Leslie Kinsley

A simple method for the precise determination of ≥ 40 trace elements in geological samples by ICPMS using enriched isotope internal standardisation

The combination of enriched isotopes and conventional elemental internal standards permits the precise determination of > 40 trace elements by ICPMS in a broad spectrum of geological matrixes. Enriched isotopes expand the suite of available reference isotopes spaced through the mass spectrum, so that the complex mass-dependent variations in sensitivity encountered during ICPMS analysis can be monitored and deconvolved. The method we have developed is straightforward, entailing simple sample preparation, instrument calibration, and data reduction procedures, as well as providing extended element coverage, improved precision, and both time and cost benefits compared to alternative analytical strategies. Analytical precision near or better than 1% RSD (relative standard deviation) is achieved for most elements with mass > 80 amu and between 1% and 4% (RSD) for elements with mass 80 amu and < 10 ng g−1 to 1 μg g−1 for elements with mass < 80 amu). The subtle geochemical differences which can be resolved using this method are demonstrated by analyses of Nb, Ta, Zr, and Hf in magmas from ocean islands and subduction zones. These data reveal significant departures from chondritic Zr/Hf and Nb/Ta values, and systematic trends which are consistent with greater incompatibility of Zr relative to Hf and also of Nb relative to Ta during melting of the upper mantle. The occurrence of significantly subchondritic Zr/Hf and Nb/Ta ratios in Nb-poor subduction zone magmas, supports the notion that the depletion of high-field strength elements in subduction magmas is due to their removal from the mantle wedge by prior melting events.

High resolution analysis of trace elements in corals by laser ablation ICP-MS

Abstract A method has been developed using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for rapid high resolution analysis of B, Mg, Sr, Ba, and U in corals. Corals represent a challenge for a microbeam technique due to their compositional and structural heterogeneity, their nonsilicate matrix, and their unusual range of trace element compositions relative to available standards. The method employs an argon-fluoride excimer laser (λ = 193 nm), masked to produce a beam 600 μm wide by 20 μm across to average ablation sampling over a range of structural features. Coral sections are scanned at a constant rate beneath the laser to produce a continuous sampling of the coral surface. Sensitivity drift is controlled by careful preconditioning of the ICP-MS to carbonate material, and standardisation is carried out by bracketing each traverse down the coral sample by analyses of a CaSiO3 glass synthesised from coral powder. The method demonstrates excellent reproducibility of both the shape and magnitude of coralline trace element profiles, with typical precisions of between 1.0 and 3.7% based on analysis of the synthetic standard. Accuracy varies between 3.8% for B and 31% for U. Discrepancies are attributed to heterogeneities in the synthetic standard, and matrix differences between the silicate standard and carbonate sample. The method is demonstrated by analysis of a coral collected from Australia’s Great Barrier Reef near a weather station recording in-situ sea-surface-temperature (SST). The elements B, Mg, Sr, and U show seasonal compositional cycles, and tentative calibrations against SST have been derived. Using independent ICP-MS solution estimates of the coral composition to correct for standardisation uncertainties, the following calibrations have been derived: B/Ca (μmol/mol) = 1000 (±20) − 20.6 (±0.8) × SST Mg/Ca (mmol/mol) = 0.0 (±0.3) + 0.16 (±0.01) × SST Sr/Ca (mmol/mol) = 10.8 (±0.1) − 0.070 (±0.004) × SST U/Ca (μmol/mol) = 2.24 (±0.07) − 0.046 (±0.003) × SSTl These calibrations agree with literature within experimental errors, except for Mg which displays a 35% greater temperature dependence than reported previously. None of the elements in the coral appear to be sensitive to decreases in salinity associated with heavy rainfall in the summer of 1991/1992.

Pb−Sr−Nd−O isotopic constraints on the origin of rhyolites from the Taupo Volcanic Zone of New Zealand: evidence for assimilation followed by fractionation from basalt

A comprehensive Sr−Nd−Pb−O isotopic study is reported for rhyolites from the Maroa Volcanic Centre in the Taupo Volcanic Zone (TVZ) of New Zealand. The Sr−Nd isotopic compositions of the rhyolites (87Sr/86Sr=0.705236 to 0.705660 and ɛNd = 2.0 to 0.2) are intermediate between those of primitive basalts (87Sr/86Sr=0.70387 and ɛNd = 5.3) and the Torlesse basement (87Sr/86Sr=0.709 and ɛNd = -4.5). The relatively low ‘mantle-like’ oxygen isotopic compositions of δ18 O = 7 ± 0.5 are consistent with the Nd-Sr isotopic constraints in that they can be accounted for by ∼15% to 25% crustal contamination of a basaltic parent by relatively δ18 O-rich Torlesse metasediment. High precision Pb isotopic analyses of plagioclase separates from the Maroa rhyolites show that they have essentially the same compositions as the Torlesse metasedimentary terrane which is itself distinctive from the Western or Waipapa metasediments. Due to the high concentration of Pb in the Torlesse metasediments (>20 ppm) compared to the basalts (<2 ppm), the Pb isotopic composition of the volcanics may be controlled by relatively small amounts (>10%) of crustal contamination. All these results are shown to be consistent with derivation of the rhyolites by ∼15% to 25% contamination of relatively primitive basaltic magmas with Torlesse metasedimentary crust, followed by extensive, essentially closed system fractionation of the ‘basalt’ to a magma of rhyolite composition. It is argued that the processes of assimilation and fractionation are separated in both space and time. The voluminous high silica rhyolites, which make up >97% of the exposed volcanism in the continental margin back-are basin environment of the TVZ, therefore appear to be a product of predominantly new additions to the crust with assimilation-recycling of pre-existing crust being of secondary importance.

U-series and radiocarbon analyses of human and faunal remains from Wajak, Indonesia

Laser ablation U-series dating results on human and faunal bone fragments from Wajak, Indonesia, indicate a minimum age of between 37.4 and 28.5 ka (thousands of years ago) for the whole assemblage. These are significantly older than previously published radiocarbon estimates on bone carbonate, which suggested a Holocene age for a human bone fragment and a late Pleistocene age for a faunal bone. The analysis of the organic components in the faunal material show severe degradation and a positive δ(13)C ratio indicate a high degree of secondary carbonatisation. This may explain why the thermal release method used for the original age assessments yielded such young ages. While the older U-series ages are not in contradiction with the morphology of the Wajak human fossils or Javanese biostratigraphy, they will require a reassessment of the evolutionary relationships of modern human remains in Southeast Asia and Oceania. It can be expected that systematic direct dating of human fossils from this area will lead to further revisions of our understanding of modern human evolution.

An early modern human presence in Sumatra 73,000–63,000 years ago

Genetic evidence for anatomically modern humans (AMH) out of Africa before 75 thousand years ago (ka) and in island southeast Asia (ISEA) before 60 ka (93–61 ka) predates accepted archaeological records of occupation in the region. Claims that AMH arrived in ISEA before 60 ka (ref. 4) have been supported only by equivocal or non-skeletal evidence. AMH evidence from this period is rare and lacks robust chronologies owing to a lack of direct dating applications, poor preservation and/or excavation strategies and questionable taxonomic identifications. Lida Ajer is a Sumatran Pleistocene cave with a rich rainforest fauna associated with fossil human teeth. The importance of the site is unclear owing to unsupported taxonomic identification of these fossils and uncertainties regarding the age of the deposit, therefore it is rarely considered in models of human dispersal. Here we reinvestigate Lida Ajer to identify the teeth confidently and establish a robust chronology using an integrated dating approach. Using enamel–dentine junction morphology, enamel thickness and comparative morphology, we show that the teeth are unequivocally AMH. Luminescence and uranium-series techniques applied to bone-bearing sediments and speleothems, and coupled uranium-series and electron spin resonance dating of mammalian teeth, place modern humans in Sumatra between 73 and 63 ka. This age is consistent with biostratigraphic estimations, palaeoclimate and sea-level reconstructions, and genetic evidence for a pre-60 ka arrival of AMH into ISEA. Lida Ajer represents, to our knowledge, the earliest evidence of rainforest occupation by AMH, and underscores the importance of reassessing the timing and environmental context of the dispersal of modern humans out of Africa.

Confirmation of a late middle Pleistocene age for the Omo Kibish 1 cranium by direct uranium-series dating

While it is generally accepted that modern humans evolved in Africa, the specific physical evidence for that origin remains disputed. The modern-looking Omo 1 skeleton, discovered in the Kibish region of Ethiopia in 1967, was controversially dated at ~130 ka (thousands of years ago) by U-series dating on associated Mollusca, and it was not until 2005 that Ar-Ar dating on associated feldspar crystals in pumice clasts provided evidence for an even older age of ~195 ka. However, questions continue to be raised about the age and stratigraphic position of this crucial fossil specimen. Here we present direct U-series determinations on the Omo 1 cranium. In spite of significant methodological complications, which are discussed in detail, the results indicate that the human remains do not belong to a later intrusive burial and are the earliest representative of anatomically modern humans. Given the more archaic morphology shown by the apparently contemporaneous Omo 2 calvaria, we suggest that direct U-series dating is applied to this fossil as well, to confirm its age in relation to Omo 1.

The earliest modern humans outside Africa

Earliest modern humans out of Africa Recent paleoanthropological studies have suggested that modern humans migrated from Africa as early as the beginning of the Late Pleistocene, 120,000 years ago. Hershkovitz et al. now suggest that early modern humans were already present outside of Africa more than 55,000 years earlier (see the Perspective by Stringer and Galway-Witham). During excavations of sediments at Mount Carmel, Israel, they found a fossil of a mouth part, a left hemimaxilla, with almost complete dentition. The sediments contain a series of well-defined hearths and a rich stone-based industry, as well as abundant animal remains. Analysis of the human remains, and dating of the site and the fossil itself, indicate a likely age of at least 177,000 years for the fossil—making it the oldest member of the Homo sapiens clade found outside Africa. Science, this issue p. 456; see also p. 389 Fossilized mouthparts indicate the presence of Homo sapiens in the Levant 160,000 years ago. To date, the earliest modern human fossils found outside of Africa are dated to around 90,000 to 120,000 years ago at the Levantine sites of Skhul and Qafzeh. A maxilla and associated dentition recently discovered at Misliya Cave, Israel, was dated to 177,000 to 194,000 years ago, suggesting that members of the Homo sapiens clade left Africa earlier than previously thought. This finding changes our view on modern human dispersal and is consistent with recent genetic studies, which have posited the possibility of an earlier dispersal of Homo sapiens around 220,000 years ago. The Misliya maxilla is associated with full-fledged Levallois technology in the Levant, suggesting that the emergence of this technology is linked to the appearance of Homo sapiens in the region, as has been documented in Africa.

Homo sapiens in Arabia by 85,000 years ago

Understanding the timing and character of the expansion of Homo sapiens out of Africa is critical for inferring the colonization and admixture processes that underpin global population history. It has been argued that dispersal out of Africa had an early phase, particularly ~130–90 thousand years ago (ka), that reached only the East Mediterranean Levant, and a later phase, ~60–50 ka, that extended across the diverse environments of Eurasia to Sahul. However, recent findings from East Asia and Sahul challenge this model. Here we show that H. sapiens was in the Arabian Peninsula before 85 ka. We describe the Al Wusta-1 (AW-1) intermediate phalanx from the site of Al Wusta in the Nefud desert, Saudi Arabia. AW-1 is the oldest directly dated fossil of our species outside Africa and the Levant. The palaeoenvironmental context of Al Wusta demonstrates that H. sapiens using Middle Palaeolithic stone tools dispersed into Arabia during a phase of increased precipitation driven by orbital forcing, in association with a primarily African fauna. A Bayesian model incorporating independent chronometric age estimates indicates a chronology for Al Wusta of ~95–86 ka, which we correlate with a humid episode in the later part of Marine Isotope Stage 5 known from various regional records. Al Wusta shows that early dispersals were more spatially and temporally extensive than previously thought. Early H. sapiens dispersals out of Africa were not limited to winter rainfall-fed Levantine Mediterranean woodlands immediately adjacent to Africa, but extended deep into the semi-arid grasslands of Arabia, facilitated by periods of enhanced monsoonal rainfall.A directly dated Homo sapiens phalanx from the Nefud desert reveals human presence in the Arabian Peninsula before 85,000 years ago. This represents the earliest date for H. sapiens outside Africa and the Levant.

Least Destructive Rapid Scanning of Human Teeth to Test Their Suitability for U-Series Analysis

Excavations in the Grotte de la Chevre have taken place since the 19th century and yielded more than 100 human specimens together with numerous artifacts from the Middle Paleolithic, Upper Paleolithic, and more recent times. Unfortunately, due to considerably different excavation standards in earlier excavations, none of the specimens can be securely provenienced. Some of the remains may represent oldest humans fossils found in historic Brittany. This can only be confirmed through direct dating. On faunal materials, U-series dating is usually carried out a series of analyses along a cross-section profile, which necessitates the cutting of the specimen. Here, we present a rapid scanning method, which allows the assessment of whether a sample is actually suited for U-series dating with minimal sample damage. Laser ablation ICP-MS was used for the analysis of U-series isotopes close to the surface of the roots of two teeth from the Grotte de la Chevre. The laser analysis created pits with a diameter of about 200µm and a depth of about 100µm. This allowed the assessment of the 230 Th concentrations close to the surface of the dentine where the oldest apparent U-series ages are expected. In the first sample, all isotopic con centrations were too low for the calculation of meaningful U-series results, while the second sample yielded very low 230 Th/ 238 U activity ratios, indicating a recent age of perhaps a few thousand years. Consequently, both teeth did not require any further destruction. Rapid scanning can be applied to a large number of samples to identify those which will most likely yield reasonable age estimations, leading to informed decisions about geochronological sampling strategies, including radiocarbon. We envisage that laser ablation spot analyses also could be used to obtain U-series depth profiles, which are required for open system dating, as well as depth profiles for other isotopes (e.g., Sr, Pb) to gain insights into prehistoric human migrations.