Entropy production of soil hydrological processes and its maximisation

Hydrological processes are irreversible and produce entropy. Hence, the framework of non-equilibrium thermodynamics is used here to describe them mathematically. This means flows of water are written as functions of gradients in the gravitational and chemical potential of water between two parts of the hydrological system. Such a framework facilitates a consistent thermodynamic representation of the hydrological processes in the model. Furthermore, it allows for the calculation of the entropy production associated with a flow of water, which is proportional to the product of gradient and flow. Thus, an entropy budget of the hydrological cycle at the land surface is quantified, illustrating the contribution of different processes to the overall entropy production. Moreover, the proposed Principle of Maximum Entropy Production (MEP) can be applied to the model. This means, unknown parameters can be determined by setting them to values which lead to a maximisation of the entropy production in the model. The model used in this study is parametrised according to MEP and evaluated by means of several observational datasets describing terrestrial fluxes of water and carbon. The model reproduces the data with good accuracy which is a promising result with regard to the application of MEP to hydrological processes at the land surfac

HESS Opinions: Functional units: a novel framework to explore the link between spatial organization and hydrological functioning of intermediate scale catchments

This opinion paper proposes a novel framework for exploring how spatial organization alongside with spatial heterogeneity controls functioning of intermediate scale catchments of organized complexity. Key idea is that spatial organization in landscapes implies that functioning of intermediate scale catchments is controlled by a hierarchy of functional units: hillslope scale lead topologies and embedded elementary functional units (EFUs). We argue that similar soils and vegetation communities and thus also soil structures "co-developed" within EFUs in an adaptive, self-organizing manner as they have been exposed to similar flows of energy, water and nutrients from the past to the present. Class members of the same EFU (class) are thus deemed to belong to the same ensemble with respect to controls of the energy balance and related vertical flows of capillary bounded soil water and heat. Class members of superordinate lead topologies are characterized by the same spatially organized arrangement of EFUs along the gradient driving lateral flows of free water as well as a similar surface and bedrock topography. We hence postulate that they belong to the same ensemble with respect to controls on rainfall runoff transformation and related vertical and lateral fluxes of free water. We expect class members of these functional units to have a distinct way how their architecture controls the interplay of state dynamics and integral flows, which is typical for all members of one class but dissimilar among the classes. This implies that we might infer on the typical dynamic behavior of the most important classes of EFU and lead topologies in a catchment, by thoroughly characterizing a few members of each class. A major asset of the proposed framework, which steps beyond the concept of hydrological response units, is that it can be tested experimentally. In this respect, we reflect on suitable strategies based on stratified observations drawing from process hydrology, soil physics, geophysics, ecology and remote sensing which are currently conducted in replicates of candidate functional units in the Attert basin (Luxembourg), to search for typical and similar functional and structural characteristics. A second asset of this framework is that it blueprints a way towards a structurally more adequate model concept for water and energy cycles in intermediate scale catchments, which balances necessary complexity with falsifiability. This is because EFU and lead topologies are deemed to mark a hierarchy of "scale breaks" where simplicity with respect to the energy balance and stream flow generation emerges from spatially organized process-structure interactions. This offers the opportunity for simplified descriptions of these processes that are nevertheless physically and thermodynamically consistent. In this respect we reflect on a candidate model structure that (a) may accommodate distributed observations of states and especially terrestrial controls on driving gradients to constrain the space of feasible model structures and (b) allows testing the possible added value of organizing principles to understand the role of spatial organization from an optimality perspective

Adding our leaves: A communityâ wide perspective on research directions in ecohydrology

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/154539/1/hyp13693.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/154539/2/hyp13693_am.pd

Advancing catchment hydrology to deal with predictions under change

Throughout its historical development, hydrology as an earth science, but especially as a problem-centred engineering discipline has largely relied (quite successfully) on the assumption of stationarity. This includes assuming time invariance of boundary conditions such as climate, system configurations such as land use, topography and morphology, and dynamics such as flow regimes and flood recurrence at different spatio-temporal aggregation scales. The justification for this assumption was often that when compared with the temporal, spatial, or topical extent of the questions posed to hydrology, such conditions could indeed be considered stationary, and therefore the neglect of certain long-term non-stationarities or feedback effects (even if they were known) would not introduce a large error. However, over time two closely related phenomena emerged that have increasingly reduced the general applicability of the stationarity concept: the first is the rapid and extensive global changes in many parts of the hydrological cycle, changing formerly stationary systems to transient ones. The second is that the questions posed to hydrology have become increasingly more complex, requiring the joint consideration of increasingly more (sub-) systems and their interactions across more and longer timescales, which limits the applicability of stationarity assumptions. Therefore, the applicability of hydrological concepts based on stationarity has diminished at the same rate as the complexity of the hydrological problems we are confronted with and the transient nature of the hydrological systems we are dealing with has increased. The aim of this paper is to present and discuss potentially helpful paradigms and theories that should be considered as we seek to better understand complex hydrological systems under change. For the sake of brevity we focus on catchment hydrology. We begin with a discussion of the general nature of explanation in hydrology and briefly review the history of catchment hydrology. We then propose and discuss several perspectives on catchments: as complex dynamical systems, self-organizing systems, co-evolving systems and open dissipative thermodynamic systems. We discuss the benefits of comparative hydrology and of taking an information-theoretic view of catchments, including the flow of information from data to models to predictions. In summary, we suggest that these perspectives deserve closer attention and that their synergistic combination can advance catchment hydrology to address questions of change

Non-target screening with high-resolution mass spectrometry: critical review using a collaborative trial on water analysis

In this article, a dataset from a collaborative nontarget screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detection. This article focuses mainly on the use of high resolution screening techniques with target, suspect, and non-target workflows to identify substances in environmental samples. Specific examples are given to emphasise major challenges including isobaric and co-eluting substances, dependence on target and suspect lists, formula assignment, the use of retention information, and the confidence of identification. Approaches and methods applicable to unit resolution data are also discussed. Although most substances were identified using high resolution data with target and suspect-screening approaches, some participants proposed tentative non-target identifications. This comprehensive dataset revealed that nontarget analytical techniques are already substantially harmonised between the participants, but the data processing remains time-consuming. Although the objective of a Bfullyautomated identification workflow^ remains elusive in the short term, important steps in this direction have been taken, exemplified by the growing popularity of suspect screening approaches. Major recommendations to improve non-target screening include better integration and connection of desired features into software packages, the exchange of target and suspect lists, and the contribution of more spectra from standard substances into (openly accessible) databases.This work was supported in part by the SOLUTIONS project, which received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under Grant Agreement No. 603437