A refined solution to Earth's hidden niobium: implications for evolution of continental crust and mode of core formation

New high-precision niobium (Nb) and tantalum (Ta) concentration data are presented for early Archaean metabasalts, metabasaltic komatiites and their erosion products (mafic metapelites) from SW Greenland and the Acasta gneiss complex, Canada. Individual datasets consistently show sub-chondritic Nb/Ta ratios averaging 15.1+/-11.6. This finding is discussed with regard to two competing models for the solution of the Nb-deficit that characterises the accessible Earth. Firstly, we test whether Nb could have sequestered into the core due to its slightly siderophile (or chalcophile) character under very reducing conditions, as recently proposed from experimental evidence. We demonstrate that troilite inclusions of the Canyon Diablo iron meteorite have Nb and V concentrations in excess of typical chondrites but that the metal phase of the Grant, Toluca and Canyon Diablo iron meteorites do not have significant concentrations of these lithophile elements. We find that if the entire accessible Earth Nb-deficit were explained by Nb in the core, only ca. 17% of the mantle could be depleted and that by 3.7 Ga, continental crust would have already achieved ca. 50% of its present mass. Nb/Ta systematics of late Archaean metabasalts compiled from the literature would further require that by 2.5 Ga, 90% of the present mass of continental crust was already in existence. As an alternative to this explanation, we propose that the average Nb/Ta ratio (15.1+/-11.6) of Earth's oldest mafic rocks is a valid approximation for bulk silicate Earth. This would require that ca. 13% of the terrestrial Nb resided in the Ta-free core. Since the partitioning of Nb between silicate and metal melts depends largely on oxygen fugacity and pressure, this finding could mean that metal/silicate segregation did not occur at the base of a deep magma ocean or that the early mantle was slightly less reducing than generally assumed. A bulk silicate Earth Nb/Ta ratio of 15.1 allows for depletion of up to 40% of the total mantle. This could indicate that in addition to the upper mantle, a portion of the lower mantle is depleted also, or if only the upper mantle were depleted, an additional hidden high Nb/Ta reservoir must exist. Comparison of Nb/Ta systematics between early and late Archaean metabasalts supports the latter idea and indicates deeply subducted high Nb/Ta eclogite slabs could reside in the mantle transition zone or the lower mantle. Accumulation of such slabs appears to have commenced between 2.5 and 2.0 Ga. Regardless of these complexities of terrestrial Nb/Ta systematics, it is shown that the depleted mantle Nb/Th ratio is a very robust proxy for the amount of extracted continental crust, because the temporal evolution of this ratio is dominated by Th-loss to the continents and not Nb-retention in the mantle. We present a new parameterisation of the continental crust volume versus age curve that specifically explores the possibility of lithophile element loss to the core and storage of eclogite slabs in the transition zone. (C) 2003 Elsevier Science B.V. All rights reserved.

Late Quaternary uplift and subsidence of the west coast of Tanna, south Vanuatu, southwest Pacific: U-Th ages of raised coral reefs in the Median Sedimentary Basin

Twelve Late Quaternary TIMS U-Th ages are reported here from 10 coral samples collected in situ from five transgressive coral/algal raised reefs (height: max. 113 m, min. 8 m) and two raised lagoonal deposits (height: max. 18 m, min. 8 m) along and near the west coast of Tanna, which lies in the Median Sedimentary Basin of South Vanuatu, southwest Pacific. These reefs and raised lagoonal deposits represent several age groups: (i) 215 ka (marine oxygen-isotope stage 7) penultimate interglacial (highest elevation and oldest); (ii) one lagoonal deposit of ca 127 ka (marine oxygen-isotope stage 5e); (iii) three last interglacial reefs with ages 102, 89 and 81 ka (representing marine oxygen-isotope stages 5c, 5b and 5a, respectively, of the latter part of the last interglacial); (iv) a lagoonal deposit with a 92 ka age (5b); and (v) a Holocene reef (age >5.7-5.0 ka) (lowest elevation and youngest). A ca 4.9 ka regressive reef (at elevation of 1.5 m above sea-level) is consistent with an island-wide 6.5 m uplift (probably largely coseismic), and a probable further island-wide uplift occurred in the late Holocene. The U-series ages taken together with the heights of transgressive reefs show that uplift since 215 ka was, on average, at similar to0.52 mm/y; although since 5 ka the uplift rate was, on average, similar to1.6 mm/y (the assumption being that a 1.5 m above sea-level reef has a coseismic origin). Elevation of transgressive reefs 5a, 5b and 5c and their ages indicates an island-wide subsidence during the period ?124-89 ka (i.e. Late Quaternary uplift/subsidence was jerky). Late Quaternary uplift/subsidence on the northwest coast of Tanna is considered to be due to irregular thicknesses of crust being subducted beneath Tanna.

The Quaternary pyroclastic succession of southeast Tenerife, Canary Islands: Explosive eruptions, related caldera subsidence, and sector collapse

A much-revised Quaternary stratigraphy is presented for ignimbrites and pumice fall deposits of the Bandas del Sur, in southern Tenerife. New Ar-41/Ar-39 data obtained for the Arico, Granadilla, Fasnia, Poris, La Caleta and Abrigo formations are presented, allowing correlation with previously dated offshore marine ashfall layers and volcaniclastic sediments. We also provide a minimum age of 287 +/- 7 ka for a major sector collapse event at the Gaimar valley. The Bandas del Sur succession includes more than seven widespread ignimbrite sheets that have similar characteristics, including widespread basal Plinian layers, predominantly phonolite composition, ignimbrites with similar extensive geographic distributions, thin condensed veneers with abundant diffuse bedding and complex lateral and vertical grading patterns, lateral gradations into localized massive facies within palaeo-wadis, and widespread lithic breccia layers that probably record caldera-forming eruptions. Each ignimbrite sheet records substantial bypassing of pyroclastic material into the ocean. The succession indicates that Las Canadas volcano underwent a series of major explosive eruptions, each starting with a Plinian phase followed by emplacement of ignimbrites and thin ash layers, some of coignimbrite origin. Several of the ignimbrite sheets are compositionally zoned and contain subordinate mafic pumices and banded pumices indicative of magma mingling immediately prior to eruption. Because passage of each pyroclastic density current was characterized by phases of non-deposition and erosion, the entire course of each eruption is incompletely recorded at any one location, accounting for some previously perceived differences between the units. Because each current passed into the ocean, estimating eruption volumes is virtually impossible. Nevertheless, the consistent widespread distributions and the presence of lithic breccias within most of the ignimbrite sheets suggest that at least seven caldera collapse eruptions are recorded in the Bandas del Sur succession and probably formed a complex, nested collapse structure. Detailed field relationships show that extensive ignimbrite sheets (e.g. the Arico, Poris and La Caleta formations) relate to previously unrecognized caldera collapse events. We envisage that the evolution of the nested Las Cahadas caldera is more complex than previously thought and involved a protracted history of successive ignimbrite-related caldera collapse events, and large sector collapse events, interspersed with edifice-building phases.

Successive nonparametric estimation of conditional distributions

Spatial characterization of non-Gaussian attributes in earth sciences and engineering commonly requires the estimation of their conditional distribution. The indicator and probability kriging approaches of current nonparametric geostatistics provide approximations for estimating conditional distributions. They do not, however, provide results similar to those in the cumbersome implementation of simultaneous cokriging of indicators. This paper presents a new formulation termed successive cokriging of indicators that avoids the classic simultaneous solution and related computational problems, while obtaining equivalent results to the impractical simultaneous solution of cokriging of indicators. A successive minimization of the estimation variance of probability estimates is performed, as additional data are successively included into the estimation process. In addition, the approach leads to an efficient nonparametric simulation algorithm for non-Gaussian random functions based on residual probabilities.

Computational properties of min/max autocorrelation factors

Minimum/maximum autocorrelation factor (MAF) is a suitable algorithm for orthogonalization of a vector random field. Orthogonalization avoids the use of multivariate geostatistics during joint stochastic modeling of geological attributes. This manuscript demonstrates in a practical way that computation of MAF is the same as discriminant analysis of the nested structures. Mathematica software is used to illustrate MAF calculations from a linear model of coregionalization (LMC) model. The limitation of two nested structures in the LMC for MAF is also discussed and linked to the effects of anisotropy and support. The analysis elucidates the matrix properties behind the approach and clarifies relationships that may be useful for model-based approaches. (C) 2003 Elsevier Science Ltd. All rights reserved.

Data-driven fuzzy analysis in quantitative mineral resource assessment

The integration of geo-information from multiple sources and of diverse nature in developing mineral favourability indexes (MFIs) is a well-known problem in mineral exploration and mineral resource assessment. Fuzzy set theory provides a convenient framework to combine and analyse qualitative and quantitative data independently of their source or characteristics. A novel, data-driven formulation for calculating MFIs based on fuzzy analysis is developed in this paper. Different geo-variables are considered fuzzy sets and their appropriate membership functions are defined and modelled. A new weighted average-type aggregation operator is then introduced to generate a new fuzzy set representing mineral favourability. The membership grades of the new fuzzy set are considered as the MFI. The weights for the aggregation operation combine the individual membership functions of the geo-variables, and are derived using information from training areas and L, regression. The technique is demonstrated in a case study of skarn tin deposits and is used to integrate geological, geochemical and magnetic data. The study area covers a total of 22.5 km(2) and is divided into 349 cells, which include nine control cells. Nine geo-variables are considered in this study. Depending on the nature of the various geo-variables, four different types of membership functions are used to model the fuzzy membership of the geo-variables involved. (C) 2002 Elsevier Science Ltd. All rights reserved.

A statistical approach to predict the effect of confinement on the detonation velocity of commercial explosives

Commercial explosives behave non-ideally in rock blasting. A direct and convenient measure of non-ideality is the detonation velocity. In this study, an alternative model fitted to experimental unconfined detonation velocity data is proposed and the effect of confinement on the detonation velocity is modelled. Unconfined data of several explosives showing various levels of nonideality were successfully modelled. The effect of confinement on detonation velocity was modelled empirically based on field detonation velocity measurements. Confined detonation velocity is a function of the ideal detonation velocity, unconfined detonation velocity at a given blasthole diameter and rock stiffness. For a given explosive and charge diameter, as confinement increases detonation velocity increases. The confinement model is implemented in a simple engineering based non-ideal detonation model. A number of simulations are carried out and analysed to predict the explosive performance parameters for the adopted blasting conditions.

Early-Middle Jurassic stratigraphy of the Fortrose-Chaslands region, southernmost South Island, New Zealand

The 40 km of coastline from Fortrose to Chaslands Mistake (southeastern South Island, New Zealand) comprises sediments that are part of the Early-Middle Jurassic of the Murihiku Terrane. The sediments are dominantly fluvial with some marine beds and alluvial fan deposition, and display an evolution of fluvial style which progresses from perennial flow to seasonal flow. The McPhee Cove Conglomerate is a prominent unit to the north. It has been used to separate two formations which would otherwise, on inherent lithological grounds, be difficult to distinguish. This paper discusses several similar conglomerates which occur in the south, but which are separated from the type area of the McPhee Conglomerate by major tectonic disruption. Hence, the existing lithostratigraphic nomenclature to the north, including the McPhee Cove Conglomerate, cannot be simply extended southwards. The Fortrose-Chaslands area appears to consist of two tectonic blocks, the Slope Point Block and the Brothers Block, which are separated from each other and from the adjacent Papatowai Block by major strike faults (or fault zones). A change is proposed to the existing stratigraphy which involves recognising all terrestrial sediments as part of the False Island Formation. Four prominent clast-supported conglomerate horizons are named as members of the False Islet Formation: the White Head Conglomerate, Black Bluff Conglomerate. Hoiho Conglomerate, and Slope Point Conglomerate Members. The latter contains five named conglomerate beds.

The decomposition of starch grains in soils: implications for archaeological residue analyses

Recent research involving starch grains recovered from archaeological contexts has highlighted the need for a review of the mechanisms and consequences of starch degradation specifically relevant to archaeology. This paper presents a review of the plant physiological and soil biochemical literature pertinent to the archaeological investigation of starch grains found as residues on artefacts and in archaeological sediments. Preservative and destructive factors affecting starch survival, including enzymes, clays, metals and soil properties, as well as differential degradation of starches of varying sizes and amylose content, were considered. The synthesis and character of chloroplast-formed 'transitory' starch grains, and the differentiation of these from 'storage' starches formed in tubers and seeds were also addressed. Findings of the review include the higher susceptibility of small starch grains to biotic degradation, and that protective mechanisms are provided to starch by both soil aggregates and artefact surfaces. These findings suggest that current reasoning which equates higher numbers of starch grains on an artefact than in associated sediments with the use of the artefact for processing starchy plants needs to be reconsidered. It is argued that an increased understanding of starch decomposition processes is necessary to accurately reconstruct both archaeological activities involving starchy plants and environmental change investigated through starch analysis. (C) 2004 Elsevier Ltd. All rights reserved.

Geochemistry of late Archaean stromatolites from Zimbabwe: evidence for microbial life in restricted epicontinental seas

We report comprehensive trace element and Sr-isotope data for microbial carbonates from the Archaean Mushandike limestone, Masvingo Greenstone Belt, Zimbabwe. The stromatolites have very coherent REE + Y patterns and share the essential shale-normalised characteristics of other Archaean marine precipitates (positive La and Gd anomalies, absence of a negative Cc anomaly and a strongly superchondritic Y/Ho ratio). Mixing models constrain the maximum amount of shale contamination to 0.25-1% and calculated detritus-free carbonate REE + Y systematics require precipitation from seawater. In terms of light-REE over heavy-REE depletion, however, the studied samples are very different from all other known Archaean marine precipitates. In shale-normalised plots, the Mushandike samples yield a negative slope. A very restricted, regional input source of the dissolved load is indicated because normalisation with locally occurring tonalite gneiss REE + Y data yields a pattern closely resembling typical shale-normalised Archaean marine chemical sediments. The disappearance of a negative Eu anomaly when patterns are normalised with local tonalite gneiss strengthens this interpretation. Sr-isotope ratios are strongly correlated with trace element contents and ratios, which explains the modest scatter in Sr-isotope ratios as representing (minor) clastic contamination. Importantly, even the least contaminated samples have very radiogenic initial Sr-87/Sr-86 ratios (0.7184) implying Sr input from an ancient high Rb/Sr source, such as the early Archaean gneisses of south-central Zimbabwe. A local ancient (3.5-3.8 Ga) source is also indicated by previously published Pb-isotope datasets for the Mushandike stromatolites. This is entirely compatible with the occurrence of 3.7-3.8 Ga zircons in quartzites and metapelites from comparably old greenstone belts within less than 150 km of the studied locality. Comparison of the Pb-isotope ratios of the Mushandike stromatolites with 2.7 and 2.6 Ga old stromatolites from the neighbouring, Belingwe Greenstone Belt demonstrates differences in initial isotope composition that relate to the extent of exchange with the open ocean. The development of numerous basins on old continental crust, with water masses variably restricted from the open ocean. suggests a lack of strong vertical topography on this late Archaean craton. (C) 2004 Elsevier B.V. All rights reserved.

Alpha-cellulose δ13C variation in mangrove tree rings correlates well with annual sea level trend between 1982 and 1999

A pilot study of tree rings in a modern mangrove tree (Rhizophora apiculata) from Leizhou Peninsula, northern South China Sea shows that ( 1) the tree-rings are annual; ( 2) the ring widths decrease; and ( 3) their alpha-cellulose delta(13)C values increase from 1982 to 1999 AD, consistent with the trends of annual sea level, salinity and sea surface temperatures in the same period. We propose that such changes were caused by increasingly longer duration of waterlogging in response to sea-level rise. If this is the case, alpha-cellulose delta(13)C in mangrove tree rings can be used as a potential indicator of past sea level fluctuations.

Speleothem master chronologies: combined Holocene O-18 and C-13 records from the North Island of New Zealand and their palaeoenvironmental interpretation

The stable isotope records of four stalagmites dated by 19 TIMS uranium series ages are combined to produce master chronologies for delta(18)O and delta(13)C The delta(18)O records display good overall coherence, but considerable variation in detail. Variability in the delta(13)C records is greater, but general trends can still be discerned. This implies that too fine an interpretation of the structure of individual isotopic records can be unreliable. Speleothem delta(18)O values are demonstrated to show a positive relationship with temperature by comparing trends with other proxy records, but also to respond negatively to rainfall amount. Speleothem delta(13)C is considered to be most influenced by rainfall. The postglacial thermal optimum occur-red around 10.8 ka BP, which is similar in timing to Antarctica but up to 2000 years earlier than most Northern Hemisphere sites. Increasingly negative delta(18)O values after 7.5 ka BP indicate that temperatures declined to a late mid-Holocene minimum centred around 3 ka BP, but more positive values followed to mark a warm peak about 750 years ago which coincided with the 'Mediaeval Warm Period' of Europe. Low 5110 values at 325 years BP suggest cooling coincident with the 'Little Ice Age'. A marked feature of the delta(13)C record is an asymmetric periodicity averaging c. 2250 years and amplitude of c. 1.9parts per thousand. It is concluded that this is mainly driven by waterbalance variations with negative swings representing particularly wet intervals. The 5110 record shows a higher-frequency cyclicity with a period of c. 500 years and an amplitude of c. 0.25 parts per thousand. This is most likely to be temperature-driven, but some swings may have been amplified by precipitation.

Storm cycles in the last millennium recorded in Yongshu Reef, southern South China Sea

Large storm-relocated Porites coral blocks are widespread on the reef flats of Nansha area, southern South China Sea. Detailed investigations of coral reef ecology, geomorphology and sedimentation on Yongshu Reef indicate that such storm-relocated blocks originated from large Porites lutea corals growing on the spurs within the reef-front living coral zone. Because the coral reef has experienced sustained subsidence and reef development during the Holocene, dead corals were continuously covered by newly growing coral colonies. For this reason, the coral blocks must have been relocated by storms from the living sites and therefore the ages of these storm-relocated corals should approximate the times when the storms occurred. Rapid emplacement of these blocks is also evidenced by the lack of coral overgrowth, encrustation or subtidal alteration. U-series dating of the storm-relocated blocks as well as of in situ reef flat corals suggests that, during the last 1000 years, at least six strong storms occurred in 1064 +/- 30, 1210 +/- 5-1201 +/- 4, 1336 +/- 9, 1443 +/- 9, 1685 +/- 8-1680 +/- 6, 1872 +/- 15 AD, respectively, with an average 160-year cycle (110-240 years). The last storm, which occurred in 1872 15 AD, also led to mortality of the reef flat corals dated at similar to 130 years ago. Thus, the storm had significant impacts on coral reef ecology and morphology. (C) 2004 Elsevier B.V. All rights reserved.

U-series dating of Locality 15 at Zhoukoudian, China, and implications for hominid evolution

This paper reports U-series dates on speleothem samples from Locality 15 at Zhoukoudian, one of the richest Paleolithic sites in northern China. The age of the lower part of Layer 2 is securely bracketed between 155,000 and 284,000 yr. The underlying Layer 3 dates back at least 284,000 yr. Layer 4, further below, should be older still, possibly by a cycle on the SPECMAP time scale before 284,000 yr ago. These ages, much greater than the previous estimates of 110,000-140,000 yr from U-series and electron spin resonance dating of fossil teeth, suggest that Locality 15 was broadly contemporaneous with Locality 4 (New Cave) and with the uppermost strata of Locality 1 (Peking Man site). The physical evolution and cultural development evidenced by the timing of the Zhoukoudian localities are in line with the opinion of Chinese anthropologists for a regional transition from Homo erectus to archaic Homo sapiens. (C) 2004 University of Washington. All rights reserved.