Although the Po river is the most important fluvial system of Northern Italy, the systematic geochemical and isotopic investigations of its water are rare and were never reported for the whole basin. The present contribution aims to fill this knowledge gap, reporting a comprehensive data set including oxygen and hydrogen stable isotopes as well as major and trace element concentration of dissolved species for 54 Po river water samples, mainly collected in different hydrological conditions (peak discharge in April, drought in August) at increasing distance from the source, i.e., from the upper part of the catchment to the terminal (deltaic) part of the river at the confluence with the Adriatic Sea. The isotopic compositions demonstrate that the predominant part of the runoff derives from the Alpine sector of the catchment through important tributaries such as the Dora Baltea, Ticino, Adda, and Tanaro rivers, whereas the contribution from the Apennines tributaries is less important. The geochemical and isotopic compositions show that the Po river water attains a homogeneous composition at ca. 100 km from the source. The average composition is characterized by δ(18)O -9.8‰, δD -66.2‰, total dissolved solid (TDS) 268 mg/L, and chloride 17 mg/L and by a general Ca-HCO3 hydrochemical facies, which is maintained for most of the river stream, only varying in the terminal part where the river is diverted in a complex deltaic system affected by more significant evaporation and mixing with saline water evidenced by higher TDS and chloride content (up to 8198 and 4197 mg/L, respectively). Geochemical and isotopic maps have been drawn to visualize spatial gradients, which reflect the evolution of the river water composition at progressive distance from the source; more detailed maps were focused on the deltaic part in order to visualize the processes occurring in the transitional zone toward the Adriatic Sea. The data also highlight anthropogenic contributions, mainly represented by significant concentrations of nitrate (average 8 mg/L) and possibly arsenic (average 12 μg/L). These data allow the calculation of geochemical fluxes transferred from the river to the sea, and generally, they contribute to the definition of a "hydro-archive" which is useful to highlight ongoing variations in the related ecosystems.

The Adige River flows from the Eastern Alps to the Adriatic Sea and the understanding of its fluvial dynamics can be improved by geochemical and O-H isotopic investigation. The most negative isotopic compositions are recorded close to the source (δ(18)O between -14.1 and -13.8 ‰, δD between -100.3 and -97.0 ‰), and δD and δ(18)O values generally increase downstream through the upper part (UP, the mountainous sector), stabilizing along the lower part (LP, the alluvial plain) of the river with δ(18)O between -12.4 and -11.8 ‰, δD between -86.9 and -83.7 ‰. The isotopic variations along the stream path (δ(18)O-δD vs distance from the source) depict subparallel distributions for all the investigated periods, with less negative values recorded in winter. Total dissolved solids (TDS) concentration shows the lowest value (<100 mg/l) at the river source, jumping to 310 mg/l at the Rio Ram inflow, then decreasing down to the Isarco River confluence; from here, we observed an increase toward the river mouth, with different values in the distinct sampling periods. The lowest values (140-170 mg/l) were recorded during high discharge in spring, whereas higher TDS values (up to 250 mg/l) were recorded during winter low flow conditions. Extreme TDS values were observed in the estuarine samples (up to 450 mg/l), as result of mixing with seawater. The results allow for the identification of distinct water end-members: glacio-nival component(s) characterized by the most negative isotopic composition and extremely low TDS, a rainfall component characterized by intermediate isotopic and elemental composition and groundwater characterized by the less negative isotopic composition and comparatively higher TDS. An additional component is represented by seawater, which is recorded at the lowest reach of the river during drought periods. These contributions variously mix along the stream path in the distinct hydrological periods, and the presented data are a snapshot of the current hydroclimatic conditions. Future investigations will evaluate possible hydrological variations related to meteo-climatic changes. Monitoring is fundamental for future water management to overcome the vanishing of a significant water end-member of the basin, i.e., the glacio-nival reservoir that is severely affected by the ongoing climatic changes.

Po is the main Italian river and the δ(18)O and δ(2)H of its water reveal a similarity between the current meteoric fingerprint and that of the past represented by groundwater. As concerns the hydrochemisty, the Ca-HCO3 facies remained constant over the last 50 year, and only nitrate significantly increased from less than 1 mg/L to more than 10 mg/L in the 1980s, and then attenuated to a value of 9 mg/L. Coherently, δ(13)CDIC and δ(34)SSO4 are compatible with the weathering of the lithologies outcropping in the basin, while extremely variable δ(15)NNO3 indicates contribution from pollutants released by urban, agricultural and zootechnical activities. This suggests that although the origin of the main constituents of the Po river water is geogenic, anthropogenic contributions are locally significant. Noteworthy, the associated aquifers have the same nitrogen isotopic signature of the Po river, but are characterized by significantly higher NO(-) 3 concentration. This implies that aquifers' pollution is not ascribed to inflow of current river water, and that the attenuation of the nitrogen load recorded in the river is not occurring in the aquifers, due to their longer water residence time and delayed recovery from anthropogenic contamination.

Abstract. Recent tracer-based studies using stable isotopes of hydrogen and oxygen showed that different methods for extracting water from plant tissues can return different isotopic compositions due to the presence of organic compounds and because they extract different plant water domains. One of the most used methods to extract plant water is the cryogenic vacuum distillation (CVD), which tends to extract total plant water. Conversely, the Scholander-type pressure chamber (SPC), which is commonly used by tree physiologists to measure water potential in plant tissues and determine plant water stress, is expected to extract only the more mobile plant water (i.e., xylem and inter-cellular water). However, only few studies reported the application of SPC to extract plant water for isotopic analyses, and therefore, inter-method comparisons between SPC and CVD are of great value. In this work, we analyzed the variability in the isotopic composition of plant water extracted by SPC and CVD, also considering the potential variability in the isotopic signature of the plant water extracted by CVD from various tissues (i.e., leaves, twig without bark, twig with bark, twig close to the trunk of the tree, and wood core) and from different plant species (i.e., alder, apple, chestnut, and beech). The extraction of plant water by SPC is simple, can be carried out in the field, and it does not require specific laboratory work as in the case of CVD. However, the main limitation of SPC is the very small water volume that can be extracted from the lignified twigs under water stress conditions compared to CVD. Our results indicated that plant water extracted by SPC and CVD were significantly different. The difference in the isotopic composition obtained by the two extraction methods was smaller in the beech samples compared to alder, apple, and chestnut samples. The isotopic signature of alder, apple, and chestnut plant water extracted by SPC was more enriched in δ2H and δ18O, respectively, than the samples obtained by CVD. We conclude that plant water extraction by SPC is not an alternative for CVD as SPC mostly extracts the mobile plant water, whereas CVD tends to retrieve all water stored in the sampled tissue from both living and dead cells. However, studies aiming to quantify the relative contribution of the soil water sources to transpiration should rely more on the isotopic composition of xylem water (which is theoretically sampled by SPC) than the isotopic composition of total plant water (sampled by CVD), which also contains a fraction of water that could be stored in plant tissues for a longer time.