Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.

Dinoflagellate cyst assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes, and geochemical parameters of sediment core GeoB9508-5

In order to investigate a possible connection between tropical northeast (NE) Atlantic primary productivity, Atlantic meridional overturning circulation (AMOC), and drought in the Sahel region during Heinrich Stadial 1 (HS1), we used dinoflagellate cyst (dinocyst) assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes (d13C) and geochemical parameters of a marine sediment core (GeoB 9508-5) from the continental slope offshore Senegal. Our results show a two-phase productivity pattern within HS1 that progressed from an interval of low marine productivity between ~ 19 and 16 kyr BP to a phase with an abrupt and large productivity increase from ~ 16 to 15 kyr BP. The second phase is characterized by distinct heavy planktonic d13C values and high concentrations of heterotrophic dinocysts in addition to a significant cooling signal based on reconstructions of past sea surface temperatures (SST). We conclude that productivity variations within HS1 can be attributed to a substantial shift of West African atmospheric processes. Taken together our results indicate a significant intensification of the North East (NE) trade winds over West Africa leading to more intense upwelling during the last millennium of HS1 between ~ 16 and 15 kyr BP, thus leaving a strong imprint on the dinocyst assemblages and sea surface conditions. Therefore, the two-phase productivity pattern indicates a complex hydrographic setting suggesting that HS1 cannot be regarded as uniform as previously thought.

Sediment accumulation rates of sediment cores from the North-West African continental margin

Six soft sediment cores, up to and over 9 m in length, and additional surface samples were selected for study of their planktonic foraminifera to provide information on the Holocene and Pleistocene stratigraphy of the West African continental margin south of the present boundary of the Sahara. The material was collected by the German research vessel "Meteor" during Cruise 25 in 1971. The residues larger than 160 microns determined, counted and statistically evaluated. Stratigraphical correlations with trans- Antlantic regions are given by occurrence of Truncorotalidoides hexagonus and Globorotalia tumidula flexuosa which mark the last interglacial stage. According to the climatic record the two deep-sea cores extend down to the V-zone, considered here as equivalent to the Mindel-Riss-interglacial time, as there are three distinctly warm and two cold periods indicated in the cores by planktonic foraminiferal faunas. Z-zone = Holocene is present in all cores, Y-zone = Wuermian glacial can be divided into five section, three cold and two warm stages; the X-zone can be divided into three warm stages, separated into two cool periods. The earliest warm stage is indicated to be the warmest one. There are excellent correlations to the Camp century ice core from Greenland, to the Mediterranean, to the Carribean and to the tropical Atlantic as well as to the Barnados stage. The W-zone was correlated to the Riss-glacial. V-zone is a warm period, the upper limit of which being not sufficiently defined, which contains also some cool sections. Increasing sedimentation rates from the deep-sea to the upper slope reveal climatic and regional details in Holocene and Late Pleistocene history of the continental margin. These were based mainly on different parameters of planktonic foraminiferal thanatocoenoses which are the main components of the size fraction >160 microns of the pelagic core. They become incerasingly diluted by other faunal and terrigenous components with decreasing slope depths. Estimates of absolute abundances, ranging from 25000 specimens/gm of sediment in the deep sea to less than 100, indicate various sedimentary processes at the continental margin. An ecological correlation by dominant species is possible. Readily computed temperature indices of different scales are presented which indicate, for instance, three distinctly cold sections within the last glacial and seven warm sections within the last interglacial lime. These are used for estimates of sedimentation rates. During cold periods sedimentation rates are higher than during warmer periods. Stratigraphic correlation and faunal record, combined with absolute abundances and sedimentation rates, indicated that in the deep sea turbidity currents not only cause high sedimentation rates for short periods of time, but also that material is occasionally eroded. Effects of upwelling may be detected in the surfacc sediment samples as well as in late Pleistocene and early Holocene samples of the slope by planktonic foraminiferal data which are not influenced by sedimentary processes.

Composition of the sand fraction of sediment cores from the West-African continental margin

Seven cores from the West African continental margin in 12-18° N have been investigated by means of a coarse fraction analysis. Four of the seven cores contain allochthonous material: turbidites and debris flow deposits. The source of the allochthonous material is in about 300-600 m water depth. The age of the slide induced debris flow deposits is at the end of oxygen isotope stage 2. One debris flow deposit is covered by a turbidite (core GIK13211-1). The turbidites in the deep-sea core GIK13207-3 originate from river-influenced sediments from the West-African continental margin, whereas the autochthonous sequences are influenced by volcanic material from the Cape Verde Islands. Particle by particle supply from upper slope areas has been found in all four cores from the continental slope. Current sorting occurs on the submarine diapir (core GIK13289-3), whereas core GIK13291-1 on the NW-flanc, 200 m below core GIK13289-3, has no current sorting, except for stage 1 and parts of stage 5. The current sorting is reflected by parallel variations of median diameters of whole tests and of fragments of planktonic foraminifers, by higher median diameters of foraminifers on top of the diapir, by reduced accumulation rates and increased sand fraction percentages in core GIK13289-3 compared to core GIK13291-1. The Late Quarternary climatic history of the West-African near coastal area (12-18° N) has been redrawn: - in oxygen isotope stage 1 a humid climate is found in 12-18° N (This "humid impression" in 18° N, which is actually an arid area, is due to the poleward directed undercurrent, which transports Senegal river material to the north). - in oxygen isotope stage 2 an arid climate existed in 14-18° N, whereas in 12° N river discharfe persisted. But within stage 2 dune formation occured in 12° N on the (dry) shelf, additionally to fluviatile sediment input. - Older periods are preserved in autochthonous sediments of core GIK13289-3 and GIK13291-1, where oxygen stage 3,5 and 7 (the latter only in core GIK13289-3 present) show a humid climate (as well as in stage 5 of core GIK13255-3), interrupted by short arid intervals in core GIK12389-3, and stage 4 and 6 show an arid climate, interrupted by short humid periods The allochthonous stage 5 sediment in core GIK13211-1 also reflects a humid climate. The dissolution of planktonic foraminifers is strongest in th eLate Holocene and shows a minimum in the early Holocene, where also pteropods are preserved. The degree of carbonate dissolution is related mainly to the fine matter content (< 63 µm) whereas water depth is a less decisvive factor.

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.

Sedimentology and geochemistry of the sand fraction in surface sediments off West Africa

Surface sediments from 5 profiles between 30 and 3000 m water depth off W Africa (12-19° N) have been studied for their sand fraction composition and their total calcium carbonate and organic matter contents to evaluate the effect of climatic and hydrographic factors on actual sedimentation. On the shelf and upper slope (< 500 m), currents prevent the deposition of significant amounts of fine-grained material. The sediments forming here are characterized by high sand contents (> 60 %; in most samples > 89 %), low organic carbon contents (in most samples < 0.8 %), high median diameters of the sand fraction (120-500 µm), and by a predominance of quartz and biogenic relict shells (most abundant: molluscs and bryozoans) in the sand fraction. Median diameters of total sand fraction and of major biogenic sand fraction components (biogenic relict material, benthonic molluscs, benthonic and planktonic foraminifers) co-vary to some extent and show maximum values in 100-300 m water depth, reflectingthe sorting effect of currents (perhaps the northward flowing undercurrent). In this water depth, biogenic relict material is considerably enriched relative to wuartz, the second dominating sand fraction component on the shelf and upper slope, resulting in distinct calcium carbonate maxima of the bulk sediments. The influence of the undercurrent is also reflected in a northward transport of fine grained river load and perhaps in the distribution of the red stained, coarse silt and sand-size clay aggregates, which show maxima in 300-500 m water depth. They probably originate from tropical soils. Abundant coarse red-stained quartz on the shelf off Cape Roxo (12-130° N) suggests a southward extension of last glacial dune fields to this latitude. Below about 500 m water depth, current influence becomes negligible - as indicated by a strong decrease in sand content, a concomitant increase in sedimentary organic carbon contents (up to 2.5-3.5 %), and the occurence of high mica/quartz ratios in the sand fraction. Downslope transport, presumably due to the bioturbation mechanism, is indicated by the presence of coarse shelf-borne particles (glauconite, relict shells) down to about 1000 m water depth. The fine/coarse ratio (clay + silt/sand) of the sediments from water deoth > 500 m never exceed a value of 11 in northern latitudes (19° - 26° N), but shows distinct maxima, ranging from 50 to 120, at latitudes 18°, 17° 15°30', and 14° N in about 2000 m water depth. This distribution is attributed to the deposition of fine-grained river load at the continental slope between 18° and 14° N, brought into the sea by the Senegal and souther rivers and transported northward ny the undercurrent. Strong calcium carbonate dissolution is indicated by the complete disappearance of pteropodes (aragonite) and high fragmentation of the planktoic foraminifers (calcite) in sediments from water depth > 300-600 m. Fragmentation ratios of planktonic foraminifers were found to depend on the organic carbon/carbonate ratios of the sediment suggesting that calcite dissolution at the sea bottom may also be significant in shelf and continental slope water depths if the organic matter/carbonate ratio of the surface sediment is high and the test remain long enough within the oxidizing layer on the top of the sulfate reduction zone. The fact that in the region under study intensity and anual duration of upwelling decrease from north to south is neither reflected in the composition on the sand fraction (i.e. radiolarian and fish debris contents, radiolarian/planktonic foraminiferal ratios, benthos/plankton ratios of foraminifers), nor in the sedimentary organic carbon distribution. On the contrary, these parameters even show in comparable water depths a tendency for highest values in the south, partly because primary production rates remain high in the whole region, particularly on the shelf, due to the nutrient input by rivers in the south. In addition, several hydrographic, sedimentological and climatic factors severely affect their distribution - for example currents, dissolution, grain size composition, deposition of river load, and bulk sedimentation rats.