Pb isotopes in individual sand-sized (>150 µm) ice-rafted feldspars deposited at subpolar North Atlantic Ocean Deep Sea Drilling Project Site 611 during the late Pliocene (Marine Isotope Stages, MIS, G6 through 100)

The onset of abundant ice-rafted debris (IRD) deposition in the Nordic Seas and subpolar North Atlantic Ocean 2.72 millions of years ago (Ma) is thought to record the Pliocene onset of major northern hemisphere glaciation (NHG) due to a synchronous advance of North American Laurentide, Scandinavian and Greenland ice-sheets to their marine calving margins during marine isotope stage (MIS) G6. Numerous marine and terrestrial records from the Nordic Seas region indicate that extensive ice sheets on Greenland and Scandinavia increased IRD inputs to these seas from 2.72 Ma. The timing of ice-sheet expansion on North America as tracked by IRD deposition in the subpolar North Atlantic Ocean, however, is less clear because both Europe and North America are potential sources for icebergs in this region. Moreover, cosmogenic-dating of terrestrial tills on North America indicate that the Laurentide Ice Sheet did not extend to ~39°N until 2.4 ±0.14 Ma, at least 180 ka after the onset of major IRD deposition at 2.72 Ma. To address this problem,we present the first detailed analysis of the geochemical provenance of individual sand-sized IRD deposited in the subpolar North Atlantic Ocean between MIS G6 and 100 (~2.72-2.52 Ma). IRD provenance is assessed using laser ablation lead (Pb) isotope analyses of single ice-rafted (>150 mm) feldspar grains. To track when an ice-rafting setting consistent with major NHG first occurred in the North Atlantic Ocean during the Pliocene intensification of NHG (iNHG), we investigate when the Pb-isotope composition (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb) of feldspars deposited at DSDP Site 611 first resembles that determined for IRD deposited at this site during MIS 100, the oldest glacial for which there exists convincing evidence for widespread glaciation of North America. Whilst Quaternary-magnitude IRD fluxes exist at Site 611 during glacials from 2.72 Ma, we find that the provenance of this IRD is not constant. Instead, we find that the Pb isotope composition of IRD at our study site is not consistent with major NHG until MIS G2 (2.64 Ma). We hypothesise that IRD deposition in the North Atlantic Ocean prior to MIS G2 was dominated by iceberg calving from Greenland and Scandinavia. We further suggest that the grounding line of continental ice on Northeast America may not have extended onto the continental shelf and calved significant numbers of icebergs to the North Atlantic Ocean during glacials until 2.64 Ma.

Geochemistry, mineralogy and isotopes at DSDP Hole 62-464

The relationships between mineralogical and geochemical data on the three successive sedimentary facies at Deep Sea Drilling Project Site 464 are studied. The evolution of siliceous biogenic sediments is derived from the analyses of one Fe-Ti smectite concretion, and of siliceous aggregates occurring in the pelagic "brown clays." Along the sedimentary section, the trace elements enriching the authigenic silicates and the Fe-Mn oxyhydroxides vary, depending on the marine environment. The proportion of clays and carbonates into the siliceous deposits controls the diagenetic evolution of silica making up the quartz aggregates from the "brown clay" or the cristobalite cherts.

Description, geochemistry, mineralogy and isotopes of sulfides from ODP Site 193-1189, PACMANUS field

Chemical and isotopic data for rare massive and semimassive sulfide samples cored at Site 1189 (Roman Ruins, PACMANUS) suggest their genetic relationship with sulfide chimneys at the seafloor. Sand collected from the hammer drill after commencement of Hole 1189B indicates that at least the lower section of the cased interval was occupied by material similar to the stockwork zone cored from 31 to ~100 meters below seafloor (mbsf) in this hole, but with increased content of barite, sphalerite, and lead-bearing minerals. Fractional crystallization of ascending hydrothermal fluid involving early precipitation of pyrite may explain vertical mineralogical and chemical zoning within the stockwork conduit and the high base and precious metal contents of Roman Ruins chimneys. A mineralized volcaniclastic unit cored deep in Hole 1189A possibly represents the lateral fringe of the conduit system. Lead isotope ratios in the sulfides differ slightly but significantly from those of fresh lavas from Pual Ridge, implying that at least some of the Pb within the Roman Ruins hydrothermal system derived from a deeper, more radiogenic source than the enclosing altered volcanic rocks.

Polonium-210 and Lead-210 activities measured on 9 water bottle profiles during POLARSTERN cruise ANT-XXIV/3

As part of the GEOTRACES Polarstern expedition ANT XXIV/3 (ZERO and DRAKE), Polonium-210 and Lead-210 have been measured in the water column and on suspended particulate matter in February to April 2008. Our goal was to resolve the affinities of 210Po and 210Pb to transparent exopolymer particles (TEP) and particulate organic carbon (POC). Polonium-210 and Lead-210 in the ocean can be used to identify the sources and sinks of suspended matter. In seawater, Polonium-210 (210Po) and Lead-210 (210Pb) are produced by stepwise radioactive decay of Uranium-238. 210Po (138 days half life) and 210Pb (22.3 years half life) have high affinities for suspended particles. Those radionuclides are present in dissolved form and adsorbed onto particles. Following adsorption onto particle surfaces, 210Po especially is transported into the interior of cells where it bonds to proteins. In this way, 210Po also accumulates in the food chain. 210Po is therefore considered to be a good tracer for POC, and traces particle export over a timescale of months. 210Pb (22.3 years half life) adsorbs preferably onto structural components of cells, biogenic silica and lithogenic particles, and is therefore a better tracer more rapidly sinking matter. Water samples were taken with Niskin bottles. Dissolved Polonium-210 and Lead-210 activities refer to the fraction < 1µm. Particulate Polonium-210 and Lead-210 refer to the activity on particles >1µm retained on nucleopore filters. Zooplankton retained on the filters was systematically removed as this study focused on phytoplankton and exudates. The data have been submitted to Pangaea following a Polonium-Lead intercalibration exercise organized by GEOTRACES, where the AWI lab results range within the data standard deviation from 10 participating labs.

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

Mediterranean Outflow Water (MOW) is characterised by higher temperatures and salinities than other ambient water masses. MOW spreads at water depths between 500 and 1500 m in the eastern North Atlantic and has been a source of salinity for the Atlantic Meridional Overturning Circulation in the North Atlantic. We used high-resolution Nd and Pb isotope records of past ambient seawater obtained from authigenic ferromanganese coatings of sediments in three gravity cores at 577, 1745 and 1974 m water depth in the Gulf of Cadiz and along the Portuguese margin complemented by a selection of surface sediments to reconstruct the extent and pathways of MOWover the past 23 000 years. The surface and downcore Nd isotope data from all water depths exhibit only a very small variability close to the present day composition of MOW but do not reflect the present day Nd isotopic stratification of the water column as determined from a nearby open ocean hydrographic station. In contrast, the Pb isotope records show significant and systematic variations, which provide evidence for a significantly different pattern of the MOW pathways between 20 000 and 12 000 years ago compared with the subsequent period of time.

Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

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.