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.

Mineralogy and isotope chemistry of GISP2 and potential source areas

Samples of dust from the Greenland Ice Sheet Project 2 (GISP2) ice core, Summit, Greenland, dated within marine isotope stage 2 (between 23,340 and 26,180 calendar years B.P.) around the time of the coldest, local, last glacial temperatures, have been analyzed to determine their provenance. To accomplish this, we have compared them with approximately Coeval aeolian sediments (mostly loesses) sampled in possible source areas (PSAs) from around the northern hemisphere. The <5-µm grain-size fraction of these samples was analyzed on the basis that it corresponds to the atmospheric dust component of that time and locale, which was sufficiently fine grained to be transported over long distances. On the basis of comparison of the clay mineralogy and Sr, Nd and Pb isotope composition with ice dust and PSAs and assuming that we have sampled the most important PSAs, we have determined that the probable source area of these GISP2 dusts was in eastern Asia. The dust was not derived from either the midcontinental United States or the Sahara, two more proximal areas that have been suggested as potential sources based on atmospheric circulation modeling. Except for a brief period during an interstadial, when dust transport was exceptionally low (for glacial times) and had a mineralogical composition indicative of a slightly more southern provenance, the source area of the dust did not change significantly during times of variably higher fluxes of dust with larger mean grain size or lower fluxes of dust with smaller mean grain size. This includes the high-dust period that correlates with the Heinrich 2 period of major iceberg discharge into the North Atlantic. Variable wind strengths must therefore be invoked to account for these abrupt and significant changes in dust flux and grain size.

Chemical and isotope compositions of sediments from DSDP Hole 86-576A and Core LL44-GPC-3

A record of changes in Pb and Sr isotopic composition of two cores (DSDP 86-576A and LL44- GPC-3) from the red clay region of the central North Pacific has been determined for the past 60-65 million years. The isotope records of the eolian silicate fraction of the red clays reflect the change in source area as the core sites migrated under different wind systems. The Sr isotope compositions of eolian silicate material are consistent with Asian loess and North American arc volcanism that has been recognized from mineralogical studies. The silicate-bound eolian Pb isotopic compositions similarly reflect Asian loess and arc volcanism. The isotope records of three ferromanganese crusts from similar locations in the central Pacific are similar to the eolian component of red clays, but offset to less radiogenic values. This may be due to two mechanisms: (1) Pb that can be removed from eolian material by seawater is much less radiogenic, or less likely (2) hydrothermal Pb can be transported further away from venting sites through particle exchange with seawater, despite hydrothermal venting acting as a net sink of oceanic Pb. The temporal changes in Pb isotopes in the ferromanganese crusts, bulk red clays and eolian silicates are similar although offset from each other suggesting that eolian deposition is an important source of Pb to seawater and to ferromanganese crusts. This contrasts with the Atlantic and Southern Ocean where more intense deep water flow leads to isotopic gradients in FeMn crusts that do not reflect surface water conditions immediately above the crust. A mechanism is proposed which accounts for Pacific deepwater Pb being isotopically influenced by eolian deposition.

Geochemistry of eolian dust from sediment core LL44-GPC-3

The large-diameter piston core LL44-GPC3 from the central North Pacific Ocean records continuous sedimentation of eolian dust since the Late Cretaceous. Two intervals resolved by Nd and Pb isotopic data relate to dust coming from America (prior to ~40 Ma) and dust coming from Asia (since ~40 Ma). The Intertropical Convergence Zone (ITCZ) separates these depositional regimes today and may have been at a paleolatitude of ~23°N prior to 40 Ma. Such a northerly location of the ITCZ is consistent with sluggish atmospheric circulation and warm climate for the Northern Hemisphere of the early to middle Eocene. Since ~40 Ma, correlations between Nd (~7.55 > epsilon-Nd(t) > ~10.81) and Pb (18.625 < 206/4Pb < 18.879; 15.624 < 207/4Pb < 15.666; 38.611 < 208/4Pb < 38.960; 0.8294 < 207/6Pb < 0.8389; 2.0539 < 208/6Pb < 2.0743) isotopes reflect the progressive drying of central Asia triggered by the westward retreat of the paleo-Tethys. Comparisons between the changes with time in the isotopically well-defined dust flux and Nd and Pb isotopic compositions of Pacific deep water allow one to draw two major conclusions: (1) dust-bound Nd became a resolvable contribution to Pacific seawater only after the one order of magnitude increase in dust flux starting at ~3.5 Ma. Therefore eolian Nd was unimportant for Pacific seawater Nd prior to 3.5 Ma. (2) The lack of a response of Pacific deep water Pb to this huge flux increase suggests that dust-bound Pb has never been important. Instead, mobile Pb associated with island arc volcanic exhalatives probably consists of a significant contribution to Pacific deep water Pb and possibly to seawater elsewhere far away from landmasses.

Radiogenic lead and neodymium composition of surface sediments from the Arctic Ocean

Dolomite-rich layers of distinct pinkish colour are used as lithostratigraphic markers in the Amerasian Basin of the Arctic Ocean. However, origin of dolomite present in these sediment units has not been investigated in detail. In this study, lead (Pb) and neodymium (Nd) isotope composition of detrital clay-size fraction from different lithofacies was investigated in core PS72/340-5 recovered at the eastern flank of the Mendeleev Ridge. Prior to the geochemical analyses, grain-size distribution in sediments was analyzed in order to minimize the grain-size effect on the provenance signature. For provenance discrimination, results of isotope measurements were compared with marine surface sediment data and values for the circum-Arctic subaerial provinces. Late Quaternary sediment supply variability in core PS72/340-5 was analysed using the mixing model constrained by two tracers: 207Pb/206Pb and eNd. Variations of sediment isotopic composition are inferred to be due to mixing of volcanic and plutonic components. Usage of Pb isotopic ratios alone does not allow distinction between the volcanic and plutonic sources. Results confirm that, in the frame of the existing age model, over the last 200 ka dolomite-rich pink layers at the southern Mendeleev Ridge were deposited during events associated with intensified iceberg transport from North America. In general, however, late Quaternary sedimentation was mostly controlled by terrigenous input from the Chukchi and East Siberian Seas whereas sediment supply from the Laptev Sea area remained less important and relatively constant at the studied location.