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River networks connect terrestrial and marine ecosystems through transport of pollutants and nutrients. Lakes represent discontinuities within these river networks, which can be important biogeochemical hotspots, introducing substantial changes to the aquatic environment. Nitrogen is a key macronutrient that can potentially limit or co-limit primary production, but the processes that determine the fate of nitrogen during transport through river-lake networks are poorly understood. We studied three river systems and their lake discontinuities, spanning a range of trophic states and average water residence times, to understand the changes introduced to riverine nitrogen biogeochemistry by lake discontinuities. In-lake processes noticeably altered the concentration and speciation of nitrogen. Annually, lakes reduced up to 44% of nitrate compared to main inflow concentrations, while there was large variability in nitrate dynamics seasonally. The drawdown in surface nitrate concentrations resulted at times in phytoplankton co-limitation by nitrogen in-lake, as well as in the downstream river, where altered nitrogen patterns could persist for several kilometers. However, lakes occasionally subsidized N to downstream rivers as ammonium or dissolved organic nitrogen. Assimilation of nitrate in lake surface waters was one of the dominant processes impacting nitrogen availability; however, stable isotope data revealed an unexpected contribution of nitrification on nitrogen cycling in the epilimnion throughout the year and across trophic gradients. These changes in nitrogen concentration, as well as speciation introduced by lake discontinuities have potentially important consequences for the composition and metabolism of communities in downstream rivers and contribute to our fundamental understanding of freshwater processes.

Human activity has led to excess phosphorus (P) concentrations and the continued eutrophication of coastal and freshwaters across the United States (US). Developing more effective P management policy requires a comprehensive understanding of P sources in the environment. Public water systems across the United States widely dose water with phosphate (PO4) in order to control the corrosion of lead and copper within their distribution networks. Using public water system PO4 dosing facility data and target PO4-P dosing concentrations, we estimate that PO4 dosing added 4–14.9 kt PO4-P yr−1 into the US water distribution network in 2015. Using estimates of public water supply inputs and domestic water deliveries, we estimate that 0.7–2.6, and 0.8–3.1 kt PO4-P yr−1 were then lost from the network due to watermains leakage and outdoor water use, respectively. After accounting for these fluxes, we estimate that 9.3 kt PO4-P yr−1 was then returned to wastewater treatment plants (WWTPs) and accounted for up to 2.7% of the national WWTP influent P load. As sources of P to the environment, lower and upper estimates of combined watermains leakage and outdoor water use PO4-P fluxes exceeded P loads to surface waterbodies from documented point sources across 461–541 counties. The exceedance of these fluxes above other major components of the US P-budget emphasizes the need to include them in P source apportionment studies, both across the US and in other countries where public water supplies are dosed with PO4.

Excessive nutrient concentrations within fresh waters are a globally persistent problem. Developing effective nutrient management strategies requires improvements to nitrogen (N) mass balances, including the identification and quantification of previously unrecognized anthropogenic N fluxes. Using publicly available data, we establish that freshwater abstractions from both surface waters and groundwaters, alongside watermains leakage from public distribution networks, are responsible for significant nitrate-N (NO3-N) fluxes across the contiguous United States. Nationally, freshwater abstraction temporarily retains 417 (min-max: 190–857) kt NO3-N yr−1, equivalent to 21% of pastureland N uptake and 2% of previous global abstraction-N flux estimates. Fluxes due to irrigation, thermoelectric power, and public water supply collectively account for 87% of this total. We find large intercounty variation in area-normalized abstraction fluxes (min-max: 0–8,267 kg NO3-N km−2 yr−1), with eastern regions generally associated with larger fluxes. Watermains leakage returns 7 (min-max: 6.3–7.7) kt NO3-N yr−1 back to the environment, equivalent to 13% of NO3-N initially abstracted for public supply and 1.3% of previous global leakage flux estimates. Our analyses reveal inter-county variations in area-normalized leakage fluxes (min-max: 0–576 kg NO3-N km−2 yr−1), with this flux exceeding other major N inputs (agricultural N fertilizer) in some urbanized and coastal counties, highlighting their importance in these areas. The local and national importance of these fluxes has implications for policy makers and water resource managers aiming to better manage the impacts of N within the environment and calls for their inclusion in both US and global N budgets.

The oxygen isotope composition of dissolved inorganic phosphate (δ18Op) offers new opportunities to understand the sources and the fate of phosphorus (P) in freshwater ecosystems. However, current analytical protocols for determining δ18Op are unable to generate reliable data for samples in which ambient P concentrations are extremely low, precisely the systems in which δ18Op may provide new and important insights into the biogeochemistry of P. In this Article, we report the development, testing and initial application of a new technique that enables δ18Op analysis to be extended into such ecosystems. The twist spinning mode (TSM) protocol described here enables >1000 L of sample with a P concentration <0.016 mg P L–1 to be initially processed within the field in approximately 24 h. Combined with a new freeze-drying method to maximize the yield and minimize the contamination of silver phosphate generated for isotope ratio mass spectrometry, the TSM protocol is able to generate accurate and precise δ18Op data. We evaluated the TSM protocol using synthetic test solutions and subsequently applied the protocol to samples from locations around the Saint Lawrence River in Montreal, Canada. We believe that the novel technique reported here offers the methodological basis for researchers to extend the application of δ18Op into a much wider range of freshwater ecosystems than has been possible to date.

Understanding anthropogenic disturbance of macronutrient cycles is essential for assessing the risks facing ecosystems. For the first time, we quantified inorganic nitrogen (N) fluxes associated with abstraction, mains water leakage, and transfers of treated water related to public water supply. In England, the mass of nitrate-N removed from aquatic environments by abstraction (ABS-NO3-N) was estimated to be 24.2 kt N/year. This is equal to six times the estimates of organic N removal by abstraction, 15 times in-channel storage of organic N, and 30 times floodplain storage of organic N. ABS-NO3-N is also between 3 and 39% of N removal by denitrification in the hydrosphere. Mains water leakage of nitrate-N (MWL-NO3-N) returns 3.62 kt N/year to the environment, equating to approximately 15% of ABS-NO3-N. In urban areas, MWL-NO3-N can represent up to 20% of the total N inputs. MWL-NO3-N is predicted to increase by up to 66% by 2020 following implementation of treated water transfers. ABS-NO3-N and MWL-NO3-N should be considered in future assessments of N fluxes, in order to accurately quantify anthropogenic disturbances to N cycles. The methodology we developed is transferable, uses widely available datasets, and could be used to quantify N fluxes associated with public water supply across the world.

Effective strategies to reduce phosphorus (P)-enrichment of aquatic ecosystems require accurate quantification of the absolute and relative importance of individual sources of P. In this paper, we quantify the potential significance of a source of P that has been neglected to date. Phosphate dosing of raw water supplies to reduce lead and copper concentrations in drinking water is a common practice globally. However, mains water leakage (MWL) potentially leads to a direct input of P into the environment, bypassing wastewater treatment. We develop a new approach to estimate the spatial distribution and time-variant flux of MWL-P, demonstrating this approach for a 30-year period within the exemplar of the River Thames catchment in the UK. Our analyses suggest that MWL-P could be equivalent to up to c.24% of the P load entering the River Thames from sewage treatment works and up to c.16% of the riverine P load derived from agricultural non-point sources. We consider a range of policy responses that could reduce MWL-P loads to the environment, including incorporating the environmental damage costs associated with P in setting targets for MWL reduction, alongside inclusion of MWL-P within catchment-wide P permits.

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 (δ18OPO4), 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 δ18OPO4 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 δ18OPO4 of the source acid (average = +12.4 or +19.7‰). Dependent upon the source acid used, drinking water δ18OPO4 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 δ18OPO4 within drinking water supplies.