(Table 2) Trace element composition of seleceted clast and matrix materials from ODP Site 125-786

Shipboard examination of volcanic and sedimentary strata at Site 786 suggested that at least four types of breccias are present: flow-top breccias, associated with cooling and breakup on the upper surface of lava flows; autobreccias, formed by in-situ alteration at the base of flows; fault-gouge breccias; and true sedimentary breccias derived from weathering and erosion of underlying flows. It is virtually impossible to assess the origin of breccia matrix by textural and mineralogical analyses alone. However, it is fundamental for our understanding of breccia provenance to determine the source component of the matrix material. Whether the matrix is uniquely clastderived can be determined by geochemical fingerprinting. Trace elements that are immobile during weathering and alteration do not change their relative abundances. A contribution to the matrix from any source with an immobile trace element signature different from that of the clasts would appear as a perturbation of the trace element signature of the matrix. Trace element analysis of bulk samples from clasts and matrix material in individual breccia units was undertaken in a fashion similar to that used by Brimhall and Dietrich (1987, doi:10.1016/0016-7037(87)90070-6) in analyzing soil provenance: (1) to help distinguish between sedimentary and volcanic breccias, (2) to determine the degree of mixing and depth of erosion in sedimentary breccias, and (3) to analyze the local provenance of the individual breccia components (matrix and clasts). The following elements were analyzed by X-ray fluorescence (XRF): Rb, Sr, Ba, U, Zr, Cu, Zn, Ti, Cr, and V. Of these elements, Zr and Ti probably exhibit truly immobile behavior (Humphris and Thompson, 1978, doi:10.1016/0016-7037(78)90222-3 ). The remaining elements are useful as a reference for the extent of compositional change during the formation of matrix material (Brimhall and Dietrich, 1987, doi:10.1016/0016-7037(87)90070-6).

Major and trace element analyses of ODP Leg 120 volcanic rocks (Table 1)

Widespread Lower Cretaceous magmatism occurred along the Indian-Australian/Antarctic margins, and in the juvenile Indian Ocean, during the rifting of eastern Gondwana. The formation of this magmatic province probably began around 120-130 Ma with the eruption of basalts on the Naturaliste Plateau and at Bunbury, western Australia. On the northeast margin of India, activity began around 117 Ma with the Rajmahal continental basalts and associated lamprophyre intrusions. The formation of the Kerguelen Plateau in the Indian Ocean began no later than 114 Ma. Ultramafic lamprophyres (alnoites) were emplaced in the Prince Charles Mountains near the Antarctic continental margin at ~ 110 Ma. These events are considered to be related to a major mantle plume, the remnant of which is situated beneath the region of Kerguelen and Heard islands at the present day. Geochemical data are presented for each of these volcanic suites and are indicative of complex interactions between asthenosphere-derived magmas and the continental lithosphere. Kerguelen Plateau basalts have Sr and Nd isotopic compositions lying outside the field for Indian Ocean mid-ocean ridge basalts (MORB) but, with the exception of Site 738 at the southern end of the plateau, within the range of more recent hotspot basalts from Kerguelen and Heard Islands. However, a number of the plateau tholeiites are characterized by lower 206Pb/204Pb ratios than are basalts from Kerguelen Island, and many also have anomalously high La/Nb ratios. These features suggest that the source of the Kerguelen Plateau basalts suffered contamination by components derived from the Gondwana continental lithosphere. An extreme expression of this lithospheric signature is shown by a tholeiite from Site 738, suggesting that the southernmost part of the Kerguelen Plateau may be underlain by continental crust. The Rajmahal tholeiites mostly fall into two distinct geochemical groups. Some Group I tholeiites have Sr and Nd isotopic compositions and incompatible element abundances, similar to Kerguelen Plateau tholeiites from Sites 749 and 750, indicating that the Kerguelen-Heard mantle plume may have directly furnished Rajmahal volcanism. However, their elevated 207Pb/204Pb ratios indicate that these magmas did not totally escape contamination by continental lithosphere. In contrast to the Group I tholeiites, significant contamination is suggested for Group II Rajmahal tholeiites, on the basis of incompatible element abundances and isotopic compositions. The Naturaliste Plateau and the Bunbury Basalt samples show varying degrees of enrichment in incompatible elements over normal MORB. The Naturaliste Plateau samples (and Bunbury Basalt) have high La/Nb ratios, a feature not inconsistent with the notion that the plateau may consist of stretched continental lithosphere, near the ocean-continent divide.

Trace element concentrations and Li isotope composition in DSDP and ODP sediments from island arcs

We have studied the sedimentary and basaltic inputs of lithium to subduction zones. Various sediments from DSDP and ODP drill cores in front of the Mariana, South Sandwich, Banda, East Sunda and Lesser Antilles island arcs have been analysed and show highly variable Li contents and d7Li values. The sediment piles in front of the Mariana and South Sandwich arcs largely consist of pelagic sediments (clays and oozes). The pelagic clays have high Li contents (up to 57.3 ppm) and Li isotope compositions ranging from +1.3? to +4.1?. The oozes have lower Li contents (7.3-16 ppm) with d7Li values of the diatom oozes from the South Sandwich lower (+2.8? to +3.2?) than those of the radiolarian oozes from the Mariana arc (+8.1? to +14.5?). Mariana sediment also contains a significant portion of volcanogenic material, which is characterised by a moderate Li content (14 ppm) and a relatively heavy isotope composition (+6.4?). Sediments from the Banda and Lesser Antilles contain considerable amounts of continental detritus, and have high Li contents (up to 74.3 ppm) and low d7Li values (around 0?), caused by weathering of continental bedrock. East Sunda sediments largely consist of calcareous oozes. These carbonate sediments display intermediate to high Li contents (2.4-41.9 ppm) and highly variable d7Li values (-1.6? to +12.8?). Basaltic oceanic crust samples from worldwide DSDP and ODP drill cores are characterised by enrichment of Li compared to fresh MORB (6.6-33.1 vs. 3.6-7.5 ppm, respectively), and show a large range in Li isotope compositions (+1.7? to +11.8?). The elemental and isotopic enrichment of Li in altered basalts is due to the uptake of isotopically heavy seawater Li during weathering. However, old oceanic crust samples from Sites 417/418 exhibit lighter Li isotope compositions compared to young basaltic crust samples from Sites 332B and 504B. This lighter Li isotope signature in old crust is unexpected and further research is needed to explore this issue.

(Table 1) Isotopic and trace-element ratios of Emperor Seamount basalts

When a mantle plume interacts with a mid-ocean ridge, both are noticeably affected. The mid-ocean ridge can display anomalously shallow bathymetry, excess volcanism, thickened crust, asymmetric sea-floor spreading and a plume component in the composition of the ridge basalts (Schilling, 1973, doi:10.1038/242565a0; Verma et al., 1983, doi:10.1038/306654a0; Ito and Lin, 1995, doi:10.1130/0091-7613(1995)023<0657:OSCHIC>2.3.CO;2; Müller et al., 1998, doi:10.1038/24850). The hotspot-related volcanism can be drawn closer to the ridge, and its geochemical composition can also be affected (Ito and Lin, 1995, doi:10.1130/0091-7613(1995)023<0657:OSCHIC>2.3.CO;2; White et al., 1993, doi:10.1029/93JB02018; Kincaid et al., 1995, doi:10.1038/376758a0; Kingsley and Schilling, 1998, doi:10.1029/98JB01496 ). Here we present Sr-Nd-Pb isotopic analyses of samples from the next-to-oldest seamount in the Hawaiian hotspot track, the Detroit seamount at 51° N, which show that, 81 Myr ago, the Hawaiian hotspot produced volcanism with an isotopic signature indistinguishable from mid-ocean ridge basalt. This composition is unprecedented in the known volcanism from the Hawaiian hotspot, but is consistent with the interpretation from plate reconstructions (Mammerickx and Sharman, 1988, doi:10.1029/JB093iB04p03009) that the hotspot was located close to a mid-ocean ridge about 80 Myr ago. As the rising mantle plume encountered the hot, low-viscosity asthenosphere and hot, thin lithosphere near the spreading centre, it appears to have entrained enough of the isotopically depleted upper mantle to overwhelm the chemical characteristics of the plume itself. The Hawaiian hotspot thus joins the growing list of hotspots that have interacted with a rift early in their history.

U-Pb, trace element, and Hf isotope analysis for Macquarie Island detrital zircon

Oceanic zircon trace element and Hf-isotope geochemistry offers a means to assess the magmatic evolution of a dying spreading ridge and provides an independent evaluation of the reliability of oceanic zircon as an indicator of mantle melting conditions. The Macquarie Island ophiolite in the Southern Ocean provides a unique testing ground for this approach due to its formation within a mid-ocean ridge that gradually changed into a transform plate boundary. Detrital zircon recovered from the island records this change through a progressive enrichment in incompatible trace elements. Oligocene age (33-27 Ma) paleo-detrital zircon in ophiolitic sandstones and breccias interbedded with pillow basalt have trace element compositions akin to a MORB crustal source, whereas Late Miocene age (8.5 Ma) modern-detrital zircon collected from gabbroic colluvium on the island have highly enriched compositions unlike typical oceanic zircon. This compositional disparity between age populations is not complimented by analytically equivalent eHf data that primarily ranges from 14 to 13 for sandstone and modern-detrital populations. A wider compositional range for the sandstone population reflects a multiple pluton source provenance and is augmented by a single cobble clast with eHf equivalent to the maximum observed composition in the sandstone (~17). Similar sandstone and colluvium Hf-isotope signatures indicate inheritance from a similar mantle reservoir that was enriched from the depleted MORB mantle average. The continuity in Hf-isotope signature relative to trace element enrichment in Macquarie Island zircon populations, suggests the latter formed by reduced partial melting linked to spreading-segment shortening and transform lengthening along the dying spreading ridge.

Major, trace element and XRF data for sediments and fish tooth samples, from a shallow marine setting with varying redox conditions (Site U1356, Wilkes Land Margin, E.Antarctica)

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources. This article is protected by copyright. All rights reserved.

(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.

Inorganic major, minor, and trace element geochemistry and clay mineralogy of sediments from the Deep Sea Drilling Project Leg 96, Gulf of Mexico

Sediment samples collected at DSDP Leg 96 Mississippi Fan Sites 615, 616, 620, 621, and 623, Orca Basin Site 618, and Pigmy Basin Site 619 were analyzed for 22 major, minor, and trace elements. This study was undertaken to document the downhole variability in inorganic geochemistry between sites. The mineralogy of the clays, including those from Sites 614, 617, and 622 on the fan, was determined by X-ray diffraction to define the principal clay minerals present at the sites, examine any downhole trends in clay mineralogy, and aid in the interpretation of the geochemical signature of the sediments. Clay mineral composition at all the sites is smectite:illite:chlorite:kaolinite in the approximate percentage ratio 50:20:20:10. Geochemical results indicate only slight variation between and within the sites, with the exception of a discrete unit of carbonates that occurs near the bottom of Site 615. Variation in the major, minor, and trace element composition can be explained by a change in the relative abundance of quartz, clay minerals, and carbonates.

Characterisation of early Archaean chemical sediments by trace element signatures

Rare earth element (REE) plus yttrium (Y) patterns of modem seawater have characteristic features that can be used as chemical fingerprints. Reliable proxies for marine REE + Y chemistry have been demonstrated from a large geological time span, including Archaean banded iron formation (BIF), stromatolitic limestone, Phanerozoic reef carbonate and Holocene microbialite. Here we present new REE + Y data for two distinct suites of early Archaean (ca. 3.7-3.8 Ga) metamorphosed rocks from southern West Greenland, whose interrelationships, if any, have been much debated in recent literature. The first suite comprises mangetite-quartz BIF, magnetite-carbonate BIF and banded magnetite-rich quartz rock, mostly from the Isua Greenstone Belt (IGB). The REE + Y patterns, particularly diagnostic anomalies (Ce/Ce*, Pr/Pr*), are closely related to those of published seawater proxies. The second suite includes banded quartz-pyroxene-amphibole +/- garnet rocks with minor magnetite from the so-called Akilia Association enclaves (in early Archaean granitoid gneisses) of the coastal region, some 150 km southwest of the IGB. Rocks of this type from one much publicised and highly debated locality (the island of Akilia) have been identified by some workers [Nature 384 (1996) 55; Geochim. Cosmochim. Acta 61 (1997) 2475] as BIF-facies, and their C-13-depleted signature in trace graphite interpreted as a proxy for earliest life on Earth. However, REE + Y patterns of the Akilia Association suite (except for one probably genuine magnetite-rich BIF from Ugpik) are inconsistent with a seawater origin. We agree with published geological and geochemical (including REE) work [Science 296 (2002) 1448] that most of the analysed Akilia rocks are not chemical sediments, and that C-isotopes in such rocks therefore cannot be used as biological proxies. Application of the REE + Y discriminant for the above two rock suites has been facilitated in this study by the use of MC-ICP technique which yields a more complete and precise REE + Y spectrum than was available in many previous studies. (C) 2004 Elsevier B.V. All rights reserved.