Hydrogen isotopic composition of sediment cores from a transect off western Africa

The hydrogen isotopic composition of plant leaf-wax n-alkanes (dDwax) is a novel proxy for estimating dD of past precipitation (dDp). However, vegetation life-form and relative humidity exert secondary effects on dDwax, preventing quantitative estimates of past dDp. Here, we present an approach for removing the effect of vegetation-type and relative humidity from dDwax and thus for directly estimating past dDp. We test this approach on modern day (late Holocene; 0-3 ka) sediments from a transect of 9 marine cores spanning 21°N-23°S off the western coast of Africa. We estimate vegetation type (C3 tree versus C4 grass) using d13C of leaf-wax n-alkanes and correct dDwax for vegetation-type with previously-derived apparent fractionation factors for each vegetation type. Late Holocene vegetation-corrected dDwax (dDvc) displays a good fit with modern-day dDp, suggesting that the effects of vegetation type and relative humidity have both been removed and thus that dDvc is a good estimate of dDp. We find that the magnitude of the effect of C3 tree - C4 grass changes on dDwax is small compared to dDp changes. We go on to estimate dDvc for the mid-Holocene (6-8 ka), the Last Glacial Maximum (LGM; 19-23 ka) and Heinrich Stadial 1 (HS1; 16-18.5 ka). In terms of past hydrological changes, our leaf-wax based estimates of dDp mostly reflect changes in wet season intensity, which is complementary to estimates of wet season length based on leaf-wax d13C.

Isotopic composition of ground ice, ebullition gases and thermokarst lake water, North America

Thermokarst lakes are thought to have been an important source of methane (CH4) during the last deglaciation when atmospheric CH4 concentrations increased rapidly. Here we demonstrate that meltwater from permafrost ice serves as an H source to CH4 production in thermokarst lakes, allowing for region-specific reconstructions of dD-CH4 emissions from Siberian and North American lakes. dD CH4 reflects regionally varying dD values of precipitation incorporated into ground ice at the time of its formation. Late Pleistocene-aged permafrost ground ice was the dominant H source to CH4 production in primary thermokarst lakes, whereas Holocene-aged permafrost ground ice contributed H to CH4 production in later generation lakes. We found that Alaskan thermokarst lake dD-CH4 was higher (-334 ± 17 per mil) than Siberian lake dD-CH4 (-381 ± 18 per mil). Weighted mean dD CH4 values for Beringian lakes ranged from -385 per mil to -382 per mil over the deglacial period. Bottom-up estimates suggest that Beringian thermokarst lakes contributed 15 ± 4 Tg CH4 /yr to the atmosphere during the Younger Dryas and 25 ± 5 Tg CH4 /yr during the Preboreal period. These estimates are supported by independent, top-down isotope mass balance calculations based on ice core dD-CH4 and d13C-CH4 records. Both approaches suggest that thermokarst lakes and boreal wetlands together were important sources of deglacial CH4.

Isotopic composition of modern ice wedges and winter precipitation in the Laptev Sea region (Table 2)

The first step for the application of stable isotope analyses of ice wedges for the correct paleoclimatic reconstruction supposes the study of the isotopic composition of modern ice wedges and their relationship with the isotopic composition of modern precipitation. The purpose of this research is to present, to analyze and to discuss new data on isotopic composition (d18O, dD, 3H) of modern ice wedges obtained in the Laptev Sea region in 1998-99. Investigations were carried out at two sites: on Bykovsky Peninsula in 1998 and on Bol'shoy Lyakhovsky Island in 1999 and were based on the combined application of both tritium CH) and stable isotope (d18O, dD) analyses. Tritium analyses of the atmospheric precipitation collected during two field seasons show seasonal variations: high tritium concentration in snow (to a maximum of 207 TU) and low values of tritium concentration (<20 TU) in rain. High tritium concentrations are also observed in the surface water, in suprapermafrost ground waters, and in the upper part of permafrost. High tritium concentrations range between 30-40 TU and 750 TU in the studied modern ice wedges (active ice wedges), which let us believe that they are of modern growth. Such high tritium concentrations in ice wedges can not be associated with old thermonuclear tritium because of the radioactive decay. High tritium concentrations found in the snow cover in 1998/99, in the active layer and in the upper part of permafrost give evidence of modern (probably the last decade) technogenic tritium arrival from the atmosphere on to the Earth surface in the region. The comparison of the isotopic composition (d18O, dD and d-excess) of active ice wedges and modern winter precipitation in both sites shows: 1) the isotopic composition of snow correlates linearly with a slope close to 8.0 and parallel to the GMWL at both sites; 2) the mean isotopic composition of active ice wedges on Bykovsky Peninsula is in good agreement with the mean isotopic composition of modern snow; 3) the isotopic composition of active ice wedges and snow on Bol'shoy Lyakhovsky Island are considerably different. There are low values of d-excess in all studied active ice wedges (mean value is about 4.8 per mil), while in snow, the mean value of d-excess is about 9.5 per mil. Possible reasons for this gap are the following: 1) the modification of the isotopic composition in snow during the spring period; 2) changes in the isotopic composition of ice wedges due to the process of ice sublimation in open frost cracks during the cold period; 3) mixing of snowmelt water with different types of surface water during the spring period; 4) different moisture source regions.

Distribution and stable isotopic compositions of hydrogen and carbon of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments

Reconstructing terrestrial water budgets is of prime importance for understanding past climate and environment. To shed more light on how plant-wax derived n-alkanes may be used for this purpose we investigated the distribution and stable isotopic compositions of hydrogen (dD) and carbon (d13C) of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments in relation to hydrology along a NW-SE transect east of the Italian Apennines from the Po River to the Eastern Gulf of Taranto. The plant wax average chain length increases southward and may relate to increasing temperature and/or aridity. The plant wax dD of the terrestrial and coastal samples also increases southward and mainly reflects changes in the dD of precipitation. The d13C of plant waxes is primarily interpreted in terms of C3 vegetation changes rather than varying contributions by C4 plants. The plant wax d13C-dD composition of the Po River and Apennine rivers differs considerably from that in southern Italy, and suggests a mainly southern source for plant waxes in marine sediments of the Gulf of Taranto. This calibration provides a basis for the reconstruction of past changes in the Italian water balance and n-alkane source areas.

Chemical and isotopic compositions of deep-sea carbonate sediments and interstitial waters from DSDP Sites 30-288 and 30-289

Interstitial waters and sediments from DSDP sites 288 and 289 contain information on the chemistry and diagenesis of carbonate in deep-sea sediments and on the role of volcanic matter alteration processes. Sr/Ca ratios are species dependent in unaltered foraminifera from site 289 and atom ratios (0.0012-0.0016) exceed those predicted by distribution coefficent data (~0.0004). During diagenesis Sr/Ca ratios of carbonates decrease and reach the theoretical distribution at a depth which is identical to the depth of Sr isotopic equilibration, where 87Sr/86Sr ratios of interstitial waters and carbonates converge. Mg/Ca ratios in the carbonates do not increase with depth as found in some other DSDP sites, possibly because of diagenetic re-equilibration with interstitial waters showing decreasing Mg(2+)/Ca(2+) ratios with depth due to Ca input and Mg removal by alteration of volcanic matter. Interstitial 18O/16O ratios increase with depth at site 289 to d18O = 0.67? (SMOW), reflecting carbonate recrystallization at elevated temperatures (>/= 20°C), the first recorded evidence of this effect in interstitial waters. Interstitial Sr2+ concentrations reach high levels, up to 1 mM, chiefly because of carbonate recrystallization. However, 87Sr/86Sr ratios decrease from 0.7092 to less than 0.7078, lower than for contemporaneous sea water, showing that there is a volcanic input of strontium at depth. This volcanic component is recorded in the Sr isotopic composition of recrystallized calcites. Isotopic compositions of the unrecrystallized calcites suggests that the rate of increase of the 87Sr/86Sr ratio of sea water with time has been faster since 3 my ago than in the preceding 13 my.

Contents and isotopic composition of black carbon from ODP Sites 184-1147 and 184-1148

A 30 m.y. stable isotopic record of marine-deposited black carbon from regional terrestrial biomass burning from the northern South China Sea reveals photosynthetic pathway evolution for terrestrial ecosystems in the late Cenozoic. This record indicates that C3 plants negatively adjusted their isotopic discrimination and C4 plants appeared gradually as a component of land vegetation in East Asia since the early Miocene, a long time before sudden C4 expansion occurred during the late Miocene to the Pliocene. The changes in terrestrial ecosystems with time can be reasonably related to the evolution of East Asian monsoons, which are thought to have been induced by several intricate mechanisms during the late Cenozoic and could contribute significantly to the post-Miocene marine carbonate isotope decline.

(Table 2) Carbon and nitrogen isotopic ratios in blood sampled from arctic foxes (Vulpes lagopus) on Bylot Island between 2003-2008

Inter-individual variation in diet within generalist animal populations is thought to be a widespread phenomenon but its potential causes are poorly known. Inter-individual variation can be amplified by the availability and use of allochthonous resources, i.e., resources coming from spatially distinct ecosystems. Using a wild population of arctic fox as a study model, we tested hypotheses that could explain variation in both population and individual isotopic niches, used here as proxy for the trophic niche. The arctic fox is an opportunistic forager, dwelling in terrestrial and marine environments characterized by strong spatial (arctic-nesting birds) and temporal (cyclic lemmings) fluctuations in resource abundance. First, we tested the hypothesis that generalist foraging habits, in association with temporal variation in prey accessibility, should induce temporal changes in isotopic niche width and diet. Second, we investigated whether within-population variation in the isotopic niche could be explained by individual characteristics (sex and breeding status) and environmental factors (spatiotemporal variation in prey availability). We addressed these questions using isotopic analysis and Bayesian mixing models in conjunction with linear mixed-effects models. We found that: i) arctic fox populations can simultaneously undergo short-term (i.e., within a few months) reduction in both isotopic niche width and inter-individual variability in isotopic ratios, ii) individual isotopic ratios were higher and more representative of a marine-based diet for non-breeding than breeding foxes early in spring, and iii) lemming population cycles did not appear to directly influence the diet of individual foxes after taking their breeding status into account. However, lemming abundance was correlated to proportion of breeding foxes, and could thus indirectly affect the diet at the population scale.

Nd-Sr isotopic composition of foraminifera and bulk sediments

We present new isotopic data for sedimentary planktonic foraminifera, as well as for potential water column and sedimentary sources of neodymium (Nd), which confirm that the isotopic composition of the foraminifera is the same as surface seawater and very different from deep water and sedimentary Nd. The faithfulness with which sedimentary foraminifera record the isotopic signature of surface seawater Nd is difficult to explain given their variable and high Nd/Ca ratios, ratios that are often sedimentary foraminifera, ratios that are often much higher than is plausible for direct incorporation within the calcite structure. We present further data that demonstrate a similarly large range in Nd/Ca ratios in plankton tow foraminifera, a range that may be controlled by redox conditions in the water column. Cleaning experiments reveal, in common with earlier work, that large amounts of Nd are released by cleaning with both hydrazine and diethylene triamine penta-acetic acid, but that the Nd released at each step is of surface origin. While further detailed studies are required to verify the exact location of the surface isotopic signature and the key controls on foraminiferal Nd isotope systematics, these new data place the use of planktonic foraminifera as recorders of surface water Nd isotope ratios, and thus of variations in the past supply of Nd to the oceans from the continents via weathering and erosion, on a reasonably sure footing.

Lead isotopic ratios of Barremian-Aptian marine sediments

We present initial isotopic ratios of lead for Early Cretaceous (Barremian-Aptian) sections from Shatsky Rise (Pacific) and Gorgo a Cerbara (Italy). Our Pb isotopic data track an interval representing Oceanic Anoxic Event (OAE)-1a, which is characterized by quasi-global deposition of organic carbon-rich black shale. Pb isotopic compositions of sediments from Shatsky Rise decrease at the end of Barremian time, from radiogenic continental values to unradiogenic values, and subsequently remained less radiogenic until the end of early Aptian time. We explain the isotopic shift by a significant increase in supply rate of unradiogenic Pb, most likely due to massive volcanism. In contrast, the Pb isotopic compositions from the Italian section, which was situated at the western end of Tethys, are mostly identical to those of upper continental crust, showing no significant change in supply rate of unradiogenic Pb. The discrepancy between two sites is attributed to quiescent deep-submarine eruptions of Pacific large igneous provinces (LIPs) such as the Ontong Java Plateau (OJP), which severely limited dispersion of Pb-carrying particles out of the Pacific Ocean. Published Os isotopic data from the Italian section indicate two episodes of massive eruptions of OJP or contemporaneous Manihiki and Hikurangi plateaus starting from earliest Aptian time, slightly later than that indicated by the sedimentary Pb isotopic record from Shatsky Rise. Differences in isotopic variations between Pb and Os likely reflect differences in their chemical behaviors in the oceans, i.e., Pb isotopic compositions would have varied in response to local or regional changes in sediment provenances, whereas large-scale changes in Os inputs are required to explain variations in seawater Os isotopic compositions. Our Pb isotopic data, together with the published Os isotopic record, provide new evidence for the eruptive history of OJP together with contemporaneous Pacific plateaus and its environmental consequences, starting from end-Barremian time and extending through early Aptian time.