Rare earth and other element contents in surface layer bottom sediments and ferromanganese nodules along the Transatlantic profile

Behavior of rare earth elements (REE) and Th is studied along the Transatlantic transect at 22°N. It is shown that both REE and Th contents relative to Al (the most lithogenic element) increase toward the pelagic region. The increasing trend becomes more complicated due to variations in content of biogenic calcium carbonate that acts as a diluting component in sediments. REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al+Mn+Fe) and (Fe+Mn)/Ti, do not reach critical values. Variations in REE content and composition allowed to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenous type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th contents depend on Fe content in Atlantic sediments. Therefore, one can suggest that only minor amount of phosphorus is bound with bone debris. Low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic Ocean, as compared with those in pelagic regions of the Pacific Ocean.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Concentration of the rare-earth elements in metalliferous sediments from DSDP Leg 92 holes

DSDP Leg 92 drilled at four sites along an east-west transect at 19°S on the western flank of the East Pacific Rise (EPR), in an area where sediments are essentially a mixture of hydrothermal and biogenic components, with only a minimal contribution of clastic material. Rare-earth element (REE) data on the metalliferous (non-carbonate) fraction of samples ranging in age from ~2 to ~27 Ma indicate the existence of two distinct groups of patterns corresponding to two broad age groups, one <=8 Ma, the other >=10 Ma. Within each group, REE patterns have characteristics which are near-uniform, despite large variations in total REE abundances. Sediments of the younger group are enriched in light REE (LREE) relative to deep bottom waters influenced by the hydrothermal plume extending west from the EPR at 19°S. Sediments of the older groups show further relative LREE enrichment and/or heavy REE (HREE) depletion. Surficial sediments deposited beneath the lysocline have high Sum REE concentrations resulting from slow accumulation rates, and patterns resembling older sediments due to early diagenetic effects. A correlation between the mass accumulation rates (MAR) of Sum REE and Fe + Mn suggests that ferromanganese particulate matter supplied by the hydrothermal plume scavenges REE; during this process the LREE are preferentially removed from plume seawater. The MAR of Fe + Mn shows a general decrease with age above basement, whereas Sum REE concentrations in the metalliferous component increase with age above basement. This supports the Ruhlin and Owen model wherein limited scavenging of REE, due to rapid burial of sediment near the palaeo-axis, leads to low concentrations (but high MAR-values) for the REE. Following deposition and burial of the hydrothermal component, further relative flattening of the REE pattern takes place, probably the result of diagenetic reactions over several million years. Phase partitioning data indicate that the proportion of REE residing in more poorly crystalline phases tends to increase with age (from ~45% to 90% of Sum REE). This suggests that as initial ferromanganese precipitates undergo diagenetic recrystallization, REE are transferred to the poorly crystalline phases, and/or are scavenged from pore waters by these phases. Because of the various modifications to REE patterns apparently produced both in the water column and post-depositional settings, the REE patterns of metalliferous sediments will not reflect fine-scale REE variations in associated oceanic water masses.

Low-temperature magnetic remanence and hysteresis measurements on sediment core GeoB4901-8 from the Niger deep-sea fan

Low-temperature (LT) magnetic remanence and hysteresis measurements, in the range 300-5 K, were combined with energy dispersive spectroscopy (EDS) in order to characterize the magnetic inventory of strongly diagenetically altered sediments originating from the Niger deep-sea fan. We demonstrate the possibility of distinguishing between different compositions of members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series on a set of five representative samples, two from the upper suboxic and three from the lower sulfidic anoxic zone of gravity core GeoB 4901. Highly sensitive LT magnetic measurements were performed on magnetic extracts resulting in large differences in the magnetic behavior between samples from the different layers. This emphasizes that both Fe-Ti oxide phases occur in different proportions in the two geochemical environments. Most prominent are variations in the coercivity sensitive parameter coercive field (BC). At room-temperature (RT) hysteresis loops for all extracts are narrow and yield low coercivities (6-13 mT). With decreasing temperature the loops become more pronounced and wider. At 5 K an approximately 5-fold increase in BC for the suboxic samples contrasts a 20-25-fold increase for the samples from the anoxic zone. We demonstrate that this distinct increase in BC at LT corresponds to the increasing proportion of the Ti-rich hemoilmenite phase, while Fe-rich (titano-)magnetite dominates the magnetic signal at RT. This trend is also seen in the room-temperature saturation isothermal remanent magnetization (RT-SIRM) cycles: suboxic samples show remanence curves dominated by Fe-rich mineral phases while anoxic samples display curves clearly dominated by Ti-rich particles. We show that the EDS intensity ratios of the characteristic Fe Kalpha and Ti Kalpha lines of the Fe-Ti oxides may be used to differentiate between members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series. Furthermore it is possible to calculate an approximate composition for each grain if the intensity ratios of natural particles are linked to well-known standards. Thus, element spectra with high Fe/Ti intensity ratios were found to be rather typical of titanomagnetite while low Fe/Ti ratios are indicative of hemoilmenite. The EDS analyses confirm the LT magnetic results, Fe-rich magnetic phases dominate in the upper suboxic environment whereas Ti-rich magnetic phases comprise the majority of particles in the lower anoxic domain: The mineral assemblage of the upper suboxic environments is composed of magnetite (~19%), titanomagnetite (~62%), hemoilmenite (~17%) and ~2% other particles. In the lower anoxic sediments, reductive diagenetic alteration has resulted in more extensive depletion of the (titano-)magnetite phase, resulting in a relative enrichment of the hemoilmenite phase (~66%). In these strongly anoxic sediments stoichiometric magnetite is barely preserved and only ~5% titanomagnetite was detected. The remaining ~28% comprises Ti-rich particles such as pseudobrookite or rutile.

Predominance of heavily calcified coccolithophores at low CaCO3 saturation during winter in the Bay of Biscay

Coccolithophores are an important component of the Earth system, and, as calcifiers, their possible susceptibility to ocean acidification is of major concern. Laboratory studies at enhanced pCO2 levels have produced divergent results without overall consensus. However, it has been predicted from these studies that, although calcification may not be depressed in all species, acidification will produce "a transition in dominance from more to less heavily calcified coccolithophores" [Ridgwell A, et al., (2009) Biogeosciences 6:2611-2623]. A recent observational study [Beaufort L, et al., (2011) Nature 476:80-83] also suggested that coccolithophores are less calcified in more acidic conditions. We present the results of a large observational study of coccolithophore morphology in the Bay of Biscay. Samples were collected once a month for over a year, along a 1,000-km-long transect. Our data clearly show that there is a pronounced seasonality in the morphotypes of Emiliania huxleyi, the most abundant coccolithophore species. Whereas pH and CaCO3 saturation are lowest in winter, the E. huxleyi population shifts from <10% (summer) to >90% (winter) of the heavily calcified form. However, it is unlikely that the shifts in carbonate chemistry alone caused the morphotype shift. Our finding that the most heavily calcified morphotype dominates when conditions are most acidic is contrary to the earlier predictions and raises further questions about the fate of coccolithophores in a high-CO2 world.

Geochemistry of rare earth elements in basalts from Walvis Ridge

Selected basalts from a suite of dredged and drilled samples (IPOD sites 525, 527, 528 and 530) from the Walvis Ridge have been analysed to determine their rare earth element (REE) contents in order to investigate the origin and evolution of this major structural feature in the South Atlantic Ocean. All of the samples show a high degree of light rare earth element (LREE) enrichment, quite unlike the flat or depleted patterns normally observed for normal mid-ocean ridge basalts (MORBs). Basalts from Sites 527, 528 and 530 show REE patterns characterised by an arcuate shape and relatively low (Ce/Yb)N ratios (1.46-5.22), and the ratios show a positive linear relationship to Nb content. A different trend is exhibited by the dredged basalts and the basalts from Site 525, and their REE patterns have a fairly constant slope, and higher (Ce/Yb)N ratios (4.31-8.50). These differences are further reflected in the ratios of incompatible trace elements, which also indicate considerable variations within the groups. Mixing hyperbolae for these ratios suggest that simple magma mixing between a 'hot spot' type of magma, similar to present-day volcanics of Tristan da Cunha, and a depleted source, possibly similar to that for magmas being erupted at the Mid-Atlantic Ridge, was an important process in the origin of parts of the Walvis Ridge, as exemplified by Sites 527, 528 and 530. Site 525 and dredged basalts cannot be explained by this mixing process, and their incompatible element ratios suggest either a mantle source of a different composition or some complexity to the mixing process. In addition, the occurrence of different types of basalt at the same location suggests there is vertical zonation within the volcanic pile, with the later erupted basalts becoming more alkaline arid more enriched in incompatible elements. The model proposed for the origin and evolution of the Walvis Ridge involves an initial stage of eruption in which the magma was essentially a mixture of enriched and depleted end-member sources, with the N-MORB component being small. The dredged basalts and Site 525, which represent either later-stage eruptives or those close to the hot spot plume, probably result from mixing of the enriched mantle source with variable amounts and variable low degrees of partial melting of the depleted mantle source. As the volcano leaves the hot spot, these late-stage eruptives continue for some time. The change from tholeiitic to alkalic volcanism is probably related either to evolution in the plumbing system and magma chamber of the individual volcano, or to changes in the depth of origin of the enriched mantle source melt, similar to processes in Hawaiian volcanoes.

Long term low latitude and high elevation cosmogenic 3He production rate inferred from a 107 ka-old lava flow in northern Chile; 22°S-3400 m a.s.l

Available geological calibration sites used to estimate the rate at which cosmogenic 3He is produced at the Earth’s surface are mostly clustered in medium to high latitudes. Moreover, most of them have exposure histories shorter than tens of thousands of years. This lack of sites prevents a qualitative assessment of available production models used to convert cosmogenic 3He concentrations into exposure ages and/or denudation rates. It thus limits our ability to take into account the atmospheric, geomagnetic and solar modulation conditions that might have affected the production of cosmogenic nuclides in the past for longer exposure histories and in low latitude regions. We present the cosmogenic 3He production rate inferred from a new geological calibration site located in northern Chile. Five samples were collected on the surface of the largest and best-preserved lava flow of the San Pedro volcano (21.934°S-68.510°W- 3390 m a.s.l), which displays pristine crease-structure features. 40Ar/39Ar dating yield a reliable plateau age of 107±12 ka for the eruption of this lava flow. Eight pyroxene aliquots separated from the surface samples yield a weighted average cosmogenic 3He concentration of 99.3±1.2 Mat.g-1 from which a local cosmogenic 3He production rate of 928±101 at.g-1.yr-1 is calculated. The local production rate is then scaled to a sea level high latitude (SLHL) reference position using different combinations of geographic spatialization schemes, atmosphere models and geomagnetic field reconstructions, yielding SLHL production rates between 103±11 and 130±14 at.g-1.yr-1 consistent with the most recent estimates available from the literature. Finally, we use the same scaling frameworks to re-evaluate the mean global-scale cosmogenic 3He production rate in olivine and pyroxene minerals at 120±16 at.g-1.yr-1 from the compilation of previously published calibration datasets.

Experimental determination of barium isotope fractionation during diffusion and adsorption processes at low temperatures

Variations in barium (Ba) stable isotope abundances measured in low and high temperature environments have recently received increasing attention. The actual processes controlling Ba isotope fractionation, however, remain mostly elusive. In this study, we present the first experimental approach to quantify the contribution of diffusion and adsorption on mass- dependent Ba isotope fractionation during transport of aqueous Ba2+ ions through a porous medium. Experiments have been carried out in which a BaCl2 solution of known isotopic composition diffused through u-shaped glass tubes filled with silica hydrogel at 10 C and 25 C for up to 201 days. The diffused Ba was highly fractionated by up to -2.15‰ in d137/134Ba, despite the low relative difference in atomic mass. The time-dependent isotope fractionation can be successfully reproduced by a diffusive transport model accounting for mass-dependent differences in the effective diffusivities of the Ba isotope species (D137Ba/D134Ba = (m134/m137)^b). Values of b extracted from the transport model were in the range of 0.010–0.011. Independently conducted batch experiments revealed that adsorption of Ba onto the surface of silica hydrogel favoured the heavier Ba isotopes (a = 1.00015 ± 0.00008). The contribution of adsorption on the overall isotope fractionation in the diffusion experiments, however, was found to be small. Our results contribute to the understanding of Ba isotope fractionation pro- cesses, which is crucial for interpreting natural isotope variations and the assessment of Ba isotope ratios as geochemical proxies.