Geochemistry of serpentinized peridotites from ODP Holes 207-1272A and 207-1274A

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 µg/g) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 µg/g), depleted in Li (most values below 1 µg/g) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 µg/g), H2O and Cl contents and to lower Li contents (0.07-3.37 µg/g) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m * 1 m * thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.

Physical oceanography during two METEOR cruises in the subpolar North Atlantic

The detection of multi-decadal trends in the oceanic oxygen content and its possible attribution to global warming is protracted by the presence of a substantial amount of interannual to decadal variability, which hitherto is poorly known and characterized. Here we address this gap by studying interannual to decadal changes of the oxygen concentration in the Subpolar Mode Water (SPMW), the Intermediate Water (IW) and the Mediterranean Outflow Water (MOW) in the eastern North Atlantic. We use data from a hydrographic section located in the eastern North Atlantic at about 48°N repeated 12 times over a period of 19 years from 1993 through 2011, with a nearly annual resolution up to 2005. Despite a substantial amount of year-to-year variability, we observe a long-term decrease in the oxygen concentration of all three water masses, with the largest changes occurring from 1993 to 2002. During that time period, the trends were mainly caused by a contraction of the subpolar gyre associated with a northwestward shift of the Subpolar Front (SPF) in the eastern North Atlantic. This caused SPMW to be ventilated at lighter densities and its original density range being invaded by subtropical waters with substantially lower oxygen concentrations. The contraction of the subpolar gyre reduced also the penetration of IW of subpolar origin into the region in favor of an increased northward transport of IW of subtropical origin, which is also lower in oxygen. The long-term oxygen changes in the MOW were mainly affected by the interplay between circulation and solubility changes. Besides the long-term signals, mesoscale variability leaves a substantial imprint as well, affecting the water column over at least the upper 1000 m and laterally by more than 400 km. Mesoscale eddies induced changes in the oxygen concentration of a magnitude that can substantially alias analyses of long-term changes based on repeat hydrographic data that are being collected at intervals of typically 10 years.

Geochemistry of reduction haloes in ODP Holes 135-834A and 135-837A

The sediment column overlying basement in the Lau Basin consists of a sequence of volcaniclastic turbidites interbedded with hemipelagic clayey nannofossil mixed sediments, overlain in turn by a sequence of hemipelagic clayey nannofossil oozes containing sporadic calcareous turbidites. The clayey nannofossil oozes and mixed sediments are pervasively stained by hydrothermally derived iron and manganese oxyhydroxides. Sharply defined, lighter colored bands occur in the hemipelagic sediments, immediately beneath some (but by no means all) volcaniclastic and calcareous turbidites. These are identified as reduction haloes, of a type previously identified in quite different turbidite/pelagic sequences. The haloes are attributed to the burial of labile surficial Corg by turbidites, followed by the remineralization of this Corg with Mn and Fe oxyhydroxides as electron acceptors. The resultant characteristic Mn and Fe concentration/depth profiles are described, and a model is proposed for their development. The color alteration of the halo is ascribed to the removal of Mn oxyhydroxides, because, although the Fe content fluctuates through the haloes, this does not appear to affect their color. Other elements (Co, Cu, and Ni) are also at low concentration levels in the haloes like Mn, consistent with remobilization and migration out of the halo section, although the profile shapes are not identical with those of Mn. The behavior of V is distinctive in that it appears to have migrated into the haloes to be enriched there. Haloes are unlikely to form if turbidite emplacement is erosive and removes the near-surface layer, which generally is the most fluid part of the sediment and contains the highest levels of reactive Corg to drive the reduction process. Conversely, the presence of a halo implies that emplacement of the overlying turbidite did not significantly erode the pre-existing sediment/water interface.

Subdivisions of the sediment column, carbon and calcium carbonate at DSDP Hole 64-480

We analyzed 580 integrated scrape-samples from HPC Site 480 for organic and carbonate carbon. Once precise dating is available, these will provide a high-resolution framework for understanding late Quaternary Oceanographic and climatic fluctuations in this region. Organic carbon ranges mostly within a narrow band of 1.8 to 3.5% C. Calcium carbonate varies from undetectable to over 20%, with an average of only about 5%. Source of carbonate are mostly benthic and planktonic foraminifers, although some sections are dominated by diagenetic carbonate, shelly hash, or nannofossils. Detrital sources are low in carbonate. We divided the sequence into 17 calcium carbonate (CC) zones to separate pulses, low and median values. The CC-Zones show various second-order patterns of cyclicity, asymmetry, and events. Laminated zones have lowest uniform values, but a perfect correlation between carbonate content and homogeneous or laminated facies was not found. Maximum values tend to be located near the transition of these two sediment types, showing that accumulation of carbonate is favored during times of breakdown of stable Oceanographic conditions.

Detection histories for eight species of Amazona parrots in Venezuela during the NeoMaps bird surveys in 2010

Documenting changes in distribution is necessary for understanding species' response to environmental changes, but data on species distributions are heterogeneous in accuracy and resolution. Combining different data sources and methodological approaches can fill gaps in knowledge about the dynamic processes driving changes in species-rich, but data-poor regions. We combined recent bird survey data from the Neotropical Biodiversity Mapping Initiative (NeoMaps) with historical distribution records to estimate potential changes in the distribution of eight species of Amazon parrots in Venezuela. Using environmental covariates and presence-only data from museum collections and the literature, we first used maximum likelihood to fit a species distribution model (SDM) estimating a historical maximum probability of occurrence for each species. We then used recent, NeoMaps survey data to build single-season occupancy models (OM) with the same environmental covariates, as well as with time- and effort-dependent detectability, resulting in estimates of the current probability of occurrence. We finally calculated the disagreement between predictions as a matrix of probability of change in the state of occurrence. Our results suggested negative changes for the only restricted, threatened species, Amazona barbadensis, which has been independently confirmed with field studies. Two of the three remaining widespread species that were detected, Amazona amazonica, Amazona ochrocephala, also had a high probability of negative changes in northern Venezuela, but results were not conclusive for Amazona farinosa. The four remaining species were undetected in recent field surveys; three of these were most probably absent from the survey locations (Amazona autumnalis, Amazona mercenaria and Amazona festiva), while a fourth (Amazona dufresniana) requires more intensive targeted sampling to estimate its current status. Our approach is unique in taking full advantage of available, but limited data, and in detecting a high probability of change even for rare and patchily-distributed species. However, it is presently limited to species meeting the strong assumptions required for maximum-likelihood estimation with presence-only data, including very high detectability and representative sampling of its historical distribution.

(Table 2) Integrated concentration, production and dissolution of silica in the water column of the southern Pacific

An intense diatom bloom developed within a strong meridional silicic acid gradient across the Antarctic Polar Front at 61°S, 170°W following stratification of the water column in late October/early November 1997. The region of high diatom biomass and the silicic acid gradient propogated southward across the Seasonal Ice Zone through time, with the maximum diatom biomass tracking the center of the silicic acid gradient. High diatom biomass and high rates of silica production persisted within the silicic acid gradient until the end of January 1998 (ca. 70 d) driving the gradient over 500 km to the south of its original position at the Polar Front. The bloom consumed 30 to >40 µM Si(OH)4 in the euphotic zone between about 60 and 66°S leaving near surface concentrations <2.5 µM and occasionally <1.0 µM in its wake. Integrated biogenic silica concentrations within the bloom averaged 410 mmol Si/m**2 (range 162-793 mmol Si/m**2). Average integrated silica production on two consecutive cruises in December 1997 and January 1998 that sampled the bloom while it was well developed were 27.5±6.9 and 22.6±20 mmol Si/m**2/d, respectively. Those levels of siliceous biomass and silica production are similar in magnitude to those reported for ice-edge diatom blooms in the Ross Sea, Antarctica, which is considered to be among the most productive regions in the Southern Ocean. Net silica production (production minus dissolution) in surface waters during the bloom was 16-21 mmol Si/m**2/d, which is sufficient for diatom growth to be the cause of the southward displacement of the silicic acid gradient. A strong seasonal change in silica dissolution : silica production rate ratios was observed. Integrated silica dissolution rates in the upper 100-150 m during the low biomass period before stratification averaged 64% of integrated production. During the bloom integrated dissolution rates averaged only 23% of integrated silica production, making 77% of the opal produced available for export to depth. The bloom ended in late January apparently due to a mixing event. Dissolution : production rate ratios increased to an average of 0.67 during that period indicating a return to a predominantly regenerative system. Our observations indicate that high diatom biomass and high silica production rates previously observed in the marginal seas around Antarctica also occur in the deep ocean near the Polar Front. The bloom we observed propagated across the latitudinal band overlying the sedimentary opal belt which encircles most of Antarctica implying a role for such blooms in the formation of those sediments. Comparison of our surface silica production rates with new estimates of opal accumulation rates in the abyssal sediments of the Southern Ocean, which have been corrected for sediment focusing, indicate a burial efficiency of <=4.6% for biogenic silica. That efficiency is considerably lower than previous estimates for the Southern Ocean.