Preliminary Results from a New 157 nm Laser Ablation ICP-MS Instrument: New Opportunities in the Analysis of Solid Samples

Preliminary results are given from an excimer 157 nm laser ablation multiple-collector inductively coupled plasma-mass spectrometer (LA-MC-ICP-MS), used for the isotopic measurements of solid materials. Elements of geological interest with different volatilities such as Pb and U (e.g. zircon geochronology) and Cu and Zn (as examples of geochemical/biochemical tracers) were analysed. The range of ablation rates of 20-150 nm s^-1 enabled us to ablate the sample down to a depth of 45 μm for a 50 μm diameter pit. The Cu and Zn isotopic measurements gave values that were very stable with, on average, a 0.01 % standard error, comparable with that achieved in liquid mode measurements.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Pb,Hf and Nd isotope compositions of the two Réunion volcanoes (Indian Ocean): A tale of two small-scale mantle “blobs”?

Pb, Hf, Nd and Sr isotopes of basaltic lavas from the two Réunion Island volcanoes are reported in order to examine the origin of the sources feeding these volcanoes and to detect possible changes through time. Samples, chosen to cover the whole lifetime of the two volcanoes (from 2 Ma to present), yield a chemically restricted (compared to OIB lavas) but complex distribution. Réunion plume isotopic characteristics have been defined on the basis of the composition of uncontaminated shield-building lavas from the Piton de la Fournaise volcano. The average ?_Nd, ?_Hf, ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb isotope ratios calculated for this component are + 4.4, + 9.1, 0.70411, 18.97, 15.59 and 39.03, respectively. In Pb–Pb isotope space, each volcano defines a distinct linear trend but slight variations are also detected within the various volcanic sequences. The Piton des Neiges volcano yields a distinct and significantly more scattered isotopic distribution than Piton de la Fournaise for both Pb, Hf and Nd isotope tracers. A principal component analysis of the Pb isotope data from Piton de la Fournaise reveals a major contribution of the C and EM-1 components (with a clear Dupal flavor) as main components for the modern Réunion plume. The same components have been identified for Piton des Neiges but with a stronger participation of a depleted mantle component and a weaker EM-1 contribution. The compositional change of the lavas erupted by the Piton des Neiges and Piton de la Fournaise volcanoes is attributed to the impingement of two small-scale blobs of plume material at the base of the Réunion lithosphere. Compared to other hot-spots worldwide, in particular Hawaii and Kerguelen, magmas beneath Réunion are generated from a considerably more homogeneous, compositionally more primitive plume higher in ²⁰⁶Pb. Although shallow-level contamination processes have been locally detected they did not alter significantly the composition of the plume magmas. This is tentatively attributed to mantle dynamics producing small, high-velocity blobs that ascend rapidly through the lithosphere, and to the lack of a well-developed magma chamber at depth in the lithosphere.     

Analysis of coupled Sr/Ca and Sr/Sr variations in enamel using laser-ablation tandem quadrupole-multicollector ICPMS

We present in this study results obtained with a laser-ablation coupled with both a quadrupole and a multi-collector ICPMS. The simultaneous in situ Sr/Ca and ⁸⁷Sr/⁸⁶Sr measurements along growth profiles in enamel allows the concomitant diet and migration patterns in mammals to be reconstructed. Aliquots of the powdered international standard NIST “SRM1400 Bone Ash” with certified Sr and Ca contents, was sintered at high pressure and temperature and was adopted as the reference material for external reproducibility and calibration of the results. A total of 145 coupled elemental and isotopic measurements of herbivores enamel from the Kruger National Park, South Africa, gives intra-tooth Sr/Ca and ⁸⁷Sr/⁸⁶Sr variations that are well larger than external reproducibility. Sr/Ca profiles systematically decrease from the dentine-enamel junction to the outer enamel whereas ⁸⁷Sr/⁸⁶Sr profiles exhibit variable patterns. Using a simple geometric model of hypsodont teeth growth, we demonstrate that a continuous recording of the ⁸⁷Sr/⁸⁶Sr variations can be reconstructed in the tooth length axis. This suggests that the mobility of a mammal can be reconstructed over a period of more than a year with a resolution of a ten of days, by sampling enamel along growth profiles. Our geometric model of hypsodont teeth growth predicts that an optimal distance between two successive profiles is equal to the enamel thickness. However, this model does not apply to the Sr/Ca signal which is likely to be altered during the enamel maturation stage due to differential maturation processes along enamel thickness. Here, the observed constant decreases of the Sr/Ca ratios in the ungulates of Kruger National Park suggests that they did not changed of diet, while some of them were migrating.     

Europium isotopic variations in Allende CAIs and the nature of mass-dependent fractionation in the solar nebula

We measured the ¹⁵³Eu/¹⁵¹Eu ratio by MC-ICP-MS for a terrestrial basalt, two terrestrial soils, and four meteorites (whole rocks and/or chondrules of Bjurböle, Forest City, Murchison, and Allende) and found no isotopic variations. By contrast, two CAI separates from two different pieces of Allende show a ¹⁵³Eu deficit of up to one per mil. Such a shortage in the heavy isotopes, which had also been identified in Allende CAIs for Sr [Patchett, P.J. 1980b. Sr isotopic fractionation in Allende chondrules: a reflection of solar nebular processes. Earth Planet. Sci. Lett.50, 181-188], cannot reflect evaporative fractionation. The lack of Sm isotope fractionation in the same samples further makes fractionation by purely kinetic processes an unlikely cause of the anomalous Eu isotopic composition. An alternative interpretation is condensation from a vapor already significantly depleted in Eu, but in such a scenario the fate of the missing material is unclear. We therefore prefer yet another interpretation, based on the low ionization potential of Eu (and Sr), in which electromagnetic separation of the ionized gas preferentially depletes the nebular gas in heavy isotopes.     

Precise and accurate isotopic measurements using multiple-collector ICPMS

New techniques of isotopic measurements by a new generation of mass spectrometers equipped with an inductively-coupled-plasma source, a magnetic mass filter, and multiple collection (MC-ICPMS) are quickly developing. These techniques are valuable because of (1) the ability of ICP sources to ionize virtually every element in the periodic table, and (2) the large sample throughout. However, because of the complex trajectories of multiple ion beams produced in the plasma source whether from the same or different elements, the acquisition of precise and accurate isotopic data with this type of instrument still requires a good understanding of instrumental fractionation processes, both mass-dependent and mass-independent. Although physical processes responsible for the instrumental mass bias are still to be understood more fully, we here present a theoretical framework that allows for most of the analytical limitations to high precision and accuracy to be overcome. After a presentation of unifying phenomenological theory for mass-dependent fractionation in mass spectrometers, we show how this theory accounts for the techniques of standard bracketing and of isotopic normalization by a ratio of either the same or a different element, such as the use of Tl to correct mass bias on Pb. Accuracy is discussed with reference to the concept of cup efficiencies. Although these can be simply calibrated by analyzing standards, we derive a straightforward, very general method to calculate accurate isotopic ratios from dynamic measurements. In this study, we successfully applied the dynamic method to Nd and Pb as examples. We confirm that the assumption of identical mass bias for neighboring elements (notably Pb and Tl, and Yb and Lu) is both unnecessary and incorrect. We further discuss the dangers of straightforward standard-sample bracketing when chemical purification of the element to be analyzed is imperfect. Pooling runs to improve precision is acceptable provided the pooled measurements are shown to be part of a single population. Second-order corrections seem to be able to improve the precision on ¹⁴³Nd/¹⁴⁴Nd measurements. Finally, after discussing a number of potential pitfalls, such as the consequence of peak shape, correlations introduced by counting statistics, and the effect of memory on double-spike methods, we describe an optimal strategy for high-precision and accurate measurements by MC-ICPMS, which involves the repetitive calibration of cup efficiencies and rigorous assessment of mass bias combined with standard-sample bracketing. We suggest that, when these simple guidelines are followed, MC-ICPMS is capable of producing isotopic data precise and accurate to better than 15 ppm.     

Enhanced Atlantic Meridional Overturning Circulation supports the Last Glacial Inception

The Atlantic Meridional Overturning Circulation (AMOC) is a key feature of the climate system. However, its role during climate change is still poorly constrained particularly during an Interglacial to Glacial climate transition and the associated global cooling. We present here the first reconstruction of the evolution of the vertical structure of the rate of the AMOC from the Last Interglaciation to the subsequent glaciation (128,000–60,000 years ago) based on sedimentary (²³¹Pa/²³⁰Th) records. We show a deep AMOC during the interglacial warmth Marine Isotope Stage (MIS) 5.5 and a shallower glacial one during glacial MIS 4. The change between these two patterns occurred mostly during the glacial inception, i.e. the transition from MIS 5.5 to MIS 5.4. Our data show that AMOC was enhanced during this latter transition as a consequence of a large increase of the overturning rate of the Intermediate Waters, above 2500 m. We suggest that this AMOC pattern required a reinforced Gulf Stream-North Atlantic Current system that ultimately supported ice-sheet growth by providing heat and moisture to the Northern high latitudes. From MIS 5.4 to MIS 5.1, the AMOC was broadly continuous below 2000 m and supported periods of ice-sheet growth. As a result, a glacial AMOC is triggered at the beginning of MIS 4 due to the extension of ice-sheet and the subsequent reorganization of deep-water formation. This study highlights the role of intermediate waters as a major player during climate change.     

Ice sheet extent and early deglacial history of the southwestern sector of the Greenland Ice Sheet

The offshore and coastal geomorphology of southwest Greenland records evidence for the advance and decay of the Greenland Ice Sheet during the Last Glacial Maximum. Regional ice flow patterns in the vicinity of Sisimiut show an enlarged ice sheet that extended southwestwards on to the shelf, with an ice stream centred over Holsteinsborg dyb. High level periglacial terrain composed of blockfield and tors is dated to between 101 and 142 ka using ²⁶Al and ¹⁰Be cosmogenic exposure ages. These limit the maximum surface elevation of the Last Glacial Maximum ice sheet in this part of southwest Greenland to ca 750–810 m asl, and demonstrate that terrain above this level has been ice free since MIS 6. Last Glacial Maximum ice thickness on the coast of ca 700 m implies that the ice sheet reached the mid to outer continental shelf edge to form the Outer Hellefisk moraines. Exposure dates record ice surface thinning from 21.0 to 9.8 ka, with downwasting rates varying from 0.06 to 0.12 m yr⁻¹. This reflects strong surface ablation associated with increased air temperatures running up to the Bølling Interstadial (GIS1e) at ca 14 ka, and later marine calving under high sea levels. The relatively late retreat of the Itilleq ice stream inland of the present coastline is similar to the pattern observed at Jakobshavn Isbræ, located 250 km north in Disko Bugt, which also retreated from the continental shelf after ca 10 ka. We hypothesise that the ice streams of West Greenland persisted on the inner shelf until the early Holocene because of their considerable ice thickness and greater ice discharge compared with the adjacent ice sheet.