Combined chemical separation of Lu, Hf, Sm, Nd, and REEs from a single rock digest: Precise and accurate isotope Determinations of Lu-Hf and Sm-Nd using multicollector-ICPMS

A combined procedure for separating Lu, Hf, Sm, Nd, and rare earth elements (REEs) from a single sample digest is presented. The procedure consists of the following five steps: (1) sample dissolution via sodium peroxide sintering; (2) separation of the high field strength elements from the REEs and other matrix elements by a HF-free anion-exchange column procedure; (3) purification of Hf on a cation-exchange resin; (4) separation of REEs from other matrix elements by cation exchange; (5) Lu, Sm, and Nd separation from the other REEs by reversed-phase ion chromatography. Analytical reproducibilities of Sm-Nd and Lu-Hf isotope systematics are demonstrated for standard solutions and international rock reference materials. Results show overall good reproducibilities for Sm-Nd systematics independent of the rock type analyzed. For the Lu-Hf systematics, the reproducibility of the parent/daughter ratio is much better for JB-1 (basalt) than for two analyzed felsic crustal rocks (DR-N and an Archaean granitoid). It is demonstrated that this poorer reproducibility of the Lu/Hf ratio is truly caused by sample heterogeneity; thus, results are geologically reasonable.

Origin of the Archean Sask craton and its extent within the Trans-Hudson orogen: evidence from Pb and Nd isotopic compositions of basement rocks and post-orogenic intrusions

U-Pb zircon ages from the exposed Sask craton are 2450-3100 Ma, from the Peter Lake Domain 2575-2640 Ma, and from rocks of the Trans-Hudson orogen 1840-1880 Ma. U-Pb monazite and zircon ages of post-orogenic pegmatites and aplites are 1770-1800 Ma. Common Pb and Sm-Nd isotopic compositions of post-orogenic intrusions, as probes of crust beneath the orogen, were compared to Sask craton rocks and ca. 1850 Ma orogenic rocks to infer the origin and subsurface distribution of the Sask craton within the internides of the Trans-Hudson orogen. Results show that post-orogenic intrusions within most of the Glennie Domain and Hanson Lake block were derived, at least in part, from Archean source materials, demonstrating that the Sask craton lies beneath Paleoproterozoic orogenic rocks present at the surface. In contrast, common Pb and Sm-Nd isotopic compositions from pegmatites and aplites of the La Ronge Domain are essentially identical with those of the Paleoproterozoic orogenic rocks into which they are intruded, indicating derivation by partial melting of similar rocks. Thus, if the Sask craton extended to the west beneath the La Ronge Domain, it was beneath the zone of melting that produced the post-orogenic intrusions, making it unlikely that the Sask craton is a detached part of the Hearne craton. Many samples from the Sask craton have elevated Pb-208/Pb-204 ratios, unlike Superior craton or Hearne craton rocks, suggesting that the Sask craton was derived from an exotic source, such as the Wyoming craton, which shares similar elevated Pb-208/Pb-204 ratios.

The geochemistry of late Archaean microbial carbonate: Implications for ocean chemistry and continental erosion history

Trace element concentrations and combined Sr- and Nd-isotope compositions were determined on stromatolitic carbonates (microbialites) from the 2.52 Ga Campbellrand carbonate platform (South Africa). Shale-normalised rare earth element and yttrium patterns of the ancient samples are similar to those of modern seawater in having positive La and Y anomalies and in being depleted in light rare earth elements. In contrast to modem seawater (and microbialite proxies), the 2.52 Ga samples lack a negative Ce anomaly but possess a positive Eu anomaly. These latter trace element characteristics are interpreted to reflect anoxic deep ocean waters where, unlike today, hydrothermal Fe input was not oxidised, and scavenged and rare earth elements were not coprecipitated with Fe-oxyhydroxides. The persistence of a positive Eu anomaly in relatively shallow Campbellrand platform waters indicates a dramatic reversal from hydrothermally dominated (Archaean) to continental erosion-dominated (Phanerozoic) rare earth element flux ratio. The dominant hydrothermal input is also expressed in the initial Sr- and Nd-isotope ratios. There is collinear variation in Sr-Nd systematics, which range from primitive values (Sr-87/Sr-86 of 0.702386 and epsilon (Nd) of +2.1) to more evolved crustal ratios. Mixing calculations show that the range in trace element ratios (e.g., Y/Ho) and initial isotope ratios is not a result of contamination by trapped sediment, but that the chemical band isotopic variation reflects carbonate deposition in an environment where different water masses mixed. Calculated Nd flux ratios yield a hydrothermal input into the 2.52 Ga oceans one order of magnitude larger than continental input. Such a change in flux ratio most likely required substantially reduced continental inputs, which could, in turn, reflect a plate tectonic causation (e.g., reduced topography or expansion of epicontinental seas). Copyright (C) 2001 Elsevier Science Ltd.

Inheritance of early Archaean Pb-isotope variability from long-lived Hadean protocrust

Comparison of initial Pb-isotope signatures of several early Archaean (3.65-3.82 Ga) lithologies (orthogneisses and metasediments) and minerals (feldspar and galena) documents the existence of substantial isotopic heterogeneity in the early Archaean, particularly in the Pb-207/Pb-204 ratio. The magnitude of isotopic variability at 3.82-3.65 Ga requires source separation between 4.3 and 4.1 Ga, depending on the extent of U/Pb fractionation possible in the early Earth. The isotopic heterogeneity could reflect the coexistence of enriched and depleted mantle domains or the separation of a terrestrial protocrust with a U-238/Pb-204 (mu) that was ca. 20-30% higher than coeval mantle. We prefer this latter explanation because the high-p signature is most evident in metasediments (that formed at the Earth's surface). This interpretation is strengthened by the fact that no straightforward mantle model can be constructed for these high-mu lithologies without violating bulk silicate Earth constraints. The Pb-isotope evidence for a long-lived protocrust complements similar Hf-isotope data from the Earth's oldest zircons, which also require an origin from an enriched (low Lu/Hf) environment. A model is developed in which greater than or equal to3.8-Ga tonalite and monzodiorite gneiss precursors (for one of which we provide zircon U-Pb data) are not mantle-derived but formed by remelting or differentiation of ancient (ca. 4.3 Ga) basaltic crust which had evolved with a higher U/Pb ratio than coeval mantle in the absence of the subduction process. With the initiation of terrestrial subduction at, we propose, ca. 3.75 Ga, most of the greater than or equal to3.8-Ga basaltic shell (and its differentiation products) was recycled into the mantle, because of the lack of a stabilising mantle lithosphere. We argue that the key event for preservation of all greater than or equal to3.8-Ga terrestrial crust was the intrusion of voluminous granitoids immediately after establishment of global subduction because of complementary creation of a lithospheric keel. Furthermore, we argue that preservation of !3.8-Ga material (in situ rocks and zircons) globally is restricted to cratons with a high U/Pb source character (North Atlantic, Slave, Zimbabwe, Yilgarn, and Wyoming), and that the Pb-isotope systematics of these provinces are ultimately explained by reworking of material that was derived from ca. 4.3 Ga (i.e. Hadean) basaltic crust.

40Ar/39Ar constraints on a temporal link between gold mineralization, magmatism, and continental margin transtension in the Jiaodong Gold Province, eastern China

The Jiaodong gold province is the largest gold repository in China. Both mineralization and granitoid hosts are spatially related to the crustal-scale Tan-Lu strike-slip fault system, which developed along the Mesozoic continental margin in eastern China. A series of Ar-40/Ar-39 laser incremental heating analyses of hydrothermal sericite/muscovite from three major gold deposits (Jiaojia, Xincheng, and Wangershan) and igneous biotite from the granodiorite hosts were performed to establish a possible temporal link between gold mineralization, magmatism, and movement along the Tan-Lu fault zone. Magmatic biotite crystals yield well-defined and concordant plateau ages between 124.5+/-0.4 Ma and 124.0+/-0.4 Ma (2sigma), whereas sericite and muscovite samples (a total of 30 single separates) give reproducible plateau ages ranging from 121.0+/-0.4 Ma to 119.2+/-0.2 Ma (2sigma). An integration of our Ar-40/Ar-39 results with age data from other major gold deposits in Jiaodong demonstrates that widespread gold mineralization occurred contemporaneously during a 2-3-m.yr. period. Most gold deposits show intimate spatial associations with abundant mafic to intermediate dikes. The mafic dikes have K-Ar ages of 123.5-119.6 Ma, in excellent agreement with those of the gold deposits. These newly obtained Ar-40/Ar-39 ages, in combination with other independent geological and geochronological data on granodioritic intrusions (130-126 Ma), volcanic rocks (1243.6-114.7 Ma), and deformed rocks within strike-slip faults (132-120 Ma) in Jiaodong or adjacent areas, also support the idea that gold mineralization postdated the granodioritic magmatism but was contemporaneous with mafic magmatism and volcanism, all controlled by the transtensional motion along the Tan-Lu fault in the Early Cretaceous.

Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay. minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite-smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R greater than or equal to 3) illite-smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less. illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)(sn) ratios show negative correlations with the illite content in illite-smectite and positive correlations with the delta(18)O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)(sn) ratios and illite content in illite-smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/ rock ratio conditions. Increasing HREE enrichment with delta(18)O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin. Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins. (C) 2003 Elsevier Science B.V. All rights reserved.

A new estimate for the composition of weathered young upper continental crust from alluvial sediments, Queensland, Australia

We present new major element, trace element and Nd-isotope data for 30 alluvial sediments collected from 25 rivers in Queensland, E Australia. Samples were chosen to represent drainage from the region's most important lithologies, including Tertiary intraplate volcanic rocks, a Cretaceous igneous province (and sedimentary rocks derived thereof) as well as Proterozoic blocks. In most chemical and isotopic aspects, the alluvial sediments represent binary or ternary mixing relationships, with absolute abundances implied to reflect the proportion of lithologies in the catchments. When averaged, the studied sediments differ from other proxies of upper continental crust (UCC) mainly in their relative middle rare earth element enrichment (including an elevated Sm/Nd ratio), higher relative Eu abundance and higher Nb/Ta ratio. These features are inherited from eroded Tertiary intraplate basalts, which commonly form topographic highs in the studied region. Despite the high degree of weathering strong to excellent coherence between similarly incompatible elements is found for all samples. From this coherence, we suggest revisions of the following upper crustal element ratios: Y/Ho = 26.2, Yb/Tm = 6.37, Th/W = 7.14, Th/Tl = 24 and Zr/Hf = 36.9. Lithium, Rb, Cs and Be contents do not seem depleted relative to UCC, which may reflect paucity of K-feldspar in the eroded catchments. Nickel, Cr, Pb, Cu and Zn concentrations are elevated in polluted rivers surrounding the state capital. River sediments in the Proterozoic Georgetown Inlier are elevated in Pb, Cu and Zn but this could be a natural phenomenon reflecting abundant sulphide mineralisation in the area. Except for relative Sr concentrations, which broadly anticorrelate with mean annual rainfall in catchments, there is no obvious relationship between the extent of weathering and climate types, which range from and to tropical. The most likely explanation for this observation is that the weathering profiles in many catchments are several Myr old, established during the much wetter Miocene period. The studied sediment compositions (excluding those from the Proterozoic catchments) are used to propose a new trace element normalisation termed MUQ (MUd from Queensland), which serves as an alternative to UCC proxies derived from sedimentary rocks. Copyright (C) 2005 Elsevier Ltd

Investigation of electrical conductivity as a function of dopant-ion radius in the systems Zr0.75Ce0.08M0.17O1.92 (M=Nd, Sm, Gd, Dy, Ho, Y, Er, Yb, Sc)

Electrical conductivity versus dopant ionic radius studies in zirconia- and ceria-based, solid oxide fuel cell (SOFC) electrolyte systems have shown that oxygen-ion conductivity is highest when the host and dopant ions are similar in size [J. Am. Ceram. Soc. 48 (1965) 286; Solid State Ionics 37 (1989) 67; Solid State Ionics 5 (1981) 547]. Under these conditions, it is thought that the conduction paths within the crystal lattice become less distorted [Solid State Ionics 8 (1983) 201]. In this study, binary ZrO2-M2O3 unit cells were expanded, via the partial substitution of Ce+4 for Zr+4 into the lattice, in an attempt to identify new, ternary, zirconia/ceria-based electrolyte systems with enhanced electrical conductivity. The compositions Zr0.75Ce0.08M0.17O1.92 (M = Nd, Sm, Gd, Dy, Ho, Y, Yb, Sc) were prepared using traditional solid state techniques. Bulk phase characterisation and precise lattice parameter measurements were performed with X-ray diffraction techniques. Four-probe DC conductivity measurements between 400 and 900 degreesC showed that the dopant-ion radius influenced electrical conductivity. The conductivity versus dopant-ion radius trends previously observed in zirconia-based, binary systems are clearly apparent in the ternary systems investigated in this study. The addition of ceria was found to have a negative influence on the electrical conductivity over the temperature range 400-900 degreesC. It is suggested that distortion of the oxygen-ion conduction path by the presence of the larger M+3 and Ce+4 species (relative to Zr+4) is the reason for the decreasing electrical conductivity as a function of increasing dopant size and ceria addition, respectively. (C) 2002 Elsevier Science B.V. All rights reserved.

Crystal structure of a heptameric Sm-like protein complex from archaea: Implications for the structure and evolution of snRNPs

The Sm/Lsm proteins associate with small nuclear RNA to form the core of small nuclear ribonucleoproteins, required for processes as diverse as pre-mRNA splicing, mRNA degradation and telomere formation. The Lsm proteins from archaea are likely to represent the ancestral Sm/Lsm domain. Here, we present the crystal structure of the Lsm alpha protein from the thermophilic archaeon Methanobacterium thermoautrophicum at 2.0 Angstrom resolution. The Lsm alpha protein crystallizes as a heptameric ring comprised of seven identical subunits interacting via beta -strand pairing and hydrophobic interactions. The heptamer can be viewed as a propeller-like structure in which each blade consists of a seven-stranded antiparallel beta -sheet formed from neighbouring subunits. There are seven slots on the inner surface of the heptamer ring, each of which is lined by Asp, Asn and Arg residues that are highly conserved in the Sm/Lsm sequences. These conserved slots are likely to form the RNA-binding site. In archaea, the gene encoding Lsm alpha is located next to the L37e ribosomal protein gene in a putative operon, suggesting a role for the Lsm alpha complex in ribosome function or biogenesis. (C) 2001 Academic Press.

Phase and microstructural evolution during the heat treatment of Sm-Ca-alpha-sialon ceramics

The phase and microstructural evolution of multi-cation Sm-Ca-alpha-sialon ceramics was investigated. Six samples were prepared, ranging from a pure Sm-sialon to a pure Ca-sialon, with calcium replacing samarium in 20 eq% increments, thus maintaining an equivalent design composition in all samples. After pressureless sintering at 1820 degreesC for 2 It, all samples were subsequently heat treated up to 192 h at 1450 and 1300 degreesC. The amount of grain boundary glass in the samples after sintering was observed to decrease with increasing calcium levels. A M-ss' or M-ss',-gehlenite solid solution was observed to form during the 1450 degreesC heat treatment of all Sm-containing samples, and this phase forms in clusters in the high-Sm samples. The thermal stability of the alpha-sialon phase was improved in the multi-cation systems. Heat treatment at 1300 degreesC produces SmAlO3 in the high-Sm samples, a M-ss',-gehlenite solid solution in the high-Ca samples, and a Sm-Ca-apatite phase in some intermediate samples. (C) 2002 Elsevier Science Ltd. All rights reserved.

α′ phase stability in Nd-Li-sialon systems

The formability and stability of the alpha-sialon (alpha') phase was investigated in multi-cation Nd-Li-sialon systems. Four samples were prepared, ranging from a pure Nd-sialon to a pure Li-sialon, with two intermediate samples being prepared with either lithium or neodymium replacing the other alpha'-stabilising additive by 20 eq.%, as to maintain an equivalent design composition in all samples. After sintering, all samples were subsequently heat treated up to 192 h at 1450 and 1300 degreesC. While significant quantities of the beta'-sialon (beta' phase were found in most samples, the high-lithium Li-Nd-sialon sample was found to be almost pure a' phase after sintering. Furthermore, the long-term stability of the a' phase on heat treatment was also found to be superior in both multi-cation samples than in either of the single-alpha'-stabilising-cation samples. This is thought to be related to improved retention of the lithium in the multi-cation systems, as much of the lithium was found to volatilise during sintering in the neodymium-free sample. (C) 2002 Elsevier Science Ltd. All rights reserved.

Homomeric ring assemblies of eukaryotic Sm proteins have affinity for both RNA and DNA - Crystal structure of an oligomeric complex of yeast SmF

Sm and Sm-like proteins are key components of small ribonucleoproteins involved in many RNA and DNA processing pathways. In eukaryotes, these complexes contain seven unique Sm or Sm-like (Lsm) proteins assembled as hetero-heptameric rings, whereas in Archaea and bacteria six or seven-membered rings are made from only a single polypeptide chain. Here we show that single Sm and Lsm proteins from yeast also have the capacity to assemble into homo-oligomeric rings. Formation of homo-oligomers by the spliceosomal small nuclear ribonucleoprotein components SmE and SmF preclude hetero-interactions vital to formation of functional small nuclear RNP complexes in vivo. To better understand these unusual complexes, we have determined the crystal structure of the homomeric assembly of the spliceosomal protein SmF. Like its archaeal/bacterial homologs, the SmF complex forms a homomeric ring but in an entirely novel arrangement whereby two heptameric rings form a co-axially stacked dimer via interactions mediated by the variable loops of the individual SmF protein chains. Furthermore, we demonstrate that the homomeric assemblies of yeast Sm and Lsm proteins are capable of binding not only to oligo(U) RNA but, in the case of SmF, also to oligo(dT) single-stranded DNA.