n-alkane carbon isotope ratios in plants and recent lake sediments from Cameroon

Trees and shrubs in tropical Africa use the C3 cycle as a carbon fixation pathway during photosynthesis, while grasses and sedges mostly use the C4 cycle. Leaf-wax lipids from sedimentary archives such as the long-chain n-alkanes (e.g., n-C27 to n-C33) inherit carbon isotope ratios that are representative of the carbon fixation pathway. Therefore, n-alkane d13C values are often used to reconstruct past C3/C4 composition of vegetation, assuming that the relative proportions of C3 and C4 leaf waxes reflect the relative proportions of C3 and C4 plants. We have compared the d13C values of n-alkanes from modern C3 and C4 plants with previously published values from recent lake sediments and provide a framework for estimating the fractional contribution (areal-based) of C3 vegetation cover (fC3) represented by these sedimentary archives. Samples were collected in Cameroon, across a latitudinal transect that accommodates a wide range of climate zones and vegetation types, as reflected in the progressive northward replacement of C3-dominated rain forest by C4-dominated savanna. The C3 plants analysed were characterised by substantially higher abundances of n-C29 alkanes and by substantially lower abundances of n-C33 alkanes than the C4 plants. Furthermore, the sedimentary d13C values of n-C29 and n-C31 alkanes from recent lake sediments in Cameroon (-37.4 per mil to -26.5 per mil) were generally within the range of d13C values for C3 plants, even when from sites where C4 plants dominated the catchment vegetation. In such cases simple linear mixing models fail to accurately reconstruct the relative proportions of C3 and C4 vegetation cover when using the d13C values of sedimentary n-alkanes, overestimating the proportion of C3 vegetation, likely as a consequence of the differences in plant wax production, preservation, transport, and/or deposition between C3 and C4 plants. We therefore tested a set of non-linear binary mixing models using d13C values from both C3 and C4 vegetation as end-members. The non-linear models included a sigmoid function (sine-squared) that describes small variations in the fC3 values as the minimum and maximum d13C values are approached, and a hyperbolic function that takes into account the differences between C3 and C4 plants discussed above. Model fitting and the estimation of uncertainties were completed using the Monte Carlo algorithm and can be improved by future data addition. Models that provided the best fit with the observed d13C values of sedimentary n-alkanes were either hyperbolic functions or a combination of hyperbolic and sine-squared functions. Such non-linear models may be used to convert d13C measurements on sedimentary n-alkanes directly into reconstructions of C3 vegetation cover.

Stable oxygen isotope data and geophysical measurements from Red Sea of core M174/Kl11

To settle debate on the timing of sea level fluctuations during marine isotope stage (MIS) 3, we present records of d18O ruber (sea level proxy) and magnetic susceptibility from the same samples within the single sediment archive (i.e., "coregistered") of central Red Sea core GeoTü-KL11. Core-scanning X-ray fluorescence and environmental magnetic data establish the suitability of magnetic susceptibility as a proxy for eolian dust content in Red Sea sediments. The eolian dust data record similar variability as Greenland d18O ice during early to middle MIS 3, in agreement with previous observations that regional Arabian Sea climate fluctuated with a timing similar to that of Greenland climate variations. In contrast, the sea level record fluctuates with a timing similar to that of Antarctic-style climate variations. The coregistered nature of the two records in core KL11 unambiguously reveals a distinct offset in the phase relationship between sea level and eolian dust fluctuations. The results confirm that sea level rises, indicated by shifts in Red Sea d18O ruber to lighter values, occurred during cold episodes in Greenland during early to middle MIS 3. This indicates that the amplitudes of the reconstructed MIS 3 sea level fluctuations would not be reduced by inclusion of regional climate fluctuations in the Red Sea sea level method. Our analysis comprehensively supports our earlier conclusions of large-amplitude sea level variations during MIS 3 with a timing that is strongly similar to Antarctic-style climate variations.

(Table 1) Sulfur contents and isotope composition in rocks and minerals from DSDP/ODP Hole 504B

DSDP Hole 504B is the only hole in oceanic crust to penetrate through the volcanic section and into hydrothermally altered sheeted dikes. We have carried out petrologic and sulfur isotopic analyses of sulfide and sulfate minerals and whole rocks from the core in order to place constraints on the geochemistry of sulfur during hydrothermal alteration of ocean crust. The nearly 600 m-thick pillow section has lost sulfur to seawater and has net d34S = -1.8 per mil due to degassing of SO2 during crystallization and subsequent low temperature interaction with seawater. Hydrothermally altered rocks in the 200 m-thick transition zone are enriched in S and 34S (4300 ppm and +3.0 +/-1.2 per mil, respectively), whereas the more than 500 m of sheeted dikes contain 720 ppm S with d34S = +0.6 +/-1.4 per mil. These data are consistent with the presence of predominantly basaltic sulfur in hydrothermal fluids deep in the crust: following precipitation of anhydrite during seawater recharge, small amounts of seawater sulfate were reduced at temperatures >250°C through conversion of igneous pyrrhotite to secondary pyrite and minor oxidation of ferrous iron in the crust. The S- and 34S-enrichments of the transition zone are the results of seawater sulfate reduction and sulfide deposition during subsurface mixing between upwelling hot (up to 350°C) hydrothermal fluids and seawater. Seawater sulfate was probably reduced through oxidation of ferrous iron in hydrothermal fluids and in the transition zone rocks. Alteration of the upper crust resulted in loss of basaltic sulfur to seawater, fixation of minor seawater sulfur in the crust and redistribution of magmatic sulfur within the crust. This caused net increases in sulfur content and d34S of the upper 1.8 km of the oceanic crust.

Lead isotope ratios of basalts from DSDP Leg 37 (Table 1)

Analyses of Pb from mid-ocean ridge basalts obtained from DSDP Leg 37 lie on a line of near-zero-age slope. The data seem consistent with an evolutionary model of three stages, the beginning of the second stage being at about 600 m.y. - the model age obtained for the least radiogenic Pb. The beginning of the third stage of evolution at the time of formation of the rocks apparently did not change the average Th/U ratio since measured values are consistent with the ratio deduced from Pb isotope ratios. Ratios of U/Pb are not consistent with Pb isotope ratios, however, thus ruling out a simple two-stage evolutionary model.

Oxygen isotope ratios amd Li concentrations in spilitized basaltic rocks of DSDP Hole 83-504B (Table 5)

Li-delta18O-SiO2 relationships have been examined for suites of spilitized basaltic rocks (DSDP 504B; Xigaze Ophiolite; Blanco Fracture Zone; Greater Caucasus; Rhenohercynian Fold Belt) and intra-plate evolved tholeiites (Northern Hessian Depression and Vogelsberg, W Germany; Mount Falla, Transantarctic Mountains). Relative to unaltered MORB and intra-plate primary olivine tholeiites, both the spilitic rocks and the evolved tholeiites are characterized by Li and 18O enrichment. For the spilitic rocks, Li and 18O enrichment is accompanied by a loss of SiO2 as a result of seawater hydrothermal alteration, whereas the evolved tholeiites have gained SiO2, Li and 18O from fractionation of mafic phases and assimilation of crustal rocks. On Li vs. SiO2 and delta18O vs. SiO2 diagrams, the two rock groups plot largely in distinct fields, suggesting the possibility of so distinguishing between such lithologies in the ancient rock record. Mafic granulite xenoliths from the Northern Hessian Depression have elevated Li and 18O abundances at low SiO2 contents. Even after correction for extraction of felsic components, their Li-delta18O-SiO2 signatures plot within the field of spilitic protoliths, suggesting that the lower crust in this region contains relics of spilitic rocks from a former oceanic crust.

Nd- and Sr- isotope ratios of oceanic basalts

143Nd/144Nd ratios have been determined on 37 samples of oceanic basalt, with a typical precision of +/- 2-3 * 10**-5 (2 sigma). Ocean island and dredged and cored submarine basalts are included for which reliable measurements of 87Sr/86Sr ratios exist in the literature or have been measured as part of this study. A strong negative correlation exists between 143Nd/144Nd and 87Sr/86Sr ratios in basalts from Iceland and the Reykjanes Ridge, but such a clear correlation does not exist for samples from the Hawaiian Islands. However, when other ocean island basalts from the Atlantic are included there is an overall correlation between these two parameters. Increases and decreases in Rb/Sr in oceanic basalt source regions have in general been accompanied by decreases and increases respectively in Sm/Nd ratios. The compatibility of the data with single-stage models is assessed and it is concluded that enrichment and depletion events, which are consistent with transfer of silicate melts, are responsible for the observed variation.

Stable carbon and oxygen isotope record of foraminifera from DSDP Hole 30-289

Sediments accumulate on the sea floor far from land with rates of a few millimetres to a few centimetres per thousand years. Sediments have been accumulating under broadly similar conditions, subject to similar controls, for the past 10 8 years and more. In principle we should be able to study the distribution of climatic variance with frequencies over the range 10**-3 to 10**-7 cycles per year with comparative ease. In fact, nearly all our data are heavily weighted towards the youngest part of the geological record. We study frequencies higher than 10**-4 cycles per year in the special case of a Pleistocene interglacial (the present one), and frequencies in the range 10**-4 to 10**-5 cycles per year in the special case of an ice-age. Although these may be of more direct interest to mankind than earlier periods, it may well be that we will understand the causes of climatic variability better if we can examine their operation over a longer time scale and under different boundary conditions. Rather than review the available data, I have collected some new data to show the feasibility of gathering a data base for examining climatic variability without this usual bias toward the recent. The most widely applicable tool for extracting climatic information from deep-sea sediments is oxygen isotope analysis of calcium carbonate microfossils. It is generally possible to select from the sediment both specimens of benthonic Foraminifera (that is, those that lived in ocean deep water at the sediment-water interface) and specimens of planktonic Foraminifera (that is, those that lived and formed their shells near the ocean surface, and fell to the sediment after death). Thus one is able to monitor conditions at the surface and at depth at simultaneous moments in the geological past. The necessity to analyse calcareous microfossils restricts investigation to calcareous sediments, but even with this restriction in sediment type there are many factors governing the rate of sediment accumulation. On a global scale, sediment accumulates so as to balance the input to the oceans from continental erosion. Even when averaged globally, long-term accumulation rates have varied by almost a factor of ten (Davies et al., 1977, doi:10.1126/science.197.4298.53). At the regional scale, surface productivity and deep-water physical and chemical conditions also affect the sediment accumulation rate. Since all these are susceptible to variation and may well vary in response to climatic change as well as other factors, it is extremely hazardous to attempt to express any climatic variable as a function of time on the basis of measurements originally made as a function of depth in sediment. Although time has been used as a basis for plotting Figs. i-8, these should be regarded as freehand sketches of climatic history rather than as time-series plots.

Strontium isotope and rare earth element geochemistry of basalts from DSDP Leg 37

87Sr/S6Sr ratios have been determined on eleven whole rock basalt samples from DSDP Leg 37. The 87Sr/S6Sr ratios range from 0.70305 +/- 4 to 0.70451 +/- 4 due to alteration and contamination with seawater Sr. Leaching with 5% HF has only a small effect on the 87Sr/86Sr of the samples. However, treatment with 6M HCl in acid digestion bombs at 130°C removes the contaminant more effectively. Altered plagioclase and olivine are dissolved during this process. The mean 87Sr/86Sr of four HCl-treated samples from hole 332A is 0.70299 and that for five samples from hole 332B is 0.70297. The 87Sr/86Sr ratios of treated samples from holes 333A and 335 are 0.70304 +/- 4 and 0.70316 +/- 4, respectively. These 87Sr/86Sr ratios are within the range observed for other basalts elsewhere along the Mid-Atlantic Ridge in the North Atlantic. REE distribution patterns have been determined for four samples, three from hole 332B and one from hole 335. CeN/YbN ratios range from 0.58 to 1.30 and do not correlate with 87Sr/86Sr ratios. The source regions of these basalts appear to have been variable in REE abundances.

Age determination with strontium isotopes on sediment core CRP-1 from the Ross Sea, Antarctica

Strontium isotope stratigraphy was used to date five discrete horizons within CRP-1. Early and late Quaternary (0.87-1.3 Ma and 0-0.67 Ma respectively) age sediments overlie a major sequence boundary at 43.15 meters below sea floor (mbsf). This hiatus is estimated to account for ~16 m.y. of missing section. Early Miocene (16.6-~20.8-25 Ma) age deposits below this boundary are in turn cut by multiple erosion surface representing hiatus is of between 0.2 and 1.2 m.y. Estimated minimum sedimentation rates range between 0.9 and 2.8 cm/k.y. in the Quaternary, and 1.5 and 6.4 cm/ky in the lower Miocene.

Isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) at different cold seep provinces

Anaerobic methane-oxidizing microbial communities in sediments at cold methane seeps are important factors in controlling methane emission to the ocean and atmosphere. Here, we investigated the distribution and carbon isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) responsible for the anaerobic oxidation of methane (AOM) at different cold seep provinces of Hydrate Ridge, Cascadia margin. The special focus was on their relation to in situ cell abundances and methane turnover. In general, maxima in biomarker abundances and minima in carbon isotope signatures correlated with maxima in AOM and sulphate reduction as well as with consortium biomass. We found ANME-2a/DSS aggregates associated with high abundances of sn-2,3-di-O-isoprenoidal glycerol ethers (archaeol, sn-2-hydroxyarchaeol) and specific bacterial fatty acids (C16:1omega5c, cyC17:0omega5,6) as well as with high methane fluxes (Beggiatoa site). The low to medium flux site (Calyptogena field) was dominated by ANME-2c/DSS aggregates and contained less of both compound classes but more of AOM-related glycerol dialkyl glycerol tetraethers (GDGTs). ANME-1 archaea dominated deeper sediment horizons at the Calyptogena field where sn-1,2-di-O-alkyl glycerol ethers (DAGEs), archaeol, methyl-branched fatty acids (ai-C15:0, i-C16:0, ai-C17:0), and diagnostic GDGTs were prevailing. AOM-specific bacterial and archaeal biomarkers in these sediment strata generally revealed very similar d13C-values of around -100 per mill. In ANME-2-dominated sediment sections, archaeal biomarkers were even more 13C-depleted (down to -120 per mill), whereas bacterial biomarkers were found to be likewise 13C-depleted as in ANME-1-dominated sediment layers (d13C: -100 per mill). The zero flux site (Acharax field), containing only a few numbers of ANME-2/DSS aggregates, however, provided no specific biomarker pattern. Deeper sediment sections (below 20 cm sediment depth) from Beggiatoa covered areas which included solid layers of methane gas hydrates contained ANME-2/DSS typical biomarkers showing subsurface peaks combined with negative shifts in carbon isotopic compositions. The maxima were detected just above the hydrate layers, indicating that methane stored in the hydrates may be available for the microbial community. The observed variations in biomarker abundances and 13C-depletions are indicative of multiple environmental and physiological factors selecting for different AOM consortia (ANME-2a/DSS, ANME-2c/DSS, ANME-1) along horizontal and vertical gradients of cold seep settings.

Chronostratigraphy on sediment core CRP-2 from the Ross Sea, Antarctica

Strontium isotope stratigraphy was used to date 16 discrete horizons within the CRP-2/2A drillhole. Reworked Quaternary (<1.7 Ma) and possible Pliocene (<2.4 Ma) sediments overlie a major sequence boundary at 25.92 meters below sea floor (mbsf). This hiatus is estimated to account for c. 16 Myr of missing section. Early Miocene to ?earliest Oligocene (c. 18.6 to >31 Ma) deposits below this boundary were cut by multiple erosion surfaces of uncertain duration. Strontium isotope ages are combined with 40Ar/39Ar dates, diatom and calcareous nannofossil datum and a palaeomagnetic polarity zonation, to produce an age model for the core.