Mass fractionation processes of transition metal isotopes

Macromolecular Biochemistr

Early Archaean rocks and geochemical evolution of the earth's crust

Remnants of Early Archaean rocks (>FX3000 m.y. old) are reported from most continents. A critical review of the radiometric data shows that few of these are well authenticated and most are very limited in extent. The oldest are predominantly plutonic gneisses of tonalitic-to-granitic composition (e.g., the basement gneisses of West Greenland, Labrador, Rhodesia and South Africa). In all cases there are inclusions of meta-volcanic and sedimentary rocks with greenstone belt affinities which probably represent crust into which the igneous parents of the gneisses were intruded. The trace element chemistry of these very old rocks is reviewed in an attempt to establish the mechanism of formation of early crust and place constraints on the chemical evolution of the earth's mantle. “Mantle-type” Sr isotope compositions show that the sialic members of both early gneisses and greenstone belts were not derived from much older crustal differentiates, either at 3800 or at 2800 m.y. ago. However, trace element ratios such as K/Rb and Sr/Ba, and rare earth element abundances, are not consistent with direct derivation of the plutonic suite from the upper mantle and also rule out a common parentage for the tonalites and granites. An origin by partial melting of metamorphosed juvenile crust with a composition range equivalent to that represented by the greenstone belts is preferred. Tonalites resulted from high-pressure melting of mafic garnet-amphibolite and at least some of the granites from low-pressure melting of more felsic (possibly even sedimentary) material. The trace element chemistry of the greenstone belt volcanics is thought to characterize the composition of early mantle melts, although the best preserved and best documented cases are about 500–1000 m.y. younger than the oldest known gneisses. The dominant type is tholeiite with low incompatible element contents and light-depleted or essentially flat rare earth patterns, features even more marked in the ultramafic komatiites which represent large degrees of melting. More evolved calc-alkaline rocks with relative incompatible and light rare earth element enrichment are also important. With the exception of the ultramafic lavas, all these types can be matched by the chemistry of present-day oceanic volcanism. It is concluded that the range of trace element variations in the earth's mantle was comparable in early Archaean times to that at the present. This is supported by mass balance calculations for the lithophile elements which have been preferentially extracted into the crust. Thus the isotope and trace element evidence of the oldest rocks argues against primary differentiation of the crust either during accretion of the earth or during its first 500 m.y. as a solid body. Crust formation has probably occurred continuously, although worldwide evidence for magmatism at around 2800 m.y. ago probably marks a particularly active period

Nd- and Pb- isotope time series from Atlantic ferromanganese crusts: Implications for changes in provenance and paleocirculation over the last 8 Myr

High-resolution Nd- and Pb-isotope time series for the last 8 Myr are reported for four Atlantic ferromanganese crusts, dated by 10Be/9Be chronology. These are compared to new high-resolution and high-precision Pb-isotope time series and recently published Nd-isotope time series for two previously studied crusts from the NW Atlantic Ocean. These records allow a more detailed examination of Atlantic deepwater variability over the time period of intensification of Northern Hemisphere Glaciation (NHG). Changes in the Pb-isotope time series started after 3 Ma, but were most dramatic over the last 1.8 Myr, coinciding with changes of Pb-isotopes in the Arctic Ocean. This latter change post-dates the intensification of NHG at 3.1 to 2.5 Ma and reflects an increase in the input of material eroded from the Archean Shield of Canada and Greenland. Shifts in Nd- and Pb-isotope compositions in a crust from the Blake Plateau occur before ∼5 Ma and most prominent at ∼8 Ma suggest that water masses from either the Pacific or Southern Ocean influenced the isotope composition of this crust. The relatively high εNd values around 8 Ma recorded by the Blake Plateau crust are explained by a contribution of eastward flowing Pacific water through the Panama Gateway into the Caribbean Sea. This high εNd signal decreased between 8 and 5 Ma suggesting that the supply of Pacific water into the Caribbean became restricted. This is earlier than the Caribbean seawater salinity increase at 4.2 Ma deduced from δ18O data, and may indicate that there was only a surface water connection between the Caribbean and Pacific between ∼5 and 4.2 Ma. The closure of the Panama Gateway to intermediate and deep water exchange (>200 m depth) apparently occurred much earlier than the intensification of Northern Hemisphere Glaciation at 3.1–2.5 Ma, and cannot therefore have been a direct cause of this climatic change, but may, as recently argued, only have been a necessary preconditio

60 Myr records of major elements and Pb-Nd isotopes from hydrogenous ferromanganese crusts: Reconstruction of seawater paleochemistry

We compare the time series of major element geochemical and Pb- and Nd-isotopic composition obtained for seven hydrogenous ferromanganese crusts from the Atlantic, Indian, and Pacific Oceans which cover the last 60 Myr. Average crust growth rates and age-depth relationships were determined directly for the last about 10 Myr using Be-10/Be-9 profiles. In the absence of other information these were extrapolated to the base of the crusts assuming constant growth rates and constant initial Be-10/Be-9 ratios due to the lack of additional information. Co contents have also been used previously to estimate growth rates in Co-rich Pacific and Atlantic seamount crusts (Puteanus and Halbach, 1988). A comparison of Be-10/Be-9- and Co-based dating of three Co-rich crusts supports the validity of this approach and confirms the earlier chronologies derived from extrapolated Be-10/Be-9-based growth rates back to 60 Ma. Our data show that the flux of Co into Co-poor crusts has been considerably lower. The relationship between growth rate and Co content for the Co-poor crusts developed from these data is in good agreement with a previous study of a wider range of marine deposits (Manheim, 1986). The results suggest that the Co content provides detailed information on the growth history of ferromanganese crusts, particularly prior to 10-12 Ma where the Be-10-based method is not applicable. The distributions of Pb and Nd isotopes in the deep oceans over the last 60 Myr are expected to be controlled by two main factors: (a) variations of oceanic mixing patterns and flow paths of water masses with distinct isotopic signatures related to major paleogeographic changes and (b) variability of supply rates or provenance of detrital material delivered to the ocean, linked to climate change (glaciations) or major tectonic uplift. The major element profiles of crusts in this study show neither systematic features which are common to crusts with similar isotope records nor do they generally show coherent relationships to the isotope records within a single crust. Consequently, any interpretation of time series of major element concentrations of a single crust in terms of paleoceanograghic variations must be considered with caution. This is because local processes appear to have dominated over more basin wide paleoceanographic effects. In this study Co is the only element which shows a relationship to Pb and Nd isotopes in Pacific crusts. A possible link to changes of Pacific deep water properties associated with an enhanced northward advection of Antarctic bottom water from about 14 Ma is consistent with the Pb but not with the Nd isotopic results. The self-consistent profiles of the Pb and Nd isotopes suggest that postdepositional diagenetic processes in hydrogenous crusts, including phosphatization events, have been insignificant for particle reactive elements such as Pb, Be, and Nd. Isotope time series of Pb and Nd show no systematic relationships with major element contents of the crusts, which supports their use as tracers of paleo-seawater isotopic compositio

The origin of hydrothermal and other gases in the Kenya Rift Valley

The Kenya Rift Valley (KRV) is part of a major continental rift system from which much outgassing is presently occurring. Previous research on gases in the KRV has tended to concentrate on their geothermal implications; the present paper is an attempt to broaden the interpretation by consideration of new data including helium and carbon isotope analyses from a wide cross-section of sites. In order to do this, gases have been divided into categories dependent on origin. N2 and noble gases are for the most part atmospherically derived, although their relative concentrations may be altered from ASW ratios by various physical processes. Reduced carbon (CH4 and homologues) appears to be exclusively derived from the shallow crust, with thermogenic δ13C values averaging −25‰ PDB for CH4. H2 is likely also to be crustally formed. CO2, generally a dominant constituent, has a narrow δ13C range averaging −3.7‰ PDB, and is likely to be derived with little modification from the upper mantle. Consideration of the ratio C/3He supports this view in most cases. Sulphur probably also originates there. Ratios of 3He/4He reach a MORB-like maximum of 8.0 R/RA and provide the best indication of an upper mantle source of gases beneath the KRV. A correlation between 3He/4He and the hydrocarbon parameter log (C1/ΣC2–4) appears to be primarily temperature related. The highest 3He/4He ratios in spring waters are associated with basalts, perhaps because of the leaching of basalt glasses. There may be a structural control on 3He/4He ratios in the KRV as a whole

A geochemical study of island-arc and back-arc tholeiites from the Scotia Sea

Elsevier Earth and Planetary Science Letters Volume 36, Issue 2, September 1977, Pages 253-262 Earth and Planetary Science Letters A geochemical study of island-arc and back-arc tholeiites from the Scotia Sea Author links open overlay panel C.J. Hawkesworth 1, R.K. O'Nions 2, R.J. Pankhurst 3, P.J. Hamilton 2, N.M. Evensen 21Department of Earth Sciences, University of Leeds, Leeds Great Britain2Lamont-Doherty Geological Observatory of Columbia University, Palisades, N.Y. 10964USA3British Antarctic Survey, c/o Institute of Geological Sciences, London, WCIX 8N6Great Britain Received 22 April 1977, Revised 9 June 1977, Available online 23 October 2002. Show less https://doi.org/10.1016/0012-821X(77)90207-2Get rights and content Abstract 87Sr/86Sr and143Nd/144Nd ratios, REE and selected minor and trace elements are presented and compared for present-day volcanic rocks in the Scotia Sea. Tholeiitic basalts from the South Sandwich Islands show widely ranging contents of some lithophile elements, e.g. K2O (0.09–0.55%) and Rb (1.55–14.2 ppm), but fairly constant Na2O and Sr. Total REE contents range from about 4–20 times chondritic abundances with significant light-REE depletion and both positive and negative Eu anomalies. The variations in minor and trace element abundances are consistent with low-pressure fractional crystallization of plagioclase and clinopyroxene but only minor amounts of olivine. The87Sr/86Sr and143Nd/144Nd ratios of the parental magmas are thought be 0.7038–0.7039 and 0.51301–0.51314 respectively, and indicate derivation of at least some87Sr from subducted ocean crust. The back-arc tholeiites in the Scotia Sea have lower87Sr/86Sr ratios (0.7028–0.7033), similar143Nd/144Nd ratios (0.51305) and are variably light-REE-enriched(CeN/YbN= 1.0–1.6). Total REE contents are comparable to those of the South Sandwich Islands tholeiites

The Hf isotope composition of global seawater and the evolution of Hf isotopes in the deep Pacific Ocean from Fe-Mn crusts

This paper presents a revised chemical purification method of Hf for the measurement of Hf isotope ratios of Fe–Mn crusts on a new generation of double focusing multiple collector plasma source mass spectrometer (MC-ICP-MS). By measuring surface scrapings of hydrogenetic Fe–Mn crusts distributed over the three major ocean basins, the present-day Hf isotope distribution of oceanic deep water is assessed in detail. The results show an εHf provinciality correlated with those of other radiogenic isotope tracers such as Nd and Pb in agreement with previous studies. This supports the use of Hf isotopes as tracer of element source provenance and water masses. Fe–Mn crusts display the same present-day Hf–Nd isotope array as given before for Mn nodules. The smaller isotopic variability of Hf compared with Nd may either be caused by a more efficient mixing of Hf than Nd in the ocean due to a longer residence time or may be a consequence of a systematically more radiogenic Hf than Nd isotope signature delivered to the oceans by weathering of continental crust. A Hf isotope time series was measured on crust VA13/2 to assess the Hf isotope compositions of the Central Pacific deep water over the past 26 Ma. No consistency is observed between the Hf and Pb isotope time series. In contrast, Hf and Nd isotope time series display similar patterns which are, however, apparently offset by 2 Ma prior to 14 Ma. Differential diffusion of Hf and Nd does not explain this offset. The smaller amplitude in the Hf isotope variations compared with the Nd isotopes rather argues for more efficient mixing of Hf in the ocean. We suggest that both isotope systems have responded in a similar way to the processes affecting the dissolved radiogenic isotope composition of Pacific deep water during this time interval. The parallel increase in εHf and εNd observed between 14 and 3 Ma may probably be attributed to the increased inputs of Hf and Nd into the Central Pacific Ocean derived from the weathering of the Pacific Islands Arcs. Over the past 3 Ma an increased aeolian continental input derived from Asia most likely caused negative shifts in εNd and εHf recorded by VA13/2. The fact that Hf and Nd isotope compositions plot along the present-day array for Fe–Mn crusts and Mn nodules over the entire past 26 Ma suggests that aeolian supply of Hf to the Pacific Ocean has been a long-term important feature