Laser ablation coupled with ICP-MS applied to U–Pb zircon geochronology: A review of recent advances

Improvements in the technology of laser ablation and ICP-MS instruments make LA-MC-ICPMS a rapid, precise and accurate method for U–Pb zircon geochronology. In this review we describe the main stages of the evolution of this in situ approach from the early 1990s to the present time. Some key points have been progressively improved. The crater size has been reduced to achieve real in situ measurements. The laser wavelength has been reduced as well as the duration of each pulse in order to lower inter-element fractionation. The blank from the gas has to be lowered as far as possible. Double focusing instruments and magnetic field sectors allow flat-topped peaks required for precise isotope ratio measurement to be obtained. The use of a multi-ion counting system significantly improves the sensitivity of the method and the static mode of integration favours the precision of measurement of the transient signal originating from a noisy laser ablated particle beam.Combining the use of a 213 nm UV laser and a MC-ICPMS equipped with a multi-ion counting system operating in static mode, the common precisions achieved for the key ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U are better than 1% and 3% (2σ) respectively, including error propagation associated with standard normalization. Until now, the use of a zircon standard has remained necessary to ensure the accuracy of the calculated age. A strategy for common-Pb correction is proposed according to the age of the zircon and according to the Th/U ratio of the grains. After recording sixteen to twenty spot analyses the precision usually achieved on the age is about 1% and even significantly better for Proterozoic samples.In order to show the performance achieved by modern LA-MC-ICPMS geochronology, we tested four zircon samples covering a wide age range from 290 to 2440 Ma. These new age determinations can be compared in term of precision and accuracy since they have already been dated by reference methods (ID-TIMS and SHRIMP). Further developments in the technology of ion counters equipping modern MC-ICPMS and in laser systems will certainly be applied to a large field of geochronology studies in the near future as an alternative to SIMS for in situ age determination.     

Octahedral-site Fe2+ quadrupole splitting distributions from Mössbauer spectroscopy along the (OH, F)-annite join

We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe²⁺ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QS_HH2.55 mm/s for Fe²⁺O₄(OH)₂ octahedra (cis and trans not resolved), QS_HF 2.35 mm/s for Fe²⁺O₄(OH)F octahedra (cis and trans not resolved), QS_cFF2.15 mm/s for cis-Fe²⁺O₄F₂ octahedra, and QS_tFF 1.5 mm/s for trans-Fe²⁺O₄F₂ octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe²⁺O₅(OH) and Fe²⁺O₅F octahedra probably also contribute to the overall Fe²⁺ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe³⁺ contributions are seen and interpreted as being due mainly to Fe³⁺O₅OH and Fe³⁺O₅F octahedra, respectively. Tetrahedral Fe³⁺ is seen only in the OH-annite end-member and the total Fe³⁺ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China     

Calorimetric study of the coesite-stishovite transformation and calculation of the phase boundary

High temperature drop-solution calorimetry in molten 2 PbO · B₂O₃ at 1044 K for coesite and stishovite polymorphs of silica was carried out to determine the enthalpy of the coesite-stishovite transition. These experiments were performed on high-purity, single-phase samples of coesite and stishovite. Our new value for the enthalpy of the coesitestishovite transition (ΔH ₂₉₈ ⁰ ) is 29.85 ± 0.78 kJ/mol, which is about 35% lower than previously reported by Akaogi and Navrotsky (1984) and Holm et al. (1967), but which compares well with new measurements by Akaogi et al. (1994b). Using these new data, we have calculated the equilibrium phase boundary between coesite and stishovite and obtained a slope, dP/dT=0.0031 (2) GPa/K. This calculated slope is in good agreement with that determined [0.0026 (2) GPa/K] from the in-situ X-ray diffraction study of Zhang et al. (1996).     

The ‘ultimate objective’ of the framework convention on climate change requires a new approach in climate change research

In the Framework Convention on Climate Change an ultimate objective is formulated that calls for stabilization of the concentrations of greenhouse gases in the atmosphere at a level that would allow ecosystems to adapt naturally, safeguard food supply and enable sustainable development to proceed in a sustainable manner. This paper addresses the possible contribution of science to translate this rather vague and ambiguous objective into more practicable terms. We propose a regionalized, risk-based six-step approach that couples an analysis of ecosystem vulnerability to the results of simulations of climate change. An ultimate objective level could be determined in terms of stabilized concentrations of greenhouse gases in the atmosphere. The level and timing of this stabilization would be determined by a political appreciation of associated risks for managed and unmanaged ecosystems. These risks would be assessed by region in an internationally coordinated scientific effort, followed by a global synthesis.     

New paleomagnetic results from the Aegean extensional province

Various Oligocene formations from NE Greece (ignimbrites from the Medousa area, rhyolites from Zagradenia, granodiorites from Elatia) show discordant paleomagnetic signatures, in each case indicating small cw (clockwise) rotation and also inclination flattening. Marls from Pithion were partly remagnetized in a present-day field. Samples that contain ancient magnetization components also indicate small cw rotation and inclination flattening. However, the magnetization of andesites from Peplos reflects a considerably larger rotation, likely owing to local tectonics. In the context of previous work in the area, these results are used to propose a subdivision of NE Greece into four structural zones of distinctive rotational behaviour (from east to west): sites in zone 1, east of the Kavala-Xanthi-Komotini fault (KXK), show various cw and ccw (counterclockwise) rotation angles owing to complex kinematics resulting from the interaction of the KXK and the north-Anatolian fault zone. However, zone 2, between the KXK and the Strymon valley, is structurally homogeneous ( 10° cw rotation). The paleomagnetic signature of the Vertiskos massif (zone 3) implies a larger (> 30°) cw rotation, whereas sites in the Vardar basin (zone 4) contain a paleomagnetic signature similar to that of zone 2. This suggests a motion of the Vertiscos massif, a meta-ophiolitic nappe, relative to underlying strata. Indeed, zones 2 and 4 may be parts of the same structural unit which underlies this nappe.     

Interstellar water in meteorites?

D/H ratios of two meteorites (Renazzo CR and Semarkona LL3), which are known to exhibit the largest departures from the terrestrial hydrogen isotopic ratios, have been determined with the CRPG Nancy ion microprobe. Correlations between the D/H ratios and the chemical compositions (H2O, K, Si, C/H) of plausible hydrogen carriers were observed. From these correlations, it is possible to show that, contrary to previous interpretations, phyllosilicates are the carriers of the deuterium-rich hydrogen in Semarkona and Renazzo: 870 x 10(-6) > or = D/H > or = 670 x 10(-6) (+4600 > or = deltaD > or = 3300%) and > or = 320 x 10(-6) (deltaD > or = 1050%), respectively. Hydrogen is also present in the chondrules of these two deuterium-rich meteorites. The large differences in D/H ratios between matrix (up to 700 x 10(-6), deltaD up to +3500%) and chondrules (from 120 x 10(-6) (deltaD = -230%) to 230 x 10(-6) (deltaD = +475%)) show that hydrogen in chondrules cannot originate from the matrix by simple contamination or diffusion processes. The high D/H ratios measured in water-bearing minerals could not have been produced thermally within a dense solar nebula. Chemical reactions (i.e., involving ions or radicals), taking place in interstellar space or in the outer regions of the nebula at 110-140K are presently the only conceivable mechanisms capable of yielding such isotopic enrichments. Water in these meteorites should no longer be considered as a simple product of nebular condensation under equilibrium thermodynamic conditions at T > or = 160K.     

Rejuvenation of Lake Erie

The positive ecological changes that have occurred in Lake Erie since the mid-1970, demonstrate that an extensively degraded aquatic ecosystem can be rejuventated. This rejuvenation should provide encouragement to other who are attempting to save such habitats as the Aral Sea. This paper summarizes the problems of Lake Erie, the meassures instituted to correct the problems and the result of remediation efforts.     

On the use of ‘first spotless day’ as a predictor for sunspot minimum

Defining the first spotless day of a sunspot cycle as the first day without spots relative to sunspot maximum during the decline of the solar cycle, one finds that the timing of that occurrence can be used as a predictor for the occurrence of solar minimum of the following cycle. For cycle 22, the first spotless day occurred in April 1994, based on the International sunspot number index, although other indices (Boulder and American) indicated the first spotless day to have occurred earlier (September 1993). For cycles 9–14, sunspot minimum followed the first spotless day by about 72 months, having a range of 62–82 months; for cycles 15–21, sunspot minimum followed the first spotless day by about 35 months, having a range of 27–40 months. Similarly, the timing of first spotless day relative to sunspot minimum and maximum for the same cycle reveals that it followed minimum (maximum) by about 69 (18) months during cycles 9–14 and by about 90 (44) months during cycles 15–21. Accepting April 1994 as the month of first spotless day occurrence for cycle 22, one finds that it occurred 91 months into the cycle and 57 months following sunspot maximum. Such values indicate that its behavior more closely matches that found for cycles 15–21 rather than for cycles 9–14. Therefore, one infers that sunspot minimum for cycle 23 will occur in about 2–3 years, or about April 1996 to April 1997. Accepting the earlier date of first spotless day occurrence indicates that sunspot minimum for cycle 23 could come several months earlier, perhaps late 1995.The U.S. Government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

The solar surface differential rotation from disk-integrated chromospheric fluxes

Disk-integrated solar chromospheric Caii K-line (3933.68 ) fluxes have been measured almost daily at Sacramento Peak Observatory since 1977. Using observing windows selected to mimic seasonal windows for chromospheric measurements of lower Main-Sequence stars such as those observed by Mount Wilson Observatory's HK Project, we have measured the solar rotation from the modulation of the Caii K-line flux. We track the change of rotation period from the decline of cycle 21 through the maximum of cycle 22. This variation in rotation period is shown to behave as expected from the migration of active regions in latitude according to Maunder's butterfly diagram, including an abrupt change in rotation period at the transition from cycle 21 to cycle 22. These results indicate the successful detection of solar surface differential rotation from disk-integrated observations. We argue that the success of our study compared to previous investigations of the solar surface differential rotation from disk-integrated fluxes lies primarily with the choice of the length of the time-series window. Our selection of 200 days is shorter than in previous studies whose windows are typically on the order of one year. The 200-day window is long enough to permit an accurate determination of the rotation period, yet short enough to avoid complications arising from active region evolution. Thus, measurements of the variation of rotation period in lower Main-Sequence stars, especially those that appear to be correlated with long-term changes in chromospheric activity (i.e., cycles), are probably evidence for stellar surface differential rotation.     

Spectral reflectance change and luminescence of selected salts during 2–10 KeV proton bombardment: Implications for Io

Radiation damage and luminescence, caused by magnetospheric charged particles, have been suggested by several authors as mechanisms for explaining some of the peculiar spectral/albedo features of Io. We have pursued this possibility by measuring the uv-visual spectral reflectance and luminescent efficiency of several proposed Io surface constituents during 2 to 10-keV proton irradiation at room temperature and at low temperature (120 < T < 140°K). The spectral reflectance of NaCl and KCl during proton irradiation exhibits the well-known F-center absorption bands at 4580 and 5560 Å. Na₂SO₄ shows a generalized darkening which increases toward longer wavelengths. NaNO₃ shows a spectral reflectance change indicative of the partial alteration of NaNo₃ to NaNo₂. NaNO₂ shows no change. The luminescent efficiencies of NaCl and KCl are ～10^?4 at 300°K and increase by one-half order of magnitude at ～130°K. The efficiencies of K₂CO₃, Na₂CO₃, Na₂SO₄, and NaNO₃ are 10^?4, 10^?4, 10^?5 and 10^?6, respectively, at 300°K and they all decrease by one-half order of magnitude at ～130°K. These results indicate that magnetospheric proton irradiation of Io could cause spectral features in its observed ultraviolet and visible reflection spectrum if salts such as those studied here are present on its surface. However, because the magnitude of these spectral effects is dependent on competing factors such as surface temperature, incident particle energy flux, solar bleaching effects, and trace element abundance, we are unable at this time to make a quantitative estimate of the strength of these spectral effects on Io. The luminescent efficiencies of pure samples that we have studied in the laboratory suggest that charged-particle induced luminescence from Io's surface might be observable by a spacecraft such as Voyager when viewing Io's dark side.