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Thesisbotter Printfeb2 Nocv Copy Research Collection Doctoral Thesis Solute export dynamics across scales – From data-based diagnosis to mechanistic modelling predictions Author(s): Botter, Martina Publication Date: 2020 Permanent Link: https://doi.org/10.3929/ethz-b-000475970 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library Diss.- No. ETH No. 27098 Solute export dynamics across scales - From data-based diagnosis to mechanistic modelling predictions A thesis submitted to attain the degree of DOCTOR OF SCIENCES of ETH ZURICH (Dr. sc. ETH Zurich) presented by MARTINA BOTTER MSc in Environmental and Land Planning Engineering Politecnico di Milano born on 15.03.1991 citizen of Italy accepted on the recommendation of Prof. Dr. Paolo Burlando, examiner Prof. Dr. Simone Fatichi, co-examiner Prof. Dr. Gianluca Botter, co-examiner Prof. Dr. Laurent Pfister, co-examiner 2020 i ii Ai miei genitori, fonte di ispirazione per la loro determinazione, costanza e ambizione. iii iv Abstract Water management strategies have become crucial in order to preserve or restore the health of water bodies under the constantly increasing anthropic pressure. The key for effective water management strategies lies in a reliable diagnosis of the environmental impairment and a consequent robust assessment of possible mitigation strategies. Understanding the export dynamics of potentially polluting solutes has become a crucial task for scientists. Research in this field is particularly demanding because solute export dynamics are shaped by the interplay of different factors such as biogeochemical cycles, water and energy fluxes, and water transport across various compartments of the land surface. The general lack of solutes input makes the investigations even more challenging. This study investigates the export dynamics of different solutes across different scales with the goal of understanding (1) the general export behavior of different substances across catchments, (2) the relationship between the input and the export dynamics of different solutes and (3) how agricultural practices affect the diffusion of polluting compounds in water resources. In the first part of the study, long-term solute concentrations and discharge data of 11 Swiss rivers are analysed. Given the variety of catchments included in the database, from pristine forested to predominantly agricultural ones, signatures of either anthropic activities or natural catchment characteristics (e.g., bedrock composition) in the stream water quality are investigated. Solutes are also classified based on the long-term pattern of the concentration- discharge (C-Q) relations, which determine the solute export behaviour. Anthropic pressure impacts the magnitude, seasonality and also the long-term behaviour of certain substances (nitrate, phosphorous and total nitrogen). Signatures of the bedrock composition or of catchment steepness are sometimes detectable, but, in general, the influence of catchment natural characteristics is not easy to discern, also due to the limited sample of catchments. In the second part of the study the concentration-discharge database is enlarged including records from 585 rivers around the world. This newly assembled database provides a generalizable perspective of the solute export behaviour at the catchment scale. Results of data analysis lead to the hypothesis that solute export behaviour might be shaped by the timing of the solute input in the catchment and/or by the vertical distribution of the solute sources in the catchment compartments. This hypothesis is tested running synthetic experiments with a tracer-aided distributed hydrological model. The results reveal that the depth of solute generation is likely the most important control on the C-Q relation for a number of solutes. This study highlights the uncertainty around the definition of nutrients (nitrogen, phosphorous) behavior compared to geogenic solutes, which consistently dilute (e.g., their concentration decreases with increasing discharge) across a wide range of catchments. In the last part the focus is on the dynamics of nitrate, which is the main nutrient component of fertilizers and responsible for water quality issues like eutrophication. The nitrogen cycle is particularly complex because it interacts with the carbon cycle, vegetation dynamics, soil hydrology, and energy exchanges at the soil-atmosphere interface. Long-term datasets have limited capability to capture short-term dynamics determining the nitrate export. Therefore, a mechanistic model capable of integrating all these aspects is applied to simulate the nitrogen dynamics across 9 managed Alpine grasslands. Nitrate losses in the environment are assessed under different fertilization scenarios. The fraction of nitrate, that eventually impacts water quality is found to be relatively small. However, it varies considerably across sites depending on the grassland efficiency in uptaking nitrate. Nitrogen use efficiency is not only limited by v the length of the growing season, but hydrological fluxes also play a major role on nitrogen availability for grasslands. This heterogeneity in grassland response should be considered while setting guidelines for management practices. vi Sommario La gestione delle risorse idriche è fondamentale per preservare o ristabilire il buono stato dei corpi idrici sotto la crescente pressione antropica a cui questi vanno incontro. La chiave per il successo delle strategie di gestione delle risorse idriche sta sia in una diagnosi affidabile dell’inquinamento ambientale che nella conseguente valutazione di possibili robuste strategie di mitigazione dei rischi ambientali. Comprendere la dinamica di produzione e trasporto di soluti potenzialmente inquinanti è quindi diventato un compito cruciale per gli scienziati. La ricerca in questo settore è particolarmente impegnativa perché le dinamiche dei soluti sono determinate dall’interazione di svariati fattori come i cicli biogeochimici, flussi di acqua ed energia, e il trasporto da parte dell’acqua attraverso i vari comparti della superficie terrestre. Inoltre, la generale mancanza di dati sugli input di soluti rende lo studio ancora più impegnativo. Questa tesi analizza la dinamica di trasporto di vari soluti attraverso diverse scale spaziali con l’obiettivo di capire (1) il comportamento generale dell’output di diversi soluti in diversi bacini idrologici, (2) la relazione tra la dinamica di input e di output di diversi soluti e (3) come le pratiche agricole influenzano la produzione di composti inquinanti come il nitrato. Nella prima parte dello studio vengono analizzati i dati di concentrazione dei soluti e di portata sul lungo periodo in 11 fiumi svizzeri. La diversità di bacini inclusa nel database, che comprende foreste incontaminate e bacini prevalentemente agricoli, offre l’opportunità di analizzare l’eventuale presenza di tracce indicative o delle attività antropiche o delle caratteristiche naturali dei bacini (per esempio la composizione chimica del sottosuolo) nei dati di qualità dell’acqua. I soluti vengono classificati anche in base alla relazione concentrazione-portata (C-Q), calcolata sul lungo periodo, la quale definisce il comportamento dell’output del soluto. La pressione antropica ha un impatto sull’ordine di grandezza, sulla stagionalità e anche sul comportamento a lungo termine di determinate sostanze (nitrati, fosforo ed azoto totale). Sono talvolta rintracciabili impatti della composizione del sottosuolo o della pendenza dei versanti nel bacino, ma, in generale, le caratteristiche naturali del bacino non sono facilmente discernibili, anche a causa del numero limitato di bacini analizzati. Nella seconda parte dello studio il database delle relazioni concentrazione-portata viene espanso includendo dati da 585 fiumi sparsi in varie parti del mondo. Il nuovo database fornisce una prospettiva generalizzabile del comportamento dei soluti nei fiumi. L’analisi di questi dati ha portato alla formulazione dell’ipotesi che l’output dei soluti possa essere determinato dal timing dell’input del soluto e dalla distribuzione verticale della produzione dei soluti nei vari comparti del bacino idrografico. Questa ipotesi viene testata eseguendo esperimenti numerici con un modello idrologico distribuito che è in grado di tener conto dei traccianti. I risultati hanno rivelato che la profondità delle zone di generazione del soluto è il controllo principale sulla relazione concentrazione-portata per vari soluti. L’analisi inoltre evidenzia l’incertezza intorno alla definizione del comportamento dei nutrienti (azoto, fosforo) rispetto ai soluti geogenici, i quali coerentemente diluiscono (cioè la loro concentrazione diminuisce all’aumentare della portata) per la maggior parte dei bacini idrografici. Nell’ultima parte ci si è concentrati sulla dinamica del nitrato, un nutriente, nonché componente principale dei fertilizzanti, responsabile dei problemi di qualità dell’acqua come l’eutrofizzazione. Il ciclo dell’azoto è particolarmente complesso perché interagisce con il ciclo del carbonio, con la dinamica della vegetazione, l’idrologia del suolo, e gli scambi energetici all’interfaccia tra suolo e atmosfera. I dati analizzati precedentemente sul lungo vii periodo hanno una limitata capacità di catturare dinamiche a breve termine che determinano la produzione di nitrato. Pertanto, si è applicato un modello meccanicistico capace
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