Organic matter, isotopic composition of calcite veins in basement basalt and pore water at DSDP Leg 78A Holes

Sediments of the Barbados Ridge complex, cored on DSDP Leg 78A, contain low concentrations of acid-insoluble carbon (0.05-0.25%) and nitrogen (C/N 1.5-5) and dispersed C1-C6 hydrocarbons (100-800 ppb). The concentrations of organic carbon and 13C in organic carbon decrease with depth, whereas the concentration of dispersed hydrocarbons increases slightly with depth. These trends may reflect the slow oxidation of organic matter, with selective removal of 13C and slow conversion of the residual organic matter to hydrocarbons. Very minor indications of nitrogen gas were observed at about 250 meters sub-bottom at two of the drilling sites. Basement basalts have calcite veins with d13C values in the range of 2.0 to 3.2 per mil and d18O-SMOW values ranging from 28.5 to +30.6 per mil. Interstitial waters have d18O-SMOW of 0.2 to -3.5 per mil and dD-SMOW of -2 to -15 per mil. The oxygen isotopic composition of the calcite veins in the basement basalts gives estimated equilibrium fractionation temperatures in the range of 11 to 24°C, assuming precipitation from water with d18O-SMOW in the range of +0.1 to -1.0 per mil. This suggests that basalt alteration and precipitation of vein calcite occurred in contact either with warmer Campanian seawater or, later, with pore water, after burial to depths of 200- 300 meters. Pore waters from all three sites are depleted in deuterium and 18O, and dissolved sulfate is enriched in 34S at Sites 541 and 542, but not at Site 543.

Geochemistry of volcanic rocks of ODP Holes 126-792E and 126-793B

The Izu-Bonin forearc basement volcanic rocks recovered from Holes 792E and 793B show the same phenocrystic assemblage (i.e., plagioclase, two pyroxenes, and Fe-Ti oxides ±olivine), but they differ in the crystallization sequence and their phenocryst chemistry. All the igneous rocks have suffered low-grade hydrothermal alteration caused by interaction with seawater. As a result, only clinopyroxenes, plagioclases, and oxides have preserved their primary igneous compositions. The Neogene olivine-clinopyroxene diabasic intrusion (Unit II) recovered from Hole 793B differs from the basement basaltic andesites because it lacks Cr-spinels and contains abundant titanomagnetites (Usp38.5-46.4) and uncommon FeO-rich (FeO = 29%) spinels. It displays petrological and geochemical similarities to the Izu Arc volcanoes and, thus, can be considered as related to Izu-Bonin Arc magmatic activity. The titanomagnetites (Usp28.5-33) in the calc-alkaline andesitic fragments of the Oligocene volcaniclastic breccia in Hole 793B (Unit VI) represent an early crystallization phase. The Plagioclase phenocrysts enclosed in these rocks show oscillatory zoning and are less Ca-rich (An78.6-67.8) than the plagioclase phenocrysts of the diabase sill and the basement basaltic andesites. Their clinopyroxenes are Fe-rich augites (Fs ? 19.4; FeO = 12%) and thus, differ significantly from the clinopyroxenes of the Hole 793B arc-tholeiitic igneous rocks. The 30-32 Ma porphyritic, two-pyroxene andesites recovered from Hole 792E are very similar to the andesitic clasts of the Neogene breccia recovered in Hole 793B (Unit VI). Both rocks have the same crystallization sequence, and similar chemistry of the Fe-Ti oxides, clinopyroxenes, and plagioclases: that is, Ti-rich (Usp25.5-30.4) magnetites, Fe-rich augites, and intensely oscillatory zoned plagioclases with bytownitic cores (An86-63) and labradorite rims (An73-68). They display a calc-alkaline differentiation trend (Taylor et al., this volume). So, the basement highly porphyritic andesites recovered at Hole 792E, and the Hole 793B andesitic clasts of Unit VI show the same petrological and geochemical characteristics, which are that of calc-alkaline suites. These Oligocene volcanic rocks represent likely the remnants of the Izu-Bonin normal arc magmatic activity, before the forearc rifting and extension. The crystallization sequence in the basaltic andesites recovered from Hole 793B is olivine-orthopyroxene-clinopyroxene-plagioclase-Fe-Ti oxides, indicating a tholeiitic differentiation trend for these volcanic rocks. Type i is an olivine-and Cr-spinel bearing basaltic andesite whereas Type ii is a porphyritic pyroxene-rich basaltic andesite. The porphyritic plagioclase-rich basaltic andesite (Type iii) is similar, in most respects, to Type ii lavas but contains plagioclase phenocrysts. The last, and least common lava is an aphyric to sparsely phyric andesite (Type iv). Cr-spinels, included either in the olivine pseudomorphs of Type i lavas or in the groundmass of Type ii lavas, are Cr-rich and Mg-rich. In contrast, Cr-spinels included in clinopyroxenes and orthopyroxenes (Types i and ii lavas) show lower Cr* and Mg* ratios and higher aluminium contents. Orthopyroxenes from all rock types are Mg-rich enstatites. Clinopyroxenes display endiopsidic to augitic compositions and are TiO2 and Al2O3 depleted. All the crystals exhibit strong zoning patterns, usually normal, although, reverse zoning patterns are not uncommon. The plagioclases show compositions within the range of An90-64. The Fe-Ti oxides of the groundmass are TiO2-poor (Usp16-17). The Hole 793B basaltic andesites show, like the Site 458 bronzites from the Mariana forearc, intermediate features between arc tholeiites and boninites: (1) Cr-spinel in olivine, (2) presence of Mg-rich bronzite, Ca-Mg-rich clinopyroxenes, and Ca-plagioclase phenocrysts, and (3) transitional trace element depletion and epsioln-Nd ratios between arc tholeiites and boninites. Thus, the forearc magmatism of the Izu-Bonin and Mariana arcs, linked to rifting and extension, is represented by a depleted tholeiitic suite that displays boninitic affinities.

Sediment and pore water N and d15N concentrations of ODP Holes 202-1234A and 202-1235A

The isotopic composition of nitrogen in pore water ammonium and in sedimentary organic matter (Norg) was measured at Sites 1234 and 1235 in order to evaluate the impact of long-term (>100 k.y.) diagenesis on d15N of preserved organic matter. At both sites, the average d15N of pore water ammonium and Norg are within 0.2 per mil to 0.4 per mil. The small difference is less than the analytical uncertainty, indicating that no significant isotopic fractionation is associated with decomposition of organic matter in these sediments. A mass balance for nitrogen was also computed, indicating that ~20% of the organic matter flux buried below 1.45 meters composite depth (mcd) is degraded between this depth and 40 mcd (Site 1235) to 60 mcd (Site 1234) depth. Two factors determine the absence of isotopic fractionation in these sediments: 1. A high degree of organic matter preservation due to rapid sediment accumulation rates at both sites. 2. The dominance of a marine component in the sedimentary organic matter (with only a small fraction contributed by a terrestrial component).

Isotopic and micropaleontological record of sediments of the Baffin Bay

The oxygen and carbon isotopic compositions of the planktonic foraminifer, Neogloboquadrina pachyderma (sinistral), were determined at 20-cm intervals through the 'composite' top ~ 22 m of sediments at ODP Site 645 (Holes 645B, 645C, 645F, and 645G) and at 10-cm intervals through a 9-m piston core (85-027-016) collected during the Hudson site survey. Quantitative analyses of palynomorphs, notably dinocysts, and of planktonic foraminifers were performed. Organic and nitrogen contents and isotopic composition of nitrogen and carbon in organic matter also were determined. These data provide a high-resolution record of changes that occurred in surface-water masses during the last glacial cycle in Baffin Bay. The basin experienced low planktonic productivity during most of the late Pleistocene, either from dilution in surface water by meltwater discharges from the surrounding ice-sheet or from the presence of a relatively dense sea-ice cover. Peaks of meltwater discharge are indicated by d18O values as low as about 1.5 per mil, correlative d13C- d18O shifts, low concentration of planktonic foraminifers, high concentrations of glacially reworked pre-Quaternary palynomorphs, and low-salinity dinocyst assemblages. As a whole, d18O values ranging between 4.5 and 2.5 per mil allow the establishment of an 18O stratigraphy spanning isotopic stages 5 to 1. Because of the poor core recovery, the general paucity of microflora and microfauna, and the possible occurrence of slumping or debris flow at Site 645, further interpretation remains problematic.

Chemical and isotope composition of rocks from the Omgon Range, Western Kamchatka coastal area

Hypabyssal rocks of the Omgon Range, Western Kamchatka that intrude Upper Albian-Lower Campanian deposits of the Eurasian continental margin belong to three coeval (62.5-63.0 Ma) associations: (1) ilmenite gabbro-dolerites, (2) titanomagnetite gabbro-dolerites and quartz microdiorites, and (3) porphyritic biotite granites and granite-aplites. Early Paleocene age of ilmenite gabbro-dolerites and biotite granites was confirmed by zircon and apatite fission-track dating. Ilmenite and titanomagnetite gabbro-dolerites were produced by multilevel fractional crystallization of basaltic melts with, respectively, moderate and high Fe-Ti contents and contamination of these melts with rhyolitic melts of different compositions. Moderate- and high-Fe-Ti basaltic melts were derived from mantle spinel peridotite variably depleted and metasomatized by slab-derived fluid prior to melting. The melts were generated at variable depths and different degrees of melting. Biotite granites and granite aplites were produced by combined fractional crystallization of a crustal rhyolitic melt and its contamination with terrigenous rocks of the Omgon Group. The rhyolitic melts were likely derived from metabasaltic rocks of suprasubduction nature. Early Paleocene hypabyssal rocks of the Omgon Range were demonstrated to have been formed in an extensional environment, which dominated in the margin of the Eurasian continent from Late Cretaceous throughout Early Paleocene. Extension in the Western Kamchatka segment preceded the origin of the Western Koryakian-Kamchatka (Kinkil') continental-margin volcanic belt in Eocene time. This research was conducted based on original geological, mineralogical, geochemical, and isotopic (Rb-Sr) data obtained by the authors.

Analysis of soils from King George Island and Casey station, Antarctica

A comparative study was carried out on soils of the maritime (Arctowski, King George Island) and the continental (Casey, Wilkes Land) Antarctic. Soil sampIes are described for surface layers (0-10 cm) by their in situ temperature profiles as well as by field and laboratory analyses of grain sizes, pH and nutrient contents. Active cryoturbation is a main factor of mixing processes in surfaces with high silt and clay content. In both regions processes of podzolisation were recognized. Microclimatic conditions show the importance of small scale processes which are of special importance for freeze-thaw cycles. The distribution of nutrients and other inorganic components is rather homogeneous in regosols and leptosols. But in soils with organic top layers by lichen and moss cushions (crusts) accumulation occurs as well as displacement of metal ions into deeper layers (>10 cm). Histosols show patterns of brown soils. Special attention is given to the origin of nitrogen compounts and the different ways of import of other components (e.g. chloride) into the Antarctic system are discussed.

(Table 2) Production characteristics of phytoplankton and selected related factors at bottle sampling stations in the subtropical and tropical Atlantic Ocean

In October and November 2002, high and relatively high values of chlorophyll a concentration at the sea surface (Cchl) were observed in the English Channel (0.47 mg/m**3), in waters of the North Atlantic Current (0.25 mg/m**3 ), in the tropical and subtropical anticyclonic gyres (0.07-0.42 mg/m**3), and also in the southwestern region of the southern subtropical anticyclonic gyre (usually 0.11-0.23 mg/m**3). The central regions of the southern subtropical anticyclonic gyre (SATG) and the North Atlantic tropical gyre (NATR) were characterized by lower values of Cchl (0.02-0.08 mg/m**3 for the SATG and 0.07-0.14 mg/m**3 for the NATR). At most of the SATG stations, values of surface primary production (Cphs) varied from 2.5 to 5.5 mg C/m**3 per day and were mainly defined by fluctuations of Cchl (r = +0.78) rather than by those of the assimilation number (r = +0.54). Low assimilation activity of phytoplankton in these waters (1.3-4.6 mg chl a per hour) pointed to a lack of nutrients. Analysis of variability of their concentration and composition of photosynthetic pigments showed that, in waters north of 30°N, the growth of phytoplankton was mostly restricted by deficiency of nitrogen, while, in more southern areas, at the majority of stations (about 60%), phosphorus concentrations were minimal. At low concentrations of nitrates and nitrites, ammonium represented itself as a buffer that prevented planktonic algae from extreme degrees of nitric starvation. In tropical waters and in waters of the SATG, primary production throughout the water column varied from 240 to 380 mg C/m**2 30° per day. This level of productivity at stations with low values of C chl (<0.08 mg/m**3) was provided by a well-developed deep chlorophyll maximum and high transparency of water. Light curves of photosynthesis based on in situ measurements point to high efficiency of utilizing penetrating solar radiation by phytoplankton on cloudy days.

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.

(Table 1) Mercury concentrations and carbon and nitrogen isotopic ratios in 14 marine species from West Greenland sampled between 2003-2004

Total mercury (THg), methylmercury (MeHg) and stable isotopes of nitrogen (d15N) and carbon (d13C) were measured in three invertebrate, five fish, three seabird and three marine mammal species of central West Greenland to investigate trophic transfer of mercury in this Arctic marine food web. The food web magnification factor (FWMF) estimated as the slope of the regression between the natural logarithm of THg or MeHg concentrations (mg/kg dw) and tissue d15N (per mil) was estimated to 0.183 (SE = 0.052) for THg and 0.339 (SE = 0.075) for MeHg. The FWMFs were not only comparable with those reported for other Arctic marine food webs but also with quite different food webs such as freshwater lakes in the sub-Arctic, East Africa and Papua New Guinea. This suggests similar mechanisms of mercury assimilation and isotopic (d15N) discrimination among a broad range of aquatic taxa and underlines the possibility of broad ecosystem comparisons using the combined contaminant and stable isotope approach.

Mercury content and isotopic composition of teeth, and sex and age of skulls of polar bears collected in Svalbard

We examined the use of mercury (Hg) and nitrogen and carbon stable isotopes in teeth of polar bear (Ursus maritimus) from Svalbard as biotracers of temporal changes in Hg pollution exposure between 1964 and 2003. Teeth were regarded as a good matrix of the Hg exposure, and in total 87 teeth of polar bears were analysed. Dental Hg levels ranged from 0.6 to 72.3 ng/g dry weight and increased with age during the first 10 years of life. A decreasing time trend in Hg concentrations was observed over the recent four decades while no temporal changes were found in the stable isotope ratios of nitrogen (d15N) and carbon (d13C). This suggests that the decrease of Hg concentrations over time was more likely due to a lower environmental Hg exposure in this region rather than a shift in the feeding habits of Svalbard polar bears.

National nitrogen budget for Denmark (excel-file 125 kB)

The data describe the flows of nitrogen between different pools and economic sectors within Denmark. The data are stored in an Excel spreadsheet that is divided into a number of worksheets. The National worksheet contains the national flows of nitrogen for the years 1990 to 2010 (note that for some flows, the data series is not complete for all years). These data underlie the national nitrogen flow figures in the main text of the paper. The remaining worksheets contain the data that underlie the figures presented in the detailed description of nitrogen flows between pools/sectors, that is in the Supplementary Material associated with the paper.

Bioturbation determines the response of benthic ammonia-oxidizing microorganisms to ocean acidification

Ocean acidification (OA), caused by the dissolution of increasing concentrations of atmospheric carbon dioxide (CO2) in seawater, is projected to cause significant changes to marine ecology and biogeochemistry. Potential impacts on the microbially driven cycling of nitrogen are of particular concern. Specifically, under seawater pH levels approximating future OA scenarios, rates of ammonia oxidation (the rate-limiting first step of the nitrification pathway) have been shown to dramatically decrease in seawater, but not in underlying sediments. However, no prior study has considered the interactive effects of microbial ammonia oxidation and macrofaunal bioturbation activity, which can enhance nitrogen transformation rates. Using experimental mesocosms, we investigated the responses to OA of ammonia oxidizing microorganisms inhabiting surface sediments and sediments within burrow walls of the mud shrimp Upogebia deltaura. Seawater was acidified to one of four target pH values (pHT 7.90, 7.70, 7.35 and 6.80) in comparison with a control (pHT 8.10). At pHT 8.10, ammonia oxidation rates in burrow wall sediments were, on average, fivefold greater than in surface sediments. However, at all acidified pH values (pH < = 7.90), ammonia oxidation rates in burrow sediments were significantly inhibited (by 79-97%; p < 0.01), whereas rates in surface sediments were unaffected. Both bacterial and archaeal abundances increased significantly as pHT declined; by contrast, relative abundances of bacterial and archaeal ammonia oxidation (amoA) genes did not vary. This research suggests that OA could cause substantial reductions in total benthic ammonia oxidation rates in coastal bioturbated sediments, leading to corresponding changes in coupled nitrogen cycling between the benthic and pelagic realms.

(Table 3) Leaf area and leaf nitrogen for deciduous, evergreen, forb and graminoid species at Barrow, Svalbard and Zackenberg

Arctic vegetation is characterized by high spatial variability in plant functional type (PFT) composition and gross primary productivity (P). Despite this variability, the two main drivers of P in sub-Arctic tundra are leaf area index (LT) and total foliar nitrogen (NT). LT and NT have been shown to be tightly coupled across PFTs in sub-Arctic tundra vegetation, which simplifies up-scaling by allowing quantification of the main drivers of P from remotely sensed LT. Our objective was to test the LT-NT relationship across multiple Arctic latitudes and to assess LT as a predictor of P for the pan-Arctic. Including PFT-specific parameters in models of LT-NT coupling provided only incremental improvements in model fit, but significant improvements were gained from including site-specific parameters. The degree of curvature in the LT-NT relationship, controlled by a fitted canopy nitrogen extinction co-efficient, was negatively related to average levels of diffuse radiation at a site. This is consistent with theoretical predictions of more uniform vertical canopy N distributions under diffuse light conditions. Higher latitude sites had higher average leaf N content by mass (NM), and we show for the first time that LT-NT coupling is achieved across latitudes via canopy-scale trade-offs between NM and leaf mass per unit leaf area (LM). Site-specific parameters provided small but significant improvements in models of P based on LT and moss cover. Our results suggest that differences in LT-NT coupling between sites could be used to improve pan-Arctic models of P and we provide unique evidence that prevailing radiation conditions can significantly affect N allocation over regional scales.