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Calcium oxalate minerals of the general formula CaC 2 O 4 . x H 2 O are widely present in nature and usually associated with pathological calcifications, constituting up to 70-80% of the mineral component of renal calculi. The monohydrate phase (CaC 2 O 4 . H 2 O, COM) is the most stable form, accounting for the majority of the hydrated calcium oxalates found. These mineral phases have been studied extensively via X-ray diffraction and IR spectroscopy and, to a lesser extent, using 1 H, 13 C, and 43 Ca solid-state NMR spectroscopy. However, several aspects of their structure and reactivity are still unclear, such as the evolution from low- to high-temperature COM structures (LT-COM and HT-COM, respectively) and the involvement of water molecules in this phase transition. Here, we report for the first time a 17 O and 2 H solid-state NMR investigation of the local structure and dynamics of water in the COM phase. A new procedure for the selective 17 O- and 2 H-isotopic enrichment of water molecules within the COM mineral is presented using mechanochemistry, which employs only microliter quantities of enriched water and leads to exchange yields up to ∼30%. 17 O NMR allows both crystallographically inequivalent water molecules in the LT-COM structure to be resolved, while 2 H NMR studies provide unambiguous evidence that these water molecules are undergoing different types of motions at high temperatures without exchanging with one another. Dynamics appear to be essential for water molecules in these structures, which have not been accounted for in previous structural studies on the HT-COM structure due to lack of available tools, highlighting the importance of such NMR investigations for refining the overall knowledge on biologically relevant minerals like calcium oxalates., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Sustainable groundwater management implies a good knowledge of recharge processes, especially in areas with water deficit, like the semi-arid region of Banabuiú watershed (Ceará State, Northeast of Brazil). In this zone, phreatic aquifers consist of Precambrian crystalline fractured reservoirs characterised by a high spatial anisotropy, both in terms of hydrodynamics and water quality. This study implemented a multi-tracer approach ( 18 O, 2 H, 14 C, 3 H, CFC, SF 6 ), combined with hydrodynamic data (i.e. groundwater levels) to identify the groundwater recharge origin and the recharge mechanisms, and to estimate the groundwater residence time. At the basin scale, hydrodynamic data and local observations indicated the high reactivity of aquifers to precipitation and suggested that infiltration processes occur mostly through preferential infiltration zones. Stable isotope data showed a major contribution of evaporated surface water in the recharge process from many artificial or natural ponds. Groundwater residence time determination highlighted the spatio-temporal heterogeneity of flow path organisation within aquifers, with variable contributions between fast vertical flow (present-day end-member; 15-85 %) and a slower horizontal flow (old end-member <1960), underlining the vulnerability of aquifers to present-day environmental stress or pollution.

Water isotopes from plant xylem and surrounding environment are increasingly used in eco-hydrological studies. Carrière et al. [1] analyzed a dataset of water isotopes in (i) the xylem of three different tree species, (ii) the surrounding soil and drainage water and (iii) the underlying karst groundwater, to understand tree water uptake during drought in two different Mediterranean forests on karst setting. The xylem and soil water were extracted by cryogenic distillation. The full dataset was obtained with Isotope Ratio Mass Spectrometry (IRMS) and Isotope Ratio Infrared Spectrometer (IRIS), and included 219 measurements of δ 2 H and δ 18 O. Prompted by unexpected isotopic data characterized by a very negative deuterium excess, a subsample of 46 xylem samples and 9 soil water samples were double checked with both analytical techniques. IRMS and IRIS analyses yielded similar data. Therefore, the results reveal that laser spectrometry allows an accurate estimation of xylem and soil water isotopes. The dataset highlights a strong 2 H depletion in xylem water for all species. Deuterium does not seem adequate to interpret ecological processes in this dataset given the strong fractionation., (© 2020 The Author(s).)

Karst environments are unusual because their dry, stony and shallow soils seem to be unfavorable to vegetation, and yet they are often covered with forests. How can trees survive in these environments? Where do they find the water that allows them to survive? This study uses midday and predawn water potentials and xylem water isotopes of branches to assess tree water status and the origin of transpired water. Monitoring was conducted during the summers of 2014 and 2015 in two dissimilar plots of Mediterranean forest located in karst environments. The results show that the three monitored tree species (Abies alba Mill, Fagus sylvatica L, and Quercus ilex L.) use deep water resources present in the karst vadose zone (unsaturated zone) more intensively during drier years. Quercus ilex, a species well- adapted to water stress, which grows at the drier site, uses the deep water resource very early in the summer season. Conversely, the two other species exploit the deep water resource only during severe drought. These results open up new perspectives to a better understanding of ecohydrological equilibrium and to improved water balance modeling in karst forest settings., (Copyright © 2019 Elsevier B.V. All rights reserved.)