Depth profiles of pore-water and solid-phase constituents, respiration rates and grain size distribution in sediments of the Clarion-Clipperton Fracture Zone

Manganese nodules of the Clarion-Clipperton Fracture Zone (CCFZ) in the NE Pacific Ocean are highly enriched in Ni, Cu, Co, Mo and rare-earth elements, and thus may be the subject of future mining operations. Elucidating the depositional and biogeochemical processes that contribute to nodule formation, as well as the respective redox environment in both, water column and sediment, supports our ability to locate future nodule deposits and evaluates the potential ecological and environmental effects of future deep-sea mining. For these purposes we evaluated the local hydrodynamics and pore-water geochemistry with respect to the nodule coverage at four sites in the eastern CCFZ. Furthermore, we carried out selective leaching experiments at these sites in order to assess the potential mobility of Mn in the solid phase, and compared them with the spatial variations in sedimentation rates. We found that the oxygen penetration depth is 180 - 300 cm at all four sites, while reduction of Mn and NO3- is only significant below the oxygen penetration depth at sites with small or no nodules on the sediment surface. At the site without nodules, potential microbial respiration rates, determined by incubation experiments using 14C-labelled acetate, are slightly higher than at sites with nodules. Leaching experiments showed that surface sediments covered with big or medium-sized nodules are enriched in mobilizable Mn. Our deep oxygen measurements and pore-water data suggest that hydrogenetic and oxic-diagenetic processes control the present-day nodule growth at these sites, since free manganese from deeper sediments is unable to reach the sediment surface. We propose that the observed strong lateral contrasts in nodule size and abundance are sensitive to sedimentation rates, which in turn, are controlled by small-scale variations in seafloor topography and bottom-water current intensity.

(Table 1) Trace element and isotopic data for ODP Hole 145-887D basalts

Age-progressive, linear seamount chains in the northeast Pacific appear to have formed as the Pacific plate passed over a set of stationary hotspots; however, some anomalously young ages and the lack of an "enriched" isotopic signature in basalts from the seamounts do not fit the standard hotspot model. For example, published ages (28-30 Ma) for basalts dredged from the Patton-Murray seamount platform in the Gulf of Alaska are 2-4 m.y. younger than the time when the platform was above the Cobb hotspot. However, the lowermost basalt recovered by ocean drilling on Patton-Murray yielded a 40Ar-39Ar age of 33 Ma. This age exactly coincides with the time when the seamount platform was above the Cobb hotspot, consistent with a stationary, long-lived mantle plume. A 27 Ma alkalic basalt flow recovered 8 m above the 33 Ma basalt is similar in age and composition to the previously dredged basalts, and may be the alkalic capping phase typical of many hotspot volcanoes. A 17 Ma tholeiitic basalt sill recovered 5 m above the 27 Ma basalt was emplaced long after the seamount platform moved away from the hotspot, and may be associated with a period of intraplate extension. Anomalously young phases of volcanism on this and other hotspot seamounts suggest that they can be volcanically rejuvenated by nonhotspot causes, but this rejuvenation does not rule out the hotspot model as an explanation for the initial creation of the seamount platform. The lack of an "enriched" isotopic signature in any of these basalts shows that enriched compositions are not necessary characteristics of plume-related basalts. The isotopic compositions of the lower basalts are slightly more depleted than the 0-9 Ma products of the Cobb hotspot, despite the fact that the hotspot was closer to a spreading ridge at 0-9 Ma. It appears that this hotspot, like several others, has become more enriched with time.

B-isotope and Mg/Ca ratios of planktonic foraminifera from ODP Hole 108-668B and esimates of salinity, alkalinity and pCO2 (Table 1)

Knowledge of past atmospheric pCO2 is important for evaluating the role of greenhouse gases in climate forcing. Ice core records show the tight correlation between climate change and pCO2, but records are limited to the past ~900 kyr. We present surface ocean pH and pCO2 data, reconstructed from boron isotopes in planktonic foraminifera over two full glacial cycles (0-140 and 300-420 kyr). The data co-vary strongly with the Vostok pCO2-record and demonstrate that the coupling between surface ocean chemistry and the atmosphere is recorded in marine archives, allowing for quantitative estimation of atmospheric pCO2 beyond the reach of ice cores.

(Appendix) Petrographic information, trace element and Sr isotope ratios of Pito Deep samples

Fluid flow through the axial hydrothermal system at fast spreading ridges is investigated using the Sr-isotopic composition of upper crustal samples recovered from a tectonic window at Pito Deep (NE Easter microplate). Samples from the sheeted dike complex collected away from macroscopic evidence of channelized fluid flow, such as faults and centimeter-scale hydrothermal veins, show a range of 87Sr/86Sr from 0.7025 to 0.7030 averaging 0.70276 relative to a protolith with 87Sr/86Sr of ~0.7024. There is no systematic variation in 87Sr/86Sr with depth in the sheeted dike complex. Comparison of these new data with the two other localities that similar data sets exist for (ODP Hole 504B and the Hess Deep tectonic window) reveals that the extent of Sr-isotope exchange is similar in all of these locations. Models that assume that fluid-rock reaction occurs during one-dimensional (recharge) flow lead to significant decreases in the predicted extent of isotopic modification of the rock with depth in the crust. These model results show systematic misfits when compared with the data that can only be avoided if the fluid flow is assumed to be focused in isolated channels with very slow fluid-rock exchange. In this scenario the fluid at the base of the crust is little modified in 87Sr/86Sr from seawater and thus unlike vent fluids. Additionally, this model predicts that some rocks should show no change from the fresh-rock 87Sr/86Sr, but this is not observed. Alternatively, models in which fluid-rock reaction occurs during upflow (discharge) as well as downflow, or in which fluids are recirculated within the hydrothermal system, can reproduce the observed lack of variation in 87Sr/86Sr with depth in the crust. Minimum time-integrated fluid fluxes, calculated from mass balance, are between 1.5 and 2.6 * 10**6 kg/m**2 for all areas studied to date. However, new evidence from both the rocks and a compilation of vent fluid compositions demonstrates that some Sr is leached from the crust. Because this leaching lowers the fluid 87Sr/86Sr without changing the rock 87Sr/86Sr, these mass balance models must underestimate the time-integrated fluid flux. Additionally, these values do not account for fluid flow that is channelized within the crust.

(Table A1) Isotopic ratios of Sr, Nd, and Pb for sediments in ODP Leg 138 sites

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). epsilon-Nd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from ~5.46 to ~3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the epsilon-Nd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene epsilon-Nd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

Trioctahedral micas in xenolithic ejecta from recent volcanism of the Somma-Vesuvius

This study reports the first crystal chemical database resulting from a detailed structural investigation of trioctahedral micas found in xenolithic ejecta produced during the AD 1631, 1872 and 1944 eruptions, three explosive episodes of recent volcanic period of Vesuvius volcano (Southern Italy). Three xenolith types were selected: metamorphic/metasomatic skarns, pyrometamorphic/hydrothermally altered nodules and mafic cumulates. They are related to different magma chemistry and effusive styles: from sub-plinian and most evolved (AD 1631 eruption) to violent strombolian with medium evolution degree (AD 1872 eruption) to vulcanian-effusive, least evolved (AD 1944 eruption) event, respectively. Both xenoliths and micas were investigated employing multiple techniques: the xenoliths were characterized by X-ray fluorescence, inductively-coupled plasma-mass spectrometry, optical microscopy, X-ray powder diffraction, and quantitative energy-dispersive microanalysis; the micas were studied by electron probe microanalysis and single crystal X-ray diffraction. The mica-bearing xenoliths show variable texture and mineralogical assemblage, clearly related to their different origin. Based on the major oxide chemistry, only one xenolithic sample falls in the skarn compositional field from the Somma-Vesuvius literature, some fall close to the skarns and cumulate fields, others plot close to the syenite/foidolite/essexite field. A subgroup of the selected ejecta does not fall or approach any of the compositional fields. Trace and rare earth element patterns show some petrological affinity between studied xenoliths and erupted magmas with typical Eu, Ta and Nb negative anomalies. Strongly depleted patterns were detected for the 1631 metamorphic/metasomatic skarns xenoliths. Three distinct mica groups were distinguished: 1) Mg-, Al-rich, low Ti-bearing, low to moderate F-bearing varieties (1631 xenolith), 2) Al-moderate, F- and Mg-rich, Ti-, Fe-poor varieties (1872 xenolith), and 3) Al-, Ti- and Fe-rich, F-poor phases (1944 xenolith). All the analysed mica crystals are 1M polytypes with the expected space group C2/m. Micas from xenoliths of the 1631 Vesuvius eruption are phlogopites characterized by a combination of low extent of oxy-type and variable extent OH-F-substitutions, as testified by the range of F concentration (from ~ 0.20 to 0.80 apfu). Micas from xenoliths of the 1872 Vesuvius eruption exhibit structural peculiarities typical of fluorophlogopites, i.e. OH-F-substitution is predominant. Micas from the xenolith of the 1944 Vesuvius eruption display features typical of oxy-substituted micas. The variability of the crystal chemical features of the studied micas are consistent with the remarkable variation of their host rocks. Micas from 1631 nodules are related to metasomatic, skarn-type environment, deriving from the metamorphosed wall-rocks hosting the magma reservoir. The fluorophlogopites from the 1872 xenoliths testify for strongly dehydrated environmental conditions compared to those of the 1631 and 1944 hosts. Finally, magma storage condition at depth, associated to a decreasing aH2O may have promoted major oxy-type substitutions in 1944 biotites.