Wetland maps including open water extent dynamics based on ENVISAT ASAR WS for Siberia, 2007 and 2008, links to GeoTIFFs

Wetlands store large amounts of carbon, and depending on their status and type, they release specific amounts of methane gas to the atmosphere. The connection between wetland type and methane emission has been investigated in various studies and utilized in climate change monitoring and modelling. For improved estimation of methane emissions, land surface models require information such as the wetland fraction and its dynamics over large areas. Existing datasets of wetland dynamics present the total amount of wetland (fraction) for each model grid cell, but do not discriminate the different wetland types like permanent lakes, periodically inundated areas or peatlands. Wetland types differently influence methane fluxes and thus their contribution to the total wetland fraction should be quantified. Especially wetlands of permafrost regions are expected to have a strong impact on future climate due to soil thawing. In this study ENIVSAT ASAR Wide Swath data was tested for operational monitoring of the distribution of areas with a long-term SW near 1 (hSW) in northern Russia (SW = degree of saturation with water, 1 = saturated), which is a specific characteristic of peatlands. For the whole northern Russia, areas with hSW were delineated and discriminated from dynamic and open water bodies for the years 2007 and 2008. The area identified with this method amounts to approximately 300,000 km**2 in northern Siberia in 2007. It overlaps with zones of high carbon storage. Comparison with a range of related datasets (static and dynamic) showed that hSW represents not only peatlands but also temporary wetlands associated with post-forest fire conditions in permafrost regions. Annual long-term monitoring of change in boreal and tundra environments is possible with the presented approach. Sentinel-1, the successor of ENVISAT ASAR, will provide data that may allow continuous monitoring of these wetland dynamics in the future complementing global observations of wetland fraction.

Consistent increase in dimethyl sulfide (DMS) in response to high CO2 in five shipboard bioassays from contrasting NW European waters

The ubiquitous marine trace gas dimethyl sulfide (DMS) comprises the greatest natural source of sulfur to the atmosphere and is a key player in atmospheric chemistry and climate. We explore the short-term response of DMS production and cycling and that of its algal precursor dimethyl sulfoniopropionate (DMSP) to elevated carbon dioxide (CO2) and ocean acidification (OA) in five 96 h shipboard bioassay experiments. Experiments were performed in June and July 2011, using water collected from contrasting sites in NW European waters (Outer Hebrides, Irish Sea, Bay of Biscay, North Sea). Concentrations of DMS and DMSP, alongside rates of DMSP synthesis and DMS production and consumption, were determined during all experiments for ambient CO2 and three high-CO2 treatments (550, 750, 1000 µatm). In general, the response to OA throughout this region showed little variation, despite encompassing a range of biological and biogeochemical conditions. We observed consistent and marked increases in DMS concentrations relative to ambient controls (110% (28-223%) at 550 µatm, 153% (56-295%) at 750 µatm and 225% (79-413%) at 1000 µatm), and decreases in DMSP concentrations (28% (18-40%) at 550 µatm, 44% (18-64%) at 750 µatm and 52% (24-72%) at 1000 µatm). Significant decreases in DMSP synthesis rate constants (µDMSP /d) and DMSP production rates (nmol/d) were observed in two experiments (7-90% decrease), whilst the response under high CO2 from the remaining experiments was generally indistinguishable from ambient controls. Rates of bacterial DMS gross consumption and production gave weak and inconsistent responses to high CO2. The variables and rates we report increase our understanding of the processes behind the response to OA. This could provide the opportunity to improve upon mesocosm-derived empirical modelling relationships and to move towards a mechanistic approach for predicting future DMS concentrations.

(Table 2) Integrated concentration, production and dissolution of silica in the water column of the southern Pacific

An intense diatom bloom developed within a strong meridional silicic acid gradient across the Antarctic Polar Front at 61°S, 170°W following stratification of the water column in late October/early November 1997. The region of high diatom biomass and the silicic acid gradient propogated southward across the Seasonal Ice Zone through time, with the maximum diatom biomass tracking the center of the silicic acid gradient. High diatom biomass and high rates of silica production persisted within the silicic acid gradient until the end of January 1998 (ca. 70 d) driving the gradient over 500 km to the south of its original position at the Polar Front. The bloom consumed 30 to >40 µM Si(OH)4 in the euphotic zone between about 60 and 66°S leaving near surface concentrations <2.5 µM and occasionally <1.0 µM in its wake. Integrated biogenic silica concentrations within the bloom averaged 410 mmol Si/m**2 (range 162-793 mmol Si/m**2). Average integrated silica production on two consecutive cruises in December 1997 and January 1998 that sampled the bloom while it was well developed were 27.5±6.9 and 22.6±20 mmol Si/m**2/d, respectively. Those levels of siliceous biomass and silica production are similar in magnitude to those reported for ice-edge diatom blooms in the Ross Sea, Antarctica, which is considered to be among the most productive regions in the Southern Ocean. Net silica production (production minus dissolution) in surface waters during the bloom was 16-21 mmol Si/m**2/d, which is sufficient for diatom growth to be the cause of the southward displacement of the silicic acid gradient. A strong seasonal change in silica dissolution : silica production rate ratios was observed. Integrated silica dissolution rates in the upper 100-150 m during the low biomass period before stratification averaged 64% of integrated production. During the bloom integrated dissolution rates averaged only 23% of integrated silica production, making 77% of the opal produced available for export to depth. The bloom ended in late January apparently due to a mixing event. Dissolution : production rate ratios increased to an average of 0.67 during that period indicating a return to a predominantly regenerative system. Our observations indicate that high diatom biomass and high silica production rates previously observed in the marginal seas around Antarctica also occur in the deep ocean near the Polar Front. The bloom we observed propagated across the latitudinal band overlying the sedimentary opal belt which encircles most of Antarctica implying a role for such blooms in the formation of those sediments. Comparison of our surface silica production rates with new estimates of opal accumulation rates in the abyssal sediments of the Southern Ocean, which have been corrected for sediment focusing, indicate a burial efficiency of <=4.6% for biogenic silica. That efficiency is considerably lower than previous estimates for the Southern Ocean.

Geochemistry on rocks from Shackleton Range

During the GEISHA expedition (Geologische Expedition in die Shackleton Range 1987/88), the Pioneers Escarpment was visited and sampled extensively for the first time. Most of the rock types encountered represent amphibolite facies metamorphics, but evidence for granulite facies conditions was found in cores of garnet. These conditions must have been at least partly reached during the peak of metamorphism. For the Pioneers Escarpment a varicolored succession of sedimentary and bimodal volcanic origin is typical. It comprises: quartzites muscovite quartzite, sericite quartzite, fuchsite quartzite, garnet-quartz schists etc.; pelites: mica schists and plagioclase or plagioclase-microcline gneisses, aluminous schists; marls and carbonates: grey meta-limestones, carbonaceous quartzites, but also pure white, often fine-grained, saccharoidal marble, or a variety of tremolite marble, olivine (forsterite) marble, diopside-clinopyroxene-tremolite marble, etc.; basic volcanic rocks: amphibole fels, amphibolite schist, garnet amphibolite, and acidic to intermediate volcanic rocks: garnet-biotite schist, epidote-biotite-plagioclase gneiss, microcline gneiss. These rocks are considered to be a supracrustal unit, called the Pioneers Group. In the easternmost parts of the Pioneers Escarpment, e.g. at Vindberget, nonmetamorphic shales, sandstones and greywackes crop out, which are cover rocks of possibly Jurassic age. These metasediments, which represent a quartz-pelite-carbonate (QPC) association, indicate that deposition took place on a stable shelf, i.e. on the submerged rim of a craton. Marine shallow-water sedimentation including marls and aluminous clays form the protoliths. The volcanics may be part of a bimodal volcanics-arkose-conglomerate (BVAC) association. Geochemical analyses support the assumption of volcanic protoliths. This is demonstrated especially by the elevated amounts of the immobile, incompatible high-field-strength elements (HFSE) Nb, Ta, Ti, Y, and Zr encountered in some of the gneisses. Microscopic investigation suggests the existence of ortho-amphibolites. This is confirmed by the geochemistry. A bimodal volcanic association is evident. The amphibolites plot in both the tholeiite and calc-alkaline fields. The acidic volcanics are mainly rhyolitic. The sediments and volcanics were subjected to conditions of 10-11 kbar and 600°C during the peak of metamorphism, i.e. granulite facies metamorphism, which can be deduced from the Fe mole ratios of 0.71-0.73 in the garnet cores. Due to the relatively low temperatures, no anatectic melting took placc. The rims of the garnets show a Fe mole ratio of 0.84-0.86, and the coexisting mineral association garnet-biotite-staurolite-kyanite indicate amphibolite facies. The thermobarometry shows P-T conditions of 5-6 kbar and 570-580°C for this stage. The metamorphic history indicates deep burial at depths down to 35 km (subduction?) i.e. high pressure metamorphism, followed by pressure release due to uplift associated with retrograde metamorphism. This may have happened during a pre-Ross metamorphic event or orogeny. The Ross Orogeny at about 500 Ma probably just led to the weak greenschist facies overprint that is evident in the rocks of the Pioneers Group. Finally, sedimentation resumed in the area of the present Shackleton Range, or at least in the eastern part of the Pioneers Escarpment, probably when detritus from erosion of the basement (Read Group and Pioneers Group) was deposited, forming sandstones and greywackes of possibly Jurassic age. There is no indication that these sediments belong to the former Turnpike Bluff Group.

Glacier mass balances of Stubacher Sonnblickkees, Hohe Tauern Range, Eastern Alps, Austria, 1958/1959 to 2012/2013

Stubacher Sonnblickkees (SSK) is located in the Hohe Tauern Range (Eastern Alps) in the south of Salzburg Province (Austria) in the region of Oberpinzgau in the upper Stubach Valley. The glacier is situated at the main Alpine crest and faces east, starting at elevations close to 3050 m and in the 1980s terminated at 2500 m a.s.l. It had an area of 1.7 km² at that time, compared with 1 km² in 2013. The glacier type can be classified as a slope glacier, i.e. the relief is covered by a relatively thin ice sheet and there is no regular glacier tongue. The rough subglacial topography makes for a complex shape in the surface topography, with various concave and convex patterns. The main reason for selecting this glacier for mass balance observations (as early as 1963) was to verify on a complex glacier how the mass balance methods and the conclusions - derived during the more or less pioneer phase of glaciological investigations in the 1950s and 1960s - could be applied to the SSK glacier. The decision was influenced by the fact that close to the SSK there was the Rudolfshütte, a hostel of the Austrian Alpine Club (OeAV), newly constructed in the 1950s to replace the old hut dating from 1874. The new Alpenhotel Rudolfshütte, which was run by the Slupetzky family from 1958 to 1970, was the base station for the long-term observation; the cable car to Rudolfshütte, operated by the Austrian Federal Railways (ÖBB), was a logistic advantage. Another factor for choosing SSK as a glaciological research site was the availability of discharge records of the catchment area from the Austrian Federal Railways who had turned the nearby lake Weißsee ('White Lake') - a former natural lake - into a reservoir for their hydroelectric power plants. In terms of regional climatic differences between the Central Alps in Tyrol and those of the Hohe Tauern, the latter experienced significantly higher precipitation , so one could expect new insights in the different response of the two glaciers SSK and Hintereisferner (Ötztal Alps) - where a mass balance series went back to 1952. In 1966 another mass balance series with an additional focus on runoff recordings was initiated at Vernagtfener, near Hintereisferner, by the Commission of the Bavarian Academy of Sciences in Munich. The usual and necessary link to climate and climate change was given by a newly founded weather station (by Heinz and Werner Slupetzky) at the Rudolfshütte in 1961, which ran until 1967. Along with an extension and enlargement to the so-called Alpine Center Rudolfshütte of the OeAV, a climate observatory (suggested by Heinz Slupetzky) has been operating without interruption since 1980 under the responsibility of ZAMG and the Hydrological Service of Salzburg, providing long-term met observations. The weather station is supported by the Berghotel Rudolfshütte (in 2004 the OeAV sold the hotel to a private owner) with accommodation and facilities. Direct yearly mass balance measurements were started in 1963, first for 3 years as part of a thesis project. In 1965 the project was incorporated into the Austrian glacier measurement sites within the International Hydrological Decade (IHD) 1965 - 1974 and was afterwards extended via the International Hydrological Program (IHP) 1975 - 1981. During both periods the main financial support came from the Hydrological Survey of Austria. After 1981 funds were provided by the Hydrological Service of the Federal Government of Salzburg. The research was conducted from 1965 onwards by Heinz Slupetzky from the (former) Department of Geography of the University of Salzburg. These activities received better recognition when the High Alpine Research Station of the University of Salzburg was founded in 1982 and brought in additional funding from the University. With recent changes concerning Rudolfshütte, however, it became unfeasible to keep the research station going. Fortunately, at least the weather station at Rudolfshütte is still operating. In the pioneer years of the mass balance recordings at SSK, the main goal was to understand the influence of the complicated topography on the ablation and accumulation processes. With frequent strong southerly winds (foehn) on the one hand, and precipitation coming in with storms from the north to northwest, the snow drift is an important factor on the undulating glacier surface. This results in less snow cover in convex zones and in more or a maximum accumulation in concave or flat areas. As a consequence of the accentuated topography, certain characteristic ablation and accumulation patterns can be observed during the summer season every year, which have been regularly observed for many decades . The process of snow depletion (Ausaperung) runs through a series of stages (described by the AAR) every year. The sequence of stages until the end of the ablation season depends on the weather conditions in a balance year. One needs a strong negative mass balance year at the beginning of glacier measurements to find out the regularities; 1965, the second year of observation resulted in a very positive mass balance with very little ablation but heavy accumulation. To date it is the year with the absolute maximum positive balance in the entire mass balance series since 1959, probably since 1950. The highly complex ablation patterns required a high number of ablation stakes at the beginning of the research and it took several years to develop a clearer idea of the necessary density of measurement points to ensure high accuracy. A great number of snow pits and probing profiles (and additional measurements at crevasses) were necessary to map the accumulation area/patterns. Mapping the snow depletion, especially at the end of the ablation season, which coincides with the equilibrium line, is one of the main basic data for drawing contour lines of mass balance and to calculate the total mass balance (on a regular-shaped valley glacier there might be an equilibrium line following a contour line of elevation separating the accumulation area and the ablation area, but not at SSK). - An example: in 1969/70, 54 ablation stakes and 22 snow pits were used on the 1.77 km² glacier surface. In the course of the study the consistency of the accumulation and ablation patterns could be used to reduce the number of measurement points. - At the SSK the stratigraphic system, i.e. the natural balance year, is used instead the usual hydrological year. From 1964 to 1981, the yearly mass balance was calculated by direct measurements. Based on these records of 17 years, a regression analysis between the specific net mass balance and the ratio of ablation area to total area (AAR) has been used since then. The basic requirement was mapping the maximum snow depletion at the end of each balance year. There was the advantage of Heinz Slupetzky's detailed local and long-term experience, which ensured homogeneity of the series on individual influences of the mass balance calculations. Verifications took place as often as possible by means of independent geodetic methods, i.e. monoplotting , aerial and terrestrial photogrammetry, more recently also the application of PHOTOMODELLER and laser scans. The semi-direct mass balance determinations used at SSK were tentatively compared with data from periods of mass/volume change, resulting in promising first results on the reliability of the method. In recent years re-analyses of the mass balance series have been conducted by the World Glacier Monitoring Service and will be done at SSK too. - The methods developed at SSK also add to another objective, much discussed in the 1960s within the community, namely to achieve time- and labour-saving methods to ensure continuation of long-term mass balance series. The regression relations were used to extrapolate the mass balance series back to 1959, the maximum depletion could be reconstructed by means of photographs for those years. R. Günther (1982) calculated the mass balance series of SSK back to 1950 by analysing the correlation between meteorological data and the mass balance; he found a high statistical relation between measured and determined mass balance figures for SSK. In spite of the complex glacier topography, interesting empirical experiences were gained from the mass balance data sets, giving a better understanding of the characteristics of the glacier type, mass balance and mass exchange. It turned out that there are distinct relations between the specific net balance, net accumulation (defined as Bc/S) and net ablation (Ba/S) to the AAR, resulting in characteristic so-called 'turnover curves'. The diagram of SSK represents the type of a glacier without a glacier tongue. Between 1964 and 1966, a basic method was developed, starting from the idea that instead of measuring years to cover the range between extreme positive and extreme negative yearly balances one could record the AAR/snow depletion/Ausaperung during one or two summers. The new method was applied on Cathedral Massif Glacier, a cirque glacier with the same area as the Stubacher Sonnblickkees, in British Columbia, Canada. during the summers of 1977 and 1978. It returned exactly the expected relations, e.g. mass turnover curves, as found on SSK. The SSK was mapped several times on a scale of 1:5000 to 1:10000. Length variations have been measured since 1960 within the OeAV glacier length measurement programme. Between 1965 and 1981, there was a mass gain of 10 million cubic metres. With a time lag of 10 years, this resulted in an advance until the mid-1980s. Since 1982 there has been a distinct mass loss of 35 million cubic metres by 2013. In recent years, the glacier has disintegrated faster, forced by the formation of a periglacial lake at the glacier terminus and also by the outcrops of rocks (typical for the slope glacier type), which have accelerated the meltdown. The formation of this lake is well documented. The glacier has retreated by some 600 m since 1981. - Since August 2002, a runoff gauge installed by the Hydrographical Service of Salzburg has recorded the discharge of the main part of SSK at the outlet of the new Unterer Eisboden See. The annual reports - submitted from 1982 on as a contractual obligation to the Hydrological Service of Salzburg - document the ongoing processes on the one hand, and emphasize the mass balance of SSK and outline the climatological reasons, mainly based on the met-data of the observatory Rudolfshütte, on the other. There is an additional focus on estimating the annual water balance in the catchment area of the lake. There are certain preconditions for the water balance equation in the area. Runoff is recorded by the ÖBB power stations, the mass balance of the now approx. 20% glaciated area (mainly the Sonnblickkees) is measured andthe change of the snow and firn patches/the water content is estimated as well as possible. (Nowadays laserscanning and ground radar are available to measure the snow pack). There is a net of three precipitation gauges plus the recordings at Rudolfshütte. The evaporation is of minor importance. The long-term annual mean runoff depth in the catchment area is around 3.000 mm/year. The precipitation gauges have measured deficits between 10% and 35%, on average probably 25% to 30%. That means that the real precipitation in the catchment area Weißsee (at elevations between 2,250 and 3,000 m) is in an order of 3,200 to 3,400 mm a year. The mass balance record of SSK was the first one established in the Hohe Tauern region (and now since the Hohe Tauern National Park was founded in 1983 in Salzburg) and is one of the longest measurement series worldwide. Great efforts are under way to continue the series, to safeguard against interruption and to guarantee a long-term monitoring of the mass balance and volume change of SSK (until the glacier is completely gone, which seems to be realistic in the near future as a result of the ongoing global warming). Heinz Slupetzky, March 2014

Sedimentology of ODP Leg 126 deep-water volcaniclastics

Three sites were drilled in the Izu-Bonin forearc basin during Ocean Drilling Program (ODP) Leg 126. High-quality formation microscanner (FMS) data from two of the sites provide images of part of a thick, volcaniclastic, middle to upper Oligocene, basin-plain turbidite succession. The FMS images were used to construct bed-by-bed sedimentary sections for the depth intervals 2232-2441 m below rig floor (mbrf) in Hole 792E, and 4023-4330 mbrf in Hole 793B. Beds vary in thickness from those that are near or below the resolution of the FMS tool (2.5 cm) to those that are 10-15 m thick. The bed thicknesses are distributed according to a power law with an exponent of about 1.0. There are no obvious upward thickening or thinning sequences in the bed-by-bed sections. Spaced packets of thick and very thick beds may be a response to (1) low stands of global sea level, particularly at 30 Ma, (2) periods of increased tectonic uplift, or (3) periods of more intense volcanism. Graded sandstones, most pebbly sandstones, and graded to graded-stratified conglomerates were deposited by turbidity currents. The very thick, mainly structureless beds of sandstone, pebbly sandstone, and pebble conglomerate are interpreted as sandy debris-flow deposits. Many of the sediment gravity flows may have been triggered by earthquakes. Long recurrence intervals of 0.3-1 m.y. for the very thickest beds are consistent with triggering by large-magnitude earthquakes (M = 9) with epicenters approximately 10-50 km away from large, unstable accumulations of volcaniclastic sand and ash on the flanks of arc volcanoes. Paleocurrents were obtained from the grain fabric of six thicker sandstone beds, and ripple migration directions in about 40 thinner beds; orientations were constrained by the FMS images. The data from ripples are very scattered and cannot be used to specify source positions. They do, however, indicate that the paleoenvironment was a basin plain where weaker currents were free to follow a broad range of flow paths. The data from sandstone fabric are more reliable and indicate that turbidity currents flowed toward 150? during the time period from 28.9 to 27.3 Ma. This direction is essentially along the axis of the forearc basin, from north to south, with a small component of flow away from the western margin of the basin.

Sampling data, experimental data and fecal pellet characteristics of water pump samples in the strait of Øresund between Denmark and Sweden during 2004/2005

Copepod fecal pellets are often degraded at high rates within the upper part of the water column. However, the identity of the degraders and the processes governing the degradation remain unresolved. To identify the pellet degraders we collected water from Øresund (Denmark) approximately every second month from July 2004 to July 2005. These water samples were divided into 5 fractions (<0.2, <2, <20, <100, <200 µm) and total (unfractionated). We determined fecal pellet degradation rate and species composition of the plankton from triplicate incubations of each fraction and a known, added amount of fecal pellets. The total degradation rate of pellets by the natural plankton community of Øresund followed the phytoplankton biomass, with maximum degradation rate during the spring bloom (2.5 ± 0.49 d**-1) and minimum (0.52 ± 0.14 d**-1) during late winter. Total pellet removal rate ranged from 22% d**-1 (July 2005) to 87% d**-1 (May). Protozooplankton (dinoflagellates and ciliates) in the size range of 20 to 100 µm were the key degraders of the fecal pellets, contributing from 15 to 53% of the total degradation rate. Free-living in situ bacteria did not affect pellet degradation rate significantly; however, culture-originating bacteria introduced in association with the pellets contributed up to 59% of the total degradation rate. An effect of late-stage copepod nauplii (>200 µm) was indicated, but this was not a dominating degradation process. Mesozooplankton did not contribute significantly to the degradation. However, grazing of mesozooplankton on the pellet degraders impacts pellet degradation rate indirectly. In conclusion, protozooplankton seems to include the key organisms for the recycling of copepod fecal pellets in the water column, both through the microbial loop and, especially, by functioning as an effective 'protozoan filter' for fecal pellets.

Cation exchange capacity and water content of ODP sites from Nankai

Pore fluid chlorinity lower than seawater is often observed in accretionary wedges and one of the possible causes of pore water freshening is the smectite to illite reaction. This reaction occurs during diagenesis in the 80-150°C temperature range. Low chlorinity anomalies observed at the toe of accretionary wedges have thus been interpreted as evidence for lateral fluid migration from inner parts of the wedge and the seismogenic zone. However, temperature conditions in Nankai Trough are locally high enough for the smectite to illite transition to occur in situ. Cation exchange capacity is here used as a proxy for smectite content in the sediment and the amount of interlayer water released during the smectite to illite reaction represents in average 12 water molecules per cation charge. Water and chloride budget calculations show that there is enough smectite to explain the chlorinity anomalies by in situ reactions. The shape of the pore fluid chlorinity profiles can be explained if compaction is also taken into account in the model. Lateral flow is not needed. This argument, based solely on chloride concentration, does not imply that lateral flow is absent. However, previous estimations of lateral fluid fluxes, and of the duration of transient flow events along the de.collement, should be reconsidered.

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.

Hexachlorocyclohexanes concentration in air and ocean water

Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of accumulation in biota. Shipboard measurements of HCH isomers (a-, b- and g-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. SumHCHs concentrations (the sum of a-, g- and b-HCH) in the lower atmosphere ranged from 12 to 37 pg/m**3 (mean: 27 ± 11 pg/m**3) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg/m**3 (mean: 2.8 ± 1.1 pg/m**3) in the Southern Hemisphere (SH), respectively. Water concentrations were: a-HCH 0.33-47 pg/l, g-HCH 0.02-33 pg/l and b-HCH 0.11-9.5 pg/l. Dissolved HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold trapping in high latitudes and less interhemispheric mixing process. In comparison to concentrations measured in 1987-1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2-3 orders of magnitude. Air-water exchange gradients suggested net deposition for a-HCH (mean: 3800 pg/m**2/day) and g-HCH (mean: 2000 pg/m**2/day), whereas b-HCH varied between equilibrium (volatilization: <0-12 pg/m**2/day) and net deposition (range: 6-690 pg/m**2/day). Climate change may significantly accelerate the release of "old" HCHs from continental storage (e.g. soil, vegetation and high mountains) and drive long-range transport from sources to deposition in the open oceans. Biological productivities may interfere with the air-water exchange process as well. Consequently, further investigation is necessary to elucidate the long term trends and the biogeochemical turnover of HCHs in the oceanic environment.

Stable isotope ratios of foraminifera from last glacial-interglacial sediments of the southern high latitudes

A set of numerical equations is developed to estimate past sea surface temperatures (SST) from fossil Antarctic diatoms. These equations take into account both the biogeographic distribution and experimentally derived silica dissolution. The data represent a revision and expansion of a floral data base used previously and includes samples resulting from progressive opal dissolution experiments. Factor analysis of 166 samples (124 Holocene core top and 42 artificial samples) resolved four factors. Three of these factors depend on the water mass distribution (one Subantarctic and two Antarctic assemblages); factor 4 corresponds to a 'dissolution assemblage'. Inclusion of this factor in the data analysis minimizes the effect of opal dissolution on the assemblages and gives accurate estimates of SST over a wide range of biosiliceous dissolution. A transfer function (DTF 166/34/4) is derived from the distribution of these factors versus summer SST. Its standard error is +/- 1°C in the -1 to +10 °C summer temperature range. This transfer function is used to estimate SST changes in two southern ocean cores (43°S and 55°S) which cover the last climatic cycle. The time scale is derived from the changes in foraminiferal oxygen and carbon isotopic ratios. The reconstructed SST records present strong analogies with the air temperature record over Antarctica at the Vostok site, derived from changes in the isotopic ratio of the ice. This similarity may be used to compare the oceanic isotope stratigraphy and the Vostok time scale derived from ice flow model. The oceanic time scale, if taken at face value, would indicate that large changes in ice accumulation rates occurred between warm and cold periods.

Radiocarbon dating on cold-water corals, grain size, Corg, and benthic foraminfera assemblage of two sediment cores from the Ionian Sea

Continuous sedimentary records from an eastern Mediterranean cold-water coral ecosystem thriving in intermediate water depths (~600 m) reveal a temporary extinction of cold-water corals during the Early to Mid Holocene from 11.4-5.9 cal kyr BP. Benthic foraminiferal assemblage analysis shows low-oxygen conditions of 2 ml l**-1 during the same period, compared to bottom-water oxygen values of 4-5 ml l**-1 before and after the coral-free interval. The timing of the corals' demise coincides with the sapropel S1 event, during which the deep eastern Mediterranean basin turned anoxic. Our results show that during the sapropel S1 event low oxygen conditions extended to the rather shallow depths of our study site in the Ionian Sea and caused the cold-water corals temporary extinction. This first evidence for the sensitivity of cold-water corals to low oceanic oxygen contents suggests that the projected expansion of tropical oxygen minimum zones resulting from global change will threaten cold-water coral ecosystems in low latitudes in the same way that ocean acidification will do in the higher latitudes.

Dissolved Si isotope composition measured in water samples during METEOR cruises M77/3 and M77/4

Silicon isotopes are a powerful tool to investigate the cycling of dissolved silicon (Si). In this study the distribution of the Si isotope composition of dissolved silicic acid (d30Si(OH)4) was analyzed in the water column of the Eastern Equatorial Pacific (EEP) where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Samples were collected at 7 stations along two meridional transects from the equator to 14°S at 85°50'W and 82°00'W off the Ecuadorian and Peruvian coast. Surface waters show a large range in isotope compositions d30Si(OH)4 (+2.2 per mil to +4.4 per mil) with the highest values found at the southernmost station at 14°S. This station also revealed the most depleted silicic acid concentrations (0.2 µmol/kg), which is a function of the high degree of Si utilization by diatoms and admixture with waters from highly productive areas. Samples within the upper water column and the OMZ at oxygen concentrations below 10 µmol/kg are characterized by a large range in d30Si(OH)4, which mainly reflects advection and mixing of different water masses, even though the highly dynamic hydrographic system of the upwelling area off Peru does not allow the identification of clear Si isotope signals for distinct water masses. Therefore we cannot rule out that also dissolution processes have an influence on the d30Si(OH)4 signature in the subsurface water column. Deep water masses (>2000 m) in the study area show a mean d30Si(OH)4 of +1.2±0.2 per mil, which is in agreement with previous studies from the eastern and central Pacific. Comparison of the new deep water data of this study and previously published data from the central Pacific and Southern Ocean reveal substantially higher d30Si(OH)4 values than deep water signatures from the North Pacific. As there is no clear correlation between d30Si(OH)4 and silicic acid concentrations in the entire data set the distribution of d30Si(OH)4 signatures in deep waters of the Pacific is considered to be mainly a consequence of the mixing of several end member water masses with distinct Si isotope signatures including Lower Circumpolar Deep Water (LCDW) and North Pacific Deep Water (NPDW).