Sapropels in the Mediterranean Sea

Eastern Mediterranean sediments are characterized by cyclic deposition of organic-rich sediments known as sapropels. Enhanced primary productivity combined with bottom water oxygen depletion are thought to be the main drivers for sapropel deposition. We selected sapropel layers from a suite of ODP-Leg 160 cores, and applied a set of geochemical proxies to determine paleo-productivity variations, redox conditions of the water column during deposition, and provenance of detrital material. High sedimentary Ba/Al and Corg contents indicate enhanced primary production, whereas the sedimentary La/Lu ratio, points to an enhanced contribution from a North African riverine source, during sapropel formation. These features are especially pronounced on Sapropels S5 and S7, deposited during a particularly warm climatic interval. This indicates a more intense North African drainage/weathering and consequently run-off for those sapropels that have the most enhanced expression of productivity too. Correspondingly, the latter has also resulted in bottom water redox conditions that have been more severe during these sapropels than during others. Deepwater formation from Adriatic and Aegean areas, thought to be mainly controlled by sustained cooling of preconditioned surface waters, triggers the onset of bottomwater ventilation, thus sapropel duration. Our data, therefore, suggest that the intensity of sapropel formation is determined by the North African monsoonal system, whereas their duration is directed by northern borderlands climatic conditions.

Coccolithophora and geochemistry of sapropel S1 in ODP Hole 160-964B

The cyclic development of anoxic conditions in the eastern Mediterranean deep sea waters is one of the most fascinating research topics in paleoceanographic studies. In combination with bottom water stagnation, enhanced primary production is a common explanation for the deposition of organic-rich layers (sapropels). This is supported by extensive evidence from both geochemical and micropaleontological studies. The correspondence of recent sapropel layers with peaks of the lower photic zone coccolithophore species Florisphaera profunda has been interpreted as a proxy for the development of a deep chlorophyll maximum (DCM), due to the pycnocline/nutricline shallowing into the lower part of the photic zone. We present millennial-scale data for coccolithophore assemblages from sediments across the most recent sapropel (S1), in the ODP Hole 964B drilled in the Ionian Sea. Relative and absolute abundances of taxa are compared with selected elemental composition of the bulk sediments. The Mn/Al and Ba/Al profiles are used to determine the original thickness of the S1 interval, and show that the upper part of S1 was affected by post-depositional oxidation of organic matter. The Nannofossil Accumulation Rate, defined by the number of coccoliths/cm**2/kyr, suggests that there is no evidence of increased productivity within most of the sapropel layer. In fact, coccolithophore production was at its minimum in the lower part. Minimum coccolith concentrations are reached despite the increase in F. profunda in both relative and absolute abundance. We suggest that the DCM deduced from the increased productivity of this species did not significantly contribute to the putative overall increased primary productivity during the deposition of most of the sapropel layer. Within the upper oxidized part of S1, coccolith accumulation was at least five times higher than in the lower part. This period of high coccolith productivity finds a counterpart in the increase of the Ba/Al ratio. The total concentration of coccoliths is again controlled by the amount of E. huxleyi, but it is also supported by concomitant increases in all the other groups, suggesting that coccolithophore productivity increased throughout the year and through the total vertical extent of the photic zone. At site 964, this is apparently the only moment when coccolithophores contributed substantially to the increased primary productivity generally assumed for the S1 layer.

Geochemistry and Hg isotopic composition of mid-Pleistocene sapropel of ODP Hole 161-974C

The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average d202Hg value of -0.91 per mil ± 0.15 per mil (n = 5, 1 SD) and D199Hg value of 0.11 per mil ± 0.03 per mil (n = 5, 1 SD). Background sediments have an average d202Hg of -0.76 per mil ± 0.16 per mil (n = 5, 1 SD) and D199Hg of 0.05 per mil ± 0.01 per mil (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.

Late Miocene carbon isotope and paleoproductivity record

We examine whether or not a relationship exists between the late Miocene carbon isotope shift (~7.6-6.6 Ma) and marine productivity at four sites from the Indian and Pacific Oceans (Ocean Drilling Program Sites 721, 1146, 1172, and 846). We use a multiproxy approach based on benthic foraminiferal accumulation rates, elemental ratios, and dissolution indices, and we compare these data to benthic foraminiferal d13C values measured on the same samples. Although some of these sites have been targeted previously in studies of either the late Miocene/early Pliocene "biogenic bloom" (Sites 721 and 846) or the late Miocene carbon isotope shift (Site 1172), our records are the first to establish paired proxy records of carbon isotopes and paleoproductivity allowing a direct assessment of a potential link. Our results indicate that at all sites, productivity increased sometime during the d13C shift; at three sites (721, 1146, and 846), productivity increased at the beginning of the shift. The correlation coefficients derived from linear regression between micropaleontologically derived productivity and foraminiferal d13C values are relatively high during the time interval containing the late Miocene d13C shift (and statistically significant at three of the sites). Carbon flux and isotope mass balance considerations illustrate that transfer of organic matter between the terrestrial and marine reservoirs together with enhanced oceanic upwelling best approximates observed changes in carbon isotope records and paleoproductivity. We note that long-term trend in the Site 846 paleoproductivity record can be correlated to the long-term trend in the Site 848 eolian flux reconstructions of Hovan (1995, doi:10.2973/odp.proc.sr.138.132.1995) hinting at a link between strengthened wind regime and productivity during the late Miocene.

Age model and elemental data of DSDP Holes 48-401 and 80-549

A growing body of geologic evidence suggests that emplacement of the North Atlantic Igneous Province (NAIP) played a major role in global warming during the early Paleogene as well as in the transient Paleocene-Eocene thermal maximum (PETM) event. A ~5 million year record of major and trace element abundances spanning 56 to 51 Ma at Deep Sea Drilling Project Sites 401 and 549 confirms that the majority of NAIP volcanism occurred as subaerial flows. Thus the trace element records provide constraints on the nature and scope of the environmental impact of the NAIP during the late Paleocene-early Eocene interval. Subaerial volcanism would have injected mantle CO2 directly into the atmosphere, resulting in a more immediate increase in atmospheric greenhouse gas abundances than CO2 input through submarine volcanism. The lack of significant hydrothermalism contradicts recently proposed mechanisms for thermally destabilizing methane hydrate reservoirs during the PETM. Any connection between NAIP volcanism and PETM warming had to occur through the atmosphere.

Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Geochemistry on water profiles from the Kara Sea

As a part of the Russian-German project "Siberian River-Runoff (SIRRO)" the major element composition of the dissolved load and the major and trace element composition of particulate load and bottom sediment of the Yenisei River and Estuary were analyzed and examined in context of the basin lithology and climate. In addition, the processes controlling the transformation of the river load in the estuarine mixing zone were investigated. The chemical composition of the dissolved and particulate load of the Yenisei fluvial endmember is generally comparable to that of other major world rivers. The dissolved load is chiefly controlled by carbonate weathering and the chemical composition of the river suspended particulate matter (SPM) is similar to that of the North American Shale Composite (NASC), which represents the weathering product of the upper continental crust. The Chemical Index of Alteration (CIA) of the Yenisei SPM amounts to 71, which indicates moderate chemical weathering. With regard to the SPM geochemistry, the Yenisei occupies an intermediate position between the adjacent rivers Khatanga and the Lena. Drastic changes in the composition of the river load are seen in the mixing zone between fresh and salt water. While dissolved Na, Ca, Mg, K, CI, S04, F, Br, Sr and HC03 behave conservatively, dissolved Fe is completely removed from solution at very low salinities. Particulate Mn exhibits a pronounced mid-salinity minimum concomitant with a maximum of dissolved Mn, which is probably related to suboxic conditions in the area of the so-called "marginal filter", where highest turbidities are found. The Mn-minimum in SPM is paralleled by depletions of the elements Ba, Zn, Cd, Ni, Cu and V, which can be associated with manganese particles. The estuarine bottom sediments are composed of mud and sand and the sedimentological parameters of the bottom sediments have to be considered for the interpretation of the bulk geochemical data. The chemical composition of the mud is comparable to the SPM, whereas the sand is relatively enriched in Si/Al, Ba/Al, Zr/Al and Sr/Al ratios and depleted in transition metals.

Stable isotopes, core logging data, relative paleointensity, dry bulk density, biogenic opal, CN-data (TC, TOC, CaCO3, TN), element concentrations, and coarse fraction of three sediment cores from the western Bering Sea

We used piston cores recovered in the western Bering Sea to reconstruct millennial-scale changes in marine productivity and terrigenous matter supply over the past ~180 kyr. Based on a geochemical multi-proxy approach, our results indicate closely interacting processes controlling marine productivity and terrigenous matter supply comparable to the situation in the Okhotsk Sea. Overall, terrigenous inputs were high, whereas export production was low. Minor increases in marine productivity occurred during intervals of Marine Isotope Stage 5 and interstadials, but pronounced maxima were recorded during interglacials and Termination I. The terrigenous material is suggested to be derived from continental sources on the eastern Bering Sea shelf and to be subsequently transported via sea ice, which is likely to drive changes in surface productivity, terrigenous inputs, and upper-ocean stratification. From our results we propose glacial, deglacial, and interglacial scenarios for environmental change in the Bering Sea. These changes seem to be primarily controlled by insolation and sea-level forcing which affect the strength of atmospheric pressure systems and sea-ice growth. The opening history of the Bering Strait is considered to have had an additional impact. High-resolution core logging data (color b*, XRF scans) strongly correspond to the Dansgaard-Oeschger climate variability registered in the NGRIP ice core and support an atmospheric coupling mechanism of Northern Hemisphere climates.

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

Locations of geochemical samples and tephra from ODP Site 181-1123

Approximately one thousand sediment samples from ODP Site 1123 on the Chatham Rise, east of New Zealand, have been examined for inorganic elemental concentrations. ODP 1123 provides a record of sediment drift deposition under the Deep Western Boundary Current, the main inflow of deep water to the Pacific Ocean since the Early Oligocene, though a major hiatus spans the late Early Oligocene to the Early Miocene. Normalisation of the elemental concentrations by aluminium was used to allow for the effects of variable carbonate dilution. The elemental ratios were used as proxies for sediment composition and as palaeoceanographic indices. The samples were collected at a resolution designed to sample adequately any variation in elemental ratios at the scale of the Milankovitch orbital cycles. The sampled intervals span the Early Oligocene, Early Miocene, mid-Miocene and Late Pleistocene to Recent. Anomalous Si/Al, K/Al, Ti/Al values in the upper Pleistocene section, often associated with horizons of low carbonate, are attributed to tephras derived from North Island. Not all of the tephras detected geochemically had been detected visually in the cores. A total of 37 tephra events between 1.17 Ma BP and the present are recognised based on this and the shipboard investigations. The tephra events cluster at intervals of approximately 326 000 years (326 ka) perhaps due to variations in eruption frequency on North Island and/or to variations in the regional palaeowind intensity and direction. In the Late Pleistocene to Recent P/Al (inferred nutrient availability), percent calcium carbonate (%CaCO3) and Ba/Al (inferred productivity) varied regularly at a period of 40 000 years with these factors lagging minimum global ice volumes (interglacials). During the mid-Miocene CaCO3, Ba/Al, P/Al and Si/Al all gradually increased with %CaCO3 and P/Al showing regular 138 000-yr cyclicity and Ba/Al showing 44-ka cyclicity. Inferred productivity (Ba/Al) may have been rising in association with increasing nutrient availability (P/Al) at the same time as increased vigour of the Deep Western Boundary Current that was connected to a period of rapid ice-sheet growth in Antarctica. In the Early Miocene P/Al and Si/Al were much higher than subsequently and both %CaCO3 and P/Al exhibited 131 000-yr cycles. By far the highest nutrient levels and inferred productivity at this site apparently occurred during the Early Oligocene as revealed by long-term changes in P/Al and Si/Al. A progressive rise in K/Al, but stable Ti/Al from the Early Oligocene to the Recent probably indicates increased proportions of illite in the clay mineral fraction of the drift sediments caused by increased flux of debris from the Southern Alps.

Calcareous dinoflagellate cysts and geochemistry of Mediterranean Sea sediments

Comparison of calcareous dinoflagellate cyst assemblages with Ba, Al, Mn, and Fe records from three sediment cores collected in the eastern Mediterranean Sea indicate that calcareous dinoflagellate cysts are generally resistant to postdepositional dissolution. Cyst association changes during and after sapropel S1 formation can therefore be closely related to variability in surface water productivity. Two groups of cysts are defined: those having highest abundances within the sapropelic and postsapropelic sediments. The temporal cyst distributions suggest increased freshwater input mainly from the Nile and a shallowing of the pycnocline as the most important processes increasing nutrient concentration in the photic zone, thus leading to increased productivity and organic carbon fluxes during sapropel formation. Furthermore, a general warming trend at the beginning of S1 formation and a slight salinity decrease are reconstructed.

Geochemistry of sediments cores in the Mediterranean Sea

We investigated five time-equivalent core sections (180-110 kyr BP) from the Balearic Sea (Menorca Rise), the easternmost Levantine Basin and southwest, south, and southeast of Crete to reconstruct spatial patterns of productivity during deposition of sapropels S5 and S6 in the Mediterranean Sea. Our indicators are Ba, total organic carbon and carbonate contents. We found no indications of Ba remobilization within the investigated core intervals, and used the accumulation rate of biogenic Ba to compute paleoproductivity. Maximum surface water productivity (up to 350 g C/m2/yr) was found during deposition of S5 (isotope stage 5e) but pronounced spatial variability is evident. Coeval sediment intervals in the Balearic Sea show very little productivity change, suggesting that chemical and biological environments in the eastern and western Mediterranean basins were decoupled in this interval. We interpret the spatial variability as the result of two different modes of nutrient delivery to the photic zone: riverderived nutrient input and shoaling of the pycnocline/nutricline to the photic zone. The productivity increase during the formation of S6 was moderate compared to S5 and had a less marked spatial variability within the study area of the eastern Mediterranean Sea. Given that S6 formed during a glacial interval, glacial boundary conditions such as high wind stress and/or cooler surface water temperatures apparently favored lateral and vertical mixing and prevented the development of the spatial gradients within the Eastern Mediterranean Sea (EMS) observed for S5. A non-sapropel sediment interval with elevated Ba content and depleted 18O/16O ratios in planktonic foraminifer calcite was detected between S6 and S5 that corresponds to the weak northern hemisphere insolation maximum at 150 kyr. At this time, productivity apparently increased up to five times over surrounding intervals, but abundant benthic fauna show that the deep water remained oxic. Following our interpretation, the interval denotes a failed sapropel, when a weaker monsoon did not force the EMS into permanent stratification. The comparison of interglacial and glacial sapropels illustrates the relevance of climatic boundary conditions in the northern catchment in determining the facies and spatial variability of sapropels within the EMS.

Nitrogen isotope variations along the northeast Pacific margin

Glacial-interglacial changes in sedimentary d15N over the last 120 kyr display a remarkably similar pattern in timing and amplitude in core records extending from the denitrification zone in the eastern tropical North Pacific (ETNP), where subsurface denitrification is active, to the Oregon margin, where no denitrification occurs today. Low d15N values (4-6 per mil) generally characterize glacial stages 2 and 4, and higher d15N values (7-10 per mil) are representative of the Holocene, millennial-scale periods within stage 3, and stage 5. The inferred synchroneity of d15N variations along the entire margin implies that the nitrate isotopic signal produced in the oxygen-poor subsurface waters in the ETNP is rapidly advected northward and recorded at sites far beyond the boundaries of the modern denitrification zone. Similar to d15N, primary production indicators (percent Corg, Ba/Al, and percent opal) show glacial-interglacial as well as millennial-scale variations along the NE Pacific margin, with higher primary production during warm periods. However, the relative phasing between d15N and paleoproduction tracers within individual records changes latitudinally. Whereas d15N and primary production vary approximately synchronously in the midlatitudes, production lags d15N in the ETNP by several kiloyears. This lag calls for a new understanding of the processes driving denitrification in the ETNP. We suggest that oxygen input by the Equatorial Undercurrent as well as local organic matter flux controls denitrification rates in the ETNP. Moreover, the differences in relative timing point to a time-transgressive development of upwelling-favorable winds along the NE Pacific margin after the last glaciation, with those in the north developing several kiloyears earlier.

Paleoenvironmental changes in the western Mediterranean since the last glacial maximum: High resolution multiproxy record from the Algero-Balearic basin

The present study uses a multiproxy approach in order to further understand the evolution of climate responses in the western Mediterranean as of the Last Glacial Maximum. Sediments from ODP Site 975 in the Algero-Balearic basin have been analysed at high resolution, both geochemically andmineralogicallly. The resulting data have been used as proxies to establish a sedimentary regime, primary marine productivity, the preservation of the proxies and oxygen conditions. Fluctuations in detrital element concentrations were mainly the consequence of wet/arid oscillations. Productivity has been established using Ba excess, according to which marine productivity appears to have been greatest during cold events Heinrich 1 and Younger Dryas. The S1 time interval was not as marked by increases in productivity as was the eastern Mediterranean. In contrast, the S1 interval was first characterized by a decreasing trend and then by a fall in productivity after the 8.2 ky BP dry-cold event. Since then productivity has remained low. Here we report that there was an important redox event in this basin, probably a consequence of the major oceanographic circulation change occurring in the western Mediterranean at 7.7 ky BP. This circulation change led to reventilation as well as to diagenetic remobilization of redox-sensitive elements and organic matter oxidation. Comparisons between our paleoceanographic reconstruction for this basin and those regarding other Mediterranean basins support the hypothesis that across the Mediterranean there were different types of responses to climate forcing mechanism. The Algero-Balearic basin is likely to be a key area for further understanding of the relationships between the North Atlantic and the eastern Mediterranean basins.