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.     

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.     

Spectropolarimetry of the methane and ammonia bands of Jupiter between 6800 and 8200 Å

Spectropolarimetry of Jupiter at resolutions between 22 and 35 Å reveals a strong increase of linear polarization in the 7250-$\text{A}\text{?}$ CH₄ band. This is very probably due to the decreasing contribution toward the band center of the higher orders of scattering, which have a smaller net polarization than the first few orders. The linear polarization is also enhanced in the band at 7900 $\text{A}\text{?}$ comprising the 7920-$\text{A}\text{?}$ NH₃ and 7600- to 8200-$\text{A}\text{?}$ CH₄ bands. The normalized circular polarization shows a feature at 7250 $\text{A}\text{?}$ with a dispersion shape. This is most probably produced in a double-scattering process involving either a solid or liquid aerosol with an absorption at 7250 $\text{A}\text{?}$. Methane aerosols, the obvious candidates from a spectroscopic point of view, are, however, forbidden if current estimates of the Jovian atmospheric temperature are correct.     

Venus mesosphere and thermosphere temperature structure: II. Day-night variations

A two-dimensional nonlinear hydrodynamic model has been developed for studying the global scale winds, temperature, and compositional structure of the mesosphere and thermosphere of Venus. The model is driven by absorption of solar radiation. Ultraviolet radiation produces both heating and photodissociation. Infrared solar heating and thermal cooling are also included with an accurate NLTE treatment. The most crucial uncertainty in determining the solar drive is the efficiency by which $\text{λ < 1080}\text{A}\text{?}$ solar radiation is converted to heat. This question was analyzed in Part I, where it was concluded that essentially all hot atom and O(¹D) energy may be transferred to vibrational-rotational energy of CO₂ molecules. If this is so, the minimum possible euv heating occurs and is determined by the quenching of the resulting excess rotational energy. The hydrodynamic model is integrated with this minimum heating and neglecting any small-scale vertical eddy mixing. The results are compared with predictions of another model with the same physics except that it assumes that 30% of $\text{λ < 1080}\text{A}\text{?}$ radiation goes into heat and that the heating from longer-wavelength radiation includes the O(¹D) energy. For the low-efficiency model, exospheric temperatures are ?300°K on the dayside and drop to < 180°K at the antisolar point. For the higher-efficiency model, the day-to-night temperature variation is from ?600°K to ?250°K. Both versions of the model predict a wind of several hundred meters per second blowing across the terminator and abruptly weakening to small values on the nightside with the mass flow consequently going into a strong tongue of downward motion on the nightside of the terminator. The presence of this circulation could be tested observationally by seeing if its signature can be found in temperature measurements. Both versions of the model indicate that a self-consistent large-scale circulation would maintain oxygen concentrations with ?5% mixing ratios near the dayside F-1 ionospheric peak but ?40% at the antisolar point at the same pressure level.     

Are the high-latitude torsional oscillations of the sun real?

A numerical test is made to determine if the high-latitude torsional wave is generated from the low-latitude torsional pattern as a result of our reduction procedures. The results indicate that the high-latitude motions are not an artifact of the analysis, but are true solar features. We demonstrate also that the one-wave-per-hemisphere torsional oscillation does not result from the reduction procedure. These results place the observations in conflict with the predictions of - () models of the solar cycle.Now at Institute for Astronomy, University of Hawaii, Honolulu, Hawaii 96822, U.S.A.     

Sensitivity of glaciation to initial snow cover,CO2, snow albedo,and oceanic roughness in the NCAR CCM

We present results from numerical experiments made with a GCM, the NCAR CCM1, that were designed to estimate the annual balance between snow-fall accumulation and ablation for geographically important land regions for a variety of conditions. We also attempt to assess the reliability of these results by investigating model sensitivity to changes in prescribed physical parameters. Experiments were run with an initial imposition of 1 m of (midwinter) snowcover over all northern hemisphere land points. Over Alaska, western Canada, Siberia, and the Tibetan Plateau the model tended to retain this snow cover through the summer and in some cases increase its depth as well. We define these regions as glaciation sensitive and note some correspondence between them and source regions for the Pleistocene ice sheets. An experiment with greatly reduced CO₂ (100 ppm) showed a tendency towards spontaneous glaciation, i.e., the model remained snow-covered throughout the summer over the same geographic regions noted above. With 200 ppm CO₂ (roughly equal to values at the last glacial maximum), snow cover over these regions did not quite survive the summer on a consistent basis. Combining 200 ppm CO₂ and 1 m of initial northern hemisphere snow cover yielded glaciation-sensitive conditions, agreeing remarkably well with locations undergoing glaciation during the Pleistocene. To assess the reliability of these results, we have determined minimal model uncertainty by varying two of the empirical coefficients in the model within physically plausible ranges. In one case surface roughness of all ocean gridpoints was reduced by an order of magnitude, leading to local 10% reductions in precipitation (snowfall), a change hard to distinguish from inherent model variability. In the other case, the fraction of a land grid square assumed to be occupied by snow cover for albedo purposes was varied from one-half to unity. Large changes occurred in the degree of summer melting, and in some cases the sign of the net balance changed as fractional snow cover was changed. We conclude that the model may be able to reveal regions sensitive to glaciation, but that it cannot yield a reliable quantitative computation of the magnitude of the net snow accumulation that can be implicitly or explicitly integrated through time.This paper was presented at the International Conference on Modelling of Global Climate Change and Variability, held in Hamburg 11–15 September 1989 under the auspices of the Meteorological Institute of the University of Hamburg and the Max Planck Institute for Meteorology. Guest Editor for these papers is Dr. L. Dilmenil     

Magmatism in the eastern Aleutian Arc: temporal characteristic of igneous activity on Akutan Island

Lavas from Akutan Island, located in the eastern Aleutian arc at the transition between continental and oceanic crust, show a gradual change in their petrologic and chemical characteristics over the last 4 million years. The oldest lavas exposed on the island, the Hot Springs Bay Volcanics (HSBV), range from magnesian basalt to dacite (45%–62% SiO₂). The most mafic basalts contain salitic clinopyroxene, Cr- and Al-rich spinel, and pargasitic amphibole suggesting that they were derived from relatively hydrous magmas at greater pressures than lavas from the younger Akutan Volcanics (AKV) and the modern volcano (MOD). AKV lavas also range between basalt and dacite (46%–63% SiO₂), but contain no hydrous phenocrysts and seem to have fractionated within a shallow level magma chamber. Lavas from the modern volcano are andesitic (52%–57% SiO₂) and have a mineral assemblage similar to that of AKV lavas of similar composition. With the exception of clinopyroxene and spinel in the most mafic lavas, the compositions of plagioclase (An_92?45), olivine (Fo_88?51), orthopyroxene (En_69?56), and titanomagnetite (15%–21% TiO₂) phenocrysts found in these lavas are within the range observed in lavas from other Aleutian volcanoes. Variations in the major element chemistry of the older lavas can be reproduced by fractional crystallization of the observed mineral assemblages, however closed system crystal fractionation models are inadequate to explain the trace element variations. During the last 4 million years, La/Yb ratios have decreased (6.5–3.3 for HSBV lavas and 2.9–1.9 for MOD lavas) whereas Ba/La ratios appear to have increased slightly (37–43 for HSBV and AKV, and 41–45 of MOD). The lower La/Yb ratios of MOD lavas correspond with lower total abundances of the REE and slightly higher Sr and Pb isotopic ratios. The increased⁸⁷Sr/⁸⁶Sr ratios and Pb isotopic ratios in the MOD lavas, the less enriched LREE, and the higher Ba/La ratios may result from partial melting of an arc source which has experienced previous melting events but has continued to be contaminated by a component from the subducting slab. It may also indicate a change in the degree of partial melting of the underlying mantle, which corresponds to a different percentage of a slab derived component being incorporated into the overlying mantle.