Effect of Er-Rich Precipitates on Microstructure and Electrochemical Behavior of the Al–5Zn–0.03In Alloy

The effect of Er-rich precipitates on microstructure and electrochemical behavior of the Al–Zn–In anode alloy is investigated. The results showed that with the increase in Er content, the microstructure was refined, the amount of interdendritic precipitates gradually increased, and the morphology changed from discontinuous to continuous network gradually. With the addition of Er element, the self-corrosion potential of the Al–5Zn–0.03In–xEr alloy moved positively, the self-corrosion current density decreased, and the corrosion resistance increased. When the Er content was less than 1 wt.%, the addition of Er improved the dissolution state of the Al–5Zn–0.03In–xEr alloy, and increased the current efficiency of the Al–5Zn–0.03In–xEr alloy. When the Er content was more than 1 wt.%, the current efficiency was reduced. The major precipitate of the alloy was Al3Er. According to the element composition of Al3Er in the Al–Zn–In–Er alloy, the simulated-segregated-phase alloy was melted to explain the effect of Al3Er segregation on the electrochemical behavior of alloys, and the polarization curve and AC impedance spectrum of the simulated-segregated-phase alloy and the Al–Zn–In alloy were measured. The results showed that Al3Er was an anodic segregation phase in the Al–Zn–In–Er alloy, and the preferential dissolution of the segregation phase would occur in the alloy, but the Al3Er phase itself was passivated in the dissolution process, which inhibited the further activation of the dissolution reaction of the Al–Zn–In–Er alloy to a certain extent.

Preferential dissolution of uranium-rich zircon can bias the hafnium isotope compositions of granites

Hafnium (Hf) isotopes in zircon are important tracers of granite petrogenesis and continental crust evolution. However, zircon in granites generally shows large Hf isotope variations, and the reasons for this are debated. We applied U-Pb geochronology, trace-element, and Hf isotope analyses of zircon from the Miocene Himalayan granites to address this issue. Autocrystic zircon had εHf values (at 20 Ma) of –12.0 to –4.3 (median = –9). Inherited zircon yielded εHf values (at 20 Ma) of –34.8 to +0.3 (median = –13); the majority of εHf values were lower than those of autocrystic zircon. The εHf values of inherited zircon with high U concentrations resembled those of autocrystic zircon. Geochemical data indicates that the granites were generated during relatively low-temperature (<800 °C) partial melting of metasedimentary rocks, which, coupled with kinetic hindrance, may have led to the preferential dissolution of high-U zircon that could dissolve more efficiently into anatectic melt due to higher amounts of radiation damage. Consequently, Hf values of autocrystic zircon can be biased toward the values of U-rich zircon in the source. By contrast, literature data indicate that granites generated at high temperatures (<820–850 °C) generally contain autocrystic and inherited zircons with comparable Hf isotope values. During higher-temperature melting, indiscriminate dissolution of source zircon until saturation is reached will result in near-complete inheritance of Hf isotope ratios from the source. Our results impose an extra layer of complexity to interpretation of the zircon Hf isotope archive that is not currently considered.

Supplemental Material: Preferential dissolution of uranium-rich zircon can bias the hafnium isotope compositions of granites

Methodology, supplemental Figures S1–S3), and Tables S1–S7.

Supplemental Material: Preferential dissolution of uranium-rich zircon can bias the hafnium isotope compositions of granites

Methodology, supplemental Figures S1–S3), and Tables S1–S7.

Influence of accessory phases and surrogate type on accelerated leaching of zirconolite wasteforms

A fraction of the UK Pu inventory may be immobilised in a zirconolite ceramic matrix prior to disposal. Two zirconolite compositions, targeting CaZr0.80Ce0.20Ti2O7 and CaZr0.80U0.20Ti2O7, were fabricated by hot isostatic pressing, alongside a reformulated composition, nominally Ca0.80Zr0.90Ce0.30Ti1.60Al0.40O7, with an excess of Ti and Zr added to preclude the formation of an accessory perovskite phase. Materials were subjected to accelerated leaching in a variety of acidic and alkaline media at 90 °C, over a cumulative period of 14 d. The greatest Ce release was measured from CaZr0.80Ce0.20Ti2.00O7 exposed to 1 M H2SO4, for which 14.7 ± 0.2% of the original Ce inventory was released from the wasteform into solution. The extent of Ce leaching into the solution was correlated with the quantity of perovskite present in the wasteform, and associated with the incorporation and preferential dissolution of Ce3+. CaZr0.80U0.20Ti2.00O7 exhibited improved leach resistance relative to CaZr0.80Ce0.20Ti2.00O7, attributed to the decreased proportion of accessory perovskite, with 7.1 ± 0.1% U released to in 8 M HNO3 after 7 d. The Ca0.80Zr0.90Ce0.30Ti1.60Al0.40O7 composition, with no accessory perovskite phase, presented significantly improved leaching characteristics, with < 0.4%Ce released in both 8 M HNO3 and 1 M H2SO4. These data demonstrate the need for careful compositional design for zirconolite wasteforms with regard to accessory phase formation and surrogate choice.

Formation mechanisms of hollow manganese hexacyanoferrate particles and construction of a multiple-shell structure

The core's preferential dissolution transforms the cubic-core/monoclinic-shell manganese hexacyanoferrate particles into the hollow structure. Applying an additional growth technique, multi-shell hollow particles have also been constructed.

Aragonite bias exhibits systematic spatial variation in the Late Cretaceous Western Interior Seaway, North America

Preferential dissolution of the biogenic carbonate polymorph aragonite promotes preservational bias in shelly marine faunas. While field studies have documented the impact of preferential aragonite dissolution on fossil molluscan diversity, its impact on regional and global biodiversity metrics is debated. Epicontinental seas are especially prone to conditions that both promote and inhibit preferential dissolution, which may result in spatially extensive zones with variable preservation. Here we present a multifaceted evaluation of aragonite dissolution within the Late Cretaceous Western Interior Seaway of North America. Occurrence data of mollusks from two time intervals (Cenomanian/Turonian boundary, early Campanian) are plotted on new high-resolution paleogeographies to assess aragonite preservation within the seaway. Fossil occurrences, diversity estimates, and sampling probabilities for calcitic and aragonitic fauna were compared in zones defined by depth and distance from the seaway margins. Apparent range sizes, which could be influenced by differential preservation potential of aragonite between separate localities, were also compared. Our results are consistent with exacerbated aragonite dissolution within specific depth zones for both time slices, with aragonitic bivalves additionally showing a statistically significant decrease in range size compared with calcitic fauna within carbonate-dominated Cenomanian–Turonian strata. However, we are unable to conclusively show that aragonite dissolution impacted diversity estimates. Therefore, while aragonite dissolution is likely to have affected the preservation of fauna in specific localities, time averaging and instantaneous preservation events preserve regional biodiversity. Our results suggest that the spatial expression of taphonomic biases should be an important consideration for paleontologists working on paleobiogeographic problems.

‘Cenoceras islands’ in the Blue Lias Formation (Lower Jurassic) of West Somerset, UK: nautilid dominance and influence on benthic faunas

Substantial numbers of the nautilid Cenoceras occur in a stratigraphically limited horizon within the upper part of the Lower Jurassic (Sinemurian Stage) Blue Lias Formation at Watchet on the West Somerset Coast (United Kingdom). Individual nautilid conchs are associated with clusters of encrusting organisms (sclerobionts) forming ‘islands’ that may have been raised slightly above the surrounding substrate. Despite the relatively large numbers of nautilid conchs involved, detailed investigation of their preservation suggests that their accumulation reflects a reduction in sedimentation rates rather than an influx of empty conches or moribund animals. Throughout those horizons in which nautilids are present in relative abundance, the remains of ammonites are subordinate or rare. The reason for this unclear, and preferential dissolution of ammonite conchs during their burial does seem to provide a satisfactory solution to the problem.

Were bivalves ecologically dominant over brachiopods in the late Paleozoic? A test using exceptionally preserved fossil assemblages

Interpreting changes in ecosystem structure from the fossil record can be challenging. In a prominent example, the traditional view that brachiopods were ecologically dominant over bivalves in the Paleozoic has been disputed on both taphonomic and metabolic grounds. Aragonitic bivalves may be underrepresented in many fossil assemblages due to preferential dissolution. Abundance counts may further understate the ecological importance of bivalves, which tend to have more biomass and higher metabolic rates than brachiopods. We evaluate the relative importance of the two clades in exceptionally preserved, bulk-sampled fossil assemblages from the Pennsylvanian Breathitt Formation of Kentucky, where aragonitic bivalves are preserved as shells, not molds. At the regional scale, brachiopods were twice as abundant as bivalves and were collectively equivalent in biomass and energy use. Analyses of samples from the Paleobiology Database that contain abundance counts are consistent with these results and show no clear trend in the relative ecological importance of bivalves during the middle and late Paleozoic. Bivalves were probably more important in Paleozoic ecosystems than is apparent in many fossil assemblages, but they were not clearly dominant over brachiopods until after the Permian–Triassic extinction, which caused the shelly benthos to shift from bivalve and brachiopod dominated to merely bivalve dominated.