composition of shells of benthic foraminifera collected from marine sediment cores. The statistical methodology of time series analysis has also evolved, allowing more information to be extracted from these records. Here we provide a comprehensive view of Cenozoic climate evolution by means of a coherent and systematic application of time series analytical tools to each record from a compilation spanning the interval from 4 to 61 Myr ago. We quantitatively describe several prominent features of the oxygen isotope record, taking into account the various sources of uncertainty (including measurement, proxy noise, and dating errors). The estimated transition times and amplitudes allow us to assess causal climatological-tectonic influences on the following known features of the Cenozoic oxygen isotopic record: Paleocene-Eocene Thermal Maximum, Eocene-Oligocene Transition, Oligocene-Miocene Boundary, and the Middle Miocene Climate Optimum. We further describe and causally interpret the following features: Paleocene-Eocene warming trend, the two-step, long-term Eocene cooling, and the changes within the most recent interval (Miocene-Pliocene). We review the scope and methods of constructing Cenozoic stacks of benthic oxygen isotope records and present two new latitudinal stacks, which capture besides global ice volume also bottom water temperatures at low (less than 30°) and high latitudes. This review concludes with an identification of future directions for data collection, statistical method development, and climate modeling.

Sea surface temperature reconstruction for sediment core KNO5103-0029GGC

We present a 15 kyr sea surface temperature (SST) record for a high sedimentation rate core (KNR51-29GGC) from the Feni Drift off of Ireland, based on an organic geochemical technique for paleotemperature estimation, U37 K'. We compare the U37 K' temperature record to planktonic foraminiferal delta18O and foraminiferal assemblage SST estimates from the same sample horizons. U37 K' gives SST estimates of 13°C for the early deglacial and 18°C for the Holocene and Recent, whereas assemblages give estimates of 9°C and 13°C, respectively. As in nearby core V23-81, we find Ash Zone 1, the Younger Dryas increase in Neogloboquadrina pachyderma sinistral abundance, and maximum abundance of this species during glaciation. N. pachyderma dextral oxygen isotopic analyses have a late glacial to interglacial range of 1.5 per mil. A reduction of about 1 per mil in delta18O occurred at about 12 ka, whereas U37 K' and the foraminiferal fauna indicate a 2°C warming. This implies a 0.9 per mil salinity effect on delta18O which we attribute to meltwater freshening. All three parameters indicate cooling during the Younger Dryas. U37 K' SST estimates show that the major shift from deglacial to interglacial temperatures occurred after the Younger Dryas in termination 1b, in contrast to the assemblage data, which show this jump in SST at the end of the glaciation during termination Ia. Differences between the two SST estimators, which may result from their different (floral versus faunal) sources, are more pronounced between transitions Ia and Ib. This may reflect different habitats under the unusual sea surface conditions of the deglaciation.

Strontium isotope ratios of planktonic foraminifera from sediment samples acroos the K/T boundary

Seawater 87Sr/86Sr values increase abruptly by 28 * 10**-6 across the Cretaceous/Tertiary boundary (KTB). This small, but rapid shift is superimposed on the larger scale structure of the seawater Sr isotope curve. The time scale of radiogenic Sr addition appears to be too rapid to reconcile with sources associated with volcanism, and we show that the amount of Sr required to produce even this small increase is too large to be derived from: (1) a KT bolide of the size constrained by the Ir anomaly, (2) continental crust ejecta from the impact of such a bolide, (3) soot from global wildfires initiated by an impact, or (4) any combination of these sources. The probable source of the radiogenic Sr is enhanced continental weathering, but the high rate of increase appears to rule out processes such as sea level regression, glaciation or tectonism. A plausible mechanism for rapid addition of radiogenic Sr to the oceans is enhanced weathering associated with globally distributed acid rain (pH c. 1) which is a proposed by-product of a bolide impact (Prinn and Fegley, 1987, doi:10.1016/0012-821X(87)90046-X).

Amino acid data of catchment and sediment core samples of four Indian lakes

In the present study, we report the results of comprehensive amino acid (AA) analyses of four Indian lakes from different climate regimes. We focus on the investigation of sediment cores retrieved from the lakes but data of modern sediment as well as vascular plant, soil, and suspended particulate matter samples from individual lakes are also presented. Commonly used degradation and organic matter source indices are tested for their applicability to the lake sediments, and we discuss potential reasons for possible limitations. A principal component analysis including the monomeric AA composition of organic matter of all analysed samples indicates that differences in organic matter sources and the environmental properties of the individual lakes are responsible for the major variability in monomeric AA distribution of the different samples. However, the PCA also gives a factor that most probably separates the samples according to their state of organic matter degradation. Using the factor loadings of the individual AA monomers, we calculate a lake sediment degradation index (LI) that might be applicable to other palaeo-lake investigations.

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.

Early Maastrichtian stable isotopes: changing deep water sources in the North Atlantic?

We propose that the observed short-term stable isotope fluctuations reflect changes in high- and low-latitude intermediate to deep water sources, based on a high-resolution stable isotope record of planktic and benthic foraminifera from the Early Maastrichtian (~71.3 to ~ 69.6 Ma) of Blake Nose (DSDP Site 390A, North Atlantic). Sources of these waters may have been the low-latitude eastern Tethys and high-latitude North Atlantic. Changes in intermediate to deep water sources were probably steered by eccentricity-controlled insolation fluctuations. Lower insolation favored the formation of high-latitude deep waters due to positive feedback mechanisms resulting in high-latitude cooling. This led to a displacement of low-latitude deep waters at Blake Nose. Higher insolation reduced intermediate to deep-water formation in high latitudes, yielding a more northern flow of low-latitude deep waters.

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.