Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.

(Table 1) Bulk geochemistry of sediment cores KH-79-3_L3 and KH-79-3_C3

The organic and isotopic geochemical study of two sediment cores (KH-79-3, L-3, and KH-79-3, C-3) from the Oki Ridge in the Japan Sea has revealed that total organic carbon (TOC) mass accumulation rates are extremely high in the 12-11 ka (calendar age) interval and TOC in the sections in the 24-17 ka interval is depleted in 13C by 3.5? relative to Holocene sediments. Alkenone sea surface temperature (SST) shows a decrease from 18° to 14°C from 17.5 to 11.6 ka and a sharp increase from 14° to 19°C from 11.6 to 11.1 ka. The SST changes are associated with the inflow of cold seawater with the vertical water mixing and the inflowof warm Tsushima Current into the Japan Sea. The d13C values for both 24-methylcholesta-5,22-dien-3?-ol (diatom marker) and dinosterol (dinoflagellate marker), are at their minimum from 24 to 17 ka, while those for long-chain alkenones are not. The theoretical considerations on d13C for biomarkers suggest low photosynthetic carbon demand of diatoms and dinoflagellates from 24 to 17 ka.

Climate variability in the Aegean Sea (marine record M2, Athos basin) during the past 1500 years

We provide new evidence on sea surface temperature (SST) variations and paleoceanographic/paleoenvironmental changes over the past 1500 years for the north Aegean Sea (NE Mediterranean). The reconstructions are based on multiproxy analyses, obtained from the high resolution (decadal to multi-decadal) marine record M2 retrieved from the Athos basin. Reconstructed SSTs show an increase from ca. 850 to 950 AD and from ca. 1100 to 1300 AD. A cooling phase of almost 1.5 °C is observed from ca. 1600 AD to 1700 AD. This seems to have been the starting point of a continuous SST warming trend until the end of the reconstructed period, interrupted by two prominent cooling events at 1832 ± 15 AD and 1995 ± 1 AD. Application of an adaptive Kernel smoothing suggests that the current warming in the reconstructed SSTs of the north Aegean might be unprecedented in the context of the past 1500 years. Internal variability in atmospheric/oceanic circulations systems as well as external forcing as solar radiation and volcanic activity could have affected temperature variations in the north Aegean Sea over the past 1500 years. The marked temperature drop of approximately ~2 °C at 1832 ± 15 yr AD could be related to the 1809 ?D 'unknown' and the 1815 AD Tambora volcanic eruptions. Paleoenvironmental proxy-indices of the M2 record show enhanced riverine/continental inputs in the northern Aegean after ca. 1450 AD. The paleoclimatic evidence derived from the M2 record is combined with a socio-environmental study of the history of the north Aegean region. We show that the cultivation of temperature-sensitive crops, i.e. walnut, vine and olive, co-occurred with stable and warmer temperatures, while its end coincided with a significant episode of cooler temperatures. Periods of agricultural growth in Macedonia coincide with periods of warmer and more stable SSTs, but further exploration is required in order to identify the causal links behind the observed phenomena. The Black Death likely caused major changes in agricultural activity in the north Aegean region, as reflected in the pollen data from land sites of Macedonia and the M2 proxy-reconstructions. Finally, we conclude that the early modern peaks in mountain vegetation in the Rhodope and Macedonia highlands, visible also in the M2 record, were very likely climate-driven.

Chemical and isotopic compositions of water, particulates, plankton, gases, sediments, and minerals from the Kara Sea and lower Ob and Yenisei Rivers

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea, into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions onboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The d13C varies from -22 and -24 per mil where Atlantic waters enter the Kara Sea and in the north-eastern part of the water area to -27 per mil in the Yenisei and Ob estuaries. The value of d13C of the plankton is only weakly correlated with the d13C of the organic matter from the sediments and is lower by as much as 3-4 per mil. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the river waters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the offshore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from -29 to -35 per mil in the riverine part, from -28 to -27 per mil in the estuaries, and from -27.0 to -25 per mil in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with river waters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of d13C. The complex of hydrocarbon gases extracted from the waters included methane, C2-C5, and unsaturated C2=-C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3-5 µl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with d13C from -105 to -90 per mil first occurs in the sediments at depths of 40-200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the d13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (d13C from -25 to -60 per mil) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea.

Sea-surface temperature reconstruction of sediment cores from the Skagerrak

We attempt a reconstruction of salinity levels of the central Baltic Sea based on diatom assemblages, the isotopic composition of organic matter and sedimentological expression of anoxia over the last 10 000 years. We use the data to investigate the dependence of salinity levels on climate evolution and isostasy. Changes in salinity of surface and deep waters were most pronounced from 8400 to approximately 5000 cal. BP. Density stratification between salty deep and fresher surface waters caused the frequent development of anoxic conditions and deposition of laminated sediments on large parts of the sea floor in the central Baltic Sea, and dramatic changes in organic carbon-accumulation rates. From 5000 to 3100 cal. BP, the salinity of the basin decreased, oxygenation of deep sea floors was improved, and fertility of the sea surface was significantly reduced. This is reflected by low accumulation rates of organic carbon in bioturbated sediments. Since 2800 cal. BP, salinity rose again and anoxic periods were more common. Even though the major steps in environmental evolution in the Baltic Sea coincide with known patterns of climatic change of the North Atlantic realm over the last 10 000 years, we find no conclusive evidence for synchronous changes or linear responses on submillennial timescales. However, we note that major variations in our salinity records agree with temporal patterns of reconstructed summer warmth and winter precipitation in southern Scandinavia. Both types of record suggest that climate in the mid-Holocene was far from stable. Our data also confirm that climate evolution over the late Holocene had significant impact on environmental conditions in the Baltic Sea.

Sedimentary record of the western Amundsen Sea Embayment after the last glacial maximum

Reliable dating of glaciomarine sediments deposited on the Antarctic shelf since the Last Glacial Maximum (LGM) is very challenging because of the general absence of calcareous (micro-) fossils and the recycling of fossil organic matter. As a consequence, radiocarbon (14C) ages of the acid-insoluble organic fraction (AIO) of the sediments bear uncertainties that are very difficult to quantify. In this paper we present the results of three different chronostratigraphic methods to date a sedimentary unit consisting of diatomaceous ooze and diatomaceous mud that was deposited following the last deglaciation at five core sites on the inner shelf in the western Amundsen Sea (West Antarctica). In three cores conventional 14C dating of the AIO in bulk sediment samples yielded age reversals down-core, but at all sites the AIO 14C ages obtained from diatomaceous ooze within the diatom-rich unit yielded similar uncorrected 14C ages ranging from 13,517±56 to 11,543±47 years before present (yr BP). Correction of these ages by subtracting the core-top ages, which are assumed to reflect present-day deposition (as indicated by 21044 Pb dating of the sediment surface at one core site), yielded ages between ca. 10,500 and 8,400 calibrated years before present (cal yr BP). Correction of the AIO ages of the diatomaceous ooze by only subtracting the marine reservoir effect (MRE) of 1,300 years indicated deposition of the diatom-rich sediments between 14,100 and 11,900 cal yr BP. Most of these ages are consistent with age constraints between 13.0 and 8.0 ka BP for the diatom-rich unit, which we obtained by correlating the relative palaeomagnetic intensity (RPI) records of three of the sediment cores with global and regional reference curves for palaeomagnetic intensity. As a third dating technique we applied conventional 53 radiocarbon dating of the AIO included in acid-cleaned diatom hard parts that were extracted from the diatomaceous ooze. This method yielded uncorrected 14C ages of only 5,111±38 and 5,106±38 yr BP, respectively. We reject these young ages, because they are likely to be overprinted by the adsorption of modern atmospheric carbon dioxide onto the surfaces of the extracted diatom hard parts prior to sample graphitisation and combustion for 14C dating. The deposition of the diatom-rich unit in the western Amundsen Sea suggests deglaciation of the inner shelf before ca. 13 ka BP. The deposition of diatomaceous oozes on other parts of the Antarctic shelf around the same time, however, seems to be coincidental rather than directly related.

Bulk sediment parameter of three sediment cores from permafrost lowlands, Alaska Arctic Coastal Plain

Arctic lowland landscapes have been modified by thermokarst lake processes throughout the Holocene. Thermokarst lakes form as a result of ice-rich permafrost degradation and they may expand over time through thermal and mechanical shoreline erosion. We studied proximal and distal sedimentary records from a thermokarst lake located on the Arctic Coastal Plain of northern Alaska to reconstruct the impact of catchment dynamics and morphology on the lacustrine depositional environment and to quantify carbon accumulation in thermokarst lake sediments. Short cores were collected for analysis of pollen, sedimentological and geochemical proxies. Radiocarbon and Pb/Cs dating, as well as extrapolation of measured historic lake expansion rates, were applied to estimate a minimum lake age of ~ 1,400 calendar years BP. The pollen record is in agreement with the young lake age as it does not include evidence of the "alder high" that occurred in the region ~ 4.0 cal ka BP. The lake most likely initiated from a remnant pond in a drained thermokarst lake basin (DTLB) and deepened rapidly as evidenced by accumulation of laminated sediments. Increasing oxygenation of the water column as shown by higher Fe/Ti and Fe/S ratios in the sediment indicate shifts in ice regime with increasing water depth. More recently, the sediment source changed as the thermokarst lake expanded through lateral permafrost degradation, alternating from redeposited DTLB sediments, to increased amounts of sediment from eroding, older upland deposits, followed by a more balanced combination of both DTLB and upland sources. The characterizing shifts in sediment sources and depositional regimes in expanding thermokarst lakes were therefore archived in the thermokarst lake sedimentary record. This study also highlights the potential for Arctic lakes to recycle old carbon from thawing permafrost and thermokarst processes.

Multi-proxy records of Two-Yurts Lake

Within the scope of Russian-German palaeoenvironmental research, Two-Yurts Lake (TYL, Dvuh-Yurtochnoe in Russian) was chosen as the main scientific target area to decipher Holocene climate variability on Kamchatka. The 5x2 km large and 26 m deep lake is of proglacial origin and situated on the eastern flank of Sredinny Ridge at the northwestern end of the Central Kamchatka Valley, outside the direct influence of active volcanism. Here, we present results of a multi-proxy study on sediment cores, spanning about the last 7000 years. The general tenor of the TYL record is an increase in continentality and winter snow cover in conjunction with a decrease in temperature, humidity, and biological productivity after 5000-4500 cal yrs BP, inferred from pollen and diatom data and the isotopic composition of organic carbon. The TYL proxy data also show that the late Holocene was punctuated by two colder spells, roughly between 4500 and 3500 cal yrs BP and between 1000 and 200 cal yrs BP, as local expressions of the Neoglacial and Little Ice Age, respectively. These environmental changes can be regarded as direct and indirect responses to climate change, as also demonstrated by other records in the regional terrestrial and marine realm. Long-term climate deterioration was driven by decreasing insolation, while the short-term climate excursions are best explained by local climatic processes. The latter affect the configuration of atmospheric pressure systems that control the sources as well as the temperature and moisture of air masses reaching Kamchatka.