Geochemistry of sediments beneath the Tonga-Kermadec arc

The fate of subducted sediment and the extent to which it is dehydrated and/or melted before incorporation into arc lavas has profound implications for the thermo-mechanical nature of the mantle wedge and models for crustal evolution. In order to address these issues, we have undertaken the first measurements of 10Be and light elements in lavas from the Tonga-Kermadec arc and the sediment profile at DSDP site 204 outboard of the trench. The 10Be/9Be ratios in the Tonga lavas are lower than predicted from flux models but can be explained if (a) previously estimated sediment contributions are too high by a factor of 2-10, (b) the top 1-22 m of the incoming sediment is accreted, (c) large amounts of sediment erosion are proposed, or (d) the sediment component takes several Myr longer than the subducting plate to reach the magma source region beneath Tonga. The lavas form negative Th/Be-Li/Be arrays that extend from a depleted mantle source composition to lower Th/Be and Li/Be ratios than that of the bulk sediment. Thus, these arrays are not easily explained by bulk sediment addition and, using partition coefficients derived from experiments on the in-coming sediment, we show that they are also unlikely to result from fluid released during dehydration of the sediment (or altered oceanic crust). However, partial melts of the dehydrated sediment residue formed at ~800 °C during the breakdown of amphibole +/- plagioclase and in the absence of cordierite have significantly lowered Th/Be ratios. The lava arrays can be successfully modelled as 10-15% partial melts of depleted mantle after it has been enriched by the addition of 0.2-2% of these partial melts. Phase relations suggest that this requires that the top of the subducting crust reaches temperatures of ~800 °C by the time it attains ~ 80 km depth which is in excellent agreement with the results of recent numerical models incorporating a temperature-dependent mantle viscosity. Under these conditions the wet basalt solidus is also crossed yet there is no recognisable eclogitic signal in the lavas suggesting that on-going dehydration or strong thermal gradients in the upper part of the subducting plate inhibit partialmelting of the altered oceanic crust.

Geochemistry of tephra from the Taupo Volcanic Zone

The Taupo Volcanic Zone (TVZ), central North Island, New Zealand, is the most frequently active Quaternary rhyolitic system in the world. Silicic tephras recovered from Ocean Drilling Programme Site 1123 (41°47.16'S, 171°29.94'W; 3290 m water depth) in the southwest Pacific Ocean provide a well-dated record of explosive TVZ volcanism since ~1.65 Ma. We present major, minor and trace element data for 70 Quaternary tephra layers from Site 1123 determined by electron probe microanalysis (1314 analyses) and laser ablation inductively coupled plasma mass spectrometry (654 analyses). Trace element data allow for the discrimination of different tephras with similar major element chemistries and the establishment of isochronous tie-lines between three sediment cores (1123A, 1123B and 1123C) recovered from Site 1123. These tephra tie-lines are used to evaluate the stratigraphy and orbitally tuned stable isotope age model of the Site 1123 composite record. Trace element fingerprinting of tephras identifies ~4.5 m and ~7.9 m thick sections of repeated sediments in 1123A (49.0-53.5 mbsf [metres below seafloor]) and 1123C (48.1-56.0 mbsf), respectively. These previously unrecognised repeated sections have resulted in significant errors in the Site 1123 composite stratigraphy and age model for the interval 1.15-1.38 Ma and can explain the poor correspondence between d18O profiles for Site 1123 and Site 849 (equatorial Pacific) during this interval. The revised composite stratigraphy for Site 1123 shows that the 70 tephra layers, when correlated between cores, correspond to ~37-38 individual eruptive events (tephras), 7 of which can be correlated to onshore TVZ deposits. The frequency of large-volume TVZ-derived silicic eruptions, as recorded by the deposition of tephras at Site 1123, has not been uniform through time. Rather it has been typified by short periods (25-50 ka) of intense activity bracketed by longer periods (100-130 ka) of quiescence. The most active period (at least 1 event per 7 ka) occurred between ~1.53 and 1.66 Ma, corresponding to the first ~130 ka of TVZ rhyolitic magmatism. Since 1.2 Ma, ~80% of tephras preserved at Site 1123 and the more proximal Site 1124 were erupted and deposited during glacial periods. This feature may reflect either enhanced atmospheric transport of volcanic ash to these sites (up to 1000 km from source) during glacial conditions or, more speculatively, that these events are triggered by changes in crustal stress accumulation associated with large amplitude sea-level changes. Only 8 of the ~37-38 Site 1123 tephra units (~20%) can be found in all three cores, and 22 tephra units (~60%) are only present in one of the three cores. Whether a tephra is preserved in all three cores does not have any direct relationship to eruptive volume. Instead it is postulated that tephra preservation at Site 1123 is 'patchy' and influenced by the vigorous nature of their deposition to the deep ocean floor as vertical density currents. At this site, at least 5 cores would need to have been drilled within a proximity of 10's to 100's of metres of each other to yield a >99% chance of recovering all the silicic tephras deposited on the ocean surface above it in the past 1.65 Ma.

Rare earth and other chemical element contents and partitions in bottom sediments, micronodules, and nodules from the bioproductive zone of the Pacific Ocean

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50-250, 250-500, and >500 ?m), coexisting macronodules, and host sediments were studied. Samples were collected at three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of surface waters. Influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, Ce concentration inversely correlates with micronodule size and drops to the lowest value in macronodules and host sediments. Decrease of Ce concentration is generally accompanied by Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with micronodule sizes. Contribution of the diagenetic source is maximal for macronodules. REE composition distinctions for micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. Relationship and general trend in chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.

Geochemistry on Yangla copper deposit, China

The Yangla copper deposit, situated in the middle section of Jinshajiang tectonic belt between Zhongza-Zhongdian block and Changdu-Simao block, is a representative and giant copper deposit that has been discovered in Jinshajiang-Lancangjiang-Nujiang region in recent years. There are coupled relationship between Yangla granodiorite and copper mineralization in the Yangla copper deposit. Five molybdenite samples yielded a well-constrained 187Re-187Os isochron age of 233.3±3 Ma, the metallogenesis is therefore slightly younger than the crystallization age of the granodiorite. S, Pb isotopic compositions of the Yangla copper deposit indicate that the ore-forming materials were derived from the mixture of upper crust and mantle, also with the magmatic contributions. In the late Early Permian, the Jinshajiang Oceanic plate was subducted to the west, resulting in the formation of a series of gently dipping thrust faults in the Jinshajiang tectonic belt, meanwhile, accompanied magmatic activities. In the early Late Triassic, which was a time of transition from collision-related compression to extension in the Jinshajiang tectonic belt, the thrust faults were tensional; it would have been a favorable environment for forming ore fluids. The ascending magma provided a channel for the ore-forming fluid from the mantle wedge. After the magma arrived at the base of the early-stage Yangla granodiorite, the platy granodiorite at the base of the body would have shielded the late-stage magma from the fluid. The magma would have cooled slowly, and some of the ore-forming fluid in the magma would have entered the gently dipping thrust faults near the Yangla granodiorite, resulting in mineralization.

Major and rare earth element contents and their speciations in ferruginous nodules and host sediments from the Barents Sea

Contents of Fe, Mn, Al, P, and rare earth elements (REE) in ferruginous nodules and host sediments of the eastern Barents Sea were studied. A direct Fe-P correlation in reactive components of the sediments and nodules was found. The nodules were shown to be formed through Fe(II) oxidation in the surface layer of sediments and cementation of terrigenous fraction of sediments by Fe(III) oxyhydroxides. The latter accumulate phosphorus due to processes of sorption - co-precipitation, by forming Fe(III) hydrophosphates. REE composition in the sediments and nodules normalized to NASC contents is characterized by increased proportion of light REE that may be caused by regional features of their sources. Due to significant share of terrigenous matter in the Fe nodules (up to 65% for Nd), REE composition of bulk samples is similar to that of host sediments. A negative cerium anomaly in composition of reactive REE may result from REE sorption from seawater. REE bulk composition of a ferruginous crust is closer to that of seawater than one of the ferruginous nodules from the sediments because of essentially lower content of diluent terrigenous matter.

REE, Ba, and Sr abundances and Sr, Nd, and Ce isotope ratos of ODP Hole 110-504B basalts

Abundances of rare earth elements (REE), Ba, and Sr and isotopic ratios of Sr, Nd, and Ce were determined for six samples of basalts drilled at Hole 504B on Leg 111 of the Ocean Drilling Program. Analyses found that these basalts are the most depleted in Sr, Ba, and light REE among mid-ocean ridge basalts (MORB); Ba depletion is especially notable. On the other hand, Sr, Nd, and Ce isotopic ratios for basalts from Hole 504B are within the range of typical MORB values.

Geochemistry of Hawaiian volcanics

The "Ko'olau" component of the Hawaiian mantle plume represents an extreme (EM1-type) end member of Hawaiian shield lavas in radiogenic isotope space, and was defined on the basis of the composition of subaerial lavas exposed in the Makapu'u section of Ko'olau Volcano. The 679 m-deep Ko'olau Scientific Drilling Project (KSDP) allows the long-term evolution of Ko'olau Volcano to be reconstructed and the longevity of the "Ko'olau" component in the Hawaiian plume to be tested. Here, we report triple spike Pb isotope and Sr and Nd isotope data on KSDP core samples, and rejuvenation stage Honolulu Volcanics (HV) (together spanning ~2.8 m.y.), and from ~110 Ma basalts from ODP Site 843, thought to be representative of the Pacific lithosphere under Hawai'i. Despite overlapping ranges in Pb isotope ratios, KSDP and HV lavas form two distinct linear arrays in 208Pb/204Pb-206Pb/204Pb isotope space. These arrays intersect at the radiogenic end indicating they share a common component. This "Kalihi" component has more radiogenic Pb, Nd, Hf, but less radiogenic Sr isotope ratios than the "Makapu'u" component. The mixing proportions of these two components in the lavas oscillated through time with a net increase in the "Makapu'u" component upsection. Thus, the "Makapu'u" enriched component is a long-lived feature of the Hawaiian plume, since it is present in the main shield-building stage KSDP lavas. We interpret the changes in mixing proportions of the Makapu'u and Kalihi components as related to changes in both the extent of melting as well as the lithology (eclogite vs. peridotite) of the material melting as the volcano moves away from the plume center. The long-term Nd isotope trend and short-term Pb isotope fluctuations seen in the KSDP record cannot be ascribed to a radial zonation of the Hawaiian plume: rather, they reflect the short length-scale heterogeneities in the Hawaiian mantle plume. Linear Pb isotope regressions through the HV, recent East Pacific Rise MORB and ODP Site 843 datasets are clearly distinct, implying that no simple genetic relationship exists between the HV and the Pacific lithosphere. This observation provides strong evidence against generation of HV as melts derived from the Pacific lithosphere, whether this be recent or old (100 Ma). The depleted component present in the HV is unlike any MORB-type mantle and most likely represents material thermally entrained by the upwelling Hawaiian plume and sampled only during the rejuvenated stage. The "Kalihi" component is predominant in the main shield building stage lavas but is also present in the rejuvenated HV. Thus this material is sampled throughout the evolution of the volcano as it moves from the center (main shield-building stage) to the periphery (rejuvenated stage) of the plume. The presence of a plume-derived material in the rejuvenated stage has significant implications for Hawaiian mantle plume melting models.

Whole-rock geochemistry of amphibolites and metagabbros from ODP Holes 173-1067A and 173-1068A

The Leg 173 Site 1067 and 1068 amphibolites and metagabbros from the west Iberia margin exhibit variable whole-rock compositions from primitive to more evolved (Mg numbers = 49-71) that are generally incompatible trace and rare earth element enriched (light rare earth element [LREE] = 11-89 x chondrite). The Site 1067 amphibolites are compositionally similar to the basalts reported at Site 899 from this same region, based on trace and rare earth element contents. The Site 1068 amphibolites and metagabbros are similar to the Site 899 diabases but are more LREE enriched. However, the Sites 1067 and 1068 amphibolites and metagabbros are not compositionally similar to the Site 900 metagabbros, which are from the same structural high as the Leg 173 samples. The Leg 173 protoliths may be represented by basalts, diabases, and/or fine-grained gabbros that formed from incompatible trace element-enriched liquids.

Chemistry of magmatic samples of ODP Holes 134-832B and 134-833B

New petrographic and compositional data were reported for 143 samples of core recovered from Sites 832 and 833 during Ocean Drilling Program (ODP) Leg 134. Site 832 is located in the center and Site 833 is on the eastern edge of the North Aoba Basin, in the central part of the New Hebrides Island Arc. This basin is bounded on the east (Espiritu Santo and Malakula islands) and west (Pentecost and Maewo islands) by uplifted volcano-sedimentary ridges associated with collision of the d'Entrecasteaux Zone west of the arc. The currently active Central Belt volcanic front extends through the center of this basin and includes the shield volcanoes of Aoba, Ambrym, and Santa Maria islands. The oldest rocks recovered by drilling are the lithostratigraphic Unit VII Middle Miocene volcanic breccias in Hole 832B. Lava clasts are basaltic to andesitic, and the dominant phenocryst assemblage is plagioclase + augite + orthopyroxene + olivine. These clasts characteristically contain orthopyroxene, and show a low to medium K calc-alkaline differentiation trend. They are tentatively correlated with poorly documented Miocene calc-alkaline lavas and intrusives on adjacent Espiritu Santo Island, although this correlation demands that the measured K-Ar of 5.66 Ma for one clast is too young, due to alteration and Ar loss. Lava clasts in the Hole 832B Pliocene-Pleistocene sequence are mainly ankaramite or augite-rich basalt and basaltic andesite; two of the most evolved andesites have hornblende phenocrysts. These lavas vary from medium- to high-K compositions and are derived from a spectrum of parental magmas for which their LILE and HFSE contents show a broad inverse correlation with SiO2 contents. We hypothesize that this spectrum results from partial melting of an essentially similar mantle source, with the low-SiO2 high HFSE melts derived by lower degrees of partial melting probably at higher pressures than the high SiO2, low HFSE magmas. This same spectrum of compositions occurs on the adjacent Central Chain volcanoes of Aoba and Santa Maria, although the relatively high-HFSE series is known only from Aoba. Late Pliocene to Pleistocene lava breccias in Hole 833B contain volcanic clasts including ankaramite and augite + olivine + plagioclase-phyric basalt and rare hornblende andesite. These clasts are low-K compositions with flat REE patterns and have geochemical affinities quite different from those recovered from the central part of the basin (Hole 832B). Compositionally very similar lavas occur on Merelava volcano, 80 km north of Site 833, which sits on the edge of the juvenile Northern (Jean Charcot) Trough backarc basin that has been rifting the northern part of the New Hebrides Island Arc since 2-3 Ma. The basal sedimentary rocks in Hole 833B are intruded by a series of Middle Pliocene plagioclase + augite +/- olivine-phyric sills with characteristically high-K evolved basalt to andesite compositions, transitional to shoshonite. These are compositionally correlated with, though ~3 m.y. older than, the high-HFSE series described from Aoba. The calc-alkaline clasts in Unit VII of Hole 832B, correlated with similar lavas of Espiritu Santo Island further west, presumably were erupted before subduction polarity reversal perhaps 6-10 Ma. All other samples are younger than subduction reversal and were generated above the currently subduction slab. The preponderance in the North Aoba Basin and adjacent Central Chain islands of relatively high-K basaltic samples, some with transitional alkaline compositions, may reflect a response to collision of the d'Entrecasteaux Zone with the arc some 2-4 Ma. This may have modified the thermal structure of the subduction zone, driving magma generation processes to deeper levels than are present normally along the reminder of the New Hebrides Island Arc.

Geochemistry of Miocene Alborán Basin volcanism

We present new major and trace element and O-Sr-Nd-isotope data for igneous rocks from the western Mediterranean Alborán Sea, collected during the METEOR 51/1 cruise, and for high-grade schists and gneisses from the continental Alborán basement, drilled during the Ocean Drilling Programme (ODP Leg 161, Site 976). The geochemical data allow a detailed examination of crustal and mantle processes involved in the petrogenesis of the lavas and for the first time reveal a zonation of the Miocene Alborán Sea volcanism: (1) a keel-shaped area of LREE-depleted (mainly tholeiitic series) lavas in the central Alborán Sea, generated by high degrees of partial melting of a depleted mantle source and involving hydrous fluids from subducted marine sediments, that is surrounded by (2) a horseshoe-shaped zone with LREE-enriched (mainly calc-alkaline series) lavas subparallel to the arcuate Betic-Gibraltar-Rif mountain belt. We propose that the geochemical zonation of the Miocene Alborán Basin volcanism results from eastward subduction of Tethys oceanic lithosphere coupled with increasing lithospheric thickness between the central Alborán Sea and the continental margins of Iberia and Africa.

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.

Geochemistry on sediment profile PS69/335

During RV Polarstern cruise ANT-XXIII/4 in 2006, a gravity core (PS69/335-2) and a giant box core (PS69/335-1) were retrieved from Maxwell Bay off King George Island (KGI). Comprehensive geochemical (bulk parameters, quantitative XRF, Inductively Coupled Plasma Mass Spectrometry) and radiometric dating analyses (14C, 210Pb) were performed on both cores. A comparison with geochemical data from local bedrock demonstrates a mostly detrital origin for the sediments, but also points to an overprint from changing bioproductivity in the overlying water column in addition to early diagenetic processes. Furthermore, ten tephra layers that were most probably derived from volcanic activity on Deception Island were identified. Variations in the vertical distribution of selected elements in Maxwell Bay sediments further indicate a shift in source rock provenance as a result of changing glacier extents during the past c. 1750 years that may be linked to the Little Ice Age and the Medieval Warm Period. Whereas no evidence for a significant increase in chemical weathering rates was found, 210Pb data revealed that mass accumulation rates in Maxwell Bay have almost tripled since the 1940s (0.66 g cm-2 yr-1 in AD 2006), which is probably linked to rapid glacier retreat in this region due to recent warming.