A GLUE‐based uncertainty assessment framework for tritium‐inferred transit time estimations under baseflow conditions

The last decade has seen major technical and scientific improvements in the study of water transfer time through catchments. Nevertheless, it has been argued that most of these developments used conservative tracers that may disregard the oldest component of water transfer, which often has transit times greater than 5 years. Indeed, although the analytical reproducibility of tracers limits the detection of the older flow components associated with the most dampened seasonal fluctuations, this is very rarely taken into account in modelling applications. Tritium is the only environmental tracer at hand to investigate transfer times in the 5‐ to 50‐year range in surface waters, as dissolved gases are not suitable due to the degassing process. Water dating with tritium has often been difficult because of the complex history of its atmospheric concentration, but its current stabilization together with recent analytical improvements open promising perspectives. In this context, the innovative contribution of this study lies in the development of a generalized likelihood uncertainty estimation‐based approach for analysing the uncertainties associated with the modelling of transit time due to both parameter identification and tracer analytical precision issues. A coupled resampling procedure allows assessment of the statistical significance of the transfer time differences found in diverse waters. This approach was developed for tritium and the exponential‐piston model but can be implemented for virtually any tracer and model. Stream baseflow, spring and shallow aquifer waters from the Vallcebre research catchments, analysed for tritium in different years with different analytical precisions, were investigated by using this approach and taking into account other sources of uncertainty. The results showed three groups of waters of different mean transit times, with all the stream baseflow and spring waters older than the 5‐year threshold needing tritium. Low sensitivity of the results to the model structure was also demonstrated. Dual solutions were found for the waters sampled in 2013, but these results may be disambiguated when additional analyses will be made in a few years. Copyright © 2016 John Wiley & Sons, Ltd.     

Exploring lava‐flow hazards at Pico Island,Azores Archipelago (Portugal)

Pico, the youngest island of the Azores Archipelago (Portugal), is characterized by a central volcano and a 30‐km‐long fissure zone. Its eruption rate is the highest of the Azores islands, with more than 35 eruptions in the last 2000 years. Here, we estimate the lava‐flow hazard for Pico Island by combining the vent opening probability derived from the spatial distribution of eruptive fissures, the classes of expected eruptions inferred from the physical and chemical characteristics of historical eruptions, and the lava‐flow paths simulated by the MAGFLOW model. The most likely area to host new eruptions is along a WNW–ESE trend centred on the central volcano, with the highest hazard affecting the two main residential zones of Lajes do Pico and Madalena. Our analysis is the first attempt to assess the lava‐flow hazard for Pico Island, and may have important implications for decision‐making in territorial management and future land‐use planning.     

Implications of measurement metrics on soil freezing curves: A simulation of freeze–thaw hysteresis

Soil freeze–thaw events have important implications for water resources, flood risk, land productivity, and climate change. A property of these phenomena is the relationship between unfrozen water content and sub-freezing temperature, known as the soil freezing characteristic curve (SFC). It is documented that this relationship exhibits hysteretic behaviour when frozen soil thaws, leading to the definition of the soil thawing characteristic curve (STC). Although explanations have been given for SFC/STC hysteresis, the effect that ‘scale’ – particularly ‘measurement scale’ – may have on these curves has received little attention. The most commonly used measurement scale metric is the ‘support’, which is the spatial (or temporal) unit within which the measured variable is integrated or soil volume sampled. We show (a) measurement support can influence the range and shape of the SFC and (b) hysteresis can be attributed, in part, to the support and location of the measurements comprising the SFC/STC. We simulated lab measured temperature, volumetric water content (VWC), and permittivity from soil samples undergoing freeze–thaw transitions using Hydrus-1D and a modified Dobson permittivity model. To assess the effect of measurement support and location on SFC/STC, we masked the simulated temperature and VWC/permittivity extent to match the instrument's support and location. By creating a detailed simulation of the intra- and inter-support variability associated with the penetration of a freezing front, we demonstrate how measurement support and location can influence the temperature range over which water freezing events are captured. We show it is possible to simulate hysteresis in homogenous media with purely geometric considerations, suggesting that SFC/STC hysteresis may be more of an apparent phenomenon than mechanistically real. Lastly, we develop an understanding of how the location and support of soil temperature and VWC/permittivity measurements influence the temperature range over which water freezing events are captured.     

Detecting the stepwise propagation of the Eastern Sicily thrust belt (Italy): insight from thermal and thermochronological constraints

An extensive dataset of vitrinite reflectance, FTIR parameters on organic matter, illite content in mixed layers illite‐smectite, apatite fission tracks and U‐Th/He dating has been used to reconstruct the stepwise propagation of the Eastern Sicily fold‐and‐thrust belt during Late Palaeogene and Neogene times. The results indicate that the fold‐and‐thrust belt is divisible into two levels of thermal maturity. These levels consist of a less evolved level of thermal maturity that records limited sedimentary burial and minor heating, and a more evolved level of thermal maturity that indicates tectonic burial and exhumation at different times. Deformation and exhumation of shallowly buried units are linked to wedge forward propagation by low‐angle thrusts, whereas the evolution of deeply buried units is associated with tectonic imbrications by duplex formation and steep thrusts. The two tectonic styles alternate during evolution of the fold‐and‐thrust belt under low erosion rates.     

Lake sedimentary processes and vegetation changes over the last 45k cal a bp in the uplands of south-eastern Amazonia

This study addresses paleoclimate influences in a southern Amazonia ecotone based on multiproxy records from lakes of the Carajás region during the last 45k cal a bp. Wet and cool environmental conditions marked the initial deposition in shallow depressions with detrital sediments and high weathering rates until 40k cal a bp. Concomitantly, forest and C3 canga plants, along with cool-adapted taxa, developed; however, short drier episodes enabled expansion of C4 plants and diagenetic formation of siderite. A massive event of siderite formation occurred approximately 30k cal a bp under strong drier conditions. Afterwards, wet and cool environmental conditions returned and persisted until the Last Glacial Maximum (LGM). The LGM was marked by lake-level lowstands and subaerial exposure. The transition from the LGM to the Holocene is marked by the onset of oscillations in temperature and humidity, with an expansion of forest and canga plants. Cool taxa were present for the last time in the Carajás region ~ 9.5–9k cal a bp. After 10k cal a bp , shallow lakes became upland swamps due to natural infilling processes, but the current vegetation types and structures of the plateaus were acquired only after 3k cal a bp under wetter climatic conditions.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.