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As a result of the Viking missions of the early 1970s, the presence of a strong oxidant in martian soil was suggested. Here we present a hypothesis, testable by near-term missions, that iron(VI) is a likely contributor to the martian oxidative pool. In this context, ferrate(VI) salts, with [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] anion, were studied for their spectral and oxidative properties. Ferrate(VI) has distinctive spectroscopic features that make it available for detection by remote sensing reflectance spectra and contact measurements via Mossbauer spectroscopy, and the relevant miniaturized instrumentation has been developed or is under way, while for the returned samples XANES spectroscopy is shown to be a method of choice. Ferrate(VI) is capable of splitting water to yield molecular oxygen, and oxidizing organic carbon into [CO.sub.2]. These activities were strongly abated after treatment at elevated temperatures, similar to observations with martian soil samples in the Viking mission. [C] 2000 Academic Press

The presence of 244Pu (t1/2=81 Ma) in the early solar system is long established [Nature 187 (1960) 36; Science 172 (1971) 837]. 244Pu is also one of a number of isotopes which may be detectable as live radioactivity on earth, originating from the Interstellar Medium (ISM). There has been a recent attempt to measure a ISM isotope signature of 244Pu [ApJ 558 (2001) L133]. This rises the question of the presence of an anthropogenic contribution in the environment. In order to better assess the 244Pu fall-out on earth, we have started a program at VERA to measure 244Pu in surface sediments of Lake Michigan, routinely sampled for 239,240Pu measurements. Considerable amount of information on other isotopes exist for Lake Michigan. We have reproduced the expected 241Pu/239Pu and 240Pu/239Pu ratios for the global fallout. The measured 244Pu/239Pu was considerably higher than expected and was therefore most likely the result of contamination. Measurement of samples specifically prepared for the measurement of 244Pu will be tried in the future. [Copyright &y& Elsevier]

Adsorption of uranyl at the surface of calcite was investigated by using batch sorption experiments and synchrotron X-ray standing wave (XSW) measurements. Aqueous solutions containing 236U(VI) (4.5 x 10(-7) to 1.0 x 10(-4) M) and EDTA (5.0 x 10(-7) to 1.1 x 10(-4) M) were reacted for 90 s to 60 min with freshly cleaved calcite (104) surfaces and calcite powders. Surface exchange coefficients, sorption kinetics, and influence of powder surface area/solution volume (SA/V) ratio were investigated by alpha-counting of 236U. Powder sorption results at SA/V = 870 cm2/mL fit a Freundlich isotherm [log [U]surface (in monolayers) = log K + n log [U]aq (in moles/L)], where K = 1.9+/-0.5 and n = 0.9+/-0.1, consistent with uptake of U(VI) by a specific surface reaction where the availability of sorption sites is nonlimiting in the U concentration range measured. Measured U(VI) coverages along this isotherm, based on the calcite (104) surface Ca site density, ranged from 0.04% to 5.4% of a monolayer. Steady state surface coverages were obtained within 90 s. Sorption of U(VI) on calcite (104) single-crystal cleavage surfaces using identical solutions yielded higher coverages, because of increased step density induced by dissolution at the relatively low SA/V ratio (approximately 1) of these measurements. The crystallographic location of the sorbed U(VI) was examined with the synchrotron XSW technique. Measurements were performed at the Advanced Photon Source on fresh calcite (104) cleavage surfaces reacted for 90 s with U(VI) solutions. Coherent fractions for sorbed U ranged from 0.14 to 0.62, and the mean value of the U coherent position was 0.84+/-0.02. This position was independent of dissolved U(VI) concentration and corresponds to a distance between the U atom and the calcite (104) plane of 2.55+/-0.06 A. These results are consistent with U(VI) adsorption atthe calcite surface as an inner-sphere uranyl-carbonate surface complex bonded with the outer oxygen atom(s) of a single surface carbonate group. Steric considerations allow this observed U(VI) surface complex to occur both at step sites ((441)_ and (481)_) and on terrace areas adjacent to Ca vacancies.

Hafnium and zirconium are not retained on the strongly acidic cation-exchange resin Dowex 50 from a mixture consisting of methanol and 12M nitric acid (19:1) which is 0.1M in trioctylphosphine oxide. On the other hand most other elements investigated are strongly adsorbed on the resin from this medium so that they are readily separated from hafnium and zirconium. These elements include titanium, rare earths, alkali metals, alkaline earth metals, iron, cobalt, manganese and zinc. This separation technique has been found to be suitable for the separation of tracer and milligram amounts of hafnium and zirconium from accompanying metal ions. If in place of methanol other organic solvents such as acetone, tetrahydrofuran and methyl glycol are used the selectivity of the separation of zirconium and hafnium from the other elements is decreased. The same effect is observed when hydrochloric acid is used in the mixtures instead of nitric acid.