Global-scale nitrogen budgets developed to quantify anthropogenic impacts on the nitrogen cycle do not explicitly consider nitrate stored in the vadose zone. Here we show that the vadose zone is an important store of nitrate that should be considered in future budgets for effective policymaking. Using estimates of groundwater depth and nitrate leaching for 1900–2000, we quantify the peak global storage of nitrate in the vadose zone as 605–1814 Teragrams (Tg). Estimates of nitrate storage are validated using basin-scale and national-scale estimates and observed groundwater nitrate data. Nitrate storage per unit area is greatest in North America, China and Europe where there are thick vadose zones and extensive historical agriculture. In these areas, long travel times in the vadose zone may delay the impact of changes in agricultural practices on groundwater quality. We argue that in these areas use of conventional nitrogen budget approaches is inappropriate.

Knowledge of the natural baseline quality of groundwaters is an essential prerequisite for understanding pollution and for imposing regulatory limits. The natural baseline of groundwaters may show a range of concentrations depending on aquifer mineralogy, facies changes, flow paths and residence time. The geochemical controls on natural concentrations are discussed and an approach to defining baseline concentrations using geochemical and statistical tools is proposed. The approach is illustrated using a flowline from the Chalk aquifer in Berkshire, UK where aerobic and anaerobic sections of the aquifer are separately considered. The baseline concentrations for some elements are close to atmospheric values whereas others evolve through time-dependent water-rock interaction. Certain solutes (K, NH(4)(+)), often considered contaminants, reach naturally high concentrations due to geochemical controls; transition metal concentrations are generally low, although their concentrations may be modified by redox controls. It is recommended that the baseline approach be incorporated into future management strategies, notably monitoring.

This paper describes the development of the first operational seasonal hydrological forecasting service for the UK, the Hydrological Outlook UK (HOUK). Since June 2013, this service has delivered monthly forecasts of streamflow and groundwater levels, with an emphasis on forecasting hydrological conditions over the next three months, accompanied by outlooks over longer time horizons. This system is based on three complementary approaches combined to produce the outlooks: (i) national-scale modelling of streamflow and groundwater levels based on dynamic seasonal rainfall forecasts, (ii) catchment-scale modelling where streamflow and groundwater level models are driven by historical meteorological forcings (i.e. the Ensemble Streamflow Prediction, ESP, approach), and (iii) a catchment-scale statistical method based on persistence and historical analogues. This paper provides the background to the Hydrological Outlook, describes the various component methods in detail and then considers the impact and usefulness of the product. As an example of a multi-method, operational seasonal hydrological forecasting system, it is hoped that this overview provides useful information and context for other forecasting initiatives around the world.ARTICLE HISTORY

Nitrate is necessary for agricultural productivity, but can cause considerable problems if released into aquatic systems. Agricultural land is the major source of nitrates in UK groundwater. Due to the long time-lag in the groundwater system, it could take decades for leached nitrate from the soil to discharge into freshwaters. However, this nitrate time-lag has rarely been considered in environmental water management. Against this background, this paper presents an approach to modelling groundwater nitrate at the national scale, to simulate the impacts of historical nitrate loading from agricultural land on the evolution of groundwater nitrate concentrations. An additional process-based component was constructed for the saturated zone of significant aquifers in England and Wales. This uses a simple flow model which requires modelled recharge values, together with published aquifer properties and thickness data. A spatially distributed and temporally variable nitrate input function was also introduced. The sensitivity of parameters was analysed using Monte Carlo simulations. The model was calibrated using national nitrate monitoring data. Time series of annual average nitrate concentrations along with annual spatially distributed nitrate concentration maps from 1925 to 2150 were generated for 28 selected aquifer zones. The results show that 16 aquifer zones have an increasing trend in nitrate concentration, while average nitrate concentrations in the remaining 12 are declining. The results are also indicative of the trend in the flux of groundwater nitrate entering rivers through baseflow. The model thus enables the magnitude and timescale of groundwater nitrate response to be factored into source apportionment tools and to be taken into account alongside current planning of land-management options for reducing nitrate losses.

There is growing concern globally about the occurrence of anthropogenic organic contaminants in the environment, including pharmaceuticals and personal care products. This concern extends to groundwater, which is a critical water resource in Europe, and its protection is a priority to the European Commission, the European Union (EU) Member States and national agencies across Europe. Maintaining good groundwater status supports improved public health, economic growth and sustains groundwater dependant ecosystems. A range of measures have been introduced for regulating several substances that have impacted groundwater (e.g. nitrate and pesticides). However, these measures only cover a small fraction of anthropogenic substances that could pollute groundwater. Monitoring for these unregulated substances is currently very limited or not carried out at all. Therefore, a coordinated European-wide approach is needed to identify, monitor and characterise priority substances or groups of substances that have the potential to pollute groundwater. This evidence base is critical for policy development and controls on these currently unregulated substances. The European Commission highlighted this as a need during the review of the EU Groundwater Directive Annexes in 2014, when the requirement to develop a Groundwater Watch List (GWWL) was established. This paper describes the approach that has been developed through a voluntary initiative as part of the EU CIS Working Group Groundwater to establish the voluntary EU GWWL. The process for developing the GWWL is one that has brought together researchers, regulators and industry, and is described here for the first time. A summary of the key principles behind the methodology is presented as well as results from pilot studies using per-and polyfluoroalkyl substances and pharmaceuticals. These explore and support the viability of the GWWL process, an important step towards its adoption and its future use for groundwater protection across Europe.