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.

Groundwater in Africa supports livelihoods and poverty alleviation 1,2 , maintains vital ecosystems, and strongly influences terrestrial water and energy budgets 3. However, hydrologic processes governing groundwater recharge sustaining this resource, and their sensitivity to climatic variability, are poorly constrained 4,5. Here we show, through analysis of multi-decadal groundwater hydrographs across sub-Saharan Africa, how aridity controls the predominant recharge processes whereas local hydrogeology influences the type and sensitivity of precipitation-recharge relationships. Some humid locations show approximately linear precipitation-recharge relationships with small rainfall intensity exceedance thresholds governing recharge; others show surprisingly small variation in recharge across a wide range of annual precipitation. As aridity increases, precipitation thresholds governing initiation of recharge increase, recharge becomes more episodic, and focussed recharge via losses from ephemeral overland flows becomes increasingly dominant. Extreme annual recharge is commonly associated with intense rainfall and flooding events, themselves often driven by largescale climate controls. Intense precipitation, even during lower precipitation years, produces substantial recharge in some dry subtropical locations, challenging the 'high certainty' consensus that drying climatic trends will decrease water resources in such regions 4. The likely resilience of groundwater in many areas revealed by improved understanding of precipitation-recharge

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.

Abstract:National terrestrial nitrogen budgets for many developed countries have been calculated as part of the management of impacts of N on the environment, but these rarely represent the subsurface explicitly. Using estimates of vadose zone travel time and agricultural nitrate loading, we quantify, for the first time, the total mass of nitrate contained in the vadose zone of aquifers in England and Wales. This mass peaked in 2008 at 1400 kt N (800 to >1700 kt N from sensitivity analyses), which is approximately 2.5 to 6 times greater than saturated zone estimates for this period and indicates that the subsurface is an important store of reactive nitrogen. About 70% of the nitrate mass is estimated to be in the Chalk, with the remainder split between the Permo-Triassic sandstones, the Jurassic Oolitic limestones and minor aquifers. Current controls on fertilizer application mean that the vadose zone is now a nitrate source, and in 2015 we estimate the net flux from the unsaturated zone to groundwater to be 72 kt N/a. The mass of nitrate in the vadose zone should be included in future terrestrial nitrogen budgets at national and global scales to improve ecosystem management. British Geological Survey

Phosphate dosing of drinking water supplies, coupled with leakage from distribution networks, represents a significant input of phosphorus to the environment. The oxygen isotope composition of phosphate (δ(18)OPO4), a novel stable isotope tracer for phosphorus, offers new opportunities to understand the importance of phosphorus derived from sources such as drinking water. We report the first assessment of δ(18)OPO4 within drinking water supplies. A total of 40 samples from phosphate-dosed distribution networks were analyzed from across England and Wales. In addition, samples of the source orthophosphoric acid used for dosing were also analyzed. Two distinct isotopic signatures for drinking water were identified (average = +13.2 or +19.7‰), primarily determined by δ(18)OPO4 of the source acid (average = +12.4 or +19.7‰). Dependent upon the source acid used, drinking water δ(18)OPO4 appears isotopically distinct from a number of other phosphorus sources. Isotopic offsets from the source acid ranging from -0.9 to +2.8‰ were observed. There was little evidence that equilibrium isotope fractionation dominated within the networks, with offsets from temperature-dependent equilibrium ranging from -4.8 to +4.2‰. While partial equilibrium fractionation may have occurred, kinetic effects associated with microbial uptake of phosphorus or abiotic sorption and dissolution reactions may also contribute to δ(18)OPO4 within drinking water supplies.

11Riverbank filtration schemes form a significant component of public water treatment processes on a 12 global level. Understanding the resilience and water quality recovery of these systems following 13 severe flooding is critical for effective water resources management under potential future climate 14 change. This paper assesses the impact of floodplain inundation on the water quality of a shallow 15 aquifer riverbank filtration system and how water quality recovers following an extreme (1 in 17 16 year, duration > 70 days, 7 day inundation) flood event. During the inundation event, riverbank 17 filtrate water quality is dominated by rapid direct recharge and floodwater infiltration (high fraction 18 of surface water, dissolved organic carbon (DOC) > 140% baseline values, > 1 log increase in micro-19 organic contaminants, microbial detects and turbidity, low specific electrical conductivity (SEC) < 20 90% baseline, high dissolved oxygen (DO) > 400% baseline). A rapid recovery is observed in water 21 quality with most floodwater impacts only observed for 2 -3 weeks after the flooding event and a 22 *Revised manuscript with no changes marked Click here to view linked References 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 2 return to normal groundwater conditions within 6 weeks (lower fraction of surface water, higher 23 SEC, lower DOC, organic and microbial detects, DO). Recovery rates are constrained by the 24 hydrogeological site setting, the abstraction regime and the water quality trends at site boundary 25 conditions. In this case, increased abstraction rates and a high transmissivity aquifer facilitate rapid 26 water quality recoveries, with longer term trends controlled by background river and groundwater 27 qualities. Temporary reductions in abstraction rates appear to slow water quality recoveries. 28Flexible operating regimes such as the one implemented at this study site are likely to be required if 29 shallow aquifer riverbank filtration systems are to be resilient to future inundation events. 30Development of a conceptual understanding of hydrochemical boundaries and site hydrogeology 31 through monitoring is required to assess the suitability of a prospective riverbank filtration site.

We assessed the utility of online fluorescence spectroscopy for the real-time evaluation of the microbial quality of untreated drinking water. Online fluorimeters were installed on the raw water intake at four groundwater-derived UK public water supplies alongside existing turbidity sensors that are used to forewarn of the presence of microbial contamination in the water industry. The fluorimeters targeted fluorescent dissolved organic matter (DOM) peaks at excitation/emission wavelengths of 280/365 nm (tryptophan-like fluorescence, TLF) and 280/450 nm (humic-like fluorescence, HLF). Discrete samples were collected for Escherichia coli, total bacterial cell counts by flow cytometry, and laboratory-based fluorescence and absorbance. Both TLF and HLF were strongly correlated with E. coli (ρ = 0.71-0.77) and total bacterial cell concentrations (ρ = 0.73-0.76), whereas the correlations between turbidity and E. coli (ρ = 0.48) and total bacterial cell counts (ρ = 0.40) were much weaker. No clear TLF peak was observed at the sites and all apparent TLF was considered to be optical bleed-through from the neighbouring HLF peak. Therefore, a HLF fluorimeter alone would be sufficient to evaluate the microbial water quality at these sources. Fluorescent DOM was also influenced by site operations such as pump start-up and the precipitation of cations on the sensor windows. Online fluorescent DOM sensors are a better indicator of the microbial quality of untreated drinking water than turbidity and they have wide-ranging potential applications within the water industry.

Understanding temporal variability in groundwater levels is essential for water resources management. In sub-Saharan Africa, groundwater level dynamics are poorly constrained due to limited long-term observations. Here, we present the first published analysis of temporal variability in groundwater levels at the national scale in sub-Saharan Africa, using 12 multidecadal (ca. 1980s to present) groundwater level hydrographs in Burkina Faso. For each hydrograph, we developed lumped parameter models which achieved acceptable calibrations (NSE = 0.5-0.99). For eight sites not showing significant (p < 0.001) long-term groundwater level declines, we reconstructed groundwater levels to 1902, over 50 years before the earliest observations in the tropics. We standardized and clustered the eight reconstructed hydrographs to compare responses across the sites. Overall, the 12 hydrographs were categorized into three groups, which are dominated by (1) long-term declines (four sites), (2) short-term intra-annual variability (three sites), and (3) long-term multidecadal variability (five sites). We postulate that group 1 is controlled by anthropogenic influences (land use change and abstraction). Correlation of modeled water table depth and groundwater response times with hydrograph autocorrelation suggests that hydrogeological properties and structure control differences between groups 2 and 3. Group 3 shows a small recovery in groundwater levels following the 1970/1980s drought. Differences in intra-annual to multidecadal variability in groundwater levels have implications for water management and highlight the value of long-term monitoring. Reconstructions contextualize current groundwater status, forecasts, and projections. The approach developed is generic and applicable where long-term groundwater level data exist.