Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions

The topotactic oxidation and delithiation reaction from triphylite, Li(Fe,Mn)PO₄, leading to ferrisicklerite, Li_<1(Fe³⁺,Mn²⁺)PO₄, was investigated under hydrothermal conditions. A cuboid cut from a triphylite single-crystal (Palermo Mine, New Hampshire, USA) with the composition Li_0.93(3)(Fe²⁺ _0.733(6),Fe³⁺ _0.015(1),Mn²⁺ _0.210(4),Mg_0.063(2))_1.021(8)P_1.00(2)O₄ in addition with ground bulk material were treated with KMnO₄ and 30 % H₂O₂(aq) as oxidizing agent in a 0.1 N hydrochloric acid solution in the temperature range between 60 and 200 °C. At 120 °C a rim of 0.1 mm thickness of ferrisicklerite had formed around the core of unreacted triphylite. The sharp reaction boundary was clearly visible, due to the reddish brown absorption colors of ferrisicklerite, compared to colorless triphylite. Using single-crystal X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), electron probe micro-analysis (EPMA) and ⁵⁷Fe-Mössbauer spectroscopy the product ferrisicklerite was characterized and its composition determined as Li_0.30(7)(Fe²⁺ _0.049(1)Fe³⁺ _0.65(2)Mn²⁺ _0.218(5)Mg_0.062(2))_0.98(1)P_1.01(3)O₄, with unit cell parameters a?=?4.795(1), b?=?9.992(4), and c?=?5.886(2) Å. EPMA investigations across the reaction boundary showed no changes in the concentrations of Fe, Mn, Mg, and P. In contrast, SIMS measurements clearly proved the delithiated state of the ferrisicklerite product. Polarization microscopy revealed that the orientation of the ferrisicklerite rim was the same as that of the original triphylite single-crystal, confirming the strictly topotactic character of the reaction.     

A hierarchical generalized linear model with variable selection: studying the response of a representative fish assemblage for large European rivers in a multi-pressure context

Global change calls for an understanding of how temperature and flow regimes influence aquatic ecosystems. Fish assemblages are a major component of river ecosystems and are thought to exhibit more integrative informative responses than single species to environmental variations, whether rare and sudden or gradual and continuous. The use of long-term datasets is thus of primary importance, allied to statistical modeling. For each of three previously identified species clusters, we performed Bayesian variable selection and inference within a hierarchical log Poisson Generalized Linear Model using a spike and slab normal prior to pinpoint which subset of environmental variables is of importance for each fish assemblage. Fish counts from electrofishing experiments are known to provide overdispersed data and, not surprisingly, the contribution of recorded environmental effects is found to be weak compared with those of other intra-assemblage sources of variation. The posterior distribution of the regression parameters is in coherence with what was expected from biological knowledge of the three species clusters. In particular, thermophilic species tend to benefit from warmer waters, whereas the recruitment of cold water species decreases due to global warming effects. Our study provides an example of the advantages of hierarchical modeling for quantifying interspecies ecological effects and selecting common environmental variables of importance.     

Sublimation of the Martian CO2 Seasonal South Polar Cap

The polar condensation/sublimation of CO₂, that involve about one fourth of the atmosphere mass, is the major Martian climatic cycle. Early observations in visible and thermal infrared have shown that the sublimation of the Seasonal South Polar Cap (SSPC) is not symmetric around the geographic South Pole.Here we use observations by OMEGA/Mars Express in the near-infrared to detect unambiguously the presence of CO₂ at the surface, and to estimate albedo. Second, we estimate the sublimation of CO₂ released in the atmosphere and show that there is a two-step process. From Ls=180° to 220°, the sublimation is nearly symmetric with a slight advantage for the cryptic region. After Ls=220° the anti-cryptic region sublimation is stronger. Those two phases are not balanced such that there is 22% ± 9 more mass the anti-cryptic region, arguing for more snow precipitation. We compare those results with the MOLA height measurements. Finally we discuss implications for the Martian atmosphere about general circulation and gas tracers, e.g. Ar.     

Evaporation in Mediterranean conditions: Estimations based on isotopic approaches at the watershed scale

In Mediterranean regions, the marked climatic seasonality and uneven precipitation distribution complicate the application of isotope mass balances to obtain meaningful basin-wide annual average evaporation rates. In the present study, a mass balance approach carried out on the Tavignanu River watershed in Corsica (France), showed unrealistic evaporation rate estimates: 10% for 2017–2018 and 1% for 2018–2019. This suggests that not only does evaporation alter the seasonal isotopic composition in the river, but that there is complex variability of the dominant water reservoirs contributing to the streamflow. Therefore, we propose a modified mass balance approach, including monthly quantifications of different water sources contributing to the river discharge. This allows the discrimination of isotopic variation occurring by evaporation from that originating by mixing processes. By applying this modified approach, we estimated evaporation rates on the Tavignanu River watershed that were in good agreement with results obtained by hydrological modelling: 40% for 2017–2018 and 46% for 2018–2019, respectively. An uncertainty analysis showed that evaporation rates obtained with the modified isotopic approach are close to those obtained with the non-modified approach. Therefore, we recommend using this modified isotope mass balance approach to estimate evaporation rates in such regions as the Mediterranean with high seasonality in hydrological processes.     

Nature of volatile depletion and genetic relationships in enstatite chondrites and aubrites inferred from Zn isotopes

Enstatite meteorites include the undifferentiated enstatite chondrites and the differentiated enstatite achondrites (aubrites). They are the most reduced group of all meteorites. The oxygen isotope compositions of both enstatite chondrites and aubrites plot along the terrestrial mass fractionation line, which suggests some genetic links between these meteorites and the Earth as well.For this study, we measured the Zn isotopic composition of 25 samples from the following groups: aubrites (main group and Shallowater), EL chondrites, EH chondrites and Happy Canyon (impact-melt breccia). We also analyzed the Zn isotopic composition and elemental abundance in separated phases (metal, silicates, and sulfides) of the EH4, EL3, and EL6 chondrites. The different groups of meteorites are isotopically distinct and give the following values (‰): aubrite main group (−7.08 < δ⁶⁶Zn < −0.37); EH3 chondrites (0.15 < δ⁶⁶Zn < 0.31); EH4 chondrites (0.15 < δ⁶⁶Zn < 0.27); EH5 chondrites (δ⁶⁶Zn = 0.27 ± 0.09; n = 1); EL3 chondrites (0.01 < δ⁶⁶Zn < 0.63); the Shallowater aubrite (1.48 < δ⁶⁶Zn < 2.36); EL6 chondrites (2.26 < δ⁶⁶Zn < 7.35); and the impact-melt enstatite chondrite Happy Canyon (δ⁶⁶Zn = 0.37).The aubrite Peña Blanca Spring (δ⁶⁶Zn = −7.04‰) and the EL6 North West Forrest (δ⁶⁶Zn = 7.35‰) are the isotopically lightest and heaviest samples, respectively, known so far in the Solar System. In comparison, the range of Zn isotopic composition of chondrites and terrestrial samples (−1.5 < δ⁶⁶Zn < 1‰) is much smaller ( [Luck et al., 2005] and [Herzog et al., 2009]).EH and EL3 chondrites have the same Zn isotopic composition as the Earth, which is another example of the isotopic similarity between Earth and enstatite chondrites. The Zn isotopic composition and abundance strongly support that the origin of the volatile element depletion between EL3 and EL6 chondrites is due to volatilization, probably during thermal metamorphism. Aubrites show strong elemental depletion in Zn compared to both EH and EL chondrites and they are enriched in light isotopes (δ⁶⁶Zn down to −7.04‰). This is the opposite of what would be expected if Zn elemental depletion was due to evaporation, assuming the aubrites started with an enstatite chondrite-like Zn isotopic composition. Evaporation is therefore not responsible for volatile loss from aubrites. On Earth, Zn isotopes fractionate very little during igneous processes, while differentiated meteorites show only minimal Zn isotopic variability. It is therefore very unlikely that igneous processes can account for the large isotopic fractionation of Zn in aubrites. Condensation of an isotopically light vapor best explains Zn depletion and isotopically light Zn in these puzzling rocks. Mass balance suggests that this isotopically light vapor carries Zn lost by the EL6 parent body during thermal metamorphism and that aubrites evolved from an EL6-like parent body. Finally, Zn isotopes suggest that Shallowater and aubrites originate from distinct parent bodies.     

Effects of short-term ecosystem experimental warming on water-extractable organic matter in an ombrotrophic Sphagnum peatland (Le Forbonnet, France)

In a future warmer world, peatlands may change from a carbon sink function to a carbon source function. This study tracks changes in water-extractable organic matter (WEOM) after 1 year of in situ experimental warming using open top chambers (OTCs). WEOM was studied in the upper peat layers (0–10 cm) through analysis of water-extractable organic carbon (WEOC), stable C isotopic composition (δ¹³C), specific UV absorbance at 280 nm and sugar composition of cores taken from an open bog (DRY sites) and a transitional poor fen (WET sites). At the DRY sites, the impact of OTCs was weak with respect to WEOM parameters, whereas at the WET sites, the air warming treatment led to a decrease in peat water content, suggesting that the supply of heat by OTCs was used mainly for evapotranspiration. OTCs at the WET sites also induced a relative enrichment at the surface (0–5 cm depth) of aliphatic and/or aromatic compounds with concomitant decrease in WEOC, as a result of decomposition. On the contrary, WEOC and sugar content increased in the deeper peat layer (7.5–10 cm depth) probably as a result of increased leaching of phenolic compounds by roots, which then inhibits microbial activity. The different response to experimental warming at DRY and WET sites suggests that the spatial variability of moisture is critical for understanding of the impact of global warming on the fate of OM and the carbon cycle in peatlands.     

Late Glacial and Holocene avulsions of the Rio Pastaza Megafan (Ecuador–Peru): frequency and controlling factors

The geomorphological study by means of remote sensing imagery of the Rio Pastaza Megafan (Ecuador and northern Peru) reveals the traces of numerous avulsions. One hundred and eight avulsion sites have been defined. The location of these sites, the available radiocarbon ages as well as historical maps of the seventeenth century, enable us to propose an evolution history of the migration and avulsions of the Rio Pastaza since the Last Glacial Maximum. The first avulsions of the Río Pastaza occurred after the LGM in a zone close to and roughly parallel to the sudandean front, where the developed avulsion gave a distributive pattern to the ancient stream of the Río Pastaza in an area located between the modern Río Morona and Pastaza, where they caused the Rio Pastaza to develop a fan-like distributary pattern. This is interpreted as a response to thrust-related forelimb tilt, progressively shifting eastward the Rio Pastaza and the apex of the megafan. This sequence of events ended with the Great Diversion of the Rio Pastaza towards the modern Rios Corrientes and Tigre. Avulsions occurred in the Tigre-Corrientes Area between 9200 and 8,500 years Cal BP. Afterwards, the Río Pastaza was diverted to its present-day north–south course. This last significant avulsion occurred before AD 1691. In the area located between the modern Río Morona and Pastaza, avulsion frequency—probably overestimated—ranges between 100 and 200 years. In the Ríos Tigre and Corrientes area, avulsion frequency—probably underestimated—ranges from 300 to 400 years. Regional tectonics is likely to have triggered most of the avulsions in the Morona Pastaza area but its influence is restricted to this area. The factors controlling the avulsions in the Tigre-Corrientes area are less clear because the frequently described “hydrologic”-driven avulsion as observed in areas characterized by contrasted hydrologic cycles are inconsistent with the characteristics of the hydrologic cycles of the Rio Pastaza.     

Assessing waterbird habitat use in coastal evaporative systems using stable isotopes (δC, δN and δD) as environmental tracers

Isotopic patterns of biota across salinity gradients in man-made evaporative systems could assist in determining the use of these habitats by animals. Here we report δ¹³C, δ¹⁵N and δD measurements of a euryhaline fish, the Mediterranean toothcarp (Aphanius fasciatus), inhabiting a range of salinities in the Thyna saltworks near Sfax (Tunisia). The contribution of these salinity niches to egg formation of two typically piscivorous bird species breeding in the area and feeding within saltworks, Little Tern (Sternula albifrons) and Little Egret (Egretta garzetta), was inferred trough a triple-isotope (δ¹³C, δ¹⁵N and δD) Bayesian mixing model. Isotopic trends for fish δ¹⁵N and δD across the salinity gradient followed the equations: δ¹⁵N = e^{(1.1 + 47.68/Salinity)} and δD = −175.74 + Salinity + Salinity²; whereas fish δ¹³C increased as salinity rose (δ¹³C = −10.83 + 0.02·Salinity), after a sudden drop in fish isotopic values for salinities >60 (Practical Salinity Scale) (average fish δ¹³C for salinities <60 = −5.92‰). Both bird species fed largely on low hypersalinity ponds (salinity = 43; average contribution = 37% and 22% for Little Egrets and Little Terns, respectively), although the use of intermediate hypersalinities (salinities 63 and 70) by Little Terns also occurred (16% and 21%, respectively). Isotopic patterns across salinity gradients allow the use of isotopic measurements to inform studies of habitat occupancy within evaporative systems and provide further insights into how wildlife communities interact with them.