Calcium carbonate and organic carbon content, and stable isotope composition of sediment core Y71-3-2

Planktic stable isotopes by Mix for this paper and Pisias and Mix (1997)

Stable isotope record, carbonate and organic carbon content of the Miocene section of IODP Site 321-U1337

The Miocene Climatic Optimum (~17-14.7 Ma) represents one of several major interruptions in the long-term cooling trend of the past 50 million years. To date, the processes driving high-amplitude climate variability and sustaining global warmth during this remarkable interval remain highly enigmatic. We present high-resolution benthic foraminiferal and bulk carbonate stable isotope records in an exceptional, continuous, carbonate-rich sedimentary archive (Integrated Ocean Drilling Program Site U1337, eastern equatorial Pacific Ocean), which offer a new view of climate evolution over the onset of the Climatic Optimum. A sharp decline in d18O and d13C at ~16.9 Ma, contemporaneous with a massive increase in carbonate dissolution, demonstrates that abrupt warming was coupled to an intense perturbation of the carbon cycle. The rapid recovery in d13C at ~16.7 Ma, ~200 k.y. after the beginning of the MCO, marks the onset of the first carbon isotope maximum within the long-lasting "Monterey Excursion". These results lend support to the notion that atmospheric pCO2 variations drove profound changes in the global carbon reservoir through the Climatic Optimum, implying a delicate balance between changing CO2 fluxes, rates of silicate weathering and global carbon sequestration. Comparison with a high-resolution d13C record spanning the onset of the Cretaceous Oceanic Anoxic Event 1a (~120 Ma ago) reveals common forcing factors and climatic responses, providing a long-term perspective to understand climate-carbon cycle feedbacks during warmer periods of Earth's climate with markedly different atmospheric CO2 concentrations.

Stable isotope ratios, carbon content and primary production of three sediment cores from the subantarctic eastern Atlantic

We present three new benthic foraminiferal delta13C, delta18O, and total organic carbon time series from the eastern Atlantic sector of the Southern Ocean between 41°S and 47°S. The measured glacial delta13C values belong to the lowest hitherto reported. We demonstrate a coincidence between depleted late Holocene (LH) delta13C values and positions of sites relative to ocean surface productivity. A correction of +0.3 to +0.4 [per mil VPDB] for a productivity-induced depletion of Last Glacial Maximum (LGM) benthic delta13C values of these cores is suggested. The new data are compiled with published data from 13 sediment cores from the eastern Atlantic Ocean between 19°S and 47°S, and the regional deep and bottom water circulation is reconstructed for LH (4-0 ka) and LGM (22-16 ka) times. This extends earlier eastern Atlantic-wide synoptic reconstructions which suffered from the lack of data south of 20°S. A conceptual model of LGM deep-water circulation is discussed that, after correction of southernmost cores below the Antarctic Circumpolar Current (ACC) for a productivity-induced artifact, suggests a reduced formation of both North Atlantic Deep Water in the northern Atlantic and bottom water in the southwestern Weddell Sea. This reduction was compensated for by the formation of deep water in the zone of extended winter sea-ice coverage at the northern rim of the Weddell Sea, where air-sea gas exchange was reduced. This shift from LGM deep-water formation in the region south of the ACC to Holocene bottom water formation in the southwestern Weddell Sea, can explain lower preformed d13CDIC values of glacial circumantarctic deep water of approximately 0.3 per mil to 0.4 per mil. Our reconstruction brings Atlantic and Southern Ocean d13C and Cd/Ca data into better agreement, but is in conflict, however, with a scenario of an essentially unchanged thermohaline deep circulation on a global scale. Benthic delta18O-derived LGM bottom water temperatures, by 1.9°C and 0.3°C lower than during the LH at deepest southern and shallowest northern sites, respectively, agree with the here proposed reconstruction of deep-water circulation in the eastern South Atlantic Ocean.

Layer description, carbon and nitrogen content and stable isotope record of bulk sedimentary organic matter from Laguna Potrok Aike

An investigation of stable isotope (d13C TOC and d15N TN) and elemental parameters (TOC, TN contents and TOC/TN ratios) of bulk organic matter (<200 µm) from sediment cores recovered from the Patagonian lake Laguna Potrok Aike (Argentina) in the framework of the ICDP deep drilling project PASADO provided insights into past changes in lake primary productivity and environmental conditions in South Patagonia throughout the last Glacial-Interglacial transition. Stratigraphically constrained cluster analyses of all proxy parameters suggest four main phases. From ca 26,100 to 17,300 cal. years BP, lacustrine phytoplankton was presumably the predominant organic matter source in an aquatic environment with low primary productivity rates. At around 17,300 cal. years BP, abrupt and distinct shifts of isotopic and elemental values indicate that the lacustrine system underwent a rapid reorganization. Lake primary productivity (phytoplankton and aquatic macrophytes) shows higher levels albeit with large variations during most of the deglaciation until 13,000 cal. years BP. The main causes for this development can be seen in improved growing conditions for primary producers because of deglacial warming in combination with expedient availability of nutrients and likely calm wind conditions. After 13,000 cal. years BP, decreased d13C TOC values, TOC, TN contents and TOC/TN ratios indicate that the lake approached a new state with reduced primary productivity probably induced by unfavourable growing conditions for primary producers like strengthened winds and reduced nutrient availability. The steady increase in d15N TN values presumably suggests limitation of nitrate supply for growth of primary producers resulting from a nutrient shortage after the preceding phase with high productivity. Nitrate limitation and consequent decreased lacustrine primary productivity continued into the early Holocene (10,970-8400 cal. years BP) as reflected by isotopic and elemental values.

Magnetic suceptibility, carbon and oxygen stable isotope ratios and reflectance from the Bottaccione Gorge and Furlo section, Italy

The oceans at the time of the Cenomanian-Turonian transition were abruptly perturbed by a period of bottom-water anoxia. This led to the brief but widespread deposition of black organic-rich shales, such as the Livello Bonarelli in the Umbria-Marche Basin (Italy). Despite intensive studies, the origin and exact timing of this event are still debated. In this study, we assess leading hypotheses about the inception of oceanic anoxia in the Late Cretaceous greenhouse world, by providing a 6-Myr-long astronomically-tuned timescale across the Cenomanian-Turonian boundary. We procure insights in the relationship between orbital forcing and the Late Cretaceous carbon cycle by deciphering the imprint of astronomical cycles on lithologic, geophysical, and stable isotope records, obtained from the Bottaccione, Contessa and Furlo sections in the Umbria-Marche Basin. The deposition of black shales and cherts, as well as the onset of oceanic anoxia, is related to maxima in the 405-kyr cycle of eccentricity-modulated precession. Correlation to radioisotopic ages from the Western Interior (USA) provides unprecedented age control for the studied Italian successions. The most likely tuned age for the Livello Bonarelli base is 94.17 ± 0.15 Ma (tuning #1); however, a 405-kyr older age cannot be excluded (tuning #2) due to uncertainties in stratigraphic correlation, radioisotopic dating, and orbital configuration. Our cyclostratigraphic framework suggests that the exact timing of major carbon cycle perturbations during the Cretaceous may be linked to increased variability in seasonality (i.e. a 405-kyr eccentricity maximum) after the prolonged avoidance of seasonal extremes (i.e. a 2.4-Myr eccentricity minimum). Volcanism is probably the ultimate driver of oceanic anoxia, but orbital periodicities determine the exact timing of carbon cycle perturbations in the Late Cretaceous. This unites two leading hypotheses about the inception of oceanic anoxia in the Late Cretaceous greenhouse world.

Development of a stable isotope index to assess decadal-scale vegetation change and application to woodlands of the Burdekin catchment, Australia

Forty-four study sites were established in remnant woodland in the Burdekin River catchment in tropical north-east Queensland, Australia, to assess recent (decadal) vegetation change. The aim of this study was further to evaluate whether wide-scale vegetation 'thickening' (proliferation of woody plants in formerly more open woodlands) had occurred during the last century, coinciding with significant changes in land management. Soil samples from several depth intervals were size separated into different soil organic carbon (SOC) fractions, which differed from one another by chemical composition and turnover times. Tropical (C4) grasses dominate in the Burdekin catchment, and thus δ13C analyses of SOC fractions with different turnover times can be used to assess whether the relative proportion of trees (C3) and grasses (C4) had changed over time. However, a method was required to permit standardized assessment of the δ13C data for the individual sites within the 13 Mha catchment, which varied in soil and vegetation characteristics. Thus, an index was developed using data from three detailed study sites and global literature to standardize individual isotopic data from different soil depths and SOC fractions to reflect only the changed proportion of trees (C3) to grasses (C3) over decadal timescales. When applied to the 44 individual sites distributed throughout the Burdekin catchment, 64% of the sites were shown to have experienced decadal vegetation thickening, while 29% had remained stable and the remaining 7% had thinned. Thus, the development of this index enabled regional scale assessment and comparison of decadal vegetation patterns without having to rely on prior knowledge of vegetation changes or aerial photography.

Cannibalism contributes significantly to the diet of cultured sand crabs, Portunus pelagicus (L.): A dual stable isotope study

The significance of cannibalism in the diet of juvenile pond-cultured blue swimmer crabs (Portunus pelagicus (L.)) was investigated using dual stable isotope analysis of carbon and nitrogen. In a laboratory feeding experiment, δ15N demonstrated a constant trophic shift (Δδ15N ≈+ 1.6‰), and therefore seemed to be a reliable indicator for assessing trophic position for P. pelagicus. This agrees with previously reported trends. Difference in growth rate did not seem to influence δ15N values. In contrast, δ13C did not display consistent shifts between trophic levels (range of Δδ13C: + 1 to + 1.7‰). The results from the pond experiment showed that larger individuals had a more enriched δ15N than smaller individuals, which, when compared to the results from the laboratory experiment, indicates that larger individuals were at a higher trophic level. This is most likely due to cannibalism prevailing in the pond rather than a direct result of faster growth rate. Cannibalistic behaviour might further increase growth, resulting in the observed positive correlation between size and δ15N.

Isotopic fingerprints in surficial waters : Stable isotope methods applied in hydrogeological studies

The driving force behind this study has been the need to develop and apply methods for investigating the hydrogeochemical processes of significance to water management and artificial groundwater recharge. Isotope partitioning of elements in the course of physicochemical processes produces isotopic variations to their natural reservoirs. Tracer property of the stable isotope abundances of oxygen, hydrogen and carbon has been applied to investigate hydrogeological processes in Finland. The work described here has initiated the use of stable isotope methods to achieve a better understanding of these processes in the shallow glacigenic formations of Finland. In addition, the regional precipitation and groundwater records will supplement the data of global precipitation, but as importantly, provide primary background data for hydrological studies. The isotopic composition of oxygen and hydrogen in Finnish groundwaters and atmospheric precipitation was determined in water samples collected during 1995 2005. Prior to this study, no detailed records existed on the spatial or annual variability of the isotopic composition of precipitation or groundwaters in Finland. Groundwaters and precipitation in Finland display a distinct spatial distribution of the isotopic ratios of oxygen and hydrogen. The depletion of the heavier isotopes as a function of increasing latitude is closely related to the local mean surface temperature. No significant differences were observed between the mean annual isotope ratios of oxygen and hydrogen in precipitation and those in local groundwaters. These results suggest that the link between the spatial variability in the isotopic composition of precipitation and local temperature is preserved in groundwaters. Artificial groundwater recharge to glaciogenic sedimentary formations offers many possibilities to apply the isotopic ratios of oxygen, hydrogen and carbon as natural isotopic tracers. In this study the systematics of dissolved carbon have been investigated in two geochemically different glacigenic groundwater formations: a typical esker aquifer at Tuusula, in southern Finland and a carbonate-bearing aquifer with a complex internal structure at Virttaankangas, in southwest Finland. Reducing the concentration of dissolved organic carbon (DOC) in water is a primary challenge in the process of artificial groundwater recharge. The carbon isotope method was used to as a tool to trace the role of redox processes in the decomposition of DOC. At the Tuusula site, artificial recharge leads to a significant decrease in the organic matter content of the infiltrated water. In total, 81% of the initial DOC present in the infiltrated water was removed in three successive stages of subsurface processes. Three distinct processes in the reduction of the DOC content were traced: The decomposition of dissolved organic carbon in the first stage of subsurface flow appeared to be the most significant part in DOC removal, whereas further decrease in DOC has been attributed to adsorption and finally to dilution with local groundwater. Here, isotope methods were used for the first time to quantify the processes of DOC removal in an artificial groundwater recharge. Groundwaters in the Virttaankangas aquifer are characterized by high pH values exceeding 9, which are exceptional for shallow aquifers on glaciated crystalline bedrock. The Virttaankangas sediments were discovered to contain trace amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. Understanding the origin of the unusual geochemistry of the Virttaankangas groundwaters is an important issue for constraining the operation of the future artificial groundwater plant. The isotope ratios of oxygen and carbon in sedimentary carbonate minerals have been successfully applied to constrain the origin of the dispersed calcite in the Virttaankangas sediments. The isotopic and chemical characteristics of the groundwater in the distinct units of aquifer were observed to vary depending on the aquifer mineralogy, groundwater residence time and the openness of the system to soil CO2. The high pH values of > 9 have been related to dissolution of calcite into groundwater under closed or nearly closed system conditions relative to soil CO2, at a low partial pressure of CO2.

Environmental and climatic dependences of stable isotope ratios in tree rings on different temporal scales

This work examines stable isotope ratios of carbon, oxygen and hydrogen in annual growth rings of trees. Isotopic composition in wood cellulose is used as a tool to study past climate. The method benefits from the accurate and precise dating provided by dendrochronology. In this study the origin, nature and the strength of climatic correlations are studied on different temporal scales and at different sites in Finland. The origin of carbon isotopic signal is in photosynthetic fractionation. The basic physical and chemical fractionations involved are reasonably well understood. This was confirmed by measuring instantaneous photosynthetic discrimination on Scots pine (Pinus sylvestris L.). The internal conductance of CO2 was recognized to have a significant impact on the observed fractionation, and further investigations are suggested to quantify its role in controlling the isotopic signal of photosynthates. Isotopic composition of the produced biomass can potentially be affected by variety of external factors that induce physiological changes in trees. Response of carbon isotopic signal in tree ring cellulose to changes in resource availability was assessed in a manipulation experiment. It showed that the signal was relatively stable despite of changes in water and nitrogen availability to the tree. Palaeoclimatic reconstructions are typically based on functions describing empirical relationship between isotopic and climatic parameters. These empirical relationships may change depending on the site conditions, species and timeframe studied. Annual variation in Scots pine tree ring carbon and oxygen isotopic composition was studied in northern and in central eastern Finland and annual variation in tree ring latewood carbon, oxygen and hydrogen isotopic ratio in Oak (Quercus robur L.) was studied in southern Finland. In all of the studied sites at least one of the studied isotope ratios was shown to record climate strongly enough to be used in climatic reconstructions. Using the observed relationships, four-century-long climate reconstructions from living Scots pine were created for northern and central eastern Finland. Also temporal stability of the relationships between three proxy indicators, tree ring growth and carbon and oxygen isotopic composition was studied during the four-hundred-year period. Isotope ratios measured from tree rings in Finland were shown to be sensitive indicators of climate. Increasing understanding of environmental controls and physiological mechanisms affecting tree ring isotopic composition will make possible more accurate interpretation of isotope data. This study also demonstrated that by measuring multiple isotopes and physical proxies from the same tree rings, additional information on tree physiology can be obtained. Thus isotopic ratios measured from tree ring cellulose provide means to improve the reliability of climate reconstructions.

Stable isotope evidence for ca. 2.7-Ga-old Archean cap carbonates from the Dharwar Supergroup, southern India

Carbon isotope compositions of carbonate rocks from similar to 2.7-Ga-old Neoarchean Vanivilas Formation of the Dharwar Supergroup presented earlier by us are re-evaluated in this study, besides oxygen isotope compositions of a few silica dolomite pairs. The purpose of such a revisit assumes significance in view of recent field evidences that suggest a glaciomarine origin for the matrix-supported conglomerate member, the Talya conglomerate, which underlies the carbonate rocks of the Vanivilas Formation. An in-depth analysis of carbon isotope data reveals preservation of their pristine character despite the rocks having been subjected to metamorphism to different degrees (from lower greenschist to lower amphibolite facies). The dolomitic member of Vanivilas Formation of Marikanive area is characterized by highly depleted delta C-13 value (up to -5 parts per thousand VPDB) and merits as the Indian example of ca. 2.7-Ga-old cap carbonate. This inference is further supported by estimated low temperature of equilibration documented by a few silica dolomite pairs from the Vanivilas Formation collected near Kalche area. These pairs show evidence for oxygen isotopic equilibrium at low temperatures (similar to 0-20 degrees C) with depleted water (delta O-18 = -21 parts per thousand to -15 parts per thousand VSMOW) of glacial origin. We propose that the mineral pairs were deposited during the deglaciation period when the ocean temperature was in its gradual restoration phase. The dolomite of Marikanive area is the first record of cap carbonates from the Indian subcontinent with Neoarchean antiquity.