Radionuclides, Nd isotopes and biogenic Opal in Atlanic Ocean sediments

Reconstructing past modes of ocean circulation is an essential task in paleoclimatology and paleoceanography. To this end, we combine two sedimentary proxies, Nd isotopes (epsilon-Nd) and the 231Pa/230Th ratio, both of which are not directly involved in the global carbon cycle, but allow the reconstruction of water mass provenance and provide information about the past strength of overturning circulation, respectively. In this study, combined 231Pa/230Th and epsilon-Nd down-core profiles from six Atlantic Ocean sediment cores are presented. The data set is complemented by the two available combined data sets from the literature. From this we derive a comprehensive picture of spatial and temporal patterns and the dynamic changes of the Atlantic Meridional Overturning Circulation over the past ~25 ka. Our results provide evidence for a consistent pattern of glacial/stadial advances of Southern Sourced Water along with a northward circulation mode for all cores in the deeper (>3000 m) Atlantic. Results from shallower core sites support an active overturning cell of shoaled Northern Sourced Water during the LGM and the subsequent deglaciation. Furthermore, we report evidence for a short-lived period of intensified AMOC in the early Holocene.

(Table 1) Sample locations, Hf and Nd isotopic compositions and concentrations of Atlantic seawater samples with hydrographic details

The first full water column hafnium isotopic compositions of Atlantic seawater have been obtained at seven locations from the Labrador Sea to the Drake Passage. Despite subpicomolar concentrations in seawater, a precision of the Hf isotopic measurements of <0.7 epsilon-Hf units was achieved. An overall epsilon-Hf range between -3.1 in the Labrador Sea and +4.4 in Antarctic bottom water was determined, the distribution of which broadly reflects continental weathering inputs. Within particular water column profiles, significant differences of up to 4 epsilon-Hf units occur. Combined with Nd isotope data of the same samples, it is evident that the Hf isotopic composition of seawater is too radiogenic for a given Nd isotopic composition and that the largest difference between expected and measured Hf isotopic compositions in seawater occurs near the oldest continental crust in the Labrador Sea. This corroborates the previous proposition, which was mainly based on ferromanganese crust data, that the Hf isotopic composition of seawater is controlled by incongruent weathering of continental crust and possibly, to some extent, by hydrothermal contributions. Hafnium concentrations in the ocean do not increase along the deep ocean conveyer indicating an oceanic residence time of only a few hundred years, which is significantly shorter than previously assumed. The Hf isotopic composition of past seawater can therefore serve as a proxy for short distance, basin scale mixing processes and the regime and intensity of nearby continental weathering processes.

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.

(Table 1) Sr, Nd and Os isotopic composition from marine sediments of the Bengal Fan

Sr, Nd, and Os isotopic data are presented for sediments from diverse locations in the Bay of Bengal. These data allow the samples to be divided into three groups, related to their sedimentary contexts. The first group, mainly composed of sediments from the shelf off Bangladesh and the currently active fan, has Sr and Nd characteristics consistent with a dominantly Himalayan source. Their 187Os/188Os ratios (~1.2-1.5) show that the average detrital material delivered by the Ganga-Brahmaputra (G-B) river system is not unusually radiogenic. A large difference in 187Os/188Os ratio exists between these Bengal Fan sediments and Ganga bedloads (187Os/188Os ~2.5, Pierson-Wickmann et al. (2000, doi:10.1016/S0012-821X(00)00003-0)). This difference mainly reflects addition of a less radiogenic Brahmaputra component, though mineralogical sorting and loss of radiogenic Os during transport may also play some role. The second sample group contains sediments from elsewhere in the Bay, particularly those located on the continental slope. They display Os isotopic compositions (0.99-1.11) similar to that of present seawater and higher Os and Re concentrations. These characteristics suggest the presence of a large hydrogenous contribution, consistent with the lower sedimentation rate of these samples. Sr and Nd ratios indicate that a significant fraction of these sediments is derived from erosion of non-Himalayan sources, such as the Indo-Burman range. These observations could be explained by the deflection of sediments from the G-B river system by westward currents in the head of the Bay. The third group contains only one sample, but shows that in addition to a Himalayan source, sediment discharge from Sri Lanka may influence the detrital component in the distal part of the fan. The similarity between the isotopic compositions of the group I R/V Sonne samples and those of Ocean Drilling Program Leg 116 (France-Lanord et al., 1993; Reisberg et al., 1997, doi:10.1016/S0012-821X(00)00003-0) suggests that the material eroding in the Himalayas has been roughly constant since the Miocene. The high Os isotopic ratios of leachates of both Sonne group I and Miocene Leg 116 sediments imply that much of the leachable highly radiogenic Os component was conserved during transport through the estuary or interaction with seawater. In constrast, samples with lower, but still relatively high, sedimentation rates (Sonne groups II and III and Pliocene Leg 116) seem to have significantly adsorbed or exchanged Os and Re with seawater. This suggests that in some cases the Os isotopic ratios of leachates of detrital sediments can be used to constrain the ancient marine Os record, or conversely, to date unfossiliferous sediments.

Major and trace elements and Nd and Sr isotope geochemistry of basalts at DSDP Leg 74 Holes

Basement intersected in Holes 525A, 528, and 527 on the Walvis Ridge consists of submarine basalt flows and pillows with minor intercalated sediments. These holes are situated on the crest and mid- and lower NW flank of a NNW-SSE-trending ridge block which would have closely paralleled the paleo mid-ocean ridge. The basalts were erupted approximately 70 Ma, a date consistent with formation at the paleo mid-ocean ridge. The basalt types vary from aphyric quartz tholeiites on the Ridge crest to highly Plagioclase phyric olivine tholeiites on the flank. These show systematic differences in incompatible trace element and isotopic composition, and many element and isotope ratio pairs form systematic trends with the Ridge crest basalts at one end and the highly phyric Ridge flank basalts at the other. The low 143Nd/144Nd (0.51238) and high 87Sr/86Sr (0.70512) ratios of the Ridge crest basalts suggest derivation from an old Nd/Sm and Rb/Sr enriched mantle source. This isotopic signature is similar to that of alkaline basalts on Tristan da Cunha but offset by somewhat lower 143Nd/144Nd values. The isotopic ratio trends may be extrapolated beyond the Ridge flank basalts (which have 143Nd/144Nd of 0.51270 and 87Sr/86Sr of 0.70417) in the direction of typical MORB compositions. These isotopic correlations are equally consistent with mixing of depleted and enriched end-member melts or partial melting of an inhomogeneous, variably enriched mantle source. However, observed Zr-Ba-Nb-Y interelement relationships are inconsistent with any simple two-component model of magma mixing or partial melting. They also preclude extensive involvement of depleted (N-type) MORB material or its mantle sources in the petrogenesis of Walvis Ridge basalts.

Nd and Sm isotopic record from fossil fish teeth recovered from ODP Site 177-1090

Neodymium (Nd) isotopes were measured on 181 samples of fossil fish teeth recovered from Oligocene to Miocene sections at Ocean Drilling Program Site 1090 (3700 m water depth) on Agulhas Ridge in the Atlantic sector of the Southern Ocean. A long-term decreasing trend toward less radiogenic Nd isotope compositions dominates the record. This trend is interrupted by shifts toward more radiogenic compositions near the early/late Oligocene boundary and the Oligocene/Miocene boundary. Overall, epsilon-Nd values at Agulhas Ridge are more radiogenic than at other Atlantic locations, and are similar to those at Indian Ocean locations. The pattern of variability is remarkably similar to Nd isotope results from Walvis Ridge (South Atlantic) and Ninetyeast Ridge (Indian Ocean). In contrast, Agulhas Ridge and Maud Rise Nd isotope records do not show similar patterns over this interval. Results from this study indicate that deep water in the Atlantic flowed predominantly from north to south during the Oligocene and Miocene, and that export of Northern Component Water (NCW) to the Southern Ocean increased in the late Oligocene. There is also evidence for efficient exchange of deep waters between the Atlantic sector of the Southern Ocean and the Indian Ocean, although the direction of deep water flow is not entirely clear from these data. The shifts to more radiogenic Nd isotopic compositions most likely represent increases in the flux of Pacific waters through Drake Passage, and the timing of these events reflect development of a mature Antarctic Circumpolar Current (ACC). The relative timing of increased NCW export and ACC maturation support hypotheses that link deep water formation in the North Atlantic to the opening of Drake Passage.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

Nd and Sm content and isotopic composition of the carbonate-free clay fraction of sediment core HU90-013-013

Sm-Nd concentrations and Nd isotopes were investigated in the fine fraction of two Labrador Sea cores to reconstruct the deep circulation patterns through changes in sedimentary supply since the last glacial stage. Three sources are involved: the North American Shield, Palaeozoic rocks from northeastern Greenland, and mid-Atlantic volcanism. The variable input of these sources provides constraints on the relative sedimentary supply, in conjunction with inception of deep currents. During the last glacial stage a persistent but sluggish current occurred inside the Labrador Basin. An increasing discharge of volcanic material driven by the North East Atlantic Deep Water is documented since 14.3 kyr, signaling the setup of a modern-like deep circulation pattern throughout the Labrador, Irminger, and Iceland basins. During the last deglacial stage the isotopic record was punctually influenced by erosion processes related mainly to ice-sheet instabilities, especially 11.4, 10.2, and 9.2 kyr ago.

(Table 1) Nd isotope ratios of ODP Leg 208 samples

We present new Nd isotope records from Walvis Ridge Ocean Drilling Program (ODP) sites 1262-1264 (southeastern Atlantic) spanning the past 24 Ma to investigate the Neogene evolution of Atlantic thermohaline circulation. The new data indicate that deepwater epsilon-Nd(t) values from ODP Site 1262 decrease from -11.0 at 10.6 Ma to -12.5 by 7.3 Ma. This decrease parallels the Nd isotope trends contained in Fe-Mn crust records from the northwestern Atlantic; however, the shift at ODP Site 1262 (4755 m water depth) occurred up to ~6 Ma earlier than the corresponding changes in crust records from the Atlantic and earlier than any Atlantic site shallower than 2700 m paleowater depth. Recent interpretations of the rapid decrease in Fe-Mn crust Nd epsilon-Nd(t)ss values invoke changes in weathering inputs to the Labrador Sea region rather than a fundamental change in deepwater convection in the Labrador Sea. However, the new evidence for significant depth stratification of the Nd isotope signal in the southeastern Atlantic between 10.6 and 7.3 Ma suggests that the onset of deepwater convection in the Labrador Sea may have played a role in the deepwater decrease in Nd isotopic composition. Climatic conditions during the middle to late Miocene likely favored an increase in the importance of glacially induced mechanical weathering, while at the same time promoting deep convection in the Labrador Sea.

Nd/Ca ratios in plankton-towed and core top foraminifera

Planktic foraminifera have been used as recorders of the neodymium (Nd) isotopic composition of seawater, although there is still controversy over the precise provenance of the Nd signal. We present an extensive, multispecific plankton tow Nd/Ca data set from several geographic locations (SE Atlantic, NE Atlantic, Norwegian Sea, and western Mediterranean), together with core top samples from the Mediterranean region. The range of Nd/Ca ratios in plankton-towed foraminifera, cleaned only of organic material, from all regions (0.01-0.7 µmol/mol), is similar to previously published analyses of sedimentary foraminifera cleaned using both oxidative and reductive steps, with distribution coefficients (Kd) ranging between 4 and 302. For the Mediterranean, where core top and plankton tow data are both available, the range for plankton tows (0.05-0.7 µmol/mol) is essentially identical to that for the core tops (0.1-0.5 µmol/mol). Readsorption of Nd during cleaning is ruled out by the fact that the plankton tow samples underwent only an oxidative cleaning process. We find a relationship between manganese (Mn) and Nd in plankton tow samples that is mirrored by a similar correlation in core top samples. This relationship suggests that Fe-Mn coatings are of negligible importance to the Nd budgets of foraminifera as the Nd/Mn ratio it implies is over an order of magnitude greater than that seen in other Fe-Mn oxide phases. Rather, since both plankton tows and core tops present a similar behavior, the Nd/Mn relationship must originate in the upper water column. The data are consistent with the acquisition of Nd and Mn from the water column by binding to organic material and the fact that intratest organic material is shielded from both aggressive cleaning and diagenetic processes. Collectively, the results help to explain two abiding puzzles about Nd in sedimentary planktic foraminifera: their high REE contents and the fact that they record a surface water Nd isotopic signal, regardless of the cleaning procedure used.