Geochemistry and geomicrobiology profiles of ferruginous sediment, Lake Towuti, Indonesia

Lake Towuti is a tectonic basin, surrounded by ultramafic rocks. Lateritic soils form through weathering and deliver abundant iron (oxy)hydroxides but very little sulfate to the lake and its sediment. To characterize the sediment biogeochemistry, we collected cores at three sites with increasing water depth and decreasing bottom water oxygen concentrations. Microbial cell densities were highest at the shallow site - a feature we attribute to the availability of labile organic matter and the higher abundance of electron acceptors due to oxic bottom water conditions. At the two other sites, OM degradation and reduction processes below the oxycline led to partial electron acceptor depletion. Genetic information preserved in the sediment as extracellular DNA provides information on aerobic and anaerobic heterotrophs related to Actinobacteria, Nitrospirae, Chloroflexi and Thermoplasmatales. These taxa apparently played a significant role in the degradation of sinking organic matter. However, extracellular DNA concentrations rapidly decrease with core depth. Despite very low sulfate concentrations, sulfate-reducing bacteria were present and viable in sediments at all three sites, as confirmed by measurement of potential sulfate reduction rates. Microbial community fingerprinting supported the presence of taxa related to Deltaproteobacteria and Firmicutes with demonstrated capacity for iron and sulfate reduction. Concomitantly, sequences of Ruminococcaceae, Clostridiales and Methanomicrobiales indicated potential for fermentative hydrogen and methane production. Such first insights into ferruginous sediments show that microbial populations perform successive metabolisms related to sulfur, iron and methane. In theory, iron reduction could reoxidize reduced sulfur compounds and desorb OM from iron minerals to allow remineralization to methane. Overall, we found that biogeochemical processes in the sediments can be linked to redox differences in the bottom waters of the three sites, like oxidant concentrations and the supply of labile OM. At the scale of the lacustrine record, our geomicrobiological study should provide a means to link the extant subsurface biosphere to past environments.

(Table S1) Geochemistry for sediment core MD02-2515

A high-resolution, 55-kyr long record of chalcophile and redox-sensitive trace element accumulation (Ag, Cd, Re, Mo) from MD02-2515, western Guaymas Basin, is investigated in conjunction with patterns in stratigraphy and productivity. High opal concentrations (~58 wt. %), representing increased diatom production, coincide with laminated sediments, and dilute the concentrations of organic carbon (Corg) and metals. A similarity between opal and normalized Corg, Ag and Cd concentrations suggests delivery to the sediments by diatom export production, while patterns in normalized Re and Mo accumulation suggest a different emplacement mechanism. Although Mo enrichment in organic-rich, laminated sediments typically represents anoxic conditions at other locations, Mo (and Re) in Guaymas Basin is enriched in nonlaminated and bioturbated sediments that are representative of oxygenated conditions. Adsorption onto Fe- and/or Mn-oxyhydroxide surfaces during oxygenation inadequately explains both the Re and Mo enrichments. Thus, recently published mechanisms invoking direct Re and Mo removal from the water column and bioturbation-assisted irrigation of Re into the sediments are used to explain the counterintuitive observations in Guaymas Basin. The MD02-2515 stratigraphic and proxy records are also different from other records in the northeast Pacific in that there is little correspondence with Greenland Dansgaard-Oeschger interstadials. There is some correlation with Heinrich events, suggesting that ventilation of intermediate waters and/or reduced productivity may be important in controlling stratigraphy and trace element accumulation. The results question whether MD02-2515 records can be compared to northeast Pacific open-margin records, especially before 17 kyr BP.

Dinoflagellates of sediment core GeoB1523-1

Large numbers of calcareous dinoflagellate cysts and the vegetative calcareous coccoid species Thoracosphaera heimii are generally found in sediments underlying oligotrophic and/or stratified (sub)surface water environments. It is difficult to distinguish between the relative importance of these two environmental parameters on calcareous cyst and T. heimii distribution as they usually covary, but this information is essential if we want to apply cysts properly in the reconstruction of palaeoenvironments and past surface water hydrography. In the multi-proxy core GeoB 1523-1 from the Ceará Rise region in the western equatorial Atlantic Ocean (covering the past 155 ka), periods of greatest oligotrophy are not synchronous with periods of greatest stratification (Rühlemann et al., 1996, doi:10.1016/S0025-3227(96)00048-5; Mulitza et al., 1997, doi:10.1130/0091-7613(1997)025<0335:PFAROP>2.3.CO;2; 335-338; Mulitza et al., 1998, doi:10.1016/S0012-821X(98)00012-0), giving us the unique opportunity to differentiate between the effects of both parameters on cyst accumulation. The calcareous cyst record of the core reflects prominent increases in accumulation rate of nearly all observed species only during the nutrient-enriched but more stratified isotopic (sub)stages 5.5, 5.3, 5.1 and 1. In this respect, the distribution trends in the core are more similar to those of the eastern equatorial upwelling region (GeoB 1105-4) than they are to those of the oligotrophic north-eastern Brazilian continental slope (GeoB 2204-2), even though temporal changes in bioproductivity are principally in antiphase between the eastern and western equatorial regions. We conclude that stratification of the upper water column and the presence of a well-developed thermocline are probably the more important factors controlling cyst distribution in the equatorial Atlantic, whereas the state of oligotrophy secondarily influences cyst production within a well-stratified environment.

Foraminiferal assemblage and statistical analysis of surface sediment samples from the Golfe d'Arguin, Mauritania

With the growing pressure of eutrophication in tropical regions, the Mauritian shelf provides a natural situation to understand the variability in mesotrophic assemblages. Site-specific dynamics occur throughout the 1200 m depth gradient. The shallow assemblages divide into three types of warm-water mesotrophic foraminiferal assemblages, which is not only a consequence of high primary productivity restricting light to the benthos but due to low pore water oxygenation, shelf geomorphology, and sediment partitioning. In the intermediate depth (approx. 500 m), the increase in foraminiferal diversity is due to the cold-water coral habitat providing a greater range of micro niches. Planktonic species characterise the lower bathyal zone, which emphasizes the reduced benthic carbonate production at depth. Although, due to the strong hydrodynamics within the Golf, planktonic species occur in notable abundances through out the whole depth gradient. Overall, this study can easily be compared to other tropical marine settings investigating the long-term effects of tropical eutrophication and the biogeographic distribution of carbonate producing organisms.

Abundance of calcareous dinoflagellates of sediment cores from the South Atlantic Ocean

Despite the increasing interest in the South Atlantic Ocean as a key area of the heat exchange between the southern and the northern hemisphere, information about its palaeoceanographic conditions during transitions from glacial to interglacial stages, the so-called Terminations, are not well understood. Herein we attempt to increase this information by studying the calcareous dinoflagellate cysts and the shells of Thoracosphaera heimii (calcareous cysts) of five Late Quaternary South Atlantic Ocean cores. Extremely high accumulation rates of calcareous cysts at the Terminations might be due to a combined effect of increased cyst production and better preservation as result of calm, oligotrophic conditions in the upper water layers. Low relative abundance of Sphaerodinella albatrosiana compared with Sphaerodinella tuberosa in the Cape Basin may be the result of the relatively colder environmental conditions in this region compared with the equatorial Atlantic Ocean with high relative abundance of S. albatrosiana. Furthermore, the predominance of S. tuberosa during glacials and interglacials at the observed site of the western Atlantic Ocean reflects decreased salinity in the upper water layer.

Sedimentology, age models and stable isotope ratios of sediment cores from the equatorial Pacific

Based on detailed reconstructions of global distribution patterns, both paleoproductivity and the benthic d13C record of CO2, which is dissolved in the deep ocean, strongly differed between the Last Glacial Maximum and the Holocene. With the onset of Termination I about 15,000 years ago, the new (export) production of low- and mid-latitude upwelling cells started to decline by more than 2-4 Gt carbon/year. This reduction is regarded as a main factor leading to both the simultaneous rise in atmospheric CO2 as recorded in ice cores and, with a slight delay of more than 1000 years, to a large-scale gradual CO2 depletion of the deep ocean by about 650 Gt C. This estimate is based on an average increase in benthic d13C by 0.4-0.5 per mil. The decrease in new production also matches a clear 13C depletion of organic matter, possibly recording an end of extreme nutrient utilization in upwelling cells. As shown by Sarnthein et al., [1987], the productivity reversal appears to be triggered by a rapid reduction in the strength of meridional trades, which in turn was linked via a shrinking extent of sea ice to a massive increase in high-latitude insolation, i.e., to orbital forcing as primary cause.

Intact and core tetraether lipids in water column profiles of suspended particulate matter and of surface sediment samples off Cape Blanc, NW Africa

In the reconstruction of sea surface temperature (SST) from sedimentary archives, secondary sources, lateral transport and selective preservation are considered to be mainly negligible in terms of influencing the primary signal. This is also true for the archaeal glycerol dialkyl glycerol tetraethers (GDGTs) that form the basis for the TEX86 SST proxy. Our samples represent four years variability on a transect off Cape Blanc (NW Africa). We studied the subsurface production, vertical and lateral transport of intact polar lipids and core GDGTs in the water column at high vertical resolution on the basis of suspended particulate matter (SPM) samples from the photic zone, the subsurface oxygen minimum zone (OMZ), nepheloid layers (NL) and the water column between these. Furthermore we compared the water column SPM GDGT composition with that in underlying surface sediments. This is the first study that reports TEX86 values from the precursor intact polar lipids (IPLs) associated with specific head groups (IPL -specific TEX86). We show a clear deviation from the sea surface GDGT composition in the OMZ between 300 and 600 m. Since neither lateral transport nor selective degradation provides a satisfactory explanation for the observed TEX-derived temperature profiles with a bias towards higher temperatures for both core- and IPL -specific TEX86 values, we suggest that subsurface in situ production of archaea with a distinct relationship between lipid biosynthesis and temperature is the responsible mechanism. However, in the NW-African upwelling system the GDGT contribution of the OMZ to the surface sediments does not seem to affect the sedimentary TEX86 as it shows no bias and still reflects the signal of the surface waters between 0 and 60 m.

Planktic foraminifera of sediment core GeoB1710-3

In this study, we test various parameters in deep-sea sediments (bulk sediment parameters and changes in microfossil abundances and preservation character) which are generally accepted as indicators of calcium carbonate dissolution. We investigate sediment material from station GeoB 1710-3 in the northern Cape Basin (eastern South Atlantic), 280 km away from the Namibian coast, well outside today's coastal upwelling. As northern Benguela upwelling cells were displaced westward and periodically preceded the core location during the past 245 kyr (Volbers et al., submitted), GeoB 1710-3 sediments reflect these changes in upwelling productivity. Results of the most commonly used calcium carbonate dissolution proxies do not only monitor dissolution within these calcareous sediments but also reflect changes in upwelling intensity. Accordingly, these conventional proxy parameters misrepresent, to some extent, the extent of calcium carbonate dissolution. These results were verified by an independent dissolution proxy, the Globigerina bulloides dissolution index (BDX') (Volbers and Henrich, 2002, doi:10.1016/S0025-3227(02)00333-X). The BDX' is based on scanning electronic microscope ultrastructural investigation of planktonic foraminiferal tests and indicates persistent good carbonate preservation throughout the past 245 kyr, with the exception of one pronounced dissolution event at early oxygen isotopic stage (OIS) 6. The early OIS 6 is characterized by calcium carbonate contents, sand contents, and planktonic foraminiferal concentrations all at their lowest levels for the last 245 kyr. At the same time, the ratio of radiolarian to planktonic foraminiferal abundances and the ratio of benthic to planktonic foraminiferal tests are strongly increased, as are the rain ratio, the fragmentation index, and the BDX'. The sedimentary calcite lysocline rose above the core position and GeoB 1710-3 sediments were heavily altered, as attested to by the unusual accumulation of pellets, aggregates, sponge spicules, radiolaria, benthic foraminifera, and planktonic foraminiferal assemblages. Solely the early OIS 6 dissolution event altered the coarse fraction intensely, and is therefore reflected by all conventional calcium carbonate preservation proxies and the BDX'. We attribute the more than 1000 m rise of the sedimentary calcite lysocline to the combination of two processes: (a) a prominent change in the deep-water mass distribution within the South Atlantic and (b) intense degradation of organic material within the sediment (preserved as maximum total organic carbon content) creating microenvironments favorable for calcium carbonate dissolution.

Distribution of surface sediment properties along the Portuguese western margin

Organic matter contained in surface sediments from four regions on the western Portuguese shelf, which are influenced by coastal upwelling and fluvial input, was analysed with respect to elemental organic carbon (Corg) and nitrogen (Ntotal) content and isotopic carbon and nitrogen ratios (d13Corg, d15N). Corg/Ntotal weight ratios and d13Corg values are interpreted in terms of terrigenous or marine organic matter sources, supported by CaCO3 content. Organic matter in the shelf sediments is mainly of marine origin, with increasing terrigenous components only close to rivers and estuaries. In the northern shelf region the data indicates significant terrigenous supply by the Douro River. North of the Nazaré Canyon organic matter composition implies a mainly marine origin, with a higher terrestrial influence close to the canyon head. Organic matter composition in the central shelf region, which is dominated by the Tagus Estuary and the Tagus prodelta, reveals a change from a continental-type signature within the estuary to a more marine-type signature further to the west and south of the estuary mouth. In the southern region near Cape Sines the geochemical properties clearly reflect the marine origin of sedimentary organic matter. Sedimentary d15N values are interpreted to reflect various degrees of assimilation of seasonally upwelled nitrate, in relation to the upwelling centres. In the estuarine environment, inputs of agriculturally influenced dissolved inorganic nitrogen are reflected in the sediments. No evidence for N2-fixation or denitrification is found. On the central shelf north of the Nazaré canyon, sedimentary d15N values are close to marine d15NO3- and thus indicate a complete NO3- assimilation and N-limitation of marine production. Light d15N values in distal sediments off the Douro River mouth and in samples south of C. Sines reflect high NO3- supply and a close proximity to the seasonal upwelling centres. Particularly in sediments form the Sines region, light d15N values in southern samples reflect stronger upwelling further south.

Diatom-bound N isotope records over the last two glacial cycles in sediment core PS75/072-4

In a sediment core from the Pacific sector of the Antarctic Zone (AZ) of the Southern Ocean, we report diatom-bound N isotope (d15Ndb) records for total recoverable diatoms and two distinct diatom assemblages (pennate and centric rich). These data indicate tight coupling between the degree of nitrate consumption and Antarctic climate across the last two glacial cycles, with d15Ndb (and thus the degree of nitrate consumption) increasing at each major Antarctic cooling event. Coupled with evidence from opal- and barium-based proxies for reduced export production during ice ages, the d15Ndb increases point to ice age reductions in the supply of deep ocean-sourced nitrate to the AZ surface. The two diatom assemblages and species abundance data indicate that the d15Ndb changes are not the result of changing species composition. The pennate and centric assemblage d15Ndb records indicate similar changes but with a significant decline in their difference during peak ice ages. A tentative seasonality-based interpretation of the centric-to-pennate d15Ndb difference suggests that late summer surface waters became nitrate free during the peak glacials.

Bulk and molecular proxies of sediment core GeoB6518-1

A 20 kyr long sediment sequence from the Congo deep sea fan (core GeoB 6518-1), one of the world's largest deep sea river fans, has been analysed for bulk and molecular proxies in order to reconstruct the marine, soil and plant organic carbon (OC) contributions to these sediments since the last glacial maximum. The bulk proxies applied, C/N ratio and d13Corg, ranged from 10 to 12.5 and from -24.5 to -21 per mill VPDB, respectively. As molecular proxies, concentrations of marine derived alkenones and terrestrial derived odd-numbered n-alkanes were used, which varied between 0.2 and 4 µg/g dry weight sediment. In addition, the branched vs. isoprenoid tetraether (BIT) index, a proxy for soil organic matter input, was used, which varied from 0.3 to 0.5 in this core. Application of binary mixing models, based on the different individual proxies, showed estimates for terrestrial OC input varying by up to 50% due to the heterogeneous nature of the OC. Application of a three end-member mixing model using the d13Corg content, the C/N ratio and the BIT index, enabled the distinction of soil and plant organic matter as separate contributors to the sedimentary OC pool. The results show that marine OC accounts for 20% to 40% of the total OC present in the deep sea fan sediments over the last 20 kyr and that soil OC accounts for about half (45% on average) of the OC present. This suggests that soil OC represents the majority of the terrestrial OC delivered to the fan sediments. Accumulation rates of the plant and soil OC fractions over the last 20 kyr varied by a factor of up to 5, and are strongly related to sediment accumulation rates. They showed an increase starting at ca. 17 kyr BP, a decline during the Younger Dryas, peak values during the early Holocene and lower values in the late Holocene. This pattern matches with reconstructions of past central African humidity and Congo River discharge from the same core and revealed that central African precipitation patterns exert a dominant control on terrestrial OC deposition in the Congo deep sea fan. Marine OC accumulation rates are only weakly related to sediment accumulation rates and vary only little over time compared to the terrigenous fractions. These variations are likely a result of enhanced preservation during times of higher sedimentation rates and of relative small fluctuations in primary production due to wind-driven upwelling.

Sea surface temperatures reconstructed from alkenones of surface sediment samples of the Argentine Basin at stations GeoB1501-1 to GeoB2830-1

We analysed the alkenone unsaturation ratio (UK'37) in 87 surface sediment samples from the western South Atlantic (5°N-50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured UK'37 ratios were converted into temperature using the global core-top calibration of Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by -2° to -6°C are found in the regions of the Brazil-Malvinas Confluence (35-39°S) and the Malvinas Current (41-48°S). From the oceanographic evidence these low UK'37 values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating UK'37 temperatures. In this way, particles and sediments carrying a cold water UK'37 signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.

Planktonic foraminiferal flux and shell geochemistry data in the sediment trap time series JAM 1-3 off south Java

Results from sediment trap experiments conducted in the seasonal upwelling area off south Java from November 2000 until July 2003 revealed significant monsoon-, El Niño-Southern Oscillation-, and Indian Ocean Dipole-induced seasonal and interannual variations in flux and shell geochemistry of planktonic foraminifera. Surface net primary production rates together with total and species-specific planktonic foraminiferal flux rates were highest during the SE monsoon-induced coastal upwelling period from July to October, with three species Globigerina bulloides, Neogloboquadrina pachyderma dex., and Globigerinita glutinata contributing to 40% of the total foraminiferal flux. Shell stable oxygen isotopes (d18O) and Mg/Ca data of Globigerinoides ruber sensu stricto (s.s.), G. ruber sensu lato (s.l.), Neogloboquadrina dutertrei, Pulleniatina obliquiloculata, and Globorotalia menardii in the sediment trap time series recorded surface and subsurface conditions. We infer habitats of 0-30 m for G. ruber at the mixed layer depth, 60-80 m (60-90 m) for P. obliquiloculata (N. dutertrei) at the upper thermocline depth, and 90-110 m (100-150 m) for G. menardii in the 355-500 mm (>500 µm) size fraction corresponding to the (lower) thermocline depth in the study area. Shell Mg/Ca ratio of G. ruber (s.l. and s.s.) reveals an exponential relationship with temperature that agrees with published relationships particularly with the Anand et al. (2003) equations. Flux-weighted foraminiferal data in sediment trap are consistent with average values in surface sediment samples off SW Indonesia. This consistency confirms the excellent potential of these proxies for reconstructing past environmental conditions in this part of the ocean realm.

Particle fluxes of the bathypelagic sediment trap CVOO-3 in the eastern tropical North Atlantic for the period December 2009 until May 2011

Particle fluxes at the Cape Verde Ocean Observatory (CVOO) in the eastern tropical North Atlantic for the period December 2009 until May 2011 are discussed based on bathypelagic sediment trap time-series data collected at 1290 and 3439 m water depth. The typically oligotrophic particle flux pattern with weak seasonality is modified by the appearance of a highly productive and low oxygen (minimum concentration below 2 µmol kg**-1 at 40 m depth) anticyclonic modewater eddy (ACME) in winter 2010. The eddy passage was accompanied by unusually high mass fluxes of up to 151 mg m**-2 d**-1, lasting from December 2009 to May 2010. Distinct biogenic silica (BSi) and organic carbon flux peaks of ~15 and 13.3 mg m**-2 d**-1, respectively, were observed in February-March 2010 when the eddy approached the CVOO. The flux of the lithogenic component, mostly mineral dust, was well correlated with that of organic carbon, in particular in the deep trap samples, suggesting a tight coupling. The lithogenic ballasting obviously resulted in high particle settling rates and, thus, a fast transfer of epi-/meso-pelagic signatures to the bathypelagic traps. We suspect that the two- to three-fold increase in particle fluxes with depth as well as the tight coupling of mineral dust and organic carbon in the deep trap samples might be explained by particle focusing processes within the deeper part of the eddy. Molar C : N ratios of organic matter during the ACME passage were around 18 and 25 for the upper and lower trap samples, respectively. This suggests that some productivity under nutrient (nitrate) limitation occurred in the euphotic zone of the eddy in the beginning of 2010 or that a local nitrogen recycling took place. The d15N record showed a decrease from 5.21 to 3.11 per mil from January to March 2010, while the organic carbon and nitrogen fluxes increased. The causes of enhanced sedimentation from the eddy in February/March 2010 remain elusive, but nutrient depletion and/or an increased availability of dust as a ballast mineral for organic-rich aggregates might have contributed. Rapid remineralisation of sinking organic-rich particles could have contributed to oxygen depletion at shallow depth. Although the eddy formed in the West African coastal area in summer 2009, no indications of coastal flux signatures (e.g. from diatoms) were found in the sediment trap samples, confirming the assumption that the suboxia developed within the eddy en route. However, we could not detect biomarkers indicative of the presence of anammox (anaerobic ammonia oxidation) bacteria or green sulfur bacteria thriving in photic zone suboxia/hypoxia, i.e. ladderane fatty acids and isorenieratene derivatives, respectively. This could indicate that suboxic conditions in the eddy had recently developed and/or the respective bacterial stocks had not yet reached detection thresholds. Another explanation is that the fast-sinking organic-rich particles produced in the surface layer did not interact with bacteria from the suboxic zone below. Carbonate fluxes dropped from -52 to 21.4 mg m**-2 d**-1 from January to February 2010, respectively, mainly due to reduced contribution of shallow-dwelling planktonic foraminifera and pteropods. The deep-dwelling foraminifera Globorotalia menardii, however, showed a major flux peak in February 2010, most probably due to the suboxia/hypoxia. The low oxygen conditions forced at least some zooplankton to reduce diel vertical migration. Reduced "flux feeding" by zooplankton in the epipelagic could have contributed to the enhanced fluxes of organic materials to the bathypelagic traps during the eddy passage. Further studies are required on eddy-induced particle production and preservation processes and particle focusing.