Trace element concentrations in zircons from ODP Holes 147-894G and 153-923A

The trace element compositions of Hadean zircons have been used in two ways to argue for the existence of Hadean continental crust. One argument is based on low crystallization temperatures of Hadean zircons that have been determined using a novel geothermometer based on the Ti content of zircons in equilibrium with rutile. The second argument is based on using the trace element abundances in zircons to calculate their parental melt compositions, especially the rare earth elements. Here we demonstrate that zircons that grow from a melt formed by basalt differentiation at modern mid-ocean ridges cannot be unambiguously distinguished from Hadean zircons on either of these grounds. Thus, we conclude that the trace element compositions of Hadean zircons are permissive of models that do not include the generation of continental crust in the Hadean.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Major and trace element abundances of igneous rocks from DSDP Site 37-334

REE abundances in gabbros and peridotites from Site 334 of DSDP Leg 37 show that these rocks are cumulates produced by fractional crystallization of a primitive oceanic tholeiite magma. They may be part of a layered oceanic complex. The REE distributions in the residual liquids left after such a fractionation are similar to those of incompatible element-depleted oceanic tholeiites. The REE data indicate that the basalts which overlie the gabbro-peridotite complex, are not genetically related to plutonic rocks.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Elements and isotopic measurements of magmatic rock samples from ODP Hole 104-642E

Trace element and isotopic signatures of magmatic rock samples from ODP Hole 642E at the Vøring Plateau provide insight into the interaction processes of mantle melt with crust during the initial magma extrusion phases at the onset of the continental breakup. The intermediate (basaltic-andesitic) to felsic (dacitic and rhyolitic) Lower Series magmas at ODP Hole 642E appear to be produced by large amounts of melting of upper crustal material. This study not only makes use of the traditional geochemical tools to investigate crust-mantle interaction, but also explores the value of Cs geochemistry as an additional tool. The element Cs forms the largest lithophile cation, and shows the largest contrast in concentration between (depleted) mantle and continental crust. As such it is a very sensitive indicator of involvement of crustal material. The Cs data reinforce the conclusion drawn from isotopic signatures that the felsic magmas are largely anatectic crustal melts. The down-hole geochemical variation within ODP Hole 642E defines a decreasing continental crustal influence from the Lower Series into the Upper Series. This is essential information to distinguish intrinsic geochemical properties of the mantle melts from signatures imposed by crustal contamination. A comparison with data from the SE Greenland margin highlights the compositional asymmetry of the crust-mantle interactions at both sides of the paleo-Iapetus suture. While Lower Series and Middle Series rocks from the SE Greenland margin have isotopic signatures reflecting interactions with lower and middle crust, such signatures have not been observed at the mid-Norwegian margin. The geochemical data either point to a dissimilar Caledonian crustal composition and/or to different geodynamic pre-breakup rifting history at the two NE Atlantic margin segments.