Nd, Sr and Pb isotopes and clay minerals in sediment cores from the Gulf of Cadiz and the Portuguese margin

The assemblages of marine sediments on the SW Iberian shelf have been controlled by contributions from distinct sources, which have varied in response to environmental changes since the Last Glacial Maximum (LGM). The rapid, decadal scale Mediterranean overturning circulation permits mixing of suspended particles from the entire Mediterranean Sea. They are entrained into the suspended particulate matter (SPM) carried by Mediterranean Outflow Water (MOW), which enters the eastern North Atlantic through the Strait of Gibraltar and spreads at intermediate depths in the Gulf of Cadiz and along the Portuguese continental margin. Other major sediment sources that have contributed to the characteristics and budget of SPM along the flow path of MOW on the SW Iberian shelf are North African dust and river-transported particles from the Iberian Peninsula. To reconstruct climate- and circulation-driven changes in the supply of sediments over the past ~23000 cal yr B.P., radiogenic Nd, Sr and Pb isotope records of the clay-size sediment fraction were obtained from one gravity core in the Gulf of Cadiz (577 m water depth) and from two gravity cores on the Portuguese shelf (1745 m, 1974 m water depth). These records are supplemented by time series analyses of clay mineral abundances from the same set of samples. Contrary to expectations, the transition from the LGM to the Holocene was not accompanied by strong changes in sediment provenance or transport, whereas Heinrich Event 1 (H1) and the African Humid Period (AHP) were marked by significantly different isotopic signatures reflecting changes in source contributions caused by supply of ice rafted material originating from the North American craton during H1 and diminished supply of Saharan dust during the AHP. The data also reveal that the timing of variations in the clay mineral abundances was decoupled from that of the radiogenic isotope signatures.

Raw X-ray fluorescence (XRF) scannings and radiocarbon age of sediment cores GeoB8331-4, and GeoB8322-2

Variations in the sediment input to the Namaqualand mudbelt during the Holocene are assessed using an integrative terrestrial to marine, source to sink approach. Geochemical and Sr and Nd isotopic signatures are used to distinguish fluvial sediment source areas. Relative to the sediments of the Olifants River, craton outcrops in the northern Orange River catchment have a more radiogenic Sr and a more unradiogenic Nd isotopic signature. Furthermore, upper Orange River sediments are rich in heavier elements such as Ti and Fe derived from the chemical weathering of Drakensberg flood basalt. Suspension load signatures change along the Orange River's westward transit as northern catchments contribute physical weathering products from the Fish and Molopo River catchment area. Marine cores offshore of the Olifants (GeoB8323-2) and Orange (GeoB8331-4) River mouths show pulses of increased contribution of Olifants River and upper Orange River input, respectively. These pulses coincide with intervals of increased terrestrial organic matter flux and increased paleo-production at the respective core sites. We attribute this to an increase in fluvial activity and vegetation cover in the adjacent catchments during more humid climate conditions. The contrast in the timing of these wet phases in the catchment areas reflects the bipolar behavior of the South African summer and winter rainfall zones. While rainfall in the Orange River catchment is related to southward shifts in the ICTZ, rainfall in the Olifants catchment is linked to northward shifts in Southern Hemisphere Westerly storm tracks. The later may also have increased southern Benguela upwelling in the past by reducing the shedding of Agulhas eddies into the Atlantic. The high-resolution records of latitudinal shifts in these atmospheric circulation systems correspond to late Holocene centennial-millennial scale climate variability evident in Antarctic ice core records. The mudbelt cores indicate that phases of high summer rainfall zone and low winter rainfall zone humidity (at ca. 2.8 and 1 ka BP) may be synchronous with Antarctic warming events. On the other hand, dry conditions in the summer rainfall zone along with wet conditions in the winter rainfall zone (at ca 3.3, 2 and 0.5 ka BP) may be associated with Antarctic cooling events.

Concentrations and d13C compositions of n-alkanes, n-alcohols, n-alkanoic acids in a 34-month time series of suspended sediments from the outflow of the Congo River

The concentrations, distributions, and stable carbon isotopes (d13C) of plant waxes carried by fluvial suspended sediments contain valuable information about terrestrial ecosystem characteristics. To properly interpret past changes recorded in sedimentary archives it is crucial to understand the sources and variability of exported plant waxes in modern systems on seasonal to inter-annual timescales. To determine such variability, we present concentrations and d13C compositions of three compound classes (n-alkanes, n-alcohols, n-alkanoic acids) in a 34-month time series of suspended sediments from the outflow of the Congo River. We show that exported plant-dominated n-alkanes (C25-C35) represent a mixture of C3 and C4 end members, each with distinct molecular distributions, as evidenced by an 8.1 ± 0.7 per mil (±1Sigma standard deviation) spread in d13C values across chain-lengths, and weak correlations between individual homologue concentrations (r = 0.52-0.94). In contrast, plant-dominated n-alcohols (C26-C36) and n-alkanoic acids (C26-C36) exhibit stronger positive correlations (r = 0.70-0.99) between homologue concentrations and depleted d13C values (individual homologues average <= -31.3 per mil and -30.8 per mil, respectively), with lower d13C variability across chain-lengths (2.6 ± 0.6 per mil and 2.0 ± 1.1 per mil, respectively). All individual plant-wax lipids show little temporal d13C variability throughout the time-series (1 Sigma <= 0.9 per mil), indicating that their stable carbon isotopes are not a sensitive tracer for temporal changes in plant-wax source in the Congo basin on seasonal to inter-annual timescales. Carbon-normalized concentrations and relative abundances of n-alcohols (19-58% of total plant-wax lipids) and n-alkanoic acids (26-76%) respond rapidly to seasonal changes in runoff, indicating that they are mostly derived from a recently entrained local source. In contrast, a lack of correlation with discharge and low, stable relative abundances (5-16%) indicate that n-alkanes better represent a catchment-integrated signal with minimal response to discharge seasonality. Comparison to published data on other large watersheds indicates that this phenomenon is not limited to the Congo River, and that analysis of multiple plant-wax lipid classes and chain lengths can be used to better resolve local vs. distal ecosystem structure in river catchments.

(Table 1) Age determination of sediment core KY07-04-PC1

Variations in Mg/Ca-based sea surface temperature and oxygen isotope ratio (d18O) of the surface water in the northern East China Sea (ECS) were reconstructed with high resolution during the last 18 kyr using planktic foraminifera. Millennial-scale variations between warmer, more saline surface water and cooler, less saline surface water were recognized during the early deglacial period and the Holocene, suggesting changes in the mixing ratio between the Kuroshio Water and the Changjiang Diluted Water. Stronger East Asian summer monsoon (EASM) precipitation events in south China are identified at 10.5, 8.8, 7.0, 5.3, 4.7, 2.9, 1.7, and 0.5 ka, based on sea surface salinity (SSS) records of the northern ECS. Weaker EASM precipitation events are also detected at 9.3, 8.3, 7.3, 6.0, 3.3, 2.3, 0.7, and 0.4 ka during the Holocene. These events agree with the maxima in d18O records of stalagmites from various parts of the Changjiang (Yangtze) River drainage. This agreement supports that our SSS record properly captures the millennial-scale dry (less EASM precipitation) events over the drainage basin of the Changjiang River during the Holocene. These dry events are also in good agreement with North Atlantic ice-rafted events, suggesting a teleconnection between North Atlantic climate and the EASM during the Holocene.

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.

(Table 1) Age determination on monospecies planktonic foraminifera of sediment core AN25-934

Reconstruction of regional climate and the Okhotsk Sea (OS) environment for the Last Glacial Maximum (LGM), deglaciation and Holocene were performed on the basis of high-resolution records of ice rafted debris (IRD), CaCO3, opal, total organic carbon (TOC), biogenic Ba (Ba_bio) and redox sensitive element (Mn, Mo) content, and diatom and pollen results of four cores that form a north-southern transect. Age models of the studied cores were earlier established by AMS 14C data, oxygen - isotope chronostratigraphy and tephrochronology. According to received results, since 25 ka the regional climate and OS environmental conditions have changed synchronously with LGM condition, cold Heinrich event 1, Bølling -Allerød (BA) warming, Younger Dryas (YD) cooling and Pre-Boreal (PB) warming recorded in the Greenland ice core, North Atlantic sediment, and China cave stalagmites. Calculation of IRD MAR in sediment of north-south transect cores indicate an increase of sea ice formation several times in the glacial OS as compared to the Late Holocene. Accompanying ice formation, increased brine rejection and the larger potential density of surface water at the north shelf due to a drop of glacial East Asia summer monsoon precipitation and Amur River run off, led to strong enhancement of the role of the OS in glacial North Pacific Intermediate Water (NPIW) formation. The remarkable increase in OS productivity during BA and PB warming was probably related with significant reorganisation of the North Pacific deep water ventilation and nutrient input into the NPIW and OS Intermediate Water (OSIW). Seven Holocene OS millennial cold events based on the elevated values of the detrended IRD stack record over the IRD broad trend in the sediments of the studied cores have occurred synchronously with cold events recorded in the North Atlantic, Greenland ice cores and China cave stalagmites after 9 ka. Diatom production in the OS were mostly controlled by sea ice cover changes and surface water stratification induced by sea-ice melting; therefore significant opal accumulation in sediments of this basin begin from 4-6 ka ago simultaneously with a remarkable decrease of sea ice cover.

Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.