Energetics of radiation damage in natural zircon (ZrSiO4)

Transposed temperature drop calorimetry at 1000 °C was performed on natural zircons (ZrSiO₄) from Sri Lanka that were partially to completely metamict due to α-decay event damage (0.06 to 11.7×10¹⁵ α-decay events/mg). The enthalpy of annealing at room temperature (ΔH_anneal) varies sigmoidally as a function of radiation dose. ΔH_anneal reaches a saturation plateau at radiation doses greater than 5×10¹⁵ α-decay events/mg. The annealing of several samples to a crystalline structure with broadened diffraction peaks does not significantly affect the enthalpy of annealing. The large magnitude of the enthalpy of annealing plateau, ?59±3 kJ/mol, suggests that the damage to the structure is pervasive on the scale of Angstroms, consistent with the loss of mid-range order characteristic of a glass. The energetics are consistent with, but do not require, chemical heterogeneity caused by micro-domains of amorphous SiO₂-rich and ZrO₂-rich regions in the metamict state.     

Variation among fossil chironomid assemblages in surficial sediments of Bodensee-Untersee (SW-Germany): implications for paleolimnological interpretation

In paleolimnology, subfossil head capsules of chironomids play an important role as ecological indicators of lake history. It is important to determine, therefore, whether fossil assemblages are representative of former biocoenoses. There is evidence that headcapsules washed in from other places can make up a significant percentage of the total. As interpretations are usually drawn from the examination of a single core, it is of special interest to know whether a fossil assemblage of a single site properly reflects limnological conditions of the whole lake. This study examined the taxonomic distribution of subfossil chironomids in the surficial sediments of the Bodensee-Untersee, with the aim of assessing the variability in chironomid assemblages. Apparently, most of the head capsules of the profundal fossil assemblages in the Untersee had been washed in from the littoral zone or from the slope. Although the Bodensee-Untersee is a rather large lake, variability is surprisingly low among all samples. Therefore a correct interpretation from a single core may be possible.     

New variable stars from the photographic archive: semi-automated discoveries,attempts at automatic classification and the new field 104 Her

Using 172 plates taken with the 40-cm astrograph of the Sternberg Astronomical Institute(Lomonosov Moscow University) in 1976–1994 and digitized with a resolution of 2400 dpi, we discovered and studied 275 new variable stars. We present the list of our new variables with all necessary information concerning their brightness variations. As in our earlier studies, the new discoveries show a rather large number of high-amplitude Delta Scuti variables, predicting that many stars of this type remain not detected in the whole sky. We also performed automated classification of the newly discovered variable stars based on the Random Forest algorithm. The results of the automated classification were compared to traditional classification and showed that automated classification was possible even with noisy photographic data. However, further improvement of automated techniques is needed, which is especially important when considering the very large numbers of new discoveries expected from all-sky surveys.     

Testing variations within the Tagish Lake meteorite—I: Mineralogy and petrology of pristine samples

Four samples (TL5b, TL11h, TL11i, and TL11v) from the pristine collection of the Tagish Lake meteorite, an ungrouped C2 chondrite, were studied to characterize and understand its alteration history using EPMA, XRD, and TEM. We determined that samples TL11h and TL11i have a relatively smaller proportion of amorphous silicate material than sample TL5b, which experienced low‐temperature hydrous parent‐body alteration conditions to preserve this indigenous material. The data suggest that lithic fragments of TL11i experienced higher degrees of aqueous alteration than the rest of the matrix, based on its low porosity and high abundance of coarse‐ and fine‐grained sheet silicates, suggesting that TL11i was present in an area of the parent body where alteration and brecciation were more extensive. We identified a coronal, “flower”‐like, microstructure consisting of a fine‐grained serpentine core and coarse‐grained saponite‐serpentine radial arrays, suggesting varied fluid chemistry and crystallization time scales. We also observed pentlandite with different morphologies: an exsolved morphology formed under nebular conditions; a nonexsolved pentlandite along grain boundaries; a “bulls‐eye” sulfide morphology and rims around highly altered chondrules that probably formed by multiple precipitation episodes during low‐temperature aqueous alteration (≥100 °C) on the parent body. On the basis of petrologic and mineralogic observations, we conclude that the Tagish Lake parent body initially contained a heterogeneous mixture of anhydrous precursor minerals of nebular and presolar origin. These materials were subjected to secondary, nonpervasive parent‐body alteration, and the samples studied herein represent different stages of that hydrous alteration, i.e., TL5b (the least altered) < TL11h < TL11i (the most altered). Sample TL11v encompasses the petrologic characteristics of the other three specimens.     

Case study on the strategy and application of enhancement solutions to improve remediation of soils contaminated with Cu, Pb and Zn by means of electrodialysis

Numerous studies have been conducted with electrochemical removal of heavy metals from spiked kaolinite. Meanwhile, when moving from kaolinite to real soils, new factors must be taken into account—factors influencing, e.g., the buffering capacity of the soil against acidification and the adsorption/desorption processes of the heavy metals. The present study gives some examples where it is necessary to use an enhancement solution to aid desorption of Cu, Zn and Pb during electrodialytic treatment. Dependent on the composition of the pollution, different choices can be made. In the case of a Cu-polluted calcareous soil, ammonia may be used as enhancement solution, due to the formation of charged complexes between ammonia and Cu. Thus, Cu is mobile at high pH when ammonia is added and Cu can be removed without dissolving the calcareous parts. Zn is also mobilized by ammonia, but to a lesser extent than Cu. In the case of Cu, Zn and Pb at the same time, alkaline ammonium citrate may be a solution. It was shown that this enhancement solution could mobilize these three pollutants, but optimization of concentration and pH of the ammonium citrate is still needed. When choosing a remediation scheme for electrochemical treatment of an actual industrially polluted soil, this scheme must be chosen on basis of characterization of soil and pollution combination.     

Radionuclides and mercury in the salt lakes of the Crimea

90 Sr concentrations,resulting from the Chernobyl NPP accident,were determined in the salt lakes of the Crimea(Lakes Kiyatskoe,Kirleutskoe,Kizil-Yar,Bakalskoe and Donuzlav),together with the redistribution between the components of the ecosystems.The content of mercury in the waters of the studied reservoirs was also established.Vertical distributions of natural radionuclide activities( 238 U,232 Th,226 Ra,210 Pb,40 K) and anthropogenic 137 Cs concentrations(as radiotracers) were determined in the bottom sediments of the Koyashskoe salt lake(located in the south-eastern Crimea) to evaluate the longterm dynamics and biogeochemical processes.Radiochemical and chemical analysis was undertaken and radiotracer and statistical methods were applied to the analytical data.The highest concentrations of 90 Sr in the water of Lake Kiyatskoe(350.5 and 98.0 Bq/m 3) and Lake Kirleutskoe(121.3 Bq/m 3) were due to the discharge of the Dnieper water from the North-Crimean Canal.The high content of mercury in Lake Kiyatskoe(363.2 ng/L) and in seawater near Lake Kizil-Yar(364 ng/L) exceeded the maximum permissible concentration(3.5 times the maximum).Natural radionuclides provide the main contribution to the total radioactivity(artificial and natural combined) in the bottom sediments of Lake Koyashskoe.The significant concentration of 210 Pb in the upper layer of bottom sediments of the lake indicates an active inflow of its parent radionuclide—gaseous 222 Rn from the lower layers of the bottom sediment.The average sedimentation rates in Lake Koyashskoe,determined using 210 Pb and 137 Cs data,were 0.117 and 0.109 cm per year,respectively.     

Formation by silicate–fluoride + phosphate melt immiscibility of REE-rich globular segregations within aplite dikes

Aplite dikes intruding the Proterozoic 1.42(±?3) Ga Longs Peak-St. Vrain Silver Plume-type peraluminous granite near Jamestown, Colorado, contain F, P, and rare earth element (REE)-rich globular segregations, with 40–46% REE, 3.7–4.8 wt% P₂O₅, and 5–8 wt% F. A combination of textural features and geochemical data suggest that the aplite and REE-rich globular segregations co-existed as two co-genetic liquids prior to their crystallization, and we propose that they are formed by silicate–fluoride?+?phosphate (+?S?+?CO₂) melt immiscibility following ascent, cooling, and decompression of what was initially a single homogeneous magma that intruded the granite. The REE distribution coefficients between the silica-rich aplites and REE-rich segregations are in good agreement with experimentally determined distribution coefficients for immiscible silicate–fluoride?+?phosphate melts. Although monazite-(Ce) and uraninite U–Th–Pb microprobe ages for the segregations yield 1.420(±?25) and 1.442(±?8) Ga, respectively, thus suggesting a co-genetic relationship with their host granite, ε_Nd1.42Ga values for the granites and related granitic pegmatites range from ??3.3 to ??4.7 (average ??3.9), and differ from the values for both the aplites and REE-rich segregations, which range from ??1.0 to ??2.2 (average ??1.6). Furthermore, the granites and pegmatites have (La/Yb)_N <50 with significant negative Eu anomalies, which contrast with higher (La/Yb)_N >100 and absence of an Eu anomaly in both the aplites and segregations. These data are consistent with the aplite dikes and the REE-rich segregations they contain being co-genetic, but derived from a source different from that of the granite. The higher ε_Nd1.42Ga values for the aplites and REE-rich segregations suggest that the magma from which they separated had a more mafic and deeper, dryer and hotter source in the lower crust or upper mantle compared to the quartzo-feldspathic upper crustal source proposed for the Longs Peak-St. Vrain granite.     

Phase equilibrium and calorimetric study of the transition of MnTiO3 from the ilmenite to the lithium niobate structure and implications for the stability field of perovskite

The phase boundary between MnTiO₃ I (ilmenite structure) and MnTiO₃ II (lithium niobate structure) has been determined by analysis of quench products from reversal experiments in a cubic anvil apparatus at 1073–1673 K and 43–75 kbar using mixtures of MnTiO₃ I and II as starting materials. Tight brackets of the boundary give P(kbar)=121.2−0.045 T(K). Thermodynamic analysis of this boundary gives ΔH^o=5300±1000 J·mol⁻¹, ΔS^o = 1.98 ±1J·K⁻¹· mol⁻¹. The enthalpy of transformation obtained directly by transposed-temperature-drop calorimetry is 8359 ±2575 J·mol⁻¹. Possible topologies of the phase relations among the ilmenite, lithium niobate, and perovskite polymorphs are constrained using the above data and the observed (reversible with hysteresis) transformation of II to III at 298 K and 20–30 kbar (Ross et al. 1989). The observed II–III transition is likely to lie on a metastable extension of the II–III boundary into the ilmenite field. However the reversed I–II boundary, with its negative dP/ dT does represent stable equilibrium between ilmenite and lithium niobate, as opposed to the lithium niobate being a quench product of perovskite. We suggest a topology in which the perovskite occurs stably at low T and high P with a triple point (I, II, III) at or below 1073 K near 70 kbar. The I–II boundary would have a negative P-T slope while the II–III and I–III boundaries would be positive, implying that entropy decreases in the order lithium niobate, ilmenite, perovskite. The inferred positive slope of the ilmenite-perovskite transition in MnTiO₃ is different from the negative slopes in silicates and germanates. These thermochemical parameters are discussed in terms of crystal structure and lattice vibrations.     

Hyperspectral mapping of alteration assemblages within a hydrothermal vug at the Haughton impact structure,Canada

Meteorite impacts on Earth and Mars can generate hydrothermal systems that alter the primary mineralogies of rocks and provide suitable environments for microbial colonization. We investigate a calcite–marcasite‐bearing vug at the ~23 km diameter Haughton impact structure, Devon Island, Nunavut, Canada, using imaging spectroscopy of the outcrop in the field (0.65–1.1 μm) and samples in the laboratory (0.4–2.5 μm), point spectroscopy (0.35–2.5 μm), major element chemistry, and X‐ray diffraction analyses. The mineral assemblages mapped at the outcrop include marcasite; marcasite with minor gypsum and jarosite; fibroferrite and copiapite with minor gypsum and melanterite; gypsum, Fe³⁺ oxides, and jarosite; and calcite, gypsum, clay, microcline, and quartz. Hyperspectral mapping of alteration phases shows spatial patterns that illuminate changes in alteration conditions and formation of specific mineral phases. Marcasite formed from the postimpact hydrothermal system under reducing conditions, while subsequent weathering oxidized the marcasite at low temperatures and water/rock ratios. The acidic fluids resulting from the oxidation collected on flat‐lying portions of the outcrop, precipitating fibroferrite + copiapite. That assemblage then likely dissolved, and the changing chemistry and pH resulting from interaction with the calcite‐rich host rock formed gypsum‐bearing red coatings. These results have implications for understanding water–rock interactions and habitabilities at this site and on Mars.