Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Interstitial water chemistry at DSDP Leg 74 Holes

Interstitial water studies from sites drilled during a transect of the Walvis Ridge indicate that concentration increases in calcium and decreases in magnesium toward and into the basement. These trends can be understood principally in terms of reactions taking place in Layer 2 of the oceanic crust. At Site 525, however, some removal of magnesium occurs within the sediment column. Concentration maxima of dissolved strontium clearly indicate that carbonate recrystallization occurs throughout the carbonate sediments, and studies of the Sr/Ca ratio in carbonates indicate that in chalks and limestones recrystallization is essentially complete. Predictions of dissolved strontium maxima generally fail; this can be understood as removal of strontium in basal sediments and/or basalts.

Calculated sea surface temperatures of two sediment cores

The reconstruction of ocean history employs a large variety of methods with origins in the biological, chemical, and physical sciences, and uses modern statistical techniques for the interpretation of extensive and complex data sets. Various sediment properties deliver useful information for reconstructing environmental parameters. Those properties that have a close relationship to environmental parameters are called ''proxy variables'' (''proxies'' for short). Proxies are measurable descriptors for desired (but unobservable) variables. Surface water temperature is probably the most important parameter for describing the conditions of past oceans and is crucial for climate modelling. Proxies for temperature are: abundance of microfossils dwelling in surface waters, oxygen isotope composition of planktic foraminifers, the ratio of magnesium or strontium to calcium in calcareous shells or the ratio of certain organic molecules (e.g. alkenones produced by coccolithophorids). Surface water salinity, which is important in modelling of ocean circulation, is much more difficult to reconstruct. At present there is no established method for a direct determination of this parameter. Measurements associated with the paleochemistry of bottom waters to reconstruct bottom water age and flow are made on benthic foraminifers, ostracodes, and deep-sea corals. Important geochemical tracers are d13C and Cd/Ca ratios. When using benthic foraminifers, knowledge of the sediment depth habitat of species is crucial. Reconstructions of productivity patterns are of great interest because of important links to current patterns, mixing of water masses, wind, the global carbon cycle, and biogeography. Productivity is reflected in the flux of carbon into the sediment. There are a number of fluxes other than those of organic carbon that can be useful in assessing productivity fluctuations. Among others, carbonate and opal flux have been used, as well as particulate barite. Furthermore, microfossil assemblages contain clues to the intensity of production as some species occur preferentially in high-productivity regions while others avoid these. One marker for the fertility of sub-surface waters (that is, nutrient availability) is the carbon isotope ratio within that water (13C/12C, expressed as d13C). Carbon isotope ratios in today's ocean are negatively correlated with nitrate and phosphate contents. Another tracer of phosphate content in ocean waters is the Cd/Ca ratio. The correlation between this ratio and phosphate concentrations is quite well documented. A rather new development to obtain clues on ocean fertility (nitrate utilization) is the analysis of the 15N/14N ratio in organic matter. The fractionation dynamics are analogous to those of carbon isotopes. These various ratios are captured within the organisms growing within the tagged water. A number of reconstructions of the partial pressure of CO2 have been attempted using d13C differences between planktic and benthic foraminifers and d13C values of bulk organic material or individual organic components. To define the carbon system in sea water, two elements of the system have to be known in addition to temperature. These can be any combination of total CO2 , alkalinity, or pH. To reconstruct pH, the boron isotope composition of carbonates has been used. Ba patterns have been used to infer the distribution of alkalinity in past oceans. Information relating to atmospheric circulationand climate is transported to the ocean by wind or rivers, in the form of minerals or as plant andanimal remains. The most useful tracers in this respect are silt-sized particles and pollen.

Temperature Dependent Effects of Elevated CO2 on Shell Composition and Mechanical Properties of Hydroides elegans: Insights from a Multiple Stressor Experiment

The majority of marine benthic invertebrates protect themselves from predators by producing calcareous tubes or shells that have remarkable mechanical strength. An elevation of CO2 or a decrease in pH in the environment can reduce intracellular pH at the site of calcification and thus interfere with animal's ability to accrete CaCO3. In nature, decreased pH in combination with stressors associated with climate change may result in the animal producing severely damaged and mechanically weak tubes. This study investigated how the interaction of environmental drivers affects production of calcareous tubes by the serpulid tubeworm, Hydroides elegans. In a factorial manipulative experiment, we analyzed the effects of pH (8.1 and 7.8), salinity (34 and 27), and temperature (23°C and 29°C) on the biomineral composition, ultrastructure and mechanical properties of the tubes. At an elevated temperature of 29°C, the tube calcite/aragonite ratio and Mg/Ca ratio were both increased, the Sr/Ca ratio was decreased, and the amorphous CaCO3 content was reduced. Notably, at elevated temperature with decreased pH and reduced salinity, the constructed tubes had a more compact ultrastructure with enhanced hardness and elasticity compared to decreased pH at ambient temperature. Thus, elevated temperature rescued the decreased pH-induced tube impairments. This indicates that tubeworms are likely to thrive in early subtropical summer climate. In the context of climate change, tubeworms could be resilient to the projected near-future decreased pH or salinity as long as surface seawater temperature rise at least by 4°C.

Geochemistry measured on sediment core GeoB12309-5

Laminated sediment records from the oxygen minimum zone in the Arabian Sea offer unique ultrahigh-resolution archives for deciphering climate variability in the Arabian Sea region. Although numerous analytical techniques are available it has become increasingly popular during the past decade to analyze relative variations of sediment cores' chemical signature by non-destructive X-ray fluorescence (XRF) core scanning. We carefully selected an approximately 5 m long sediment core from the northern Arabian Sea (GeoB12309-5: 24°52.3' N; 62°59.9' E, 956 m water depth) for a detailed, comparative study of high-resolution techniques, namely non-destructive XRF core scanning (0.8 mm resolution) and ICP-MS/OES analysis on carefully selected, discrete samples (1 mm resolution). The aim of our study was to more precisely define suitable chemical elements that can be accurately analyzed and to determine which elemental ratios can be interpretated down to sub-millimeter-scale resolutions. Applying the Student's t-test our results show significantly correlating (1% significance level) elemental patterns for all S, Ca, Fe, Zr, Rb, and Sr, as well as the K/Ca, Fe/Ti and Ti/Al ratios that are all related to distinct lithological changes. After careful consideration of all errors for the ICP analysis we further provide respective factors of XRF Core Scanner software error's underestimation by applying Chi-square-tests, which is especially relevant for elements with high count rates. As demonstrated by these new, ultra-high resolution data core scanning has major advantages (high-speed, low costs, few sample preparation steps) and represents an increasingly required alternative over the time consuming, expensive, elaborative, and destructive wet chemical analyses (e.g., by ICP-MS/OES after acid digestions), and meanwhile also provides high-quality data in unprecedented resolution.

(Table 1) Summary of coral geochemical data and reconstructed SST

We analyzed strontium/calcium ratios (Sr/Ca) in four colonies of the Atlantic coral genus Montastrea with growth rates ranging from 2.3 to 12.6 mm/a. Derived Sr/Ca-sea surface temperature (SST) calibrations exhibit significant differences among the four colonies that cannot be explained by variations in SST or seawater Sr/Ca. For a single coral Sr/Ca ratio of 8.8 mmol/mol, the four calibrations predict SSTs ranging from 24.0° to 30.9°C. We find that differences in the Sr/Ca-SST relationships are correlated systematically with the average annual extension rate (ext) of each colony such that Sr/Ca (mmol/mol) = 11.82 (±0.13) - 0.058 (±0.004) * ext (mm/a) - 0.092 (±0.005) * SST (°C). This observation is consistent with previous reports of a link between coral Sr/Ca and growth rate. Verification of our growth-dependent Sr/Ca-SST calibration using a coral excluded from the calibration reconstructs the mean and seasonal amplitude of the actual recorded SST to within 0.3°C. Applying a traditional, nongrowth-dependent Sr/Ca-SST calibration derived from a modern Montastrea to the Sr/Ca ratios of a conspecific coral that grew during the early Little Ice Age (LIA) (400 years B.P.) suggests that Caribbean SSTs were >5°C cooler than today. Conversely, application of our growth-dependent Sr/Ca-SST calibration to Sr/Ca ratios derived from the LIA coral indicates that SSTs during the 5-year period analyzed were within error (±1.4°C) of modern values.

Sea surface temperature and salinity reconstruction of sediment core GeoB3129-1

A sediment core from the western tropical Atlantic covering the last 21,000 yr has been analysed for centennial scale reconstruction of sea surface temperature (SST) and ice volume-corrected oxygen isotopic composition of sea water (delta18O(ivc-sw)) using Mg / Ca and delta18O of the shallow dwelling planktonic foraminifer Globigerinoides ruber (white). At a period between 15.5 and 17.5 kyr BP, the Mg / Ca SST and delta18O(ivc-sw), a proxy for sea surface salinity (SSS), reveals a warming of around 2.5 °C along with an increase in salinity. A second period of pronounced warming and SSS increase occurred between 11.6 and 13.5 kyr BP. Within age model uncertainties, both warming intervals were synchronous with air temperature increase over Antarctica and ice retreat in the southern South Atlantic and terminated with abrupt centennial scale SSS decrease and slight SST cooling in conjunction with interglacial reactivation of the meridional overturning circulation (MOC). We suggest that during these warm intervals, production of saline and warm water of the North Brazil Current resulted in pronounced heat and salt accumulation, and was associated with warming in the southern Atlantic, southward displacement of the intertropical convergence zone and weakened MOC. At the termination of the Younger Dryas and Heinrich event 1, intensification of cross-equatorial heat and salt transport caused centennial scale cooling and freshening of the western tropical Atlantic surface water. This study shows that the western tropical Atlantic served as a heat and salt reservoir during deglaciation. The sudden release of accumulated heat and salt at the end of Younger Drays and Heinrich event 1 may have contributed to the rapid reinvigoration of the Atlantic MOC.

Pollen analysis, particle size analysis, end-member modelling and x-ray fluorescence measurements from sediment cores off Cape Ghir, Morocco

Understanding past human-climate-environment interactions is essential for assessing the vulnerability of landscapes and ecosystems to future climate change. This is particularly important in southern Morocco where the current vegetation is impacted by pastoralism, and the region is highly sensitive to climate variability. Here, we present a 2000-year record of vegetation, sedimentation rate, XRF chemical element intensities, and particle size from two decadal-resolved, marine sediment cores, raised from offshore Cape Ghir, southern Morocco. The results show that between 650 and 850 AD the sedimentation rate increased dramatically from 100 cm/1000 years to 300 cm/1000 years, and the Fe/Ca and pollen flux doubled, together indicating higher inputs of terrestrial sediment. Particle size measurements and end-member modelling suggest increased fluvial transport of the sediment. Beginning at 650 AD pollen levels from Cichorioideae species show a sharp rise from 10% to 20%. Pollen from Atemisia and Plantago, also increase from this time. Deciduous oak pollen percentages show a decline, whereas those of evergreen oak barely change. The abrupt increase in terrestrial/fluvial input from 650 to 850 AD occurs, within the age uncertainty, of the arrival of Islam (Islamisation) in Morocco at around 700 AD. Historical evidence suggests Islamisation led to population increase and development of southern Morocco, including expanded pastoralism, deforestation and agriculture. Livestock pressure may have changed the vegetation structure, accounting for the increase in pollen from Cichorioideae, Plantago, and Artemisia, which include many weedy species. Goats in particular may have played a dominant role as agents of erosion, and intense browsing may have led to the decline in deciduous oak; evergreen oak is more likely to survive as it re-sprouts more vigorously after browsing. From 850 AD to present sedimentation rates, Fe/Ca ratios and fluvial discharge remain stable, whereas pollen results suggest continued degradation. Pollen results from the past 150 years suggest expanded cultivation of olives and the native argan tree, and the introduction of Australian eucalyptus trees. The rapidly increasing population in southern Morocco is causing continued pressure to expand pastoralism and agriculture. The history of land degradation presented here suggests that the vegetation in southern Morocco may have been degraded for a longer period than previously thought and may be particularly sensitive to further land use changes. These results should be included in land management strategies for southern Morocco.

Geochemical composition and ages of sediment core BELQ300 obtained from Lake Belau, north Germany

Geochemical and palynological data from an annually laminated core sequence (Lake Belau, Schleswig-Holstein) are interpreted with respect to vegetation and settlement history on the basis of a chronostratigraphical model and archaeological evidence. Most settlement periods indicated by pollen and archaeological data can be geochemically identified in the sediment sequence using tracer elements such as K, Rb, Zr and the K/Zr ratio. Whilst air-borne pollen carry a more regional signal, the sedimentary flux of these trace elements is determined by the allogenic input from the catchment area of the lake and, therefore, provides information about the local history of settlement and agricultural land use in the lake's vicinity. This is exemplified for the period of the middle Neolithic Funnel Beaker Culture ('Iversen landnam'), where a time offset of 250 years between both signals has been detected. In contrast, both geochemical and pollen signals are highly synchronous during the Early Migration Period and the High Medieval Period. Additionally, the Fe/Ca and/or U/Fe ratio may serve as a sensitive tracer for human impact on the trophic state of the lake. The suggested impact of the Romans and the High Medieval civilization can clearly be seen (and quantified) from elevated lead input into Lake Belau sediments at this time. Effects of secular climatic changes on the sedimentary chemistry have not been detected and, if present, seem to have been obliterated by anthropogenic activity.

Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

Skeletal density of Porites

Paleotemperature estimates based on coral Sr/Ca have not been widely accepted because the reconstructed glacial-Holocene shift in tropical sea-surface temperature (~4-6°C) is larger than that indicated by foraminiferal Mg/Ca (~2-4°C). We show that corals over-estimate changes in sea-surface temperature (SST) because their records are attenuated during skeletogenesis within the living tissue layer. To quantify this process, we microprofiled skeletal mass accumulation within the tissue layer of Porites from Australasian coral reefs and laboratory culturing experiments. The results show that the sensitivity of the Sr/Ca and d18O thermometers in Porites will be suppressed, variable, and dependent on the relationship between skeletal growth rate and mass accumulation within the tissue layer. Our findings help explain why d18O-SST sensitivities for Porites range from -0.08 per mil/°C to -0.22 per mil/°C and are always less than the value of -0.23 per mil/°C established for biogenic aragonite. Based on this observation, we recalibrated the coral Sr/Ca thermometer to determine a revised sensitivity of -0.084 mmol/mol/°C. After rescaling, most of the published Sr/Ca-SST estimates for the Indo-Pacific region for the last ~14,000 years (-7°C to +2°C relative to modern) fall within the 95% confidence envelope of the foraminiferal Mg/Ca-SST records. We conclude that two types of calibration scales are required for coral paleothermometry; an attenuated Porites-specific thermometer sensitivity for studies of seasonal to interannual change in SST and, importantly, the rescaled -0.084 mmol/mol/°C Sr/Ca sensitivity for studies of 20th-century trends and millennial-scale changes in mean SST. The calibration-scaling concept will apply to the development of transfer functions for all geochemical tracers in corals.

Calcium isotopes in planktonic foraminifera - core tops and sediment trap samples

For paleoceanographic studies, it is important to understand the processes that influence the calcium (Ca) isotopic composition of foraminiferal calcite tests preserved in the sediment record. Seven species of planktonic foraminifera from coretop sediments collectively exhibited a Ca temperature dependent fractionation of 0.013 per mil per °C. This is in agreement with previously published estimates for most species of planktonic foraminifera as well as biogenic and inorganic calcite and aragonite. Four species of planktonic foraminifera collected from a sediment trap showed a considerable amount of scatter and no consistent temperature dependent fractionation. Analyzed size fractions of coretop samples show no significant relationship with d44/40Ca. However, preliminary results suggest that the symbiotic and spinose foraminifera G. sacculifer might exhibit a relationship between test size and d44/40Ca. A one-box model in which Ca isotopes are allowed to fractionate by Rayleigh distillation from a biomineralization reservoir (internal pool) was used to constrain the isotopic composition of the original biomineralization Ca reservoir, assuming around 85% of the Ca reservoir is precipitated and the fractionation factor during precipitation is 0.9985 + 0.00002(T ºC). To explain the foraminiferal Ca isotope data, this model indicates that the Ca isotopic composition of the biomineralization reservoir is offset from seawater (approximately -0.8per mil).

Age model and stable oxygen isotope analyses of sediment core GeoB8507-3

The present study is the first study on the stable oxygen isotope composition of the photosynthetic calcareous-walled dinoflagellate species Thoracosphaera heimii off NW Africa during the last 45,000 yr. T. heimii based temperature estimates of sediment core GeoB 8507-3 were compared with those obtained from the stable oxygen isotopes of the planktic foraminifera Globigerina bulloides and Globigerinoides ruber (pink), and the Mg/Ca ratio of G. ruber (pink). We show that the isotopic composition of T. heimii and the temperature estimates based on the equation for inorganically precipitated calcite provide comparable results to those obtained from G. ruber (pink) isotopes and Mg/Ca ratios with exception of the Early Holocene and the Younger Dryas. The recently proposed palaeotemperature equation of Zonneveld et al. (2007), however, provides unrealistic temperature reconstructions that are about 16 °C lower than those based on planktic foraminifera. Thus, this equation needs to be revised. The difference between T. heimii and G. bulloides isotopic and temperature reconstructions can be ascribed to differences in the ecology of both species, especially with regard to their depth habitat and/or seasonal production in the research area. All temperature proxies suggest comparable conditions during the last glacial and Holocene. Small differences between the reconstructed temperature values of T. heimii and the other proxies can be explained by differences in seasonal production of the individual species. The relatively low temperatures recorded by T. heimii at about 15,000 to 8,000 yr BP are interpreted to reflect an increase in duration and/or intensity of the upwelling in the vicinity of the core site in comparison to the last glacial, with an abrupt and strong decrease of upwelling intensity and/or duration during the Early Holocene and the Younger Dryas.