Carbon dioxide (CO2) fluxes in regulated Alpine rivers are driven by multiple biogeochemical and anthropogenic processes, acting on different spatiotemporal scales. We quantified the relative importance of these drivers and their effects on the dynamics of CO2 concentration and atmospheric exchange fluxes in a representative Alpine river segment regulated by a cascading hydropower system with diversion, which includes two residual flow reaches and a reach subject to hydropeaking. We combined instantaneous and time-resolved water chemistry and hydraulic measurements at different times of the year, and quantified the main CO2 fluxes by calibrating a one-dimensional transport-reaction model with measured data. As a novelty compared to previous inverse modelling applications, the model also included carbonate buffering, which contributed significantly to the CO2 budget of the case study. The spatiotemporal distribution and drivers of CO2 fluxes depended on hydropower operations. Along the residual flow reaches, CO2 fluxes were directly affected by the upstream dams only in the first ~ 2.5 km, where the supply of supersaturated water from the reservoirs was predominant. Downstream of the hydropower diversion outlets, the CO2 fluxes were dominated by systematic sub-daily fluctuations in CO2 transport and evasion fluxes (`carbopeaking') driven by hydropeaking. Hydropower operational patterns and regulation approaches in Alpine rivers affect CO2 fluxes and their response to biogeochemical drivers significantly across different temporal scales. Our findings highlight the importance of considering all scales of CO2 variations for accurate quantification and understanding of these impacts, to clarify the role of natural and anthropogenic drivers in global carbon cycling.

Flow regimes profoundly influence river organisms and ecosystem functions, but regulatory approaches often lack the scientific basis to support sustainable water allocation. In part, this reflects the challenge of understanding the ecological effects of flow variability over different temporal and spatial domains. Here, we use a process-based distributed hydrological model to simulate 23 years of natural flow regime in 100 target bioassessment sites across the Adige River network (NE Italy), and to identify typical nivo-glacial, nivo-pluvial, and pluvial reaches. We then applied spatial stream-network models (SSN) to investigate the relationships between hydrologic and macroinvertebrate metrics while accounting for network spatial autocorrelation and local habitat conditions. Macroinvertebrate metrics correlated most strongly with maximum, minimum and temporal variation in streamflow, but effects varied across flow regime types. For example: i) taxon richness appeared limited by high summer flows and high winter flows in nivo- glacial and pluvial streams, respectively; ii) invertebrate grazers increased proportionally with the annual coefficient of flow variation in nivo-glacial streams but tended to decline with flow variation in pluvial streams. SSN models revealed that most variation in macroinvertebrate metrics was accounted for by spatial autocorrelation, although local land use and water quality also affected benthic invertebrate communities, particularly at lower elevations. These findings highlight the importance of developing environmental flow management policies in ways that reflect specific hydro-ecological and land use contexts. Our analyses also illustrate the importance of spatially-explicit approaches that account for auto-correlation when quantifying flow-ecology relationships.

Rock glaciers are increasingly influencing the hydrology and water chemistry of Alpine catchments, with important implications for drinking water quality and ecosystem health under a changing climate. During summers of 2017 - 2019, we monitored the physical and chemical conditions of springs emerging from two active rock glaciers (ZRG and SRG) with distinct geomorphological settings in the Eastern Italian Alps (Solda/Sulden catchment). Both springs had constantly cold waters (1.4 ± 0.1 °C), and their ionic composition was dominated by SO42-, HCO3-, Ca2+ and Mg2+. Concentrations of major ions and trace elements, and values of water isotopes (δ18O, δ2H), increased towards autumn with an asymptotic trend at SRG, and a positive unimodal pattern at ZRG, where concentrations peaked 60 - 80 days after the end of the snowmelt. Wavelet analysis on electrical conductivity (EC) and water temperature records revealed daily cycles only at SRG, and significant weekly/biweekly fluctuations at both springs attributable to oscillations of meteorological conditions. Several rainfall events triggered a transient (0.5 - 2 hrs) EC drop and water temperature rise (dilution and warming) at SRG, whereas only intense rainfall events occasionally increased EC at ZRG (solute enrichment and thermal buffering), with a long-lasting effect (6 - 48 hrs). Our results, supported by a limited but emerging literature, suggest that: i) the distinctive composition of the bedrock drives different concentrations of major ions and trace elements in rock glacier springs; ii) pond-like and stream-like springs have distinct fluctuations of water parameters at different timescales; iii) peaks of EC/solute concentrations indicate a seasonal window of major permafrost thaw for rock glaciers feeding pond-like springs. These results provide a first quantitative description of the hydrological seasonality in rock glacier outflows, and their hydrochemical response to precipitation events, bringing relevant information for water management in the European Alps under climate change.