Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Major and trace element geochemistry of ODP Leg 178 holes

Geochemical analyses have been performed on sediment samples collected during Ocean Drilling Program Leg 178 from the continental rise and outer continental shelf of the Antarctic Peninsula. A suite of 21 trace elements was measured by neutron activation analysis in 39 sediment samples, and major element oxides were determined in 67 samples by electron microprobe analyses of fused glass beads. These geochemical data, combined with the X-ray diffraction and X-ray fluorescence data from shipboard analyses, provide a reasonable estimate of the mineral and chemical composition of sediments deposited along the western margin of the Antarctic Peninsula.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Analyses of ferromanganese micronodules from the central Arctic Ocean

In order to determine geochemical compositions of Late Cenozoic Arctic seawater, oxide fractions were chemically separated from 15 samples of hand-picked ferromanganese micronodules (50-300 mu m). The success of the chemical separation is indicated by the fact that >97% of the Sr in the oxide fraction is seawater-derived. Rare-earth element (REE) abundances of the Arctic micronodule oxide fractions are much lower than those of bulk Fe-Mn nodules from other ocean basins of the world (e.g., 33 vs. 145 ppm Nd), but the Arctic oxides are enriched in Ce relative to Nd (Ce-N/Nd-N=2.2+/-0.5) and have convex-upward, shale-normalized REE patterns (Nd-N/Gd-N=0.61+/-0.06, Gd-N/Yb-N = 1.5+/-0.2, Nd-N/Yb-N = 0.9+/-0.2), typical of other hydrogenous and diagenetic marine Fe-Mn-oxides. Bulk sediment samples from the central Arctic Ocean have REE abundances and patterns that are characteristic of those of post-Archean shale. Non-detrital fractions (calcite + oxide coatings) of Recent Arctic foraminifera have REE abundances and patterns similar to those of Recent foraminifera from the Atlantic Ocean. Electron microprobe analyses (n=178) of transition elements in 29 Arctic Fe-Mn micronodules from five different stratigraphic intervals of Late Cenozoic sediment indicate that oxide accretion occurred as a result of hydrogenetic and diagenetic processes close to the sediment-seawater interface. Transition element ratios suggest that no oxide accretion occurred during transitions from oxic to suboxic diagenetic conditions. Only K is correlated with Si and Al, and ratios of these elements suggest that they are associated with illite or phillipsite. Ca and Mg are correlated with Mn, which indicates variable substitution of these elements from seawater into the manganate phase. The geochemical characteristics of Arctic Fe-Mn micronodules indicate that the REEs of the oxide fractions were ultimately derived from seawater. However, because of minute contributions of Sr from siliciclastic detritus during diagenesis or during the chemical leaching procedure, Sr isotope compositions of the oxide fractions cannot be used to trace temporal changes in the Sr-87/Sr-86 ratio of Arctic seawater or to improve the chronostratigraphy.