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.

Eocene to Quaternary planktonic foraminifers from the Northwest Pacific

Eocene through Quaternary planktonic foraminifers were identified in cores recovered during Leg 126. Turbidites and volcanic ash beds are intercalated with hemipelagic sediments. Preservation of foraminifers is variable, ranging from excellent to poor and appears to have been affected by fluctuations in the carbonate compensation depth (CCD), depth of burial, changes in bottom water temperature, current velocity, sediment accumulation rates and seafloor topography. Preservation of foraminifers in Quaternary sediments is generally good, however, species abundance varies by a factor of I05-106 and reflects dilution by volcanogenic as well as terrigenous constituents and cannot be used for paleoceanographic reconstructions. In pre-Quaternary deposits planktonic foraminiferal tests frequently exhibit dissolution effects; biostratigraphic zonation and placement of zonal boundaries is difficult owing to hiatuses, dissolution facies, extraneously deposited sediments, and discontinuous coring. The Eocene foraminiferal faunas include specimens of the Globorotalia cerroazulensis plexus, markers of Zone P16 as well as Globigerina senni and Globigerinatheka spp., which became extinct before the end of the Eocene. Six hiatuses and/or dissolution periods, probably reflecting global cooling events and/or changes in oceanic circulation patterns were recorded at Site 792. Recrystallized, poorly preserved, possibly reworked Eocene species (Globigerina senni and Globigerapsis sp.) were recorded in sediments at Site 793.

Thermal reaction norms of growth in Atlantic and Pacific silverside fishes

How organisms may adapt to rising global temperatures is uncertain, but concepts can emerge from studying adaptive physiological trait variations across existing spatial climate gradients. Many ectotherms, particularly fish, have evolved increasing genetic growth capacities with latitude (i.e. countergradient variation (CnGV) in growth), which are thought to be an adaptation primarily to strong gradients in seasonality. In contrast, evolutionary responses to gradients in mean temperature are often assumed to involve an alternative mode, 'thermal adaptation'. We measured thermal growth reaction norms in Pacific silverside populations (Atherinops affinis) occurring across a weak latitudinal temperature gradient with invariant seasonality along the North American Pacific coast. Instead of thermal adaptation, we found novel evidence for CnGV in growth, suggesting that CnGV is a ubiquitous mode of reaction-norm evolution in ectotherms even in response to weak spatial and, by inference, temporal climate gradients. A novel, large-scale comparison between ecologically equivalent Pacific versus Atlantic silversides (Menidia menidia) revealed how closely growth CnGV patterns reflect their respective climate gradients. While steep growth reaction norms and increasing growth plasticity with latitude in M. menidia mimicked the strong, highly seasonal Atlantic coastal gradient, shallow reaction norms and much smaller, latitude-independent growth plasticity in A. affinis resembled the weak Pacific latitudinal temperature gradient.

Sedimentation patters in the eastern equatorial Pacific Ocean

The post-middle Miocene evolution of sedimentary patterns in the eastern equatorial Pacific Ocean has been deduced from a compilation and synthesis of CaCO3, opal, and nannofossil assemblage data from 11 sites drilled during Leg 138. Improvements in stratigraphic correlation and time scale development enabled the construction of lithostratigraphic and chronostratigraphic frameworks of exceptional quality. These frameworks, and the high sedimentation rates (often exceeding 4 cm/k.y.) provided a detailed and synoptic paleoceanographic view of a large and highly productive region. The three highlights that emerge are: (1) a middle late Miocene "carbonate crash" (Lyle et al., this volume); (2) a late Miocene-early Pliocene "biogenic bloom"; and (3) an early Pliocene "opal shift". During the carbonate crash, an interval of dissolution extending from -11.2 to 7.5 Ma, CaCO3 accumulation rates declined to near zero over much of the eastern equatorial Pacific, whereas opal accumulation rates remained substantially unchanged. The crash nadir, near 9.5 Ma, was marked by a brief shoaling of the regional carbonate compensation depth by more than 1400 m. The carbonate crash has been correlated over the entire tropical Pacific Ocean, and has been attributed to tectonically-induced changes in abyssal flow through the Panamanian seaway. The biogenic bloom extended from 6.7 to 4.5 Ma, and was characterized by an overall increase in biogenic accumulation and by a steepening of the latitudinal accumulation gradient toward the equator. The bloom has been observed over a large portion of the global ocean and has been linked to increased productivity. The final highlight, is a distinct and permanent shift in the locus of maximum opal mass accumulation rate at 4.4 Ma. This shift was temporally, and perhaps causally, linked to the final closure of the Panamanian seaway. Before 4.4 Ma, opal accumulation was greatest in the eastern equatorial Pacific Basin (near 0°N, 107°W). Since then, the highest opal fluxes in the equatorial Pacific have occurred in the Galapagos region (near 3°S, 92°W).

Concentrations of dissolved organic carbon and particulate organic nitrogen in the Eastern North Pacific

Data are presented on concentration of dissolved organic carbon and particulate organic nitrogen in sea water at four stations, and also of dissolved and particulate amino acids at a deep-sea station above the Japan Trench. Concentration of Corg ranged from 0.79 to 2.00 mg/l, reaching maximum in the upper productive layers, while that of particulate Norg varied from 0.0018 to 0.037 mg/l, the maximum being in the upper layer (0-100 m). Water and particulate matter contained 18 amino acids in concentrations varying from 0.150 to 0.177 mg/l in the former and from 0.010 to 0.048 mg/l in the latter. Amino acid composition is variable. Vertical distribution of dissolved Corg and particulate Norg, as well as of dissolved and particulate amino acids is greatly dependent on water dynamics.

Organic geochemistry of Lower Cretaceous sediments from the northwetsern Pacific guyits

Organic geochemical data of Lower Cretaceous shallow water sediments from two sites (865 and 866) drilled during ODP leg 143 are presented. The organic matter is mainly terrestrial at the bottom of the sedimentary column at site 865, whereas algal and/or bacterial organic matter is dominant at site 866. This is the first evidence of shallow water deposition of organic matter during the Early Cretaceous in the Northwestern Pacific. The lower Aptian organic carbon-rich layers from the shallow water sediments of site 866 are geochemically similar to coeval mid-water sediments of site 463.

Geochemistry of sediments in the central equatorial Pacific Ocean

In order to quantify changes in export production and carbonate dissolution over the past 1 Myr in the central equatorial Pacific Ocean we analyzed Ba, P, Al Ti, and Ca in 1106 samples from five piston cores gathered from 5°S to 4°N at 140°W. We focused on Ba/Ti, Al/Ti, and P/Ti ratios as export proxies and employed areally integrated time slice as well as time series strategies. Carbonate maxima from 0-560 kyr are characterized by 15-30% greater export than carbonate minima. The increases in export fall on glacial delta18O transitions rather than glacial maxima. From 560-800 kyr, overlapping with the mid-Pleistocene transition, there is a very large increase in total export yet no glacial-interglacial variability. The highest latitudes (5°S and 4°N) record minimal absolute export change from glacials to interglacials and yet record the most extreme minima in percent CaCO3, indicating that carbonate records there are dominated by dissolution, whereas near the equator they are more influenced by changes in export.

(Table 3) Contents of P2O5 and total REE in phosphorites from Pacific seamonts

Changes in concentration levels and speciation of heavy metals during sedimentation on example of a typical semi-closed bay, where bottom sediments have formed due to river run-off, are under consideration. It is shown that due to desorption of mobile manganese, zinc and copper entered the bay with river suspended matter, their total contents in bottom sediments decrease and percentages of lithogenic forms increase. Contents and speciation of iron in bottom sediments are determined by its participation in coagulation of river colloids in the mixing zone and by mechanical differentiation of sedimentary material.

Contents of P2O5, Corg, Sr, and Ba in phosphorites and host sediments from the Atlantic and Pacific oceans

Sr contents in phosphorites on shelves of the Southwest Africa, and of Chile and Peru increase with degree of their lithification, from 0.05 to 0.28% and from 0.13 to 0.16% respectively. Phosphorites from Pacific submarine seamounts have the average Sr content 0.11%, and bone phosphate from Pacific floor 0.13%. Shelf phosphorites are characterized by high correlation coefficients between Sr and P2O5 (R = +0.82) and constant Sr/P2O5 ratio (0.0084). In phosphorites from submarine sea-mounts and in bones from the ocean floor Sr/P2O5 ratio is only a little higher than a half of that in shelf phosphorites. This indicates specific and different genesis of phosphorites from submarine mountains. Ba content in recent phosphorites from the shelf of the Southwest Africa changes with increasing degree of lithification. At first their Ba contents rise from 0.031 to 0.188%, then they diminish to 0.016%, and thereafter again increase to 0.070%. This is due to successive predominance of one of the following processes going in different directions: co-precipitation with phosphate gels or formation of true separate Ba phase, loss of phosphate in crystallization and "self-purification" of concentrations, and surface adsorption. In Peru-Chile shelf phosphorites the average Ba content is 0.017%, in phosphorites from Pacific seamounts 0.192%, and in fossilized bones 0.010%.

Contents of P2O5 and REE in phosphorites from shelves and Pacific seamounts

Recent phosphorites from the Namibian shelf are characterized by low REE contents, depletion in REE compared to host sediments and sharp deficiency of lanthanum and europium. In Late Quaternary and Pre-Quaternary phosphorites from ocean shelves REE contents and patterns in general are the same as in host sediments. Phosphorites from seamounts are enriched in REE compared to shelf phosphorites and their patterns are close to one of seawater. Behavior of REE in shelf phosphorites is determined by the fact that in early stages of phosphorite formation REE are associated not primarily with phosphate, but with organic matter and terrigenous impurities. Only in the later stages of diagenesis phosphate begins to play a leading role in concentration of REE. In metasomatic phosphorites on seamounts concentration of REE depends on age and depth of these rocks, i.e. it is determined by duration and conditions of contact with sea water.

Magnetic measurements of ODP Hole 178-1095B on the Pacific continental rise of the West Antarctic Peninsula

In this study we present a late Miocene - early Pliocene record of sixty-four zones with prominent losses in the magnetic susceptibility signal, taken on a sediment drift (ODP Site 1095) on the Pacific continental rise of the West Antarctic Peninsula. The zones are comparable in shape and magnitude and occur commonly at glacial-to-interglacial transitions. High resolution records of organic matter, magnetic susceptibility and clay mineral composition from early Pliocene intervals demonstrate that neither dilution effects nor provenance changes of the sediments have caused the magnetic susceptibility losses. Instead, reductive dissolution of magnetite under suboxic conditions seems to be the most likely explanation. We propose that during the deglaciation exceptionally high organic fluxes in combination with weak bottom water currents and prominent sediment draping diatom ooze layers produced temporary suboxic conditions in the uppermost sediments. It is remarkable that synsedimentary suboxic conditions can be observed in one of the best ventilated open ocean regions of the World.