Organic compounds in surface sediments from the Pakistan continental margin

In order to assess whether the oxygen-minimum zone (OMZ) in the Arabian sea has an effect on the preservation and composition of organic matter in surface sediments we investigated samples from three different transects on the Pakistan continental margin across the OMZ. In addition to determining the total amount of organic carbon (TOC), we analyzed the extractable lipids by gas chromatography, combined gas chromatography/mass spectrometry, and compound-specific stable carbon isotope measurements. The extractable lipids are dominated by marine organic matter as indicated by the abundance of lipids typical of marine biota and by the bulk and molecular isotopic composition. Sediments from within the OMZ are enriched in organic carbon and in several extractable lipids (i.e. phytol, n-alcohols, total sterols, n-C35 alkane) relative to stations above and below this zone. Other lipid concentrations, such as those of total n-fatty acids and total n-alkanes fail to show any relation to the OMZ. Only a weak correlation of TOC with mineral surface area was found in sediments deposited within the OMZ. In contrast, sediments from outside the OMZ do not show any relationship between TOC and surface area. Among the extractable lipids, only the n-alkane concentration is highly correlated with surface area in sediments from the Hab and Makran transects. In sediments from outside the OMZ, the phytol and sterol concentrations are also weakly correlated with mineral surface area. The depositional environment of the Indus Fan offers the best conditions for an enhanced preservation of organic matter. The OMZ, together with the undisturbed sedimentation at moderate rates, seems to be mainly responsible for the high TOC values in this area. Overall, the type of organic matter and its lability toward oxic degradation, the mineral surface area, the mineral composition, and possibly the secondary productivity by (sedimentary) bacteria also appear to have an influence on organic matter accumulation and composition.

Global compilation of benthic data sets I

Approaches to quantify the organic carbon accumulation on a global scale generally do not consider the small-scale variability of sedimentary and oceanographic boundary conditions along continental margins. In this study, we present a new approach to regionalize the total organic carbon (TOC) content in surface sediments (<5 cm sediment depth). It is based on a compilation of more than 5500 single measurements from various sources. Global TOC distribution was determined by the application of a combined qualitative and quantitative-geostatistical method. Overall, 33 benthic TOC-based provinces were defined and used to process the global distribution pattern of the TOC content in surface sediments in a 1°x1° grid resolution. Regional dependencies of data points within each single province are expressed by modeled semi-variograms. Measured and estimated TOC values show good correlation, emphasizing the reasonable applicability of the method. The accumulation of organic carbon in marine surface sediments is a key parameter in the control of mineralization processes and the material exchange between the sediment and the ocean water. Our approach will help to improve global budgets of nutrient and carbon cycles.

Composition of sediments from the Arabian Sea

Thirty seven deep-sea sediment cores from the Arabian Sea were studied geochemically (49 major and trace elements) for four time slices during the Holocene and the last glacial, and in one high sedimentation rate core (century scale resolution) to detect tracers of past variations in the intensity of the atmospheric monsoon circulation and its hydrographic expression in the ocean surface. This geochemical multi-tracer approach, coupled with additional information on the grain size composition of the clastic fraction, the bulk carbonate and biogenic opal contents makes it possible to characterize the sedimentological regime in detail. Sediments characterized by a specific elemental composition (enrichment) originated from the following sources: river suspensions from the Tapti and Narbada, draining the Indian Deccan traps (Ti, Sr); Indus sediments and dust from Rajasthan and Pakistan (Rb, Cs); dust from Iran and the Persian Gulf (Al, Cr); dust from central Arabia (Mg); dust from East Africa and the Red Sea (Zr/Hf, Ti/Al). Corg, Cd, Zn, Ba, Pb, U, and the HREE are associated with the intensity of upwelling in the western Arabian Sea, but only those patterns that are consistently reproduced by all of these elements can be directly linked with the intensity of the southwest monsoon. Relying on information from a single element can be misleading, as each element is affected by various other processes than upwelling intensity and nutrient content of surface water alone. The application of the geochemical multi-tracer approach indicates that the intensity of the southwest monsoon was low during the LGM, declined to a minimum from 15,000-13,000 14C year BP, intensified slightly at the end of this interval, was almost stable during the Bölling, Alleröd and the Younger Dryas, but then intensified in two abrupt successions at the end of the Younger Dryas (9900 14C year BP) and especially in a second event during the early Holocene (8800 14C year BP). Dust discharge by northwesterly winds from Arabia exhibited a similar evolution, but followed an opposite course: high during the LGM with two primary sources-the central Arabian desert and the dry Persian Gulf region. Dust discharge from both regions reached a pronounced maximum at 15,000-13,000 14C year. At the end of this interval, however, the dust plumes from the Persian Gulf area ceased dramatically, whereas dust discharge from central Arabia decreased only slightly. Dust discharge from East Africa and the Red Sea increased synchronously with the two major events of southwest monsoon intensification as recorded in the nutrient content of surface waters. In addition to the tracers of past dust flux and surface water nutrient content, the geochemical multi-tracer approach provides information on the history of deep sea ventilation (Mo, S), which was much lower during the last glacial maximum than during the Holocene. The multi-tracer approach-i.e. a few sedimentological parameters plus a set of geochemical tracers widely available from various multi-element analysis techniques-is a highly applicable technique for studying the complex sedimentation patterns of an ocean basin, and, specifically in the case of the Arabian Sea, can even reveal the seasonal structure of climate change.

Age models, accumulation rates, and grain size distributions of sediment cores from the northern subtropical Atlantic

The terrigenous sediment proportion of the deep sea sediments from off Northwest Africa has been studied in order to distinguish between the aeolian and the fluvial sediment supply. The present and fossil Saharan dust trajectories were recognized from the distribution patterns of the aeolian sediment. The following timeslices have been investigated: Present, 6,000, 12,000 and 18,000 y. B. P. Furthermore, the quantity of dust deposited off the Saharan coast has been estimated. For this purpose, 80 surface sediment samples and 34 sediment cores have been analysed. The stratigraphy of the cores has been achieved from oxygen isotopic curves, 14C-dating, foraminiferal transfer temperatures, and carbonate contents. Silt sized biogenic opal generally accounts for less than 2 % of the total insoluble sediment proportion. Only under productive upwelling waters and off river mouths, the opal proportion exceeds 2 % significantly. The modern terrigenous sediment from off the Saharan coast is generally characterized by intensely stained quartz grains. They indicate an origin from southern Saharan and Sahelian laterites, and a zonal aeolian transport in midtropospheric levels, between 1.5 an 5.5 km, by 'Harmattan' Winds. The dust particles follow large outbreaks of Saharan air across the African coast between 15° and 21° N. Their trajectories are centered at about 18° N and continue further into a clockwise gyre situated south of the Canary Islands. This course is indicated by a sickle-shaped tongue of coarser grain sizes in the deep-sea sediment. Such loess-sized terrigenous particles only settle within a zone extending to 700 km offshore. Fine silt and clay sized particles, with grain sizes smaller than 10- 15 µm, drift still further west and can be traced up to more than 4,000 km distance from their source areas. Additional terrigenous silt which is poor in stained quartz occurs within a narrow zone off the western Sahara between 20° and 27° N only. It depicts the present dust supply by the trade winds close to the surface. The dust load originates from the northwestern Sahara, the Atlas Mountains and coastal areas, which contain a particularly low amount of stained quartz. The distribution pattern of these pale quartz sediments reveals a SSW-dispersal of dust being consistent with the present trade wind direction from the NNE. In comparison to the sediments from off the Sahara and the deeper subtropical Atlantic, the sediments off river mouths, in particular off the Senegal river, are characterized by an additional input of fine grained terrigenous particles (< 6 µm). This is due to fluvial suspension load. The fluvial discharge leads to a relative excess of fine grained particles and is observed in a correlation diagram of the modal grain sizes of terrigenous silt with the proportion of fine fraction (< 6 µm). The aeolian sediment contribution by the Harmattan Winds strongly decreased during the Climatic Optimum at 6,000 y. B. P. The dust discharge of the trade winds is hardly detectable in the deep-sea sediments. This probably indicates a weakened atmospheric circulation. In contrast, the fluvial sediment supply reached a maximum, and can be traced to beyond Cape Blanc. Thus, the Saharan climate was more humid at 6,000 y B. P. A latitudinal shift of the Harmattan driven dust outbreaks cannot be observed. Also during the Glacial, 18,000 y. B. P., Harmattan dust transport crossed the African coast at latitudes of 15°-20° N. Its sediment load increased intensively, and markedly coarser grains spread further into the Atlantic Ocean. An expanded zone of pale-quart sediments indicates an enhanced dust supply by the trade winds blowing from the NE. No synglacial fluvial sediment contribution can be recognized between 12° and 30° N. This indicates a dry glacial climate and a strengthened stmospheric circulation over the Sahelian and Saharan region. The climatic transition pahes, at 12, 000 y. B. P., between the last Glacial and the Intergalcial, which is compareable to the Alerod in Europe, is characterized by an intermediate supply of terrigenous particles. The Harmattan dust transport wa weaker than during the Glacial. The northeasterly trade winds were still intensive. River supply reached a first postglacial maximum seaward of the Senegal river mouth. This indicates increasing humidity over the southern Sahara and a weaker atmospheric circulation as compared to the glacial. The accumulation rates of the terrigenous silt proportion (> 6 µm) decrcase exponentially with increasing distance from the Saharan coast. Those of the terrigenous fine fraction (< 6 µm) follow the same trend and show almost similar gradients. Accordingly, also the terrigenous fine fraction is believed to result predominantly from aeolian transport. In the Atlantic deep-sea sediments, the annual terrigenous sediment accumulation has fluctuated, from about 60 million tons p. a. during the Late Glacial (13,500-18,000 y. B. P, aeolian supply only) to about 33 million tons p. a. during the Holocene Climatic Optimum (6,000-9,000 y. B. P, mainly fluvial supply), when the river supply has reached a maximum, and to about 45 million tons p. a. during the last 4,000 years B. P. (fluvial supply only south of 18° N).

Database of the GLAMAP project

A uniform chronology for foraminifera-based sea surface temperature records has been established in more than 120 sediment cores obtained from the equatorial and eastern Atlantic up to the Arctic Ocean. The chronostratigraphy of the last 30,000 years is mainly based on published d18O records and 14C ages from accelerator mass spectrometry, converted into calendar-year ages. The high-precision age control provides the database necessary for the uniform reconstruction of the climate interval of the Last Glacial Maximum within the GLAMAP-2000 project.

Glacial North Atlantic: Sea surface conditions reconstructed by GLAMAP 2000

The response of the tropical ocean to global climate change and the extent of sea ice in the glacial nordic seas belong to the great controversies in paleoclimatology. Our new reconstruction of peak glacial sea surface temperatures (SSTs) in the Atlantic is based on census counts of planktic foraminifera, using the Maximum Similarity Technique Version 28 (SIMMAX-28) modern analog technique with 947 modern analog samples and 119 well-dated sediment cores. Our study compares two slightly different scenarios of the Last Glacial Maximum (LGM), the Environmental Processes of the Ice Age: Land, Oceans, Glaciers (EPILOG), and Glacial Atlantic Ocean Mapping (GLAMAP 2000) time slices. The comparison shows that the maximum LGM cooling in the Southern Hemisphere slightly preceeded that in the north. In both time slices sea ice was restricted to the north western margin of the nordic seas during glacial northern summer, while the central and eastern parts were ice-free. During northern glacial winter, sea ice advanced to the south of Iceland and Faeroe. In the central northern North Atlantic an anticyclonic gyre formed between 45° and 60°N, with a cool water mass centered west of Ireland, where glacial cooling reached a maximum of >12°C. In the subtropical ocean gyres the new reconstruction supports the glacial-to-interglacial stability of SST as shown by CLIMAP Project Members (CLIMAP) [1981]. The zonal belt of minimum SST seasonality between 2° and 6°N suggests that the LGM caloric equator occupied the same latitude as today. In contrast to the CLIMAP reconstruction, the glacial cooling of the tropical east Atlantic upwelling belt reached up to 6°-8°C during Northern Hemisphere summer. Differences between these SIMMAX-based and published U37[k]- and Mg/Ca-based equatorial SST records are ascribed to strong SST seasonalities and SST signals that were produced by different planktic species groups during different seasons.

Distribution of planktic foraminifera in surface sediments of the Atlantic Ocean

We present a data set of 738 planktonic foraminiferal species counts from sediment surface samples of the eastern North Atlantic and the South Atlantic between 87°N and 40°S, 35°E and 60°W including published Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) data. These species counts are linked to Levitus's [1982] modern water temperature data for the four caloric seasons, four depth ranges (0, 30, 50, and 75 m), and the combined means of those depth ranges. The relation between planktonic foraminiferal assemblages and sea surface temperature (SST) data is estimated using the newly developed SIMMAX technique, which is an acronym for a modern analog technique (MAT) with a similarity index, based on (1) the scalar product of the normalized faunal percentages and (2) a weighting procedure of the modern analog's SSTs according to the inverse geographical distances of the most similar samples. Compared to the classical CLIMAP transfer technique and conventional MAT techniques, SIMMAX provides a more confident reconstruction of paleo-SSTs (correlation coefficient is 0.994 for the caloric winter and 0.993 for caloric summer). The standard deviation of the residuals is 0.90°C for caloric winter and 0.96°C for caloric summer at 0-m water depth. The SST estimates reach optimum stability (standard deviation of the residuals is 0.88°C) at the average 0- to 75-m water depth. Our extensive database provides SST estimates over a range of -1.4 to 27.2°C for caloric winter and 0.4 to 28.6°C for caloric summer, allowing SST estimates which are especially valuable for the high-latitude Atlantic during glacial times.

Sediment core-top GDGT data from the Arctic, the North Pacific and the Southern Ocean

TEX86 (TetraEther indeX of tetraethers consisting of 86 carbon atoms) is a sea surface temperature (SST) proxy based on the distribution of archaeal isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs). In this study, we appraise the applicability of TEX86 and TEX86L in subpolar and polar regions using surface sediments. We present TEX86 and TEX86L data from 160 surface sediment samples collected in the Arctic, the Southern Ocean and the North Pacific. Most of the SST estimates derived from both TEX86 and TEX86L are anomalously high in the Arctic, especially in the vicinity of Siberian river mouths and the sea ice margin, plausibly due to additional archaeal contributions linked to terrigenous input. We found unusual GDGT distributions at five sites in the North Pacific. High GDGT-0/crenarchaeol and GDGT-2/crenarchaeol ratios at these sites suggest a substantial contribution of methanogenic and/or methanotrophic archaea to the sedimentary GDGT pool here. Apart from these anomalous findings, TEX86 and TEX86L values in the surface sediments from the Southern Ocean and the North Pacific do usually vary with overlaying SSTs. In these regions, the sedimentary TEX86-SST relationship is similar to the global calibration, and the derived temperature estimates agree well with overlaying annual mean SSTs at the sites. However, there is a systematic offset between the regional TEX86L-SST relationships and the global calibration. At these sites, temperature estimates based on the global TEX86L calibration are closer to summer SSTs than annual mean SSTs. This finding suggests that in these subpolar settings a regional TEX86L calibration may be a more suitable equation for temperature reconstruction than the global calibration.

Compilation of 220 sediment core d13C data from the glacial Atlantic Ocean

We compare a compilation of 220 sediment core d13C data from the glacial Atlantic Ocean with three-dimensional ocean circulation simulations including a marine carbon cycle model. The carbon cycle model employs circulation fields which were derived from previous climate simulations. All sediment data have been thoroughly quality controlled, focusing on epibenthic foraminiferal species (such as Cibicidoides wuellerstorfi or Planulina ariminensis) to improve the comparability of model and sediment core carbon isotopes. The model captures the general d13C pattern indicated by present-day water column data and Late Holocene sediment cores but underestimates intermediate and deep water values in the South Atlantic. The best agreement with glacial reconstructions is obtained for a model scenario with an altered freshwater balance in the Southern Ocean that mimics enhanced northward sea ice export and melting away from the zone of sea ice production. This results in a shoaled and weakened North Atlantic Deep Water flow and intensified Antarctic Bottom Water export, hence confirming previous reconstructions from paleoproxy records. Moreover, the modeled abyssal ocean is very cold and very saline, which is in line with other proxy data evidence.

Global data compilation of benthic data sets II

In this study we present a global distribution pattern and budget of the minimum flux of particulate organic carbon to the sea floor (J POC alpha). The estimations are based on regionally specific correlations between the diffusive oxygen flux across the sediment-water interface, the total organic carbon content in surface sediments, and the oxygen concentration in bottom waters. For this, we modified the principal equation of Cai and Reimers [1995] as a basic monod reaction rate, applied within 11 regions where in situ measurements of diffusive oxygen uptake exist. By application of the resulting transfer functions to other regions with similar sedimentary conditions and areal interpolation, we calculated a minimum global budget of particulate organic carbon that actually reaches the sea floor of ~0.5 GtC yr**-1 (>1000 m water depth (wd)), whereas approximately 0.002-0.12 GtC yr**-1 is buried in the sediments (0.01-0.4% of surface primary production). Despite the fact that our global budget is in good agreement with previous studies, we found conspicuous differences among the distribution patterns of primary production, calculations based on particle trap collections of the POC flux, and J POC alpha of this study. These deviations, especially located at the southeastern and southwestern Atlantic Ocean, the Greenland and Norwegian Sea and the entire equatorial Pacific Ocean, strongly indicate a considerable influence of lateral particle transport on the vertical link between surface waters and underlying sediments. This observation is supported by sediment trap data. Furthermore, local differences in the availability and quality of the organic matter as well as different transport mechanisms through the water column are discussed.

(Appendix) Gephyrocapsa coccolith abundance and holocene paleotemperature assessment

A global sea surface temperature calibration based on the relative abundance of different morphotypes within the coccolithophore genus Gephyrocapsa in Holocene deep-sea sediments is presented. There is evidence suggesting that absolute sea surface temperature for a given location can be calculated from the relative abundance of Gephyrocapsa morphotypes in sediment samples, with a standard error comparable to temperature estimates derived from other temperature proxies such as planktic foraminifera transfer functions. A total of 110 Holocene sediment samples were selected from the Pacific, Indian, and Atlantic Oceans covering a mean sea surface temperature gradient from 13.6° to 29.3°C. Standard multiple linear regression analyses were applied to this data set, linking the relative abundance of Gephyrocapsa morphotypes to sea surface temperature. The best model revealed an r**2 of 0.83 with a standard residual error of 1.78°C for the estimation of mean sea surface temperature. This new proxy provides a unique opportunity for the reconstruction of paleotemperatures with a very small amount of sample material due to the minute size of coccoliths, permitting examination of thinly laminated sediments (e.g., a pinhead of material from laminated sediments for the reconstruction of annual sea surface temperature variations). Such fine-scale resolution is currently not possible with any other proxy. Application of this new paleotemperature proxy may allow new paleoenvironmental interpretations in the late Quaternary period and discrepancies between the different currently used paleotemperature proxies might be resolved.

Expanded GHOST database

In this study we review a global set of alkenone- and foraminiferal Mg/Ca-derived sea surface temperatures (SST) records from the Holocene and compare them with a suite of published Eemian SST records based on the same approach. For the Holocene, the alkenone SST records belong to the actualized GHOST database (Kim, J.-H., Schneider R.R., 2004). The actualized GHOST database not only confirms the SST changes previously described but also documents the Holocene temperature evolution in new oceanic regions such as the Northwestern Atlantic, the eastern equatorial Pacific, and the Southern Ocean. A comparison of Holocene SST records stemming from the two commonly applied paleothermometry methods reveals contrasting - sometimes divergent - SST evolution, particularly at low latitudes where SST records are abundant enough to infer systematic discrepancies at a regional scale. Opposite SST trends at particular locations could be explained by out-of-phase trends in seasonal insolation during the Holocene. This hypothesis assumes that a strong contrast in the ecological responses of coccolithophores and planktonic foraminifera to winter and summer oceanographic conditions is the ultimate reason for seasonal differences in the origin of the temperature signal provided by these organisms. As a simple test for this hypothesis, Eemian SST records are considered because the Holocene and Eemian time periods experienced comparable changes in orbital configurations, but had a higher magnitude in insolation variance during the Eemian. For several regions, SST changes during both interglacials were of a similar sign, but with higher magnitudes during the Eemian as compared to the Holocene. This observation suggests that the ecological mechanism shaping SST trends during the Holocene was comparable during the penultimate interglacial period. Although this "ecology hypothesis" fails to explain all of the available results, we argue that any other mechanism would fail to satisfactorily explain the observed SST discrepancies among proxies.