Land Use, Freshwater Flows and Ecosystem Services in an Era of Global Change

The purpose of this thesis is to analyse interactions between freshwater flows, terrestrial ecosystems and human well-being. Freshwater management and policy has mainly focused on the liquid water part (surface and ground water run off) of the hydrological cycle including aquatic ecosystems. Although of great significance, this thesis shows that such a focus will not be sufficient for coping with freshwater related social-ecological vulnerability. The thesis illustrates that the terrestrial component of the hydrological cycle, reflected in vapour flows (or evapotranspiration), serves multiple functions in the human life-support system. A broader understanding of the interactions between terrestrial systems and freshwater flows is particularly important in light of present widespread land cover change in terrestrial ecosystems. The water vapour flows from continental ecosystems were quantified at a global scale in Paper I of the thesis. It was estimated that in order to sustain the majority of global terrestrial ecosystem services on which humanity depends, an annual water vapour flow of 63 000 km3/yr is needed, including 6800 km3/yr for crop production. In comparison, the annual human withdrawal of liquid water amounts to roughly 4000 km3/yr. A potential conflict between freshwater for future food production and for terrestrial ecosystem services was identified. Human redistribution of water vapour flows as a consequence of long-term land cover change was addressed at both continental (Australia) (Paper II) and global scales (Paper III). It was estimated that the annual vapour flow had decreased by 10% in Australia during the last 200 years. This is due to a decrease in woody vegetation for agricultural production. The reduction in vapour flows has caused severe problems with salinity of soils and rivers. The human-induced alteration of vapour flows was estimated at more than 15 times the volume of human-induced change in liquid water (Paper II).

Probing unoccupied electronic states in aqueous solutions

Water is one of the most common compounds on earth and is essential for all biological activities. Water has, however, been a mystery for many years due to the large number of unusual chemical and physical properties, e.g. decreased volume during melting and maximum density at 4 °C. The origin of the anomalies behavior is the nature of the hydrogen bond. This thesis will presented an x-ray absorption spectroscopy (XAS) study to reveal the hydrogen bond structure in liquid water. The x-ray absorption process is faster than a femtosecond and thereby reflects the molecular orbital structure in a frozen geometry locally around the probed water molecules. The results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms. The molecular arrangement in the first coordination shell of liquid water is actually very similar as the two-hydrogen-bonded configurations at the surface of ice. This discovery suggests that most molecules in liquid water have two-hydrogen-bonded configurations with one donor and one acceptor hydrogen bond compared to the four-hydrogen-bonded tetrahedral structure in ice. This result is controversial since the general picture is that the structure of liquid water is very similar to the structure of ice. The results are, however, consistent with x-ray and neutron diffraction data but reveals serious discrepancies with structures based on current molecular dynamics simulations. The two-hydrogen-bond configuration in liquid water is rigid and heating from 25 °C to 90 °C introduce a minor change in the hydrogen-bonded configurations. Furthermore, XAS studies of water in aqueous solutions show that ion hydration does not affect the hydrogen bond configuration of the bulk. Only water molecules in the close vicinity to the ions show changes in the hydrogen bond formation. XAS data obtained with fluorescence yield are sensitive enough to resolved electronic structure of water molecules in the first hydration sphere and to distinguish between different protonated species. Hence, XAS is a useful tool to provide insight into the local electronic structure of a hydrogen-bonded liquid and it is applied for the first time on water revealing unique information of high importance.