Geochemistry on sapropel deposition in the eastern Mediterranean from cores TTR-GL94 and M25/4-KL11

The geochemistry of the youngest Mediterranean sapropel layer suggests changes in productivity and water column oxygen conditions during sapropel deposition. The Ba-enriched interval is broader than the organic-carbon-rich interval of this sapropel. We suggest that the Ba-enriched horizon records the original thickness of the sapropel prior to subsequent partial oxidation. The main carrier of Ba is barite, as microcrystals (0.5-5 µm ) having a morphology characteristic of marine barite, particularly abundant beneath high productivity regions. Ba concentrations do not change at the sapropel layer oxidation front and diagenetic barite crystals are absent, thus the Ba-enriched layer reflects original oceanic conditions of increased biological productivity during sapropel deposition and not diagenetic Ba remobilization. Paleoredox indicators point to restricted oxygenated bottom water but not to fully anoxic conditions. Detrital elements within this layer indicate a lower eolian terrigenous input, enhanced humidity, and increased precipitation/runoff, thus likely higher nutrient supply.

Inorganic geochemical record of ODP Holes 117-722B and 117-724C

High-resolution sampling from late Pleistocene (last 400 k.y.) sediments of Site 722 (upper 16 m) and Site 724 (upper 70 m), and subsequent inorganic geochemical analysis, has defined the history of productivity in the northwest Arabian Sea. Eolian dust input from the Arabian Peninsula and Somalia is characterized by the record of Ti/Al and Cr/Al. This dust record displays strong precessional periodicity (cycles at 25 k.y.) suggesting the Southwest Monsoon and associated winds play a key role in transporting terrigenous material from the land. High biological productivity results in the accumulation of biogenic CaCO3 and opal in the sediments, the latter having an unexpectedly minor contribution to the total mass flux. Due to dilution of the CaCO3 record by the terrigenous component, the record of biological productivity is best exemplified by Ba. Its record, together with that of other metals recording biological association and redox variability (Cu, Ni, Zn, V, U) clearly identifies the interglacial episodes as being more biologically productive. The striking agreement between Ba and the d18O record in planktonic foraminifers suggests that the supply of nutrients during these periods of high productivity is linked to ocean-wide changes in ocean fertility, and not just local upwelling conditions. High levels of phosphate accumulation in interglacial sediments is attributed to both diagenetic phosphorite formation and biogenic skeletal debris. This study provides a detailed record of productivity variation in the northwest Arabian Sea during the late Pleistocene.

Sedimentation rates and geochemistry of the Atlantic and Indic Ocean of Late Miocene - Early Pliocene

Studies of the late Miocene-early Pliocene biogenic bloom typically have focused on high-productivity areas in the Indian and Pacific Oceans in order to achieve high resolution samples. Thus there is a paucity of information concerning whether the Atlantic Ocean, in general or low-productivity regions in all three basins experienced this bloom. This study measured the phosphorus mass accumulation rate (PMAR). in five cores from low-productivity regions of the Atlantic and Indian Oceans. All cores exhibit a peak in productivity 4-5.5 Ma, coincident with the Indo-Pacific bloom. This suggests that nutrients were not shifted away from low-productivity regions nor out of the Atlantic Ocean. Instead, it appears that the bloom was caused by an overall increase in nutrient flux into the world oceans. Four of the cores record the bloom's PMAR peak as bimodal, indicating a pulsed increase in phosphorus to the oceans. This suggests that there may have been multiple causes of the biogenic bloom.

Age models and stable isotope ratios of SO12 and SO35 sediment cores

Based on organic carbon accumulation rates, nine time slices of oceanic export paleoproductivity (Pnew) are presented which depict the variability of Pnew on a global scale through the last 30,000 years and document that the basic distribution patterns did not change through glacial and interglacial times. However, the glacial ocean shows an increased contrast of high- versus low-productivity zones. d13C values of near-surface-dwelling planktonic foraminifera Globigerinoides ruber suggest that the same contrast applies to the glacial nutrient inventories of the ambient surface waters, with a significant glacial transfer of PO4 from low- to high-productivity zones. In this way, glacial Pnew increased by a global average of about 2-4 Gt C/yr and led, via an enhanced CaCO3 dissolution and alkalinity in the deep ocean, to a significant extraction of CO2 from the surface water and the atrnosphere.

Composition of organic matter in waters of the Barents Sea

Concentration of dissolved and suspended organic carbon in the Barents Sea decreases with increasing depth and in meridional direction from south to north. This fact is attributed to uneven supply of organic matter (OM) from different sources. Large amounts of OM are present in the water column of the Barents Sea, which is a result of high productivity of this water mass and slow decomposition of OM at low temperatures and lowered activity of microflora. Larger amount of OM reaches bottom sediments of the Barents Sea more than in seas, which have similar depth and productivity, but are located at low latitudes. Characteristic features of distribution of lipids and suspended matter in sea water are examined.

Grain size and diatom valves in sediment cores KS82-30 and KS82-31

Diatoms were studied quantitatively in six latest Quaternary (~70 kyr B.P. to Recent) piston cores from the westernmost Mediterranean, the Alboran Basin, and the Atlantic region immediately to the west of the Straits of Gibraltar. The Atlantic cores completely lack diatoms. In the Alboran Basin, diatoms are common from late Stage 3 (~27.5 kyr B.P.) to Termination lb (9 kyr B.P.) and in Recent core tops, but are absent in the other latest Quaternary intervals. Maximum accumulation of diatoms and highest abundance of species normally in sediments associated with increased productivity occurred during the latest Quaternary deglaciation, in the first phase of Termination I (~14.8 kyr B.P.). In the modern Alboran Basin, a region of high biological productivity occurs immediately east of the Gibraltar Straits. This high productivity results from upwelling associated with the interaction between the Atlantic inflow and the bottom topography near the Spanish coast. The upwelled nutrient-rich waters are then advected to the east and southeast by the surficial anticyclonic gyral circulation. Late Quaternary variations in diatom abundance are considered to reflect changes in this upwelling intensity with highest diatom abundances inferred to result from increased upwelling associated with an intensification of the anticyclonic gyral circulation. Highest inferred upwelling rates occurred during the first phase of latest Quaternary deglaciation. It is possible that an intensification of circulation within the Mediterranean Basin as a whole occurred from late Stage 3 to mid Termination I because widespread hiatus formation has been reported at this time in the Straits of Sicily due to an increase in the formation of intermediate waters. Diatoms were not preserved in other latest Quaternary intervals due to insufficient productivity to counterbalance their dissolution.

Diatoms and laminae of Mediterranean sapropels

The origins of sapropels (sedimentary layers rich in organic carbon) are unclear, yet they may be a key to understanding the influence of climate on ocean eutrophication, the mechanisms of sustaining biological production in stratified waters and the genesis of petroleum source rocks (Rohling, 1994, doi:10.1016/0025-3227(94)90202-X; Castradori, 1993, doi:10.1029/93PA00756; Calvert et al., 1992, doi:10.1038/359223a0). Recent microfossil studies of foraminifera (Rohling, 1994, doi:10.1016/0025-3227(94)90202-X) and calcareous nannofossils (Castradori, 1993, doi:10.1029/93PA00756) have focused attention on a deep chlorophyll maximum as a locus for the high production inferred (Calvert et al., 1992, doi:10.1038/359223a0) for sapropel formation, but have not identified the agent responsible. Here we report the results of a high-resolution, electron-microscope-based study of a late Quaternary laminated sapropel in which the annual flux cycle has been preserved. We find that much of the production was by diatoms, both mat-forming and other colonial forms, adapted to exploit a deep nutrient supply trapped below surface waters in a stratified water column. Reconstructed organic-carbon and opal fluxes to the sediments are comparable to those at high-productivity sites in today's oceans, and calculations based on diatom Si/C ratios suggest that the high organic-carbon content of sapropels may be entirely accounted for by sedimenting diatoms. We propose that this style of production may have been common in ancient Palaeogene and Cretaceous seas, environments for which conventional appeals to upwelling-driven production to account for the occurrence of diatomites, and some organic-carbon-rich sediments, have never seemed wholly appropriate.

Organic matter and trace element concentrations in sapropels from ODP Leg 160 sites

A distinct Pliocene eastern Mediterranean sapropel (i-282), recovered from three Ocean Drilling Program (ODP) Leg 160 Sites, has been investigated for its organic and inorganic composition. This sapropel is characterized by high organic carbon (Corg) and trace element contents, and the presence of isorenieratene derivatives. The latter suggests that the base of the photic zone was sulphidic during formation of the sapropel. Combined with evidence of bottom water anoxia (preservation of laminae, high redox-sensitive trace element contents, and the abundance and isotopic composition of pyrite) this leads to the tentative conclusion that almost the entire water column may have been anoxic. This anoxia resulted from high productivity and not from stagnation, because an approximation of the trace element budget during sapropel formation shows that water exchange with the western Mediterranean is needed. Entire water column anoxia has been suggested earlier for several black shales. With regard to the depositional environment and the Corg content, however, only the Cenomanian=Turonian Boundary Event (CTBE) black shales appear to be comparable to this sapropel. The proposed trace element removal mechanism of scavenging and (co-)precipitation in an anoxic water column, is thought to be similar for both types of deposits. The ultimate trace element source for the sapropel, however, is seawater, whereas it is hydrothermal and fluvial input for CTBE black shales (because they have a larger temporal and spatial distribution). Nonetheless, the Corg-rich eastern Mediterranean Pliocene sapropel discussed here may be considered to be a younger analogue of CTBE black shales.

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.

Coccolith fluxes in the Santa Barbara Basin

We investigate the long-term stability of El Niño-Southern Oscillation and Pacific Decadal Oscillation based on the examination of coccolithophore assemblages in a largely laminated 35 ka sedimentary record, retrieved in the Santa Barbara Basin (core MD02-2503). At a centennial scale coccolith assemblages indicate low primary production in the basin from 35 to 11.5 ka B.P., whereas the Holocene is characterized by high-productivity conditions. This pattern demonstrates the influence of the glacial-interglacial cycles on productivity and, by inference, on the nutrient supply by the upwelling cell off Point of Conception. On a shorter scale, laminations associated with Dansgaard-Oeschger events appear to be due to an injection of poorly oxygenated waters in the deepest part of the basin rather than anoxia due to high primary production. A seasonal sampling in seven laminated sections (spanning from 20 to 220 years) extracted from Holocene, Bølling-Allerød, and Dansgaard-Oeschger event 3 indicates El Niño probably existed continuously during the last 28 ka. The frequency of El Niño varied through time (between 1/2.5 and 1/5 event/a) and appearing to follow the precession cycle. El Niño exhibits higher (lower) frequencies when the precession values are lower (higher). Finally, the Holocene is characterized by a decrease in El Niño's frequencies due to the reinforcement of El Niño through this period.

Characterization of dead-zone eddies in the tropical Northeast Atlantic

Localized open-ocean low-oxygen dead-zones in the tropical Northeast Atlantic are recently discovered ocean features that can develop in dynamically isolated water masses within cyclonic eddies (CE) and anticyclonic modewater eddies (ACME). Analysis of a comprehensive oxygen dataset obtained from gliders, moorings, research vessels and Argo floats revealed that eddies with low oxygen concentrations at 50-150 m depths can be found in surprisingly high numbers and in a large area (from about 4°N to 22°N, from the shelf at the eastern boundary to 38°W). Minimum oxygen concentrations of about 9 µmol kg-1 in CEs and severely suboxic concentrations (< 1 µmol kg-1) in ACMEs were observed. In total, 173 profiles with oxygen concentrations below the minimum background concentration of 40 µmol kg-1 could be associated with 27 independent "dead-zone" eddies (10 CEs; 17 ACMEs) over a period of 10 years. The eddies' oxygen minimum is located in the eddy core beneath the mixed layer at a mean depth of 80 m. Compared to the surrounding waters, the mean oxygen anomaly between 50 and 150 m depth for CEs (ACMEs) is -38 (-79) µmol kg-1. The low oxygen concentration right beneath the mixed layer has been attributed to the combination of high productivity in the eddies' surface waters and the isolation of their cores with respect to lateral oxygen supply. Indeed, eddies of both types feature a cold sea surface temperature anomaly and enhanced chlorophyll concentrations in their center. The locally increased consumption within these eddies represents an essential part of the total consumption in the open tropical Northeast Atlantic Ocean and might be partly responsible for the formation of the shallow oxygen minimum zone. Eddies south of 12°N carry weak hydrographic anomalies in their cores and seem to be generated in the open ocean away from the boundary. North of 12°N, eddies of both types carry anomalously low salinity water of South Atlantic Central Water origin from the eastern boundary upwelling region into the open ocean. Water mass properties and satellite eddy tracking both point to an eddy generation near the eastern boundary.

Radiocarbon dating on cold-water corals and planktonic foraminifera, grain size analysis, stable oxygen isotopes, and XRF data of sediment cores from the Alboran Sea

Cold-water corals are common along the Moroccan continental margin off Melilla in the Alboran Sea (western Mediterranean Sea), where they colonise and largely cover mound and ridge structures. Radiocarbon ages of the reef-forming coral species Lophelia pertusa and Madrepora oculata sampled from those structures, reveal that they were prolific in this area during the last glacial-interglacial transition with pronounced growth periods covering the Bølling-Allerød interstadial (13.5-12.8 ka BP) and the Early Holocene (11.3-9.8 ka BP). Their proliferation during these periods is expressed in vertical accumulation rates for an individual coral ridge of 266-419 cm ka**-1 that consists of coral fragments embedded in a hemipelagic sediment matrix. Following a period of coral absence, as noted in the records, cold-water corals re-colonised the area during the Mid-Holocene (5.4 ka BP) and underwater photographs indicate that corals currently thrive there. It appears that periods of sustained cold-water coral growth in the Melilla Coral Province were closely linked to phases of high marine productivity. The increased productivity was related to the deglacial formation of the most recent organic rich layer in the western Mediterranean Sea and to the development of modern circulation patterns in the Alboran Sea.

Noble gases sampled from three cruises in the eastern tropical Atlantic

Oceanic upwelling velocities are too small to be measured directly. Deviations of the He-3/He-4 ratio in the mixed layer from solubility equilibrium provide an indirect means to infer vertical velocities at the base of the mixed layer. This method is applied to the Mauritanian upwelling region for data from three cruises in summer 2006 and winter 2007 and 2008. Diapycnal mixing coefficients are estimated from microstructure measurements, reaching from 10**-3 m**2/s over the shelf break to 10**-5 m**2/s in the open ocean. The resulting upwelling velocities in the onshore region (upto 50 km from the 50 m isobath) are of the order of 2 x 10**-5 m/s}, in agreement with Ekman theory. Further offshore, in some cases the vertical velocities inferred from the helium isotope disequilibrium exceed the values derived from the wind stress curl by one order of magnitude. The Mauritanian coastal area as part of the Canary Current upwelling system belongs to the most productive ocean regions in the world. Nutrient fluxes into the mixed layer (both advective and diffusive) are equivalent to a net community production of about 1 g C/d, and associated heat fluxes vary between 183 +/- 62 W/m**2 in summer and 97 +/- 25 W/m**2 in winter. Regarding the flux into the mixed layer, the contribution of diffusion and advection are of similar magnitude for both heat and nutrients. The upwelling, however, provides the supply of cold and nutrient rich water from below. The large offshore vertical velocities inferred from the helium method are associated with nutrient fluxes of the same order as for the onshore region, and may be responsible for observed patches of high productivity in that area. The offshore heat fluxes due to upwelling and diapycnal mixing are smaller than 70 W/m**2 for all cruises.