Nutrients and oxygen concentrations measured in water samples from the North Atlantic during the James Cook cruise JC087 in March 2013

Analysis for micro-molar concentrations of nitrate and nitrite, nitrite, phosphate, silicate and ammonia was undertaken on a SEAL Analytical UK Ltd, AA3 segmented flow autoanalyser following methods described by Kirkwood (1996). Samples were drawn from Niskin bottles on the CTD into 15ml polycarbonate centrifuge tubes and kept refrigerated at approximately 4oC until analysis, which generally commenced within 30 minutes. Overall 23 runs with 597 samples were analysed. This is a total of 502 CTD samples, 69 underway samples and 26 from other sources. An artificial seawater matrix (ASW) of 40g/litre sodium chloride was used as the inter-sample wash and standard matrix. The nutrient free status of this solution was checked by running Ocean Scientific International (OSI) low nutrient seawater (LNS) on every run. A single set of mixed standards were made up by diluting 5mM solutions made from weighed dried salts in 1litre of ASW into plastic 250ml volumetric flasks that had been cleaned by washing in MilliQ water (MQ). Data processing was undertaken using SEAL Analytical UK Ltd proprietary software (AACE 6.07) and was performed within a few hours of the run being finished. The sample time was 60 seconds and the wash time was 30 seconds. The lines were washed daily with wash solutions specific for each chemistry, but comprised of MQ, MQ and SDS, MQ and Triton-X, or MQ and Brij-35. Three times during the cruise the phosphate and silicate channels were washed with a weak sodium hypochlorite solution.

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.

Water chemistry of lakes in Zackenbergdalen between 1997-2003, East Greenland

The ecology of arctic lakes is strongly influenced by climate-generated variations in snow coverage and by the duration of the ice-free period, which, in turn, affect the physical and chemical conditions of the lakes (Wrona et al., 2005, http://www.acia.uaf.edu/PDFs/ACIA_Science_Chapters_Final/ACIA_Ch08_Final.pdf). Most arctic lakes are characterised by a long period (8-10 months) of ice-cover, cold water and low algal biomass. The water temperature and nutrient concentrations, and most probably the nutrient input from the catchments, are closely related to the duration of snow- and ice-cover in the lakes. In years when the ice-out is late, - that is, in late July, - phytoplankton photosynthesis is limited by the lack of light and nutrients. Less food is then available to the next link in the food chain, such as copepods and daphnids, with implication on their growth rates.

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.

Antarctic shallow water benthos from three stations at Potter Cove, King George Island, West Antarctic Peninsula

The West Antarctic Peninsula is one of the fastest warming regions on the planet. Faster glacier retreat and related calving events lead to more frequent iceberg scouring, fresh water input and higher sediment loads which may affect benthic marine communities. On the other hand, the appearance of newly formed ice-free areas provides new substrates for colonization. Here we investigated the effect of these conditions on four benthic size classes (microbenthos, meiofauna and macrofauna) using Potter Cove (King George Island, West Antarctic Peninsula) as a case study. We identified three sites within the cove experiencing different levels of glacier retreat-related disturbance. Our results showed the existence of different communities at the same depth over a relatively small distance (about 1 km**2). This suggests glacial activity structures biotic communities over a relatively small spatial scale. In areas with frequent ice scouring and higher sediment accumulation rates, a patchy community, mainly dominated by macrobenthic scavengers (such as Barrukia cristata), vagile organisms, and younger individuals of sessile species (such as Yoldia eigthsi) was found. Meiofauna organisms such as cumaceans are found to be resistant to re-suspension and high sedimentation loads. The nematode genus Microlaimus was found to be successful in the newly exposed ice-free site, confirming its ability as a pioneering colonizer. In general, the different biological size classes appear to respond in different ways to the ongoing disturbances, suggesting that adaptation processes may be size related. Our results suggest that with continued deglaciation, more diverse but less patchy macrobenthic assemblages can become established due to less frequent ice scouring events.

Water chemistry, and pigments and geochemistry of sediments from northern Victoria Land lakes

Total concentrations of algal pigments, organic C, C, N, P and S were determined in surface sediments from the littoral zone of 21 lakes in ice-free areas of northern Victoria Land (Antarctica) with different climatic and environmental conditions. Concentrations of major ions and nutrients were also determined in water samples from the same lakes. The latter samples had extremely variable chemical compositions; however, all the lakes resulted oligotrophic. Pigment concentrations in surface sediments were comparable to those reported for other Antarctic lakes and lower than those in oligotrophic lakes at lower latitudes. Cyanophyta, Chlorophyta and Bacillariophyta were the main taxa identified. These taxa correspond to those reported in previous microscopy-based studies on Antarctic phytoplankton and phytobenthos. Discriminant Function Analysis and Canonical Correspondence Analysis of data indicate that the distribution of pigments in these Victoria Land lakes depends mainly on their geographical location (particularly the distance from the sea) and nutrient status.

Depth profiles of pore-water and solid-phase constituents, respiration rates and grain size distribution in sediments of the Clarion-Clipperton Fracture Zone

Manganese nodules of the Clarion-Clipperton Fracture Zone (CCFZ) in the NE Pacific Ocean are highly enriched in Ni, Cu, Co, Mo and rare-earth elements, and thus may be the subject of future mining operations. Elucidating the depositional and biogeochemical processes that contribute to nodule formation, as well as the respective redox environment in both, water column and sediment, supports our ability to locate future nodule deposits and evaluates the potential ecological and environmental effects of future deep-sea mining. For these purposes we evaluated the local hydrodynamics and pore-water geochemistry with respect to the nodule coverage at four sites in the eastern CCFZ. Furthermore, we carried out selective leaching experiments at these sites in order to assess the potential mobility of Mn in the solid phase, and compared them with the spatial variations in sedimentation rates. We found that the oxygen penetration depth is 180 - 300 cm at all four sites, while reduction of Mn and NO3- is only significant below the oxygen penetration depth at sites with small or no nodules on the sediment surface. At the site without nodules, potential microbial respiration rates, determined by incubation experiments using 14C-labelled acetate, are slightly higher than at sites with nodules. Leaching experiments showed that surface sediments covered with big or medium-sized nodules are enriched in mobilizable Mn. Our deep oxygen measurements and pore-water data suggest that hydrogenetic and oxic-diagenetic processes control the present-day nodule growth at these sites, since free manganese from deeper sediments is unable to reach the sediment surface. We propose that the observed strong lateral contrasts in nodule size and abundance are sensitive to sedimentation rates, which in turn, are controlled by small-scale variations in seafloor topography and bottom-water current intensity.

(Table 1) Water-extractable and acid-extractable carbohydrates in DSDP Leg 65 samples

Selected parts of ten frozen core samples from Holes 482A, 482B, 483A, and 485A, Leg 65 of the Deep Sea Drilling Project (DSDP), were analyzed for residual carbohydrates in order to determine the provenance and history of the organic material in the sediments. The samples, which represented silty-clay, shale, and nannofossil- chalk sediments, were analyzed for water-soluble monosaccharides, acid-soluble monosaccharides, and for starch and cellulose. Most samples yielded positive results for acid-extractable (polymeric) arabinose, fucose, xylose, mannose, galactose, and glucose. Amylose was detected in seven of the samples, whereas cellulose was found in only one. Possible explanations for the relatively high levels of free sugars are suggested in the conclusions to this chapter.

Pore water chemistry of sediment core GeoB15101-7 and water chemistry of CTD casts GeoB15101-1 and GeoB15101-6

Submarine brine lakes feature sharp and persistent concentration gradients between seawater and brine, though these should be smoothed out by free diffusion in open ocean settings. The anoxic Urania basin of the Eastern Mediterranean contains an ultra sulfidic, hypersaline brine of Messinian origin above a thick layer of suspended sediments. With a dual modeling approach we reconstruct its contemporary stratification by geochemical solute transport fundamentals, and show that thermal convection is required to maintain mixing in the brine and mud layer. The origin of the Urania basin stratification was dated to 1650 years before present, which may be linked to a major earthquake in the region. The persistence of the chemoclines may be key to the development of diverse and specialized microbial communities. Ongoing thermal convection in the fluid mud layer may have important, yet unresolved consequences for sedimentological and geochemical processes, also in similar environments.

Geochemistry of pore water and sediments offshore Nicaragua and Costa Rica

Four volcanic ash-bearing marine sediment cores and one ash-free reference core were examined during research cruise RV Meteor 54/2 offshore Nicaragua and Costa Rica to investigate the chemical composition of pore waters related to volcanic ash alteration. Sediments were composed of terrigenous matter derived from the adjacent continent and contained several distinct ash layers. Biogenic opal and carbonate were only minor components. The terrigenous fraction was mainly composed of smectite and other clay minerals while the pore water composition was strongly affected by the anaerobic degradation of particulate organic matter via microbial sulphate reduction. The alteration of volcanic matter showed only a minor effect on major element concentrations in pore waters. This is in contrast to prior studies based on long sediment cores taken during the DSDP, where deep sediments always showed distinct signs of volcanic ash alteration. The missing signal of ash alteration is probably caused by low reaction rates and the high background concentration of major dissolved ions in the seawater-derived pore fluids. Dissolved silica concentrations were, however, significantly enriched in ash-bearing cores and showed no relation to the low but variable contents of biogenic opal. Hence, the data suggest that silica concentrations were enhanced by ash dissolution. Thus, the dissolved silica profile measured in one of the sediment cores was used to derive the in-situ dissolution rate of volcanic glass particles in marine sediments. A non-steady state model was run over a period of 43 kyr applying a constant pH of 7.30 and a dissolved Al concentration of 0.05 ?M. The kinetic constant (AA) was varied systematically to fit the model to the measured dissolved silica-depth profile. The best fit to the data was obtained applying AA = 1.3 * 10**-U9 mol of Si/cm**2/ s. This in-situ rate of ash dissolution at the seafloor is three orders of magnitude smaller than the rate of ash dissolution determined in previous laboratory experiments. Our results therefore imply that field investigations are necessary to accurately predict natural dissolution rates of volcanic glasses in marine sediments.