The need to integrate legacy nitrogen storage dynamics and time lags into policy and practice.

Increased fluxes of reactive nitrogen (Nr), often associated with N fertilizer use in agriculture, have resulted in negative environmental consequences, including eutrophication, which cost billions of dollars per year globally. To address this, best management practices (BMPs) to reduce Nr loading to the environment have been introduced in many locations. However, improvements in water quality associated with BMP implementation have not always been realised over expected timescales. There is a now a significant body of scientific evidence showing that the dynamics of legacy Nr storage and associated time lags invalidate the assumptions of many models used by policymakers for decision making regarding Nr BMPs. Building on this evidence, we believe that the concepts of legacy Nr storage dynamics and time lags need to be included in these models. We believe the biogeochemical research community could play a more proactive role in advocating for this change through both awareness raising and direct collaboration with policymakers to develop improved datasets and models. We anticipate that this will result in more realistic expectations of timescales for water quality improvements associated with BMPs. Given the need for multi-nutrient policy responses to tackle challenges such as eutrophication, integration of N stores will have the further benefit of aligning both researchers and policymakers in the N community with the phosphorus and carbon communities, where estimation of stores is more widespread. Ultimately, we anticipate that integrating legacy Nr storage dynamics and time lags into policy frameworks will better meet the needs of human and environmental health.

A New Technique to Determine the Phosphate Oxygen Isotope Composition of Freshwater Samples at Low Ambient Phosphate Concentration.

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.

Provenance of drinking water revealed through compliance sampling.

Understanding drinking water hydrochemistry is essential for maintaining safe drinking water supplies. Whilst targeted research surveys have characterised drinking water hydrochemistry, vast compliance datasets are routinely collected but are not interrogated amidst concerns regarding the impact of mixed water sources, treatment, the distribution network and customer pipework. In this paper, we examine whether compliance samples retain hydrochemical signatures of their provenance. We first created and subsequently undertook the first hydrochemical analysis of a novel national database of publically available drinking water compliance analyses (n = 3 873 941) reported for 2015 across England and Wales. k-means cluster analysis revealed three spatially coherent clusters. Cluster 1 is dominated by groundwater sources, with high nitrate concentrations and mineralisation, and lower organic carbon, residual chlorine and THM formation. Cluster 2 was dominated by surface water sources and characterised by low mineralisation (low conductivity and major ion concentrations), low nitrate and high organic carbon concentrations (and hence residual chlorine and THM formation). Cluster 3 shows a mixture of groundwater overlain by confining layers and superficial deposits (resulting in higher trace metal concentrations and mineralisation) and surface water sources. These analyses demonstrate that, despite extensive processing of drinking water, at the national scale signatures of the provenance of drinking water remain. Analysis of compliance samples is therefore likely to be a helpful tool in the characterisation of processes that may affect drinking water chemistry. The methodology used is generic and can be applied in any area where drinking water chemistry samples are taken.

Public Water Supply Is Responsible for Significant Fluxes of Inorganic Nitrogen in the Environment.

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.

The stocks and flows of nitrogen, phosphorus and potassium across a 30-year time series for agriculture in Huantai county, China.

In order to improve the efficiency of nutrient use whilst also meeting projected changes in the demand for food within China, new nutrient management frameworks comprised of policy, practice and the means of delivering change are required. These frameworks should be underpinned by systemic analyses of the stocks and flows of nutrients within agricultural production. In this paper, a 30-year time series of the stocks and flows of nitrogen (N), phosphorus (P) and potassium (K) are reported for Huantai county, an exemplar area of intensive agricultural production in the North China Plain. Substance flow analyses were constructed for the major crop systems in the county across the period 1983-2014. On average across all production systems between 2010 and 2014, total annual nutrient inputs to agricultural land in Huantai county remained high at 18.1kt N, 2.7kt P and 7.8kt K (696kg N ha-1; 104kgP ha-1; 300kgK ha-1). Whilst the application of inorganic fertiliser dominated these inputs, crop residues, atmospheric deposition and livestock manure represented significant, yet largely unrecognised, sources of nutrients, depending on the individual production system and the period of time. Whilst nutrient use efficiency (NUE) increased for N and P between 1983 and 2014, future improvements in NUE will require better alignment of nutrient inputs and crop demand. This is particularly true for high-value fruit and vegetable production, in which appropriate recognition of nutrient supply from sources such as manure and from soil reserves will be required to enhance NUE. Aligned with the structural organisation of the public agricultural extension service at county-scale in China, our analyses highlight key areas for the development of future agricultural policy and farm advice in order to rebalance the management of natural resources from a focus on production and growth towards the aims of efficiency and sustainability.

New approaches to enhance pollutant removal in artificially aerated wastewater treatment systems.

Freshwater ecosystems sustain human society through the provision of a range of services. However, the status of these ecosystems is threatened by a multitude of pressures, including point sources of wastewater. Future treatment of wastewater will increasingly require new forms of decentralised infrastructure. The research reported here sought to enhance pollutant removal within a novel wastewater treatment technology, based on un-planted, artificially aerated, horizontal subsurface flow constructed wetlands. The potential for these systems to treat de-icer contaminated runoff from airports, a source of wastewater that is likely to grow in importance alongside the expansion of air travel and under future climate scenarios, was evaluated. A new configuration for the delivery of air to aerated treatment systems was developed and tested, based on a phased-aeration approach. This new aeration approach significantly improved pollutant removal efficiency compared to alternative aeration configurations, achieving >90% removal of influent load for COD, BOD5 and TOC. Optimised operating conditions under phased aeration were also determined. Based on a hydraulic retention time of 1.5 d and a pollutant mass loading rate of 0.10 kg d-1 m-2 BOD5, >95% BOD5 removal, alongside final effluent BOD5 concentrations <21 mg L-1, could be achieved from an influent characterised by a BOD5 concentration > 800 mg L-1. Key controls on oxygen transfer efficiency within the aerated treatment system were also determined, revealing that standard oxygen transfer efficiency was inversely related to aeration rate between 1 L and 3 L min-1 and positively related to bed media depth between 1500 mm and 3000 mm. The research reported here highlights the potential for optimisation and subsequent widespread application of the aerated wetland technology, in order to protect and restore freshwater ecosystems and the services that they provide to human society.

A multi-stable isotope framework to understand eutrophication in aquatic ecosystems.

Eutrophication is a globally significant challenge facing aquatic ecosystems, associated with human induced enrichment of these ecosystems with nitrogen (N) and phosphorus (P). However, the limited availability of inherent labels for P and N has constrained understanding of the triggers for eutrophication in natural ecosystems and appropriate targeting of management responses. This paper proposes and evaluates a new multi-stable isotope framework that offers inherent labels to track biogeochemical reactions governing both P and N in natural ecosystems. The framework couples highly novel analysis of the oxygen isotope composition of phosphate (δ(18)OPO4) with dual isotope analysis of oxygen and N within nitrate (δ(15)NNO3, δ(18)ONO3) and with stable N isotope analysis in ammonium (δ(15)NNH4). The River Beult in England is used as an exemplar system for initial evaluation of this framework. Our data demonstrate the potential to use stable isotope labels to track the input and downstream fate of nutrients from point sources, on the basis of isotopic differentiation for both P and N between river water and waste water treatment work effluent (mean difference = +1.7‰ for δ(18)OPO4; +15.5‰ for δ(15)NNH4 (under high flow); +7.3‰ for δ(18)ONO3 and +4.4‰ for δ(15)NNO3). Stable isotope data reveal nutrient inputs to the river upstream of the waste water treatment works that are consistent with partially denitrified sewage or livestock sources of nitrate (δ(15)NNO3 range = +11.5 to +13.1‰) and with agricultural sources of phosphate (δ(18)OPO4 range = +16.6 to +19.0‰). The importance of abiotic and metabolic processes for the in-river fate of N and P are also explored through the stable isotope framework. Microbial uptake of ammonium to meet metabolic demand for N is suggested by substantial enrichment of δ(15)NNH4 (by 10.2‰ over a 100 m reach) under summer low flow conditions. Whilst the concentration of both nitrate and phosphate decreased substantially along the same reach, the stable isotope composition of these ions did not vary significantly, indicating that concentration changes are likely driven by abiotic processes of dilution or sorption. The in-river stable isotope composition and the concentration of P and N were also largely constant downstream of the waste water treatment works, indicating that effluent-derived nutrients were not strongly coupled to metabolism along this in-river transect. Combined with in-situ and laboratory hydrochemical data, we believe that a multi-stable isotope framework represents a powerful approach for understanding and managing eutrophication in natural aquatic ecosystems.

Isotopic Fingerprint for Phosphorus in Drinking Water Supplies.

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.

Long-term effects of drinking-water treatment residuals on dissolved phosphorus export from vegetated buffer strips.

The export of dissolved phosphorus (P) in surface runoff from agricultural land can lead to water quality degradation. Surface application of aluminium (Al)-based water treatment residuals (Al-WTRs) to vegetated buffer strip (VBS) soils can enhance P removal from surface runoff during single runoff events. However, the longer-term effects on P removal in VBSs following application of products such as Al-WTR remain uncertain. We used field experimental plots to examine the long-term effects of applying a freshly generated Al-WTR to VBSs on dissolved P export during multiple runoff events, occurring between 1 day and 42 weeks after the application of Al-WTR. Vegetated buffer strip plots amended with Al-WTR significantly reduced soluble reactive P and total dissolved P concentrations in surface runoff compared to both unamended VBS plots and control plots. However, the effectiveness of Al-WTR decreased over time, by approximately 70% after 42 weeks compared to a day following Al-WTR application. Reduced performance did not appear to be due to drying of Al-WTR in the field. Instead, the development of preferential flow paths as well as burying of Al-WTR with freshly deposited sediments may explain these observations. Better understanding of the processes controlling long-term P removal by Al-WTR is required for effective management of VBSs.

Phosphate oxygen isotopes within aquatic ecosystems: global data synthesis and future research priorities.

The oxygen isotope ratio of dissolved inorganic phosphate (δ(18)Op) represents a novel and potentially powerful stable isotope tracer for biogeochemical research. Analysis of δ(18)Op may offer new insights into the relative importance of different sources of phosphorus within natural ecosystems. Due to the isotope fractionations that occur alongside the metabolism of phosphorus, δ(18)Op could also be used to better understand the intracellular and extracellular reaction mechanisms that control phosphorus cycling. In this review focussed on aquatic ecosystems, we examine the theoretical basis to using stable oxygen isotopes within phosphorus research. We consider the methodological challenges involved in accurately determining δ(18)Op, given aquatic matrices in which potential sources of contaminant oxygen are ubiquitous. Finally, we synthesise the existing global data regarding δ(18)Op in aquatic ecosystems, concluding by identifying four key areas for future development of δ(18)Op research. Through this synthesis, we seek to stimulate broader interest in the use of δ(18)Op to address the significant research and management challenges that continue to surround the stewardship of phosphorus.

Enhancing soluble phosphorus removal within buffer strips using industrial by-products.

Using industrial by-products (IBPs) in conjunction with buffer strips provides a potentially new strategy for enhancing soluble phosphorus (P) removal from agricultural runoff. Here, we investigate the feasibility of this approach by assessing the P sorption properties of IBPs at different solution-IBPs contact time (1-120 min) and solution pH (3, 5.5, 7.5), as well as possible adverse environmental effects including P desorption or heavy metal mobilisation from IBPs. Batch experiments were carried out on two widely available IBPs in the UK that demonstrated high P sorption capacity but different physicochemical characteristics, specifically ochre and Aluminium (Al) based water treatment residuals (Al-WTR). A series of kinetic sorption-desorption experiments alongside kinetic modelling were used to understand the rate and the mechanisms of P removal across a range of reaction times. The results of the kinetic experiments indicated that P was initially sorbed rapidly to both ochre and Al-WTR, followed by a second phase characterised by a slower sorption rate. The excellent fits of kinetic sorption data to a pseudo-second order model for both materials suggested surface chemisorption as the rate-controlling mechanism. Neither ochre nor Al-WTR released substantial quantities of either P or heavy metals into solution, suggesting that they could be applied to buffer strip soils at recommended rates (≤30 g kg(-1) soil) without adverse environmental impact. Although the rate of P sorption by freshly-generated Al-WTR applied to buffer strips reduced following air-drying, this would not limit its practical application to buffer strips in the field if adequate contact time with runoff was provided.

Bringing diverse knowledge sources together--a meta-model for supporting integrated catchment management.

Integrated catchment management (ICM), as promoted by recent legislation such as the European Water Framework Directive, presents difficult challenges to planners and decision-makers. To support decision-making in the face of high complexity and uncertainty, tools are required that can integrate the evidence base required to evaluate alternative management scenarios and promote communication and social learning. In this paper we present a pragmatic approach for developing an integrated decision-support tool, where the available sources of information are very diverse and a tight model coupling is not possible. In the first instance, a loosely coupled model is developed which includes numerical sub-models and knowledge-based sub-models. However, such a model is not easy for decision-makers and stakeholders to operate without modelling skills. Therefore, we derive from it a meta-model based on a Bayesian Network approach which is a decision-support tool tailored to the needs of the decision-makers and is fast and easy to operate. The meta-model can be derived at different levels of detail and complexity according to the requirements of the decision-makers. In our case, the meta-model was designed for high-level decision-makers to explore conflicts and synergies between management actions at the catchment scale. As prediction uncertainties are propagated and explicitly represented in the model outcomes, important knowledge gaps can be identified and an evidence base for robust decision-making is provided. The framework seeks to promote the development of modelling tools that can support ICM both by providing an integrated scientific evidence base and by facilitating communication and learning processes.

The release of phosphorus to porewater and surface water from river riparian sediments.

Sediments can be both a source and a sink of dissolved phosphorus (P) in surface water and shallow groundwater. Using laboratory mesocosms, we studied the influence of flooding with deionized water and simulated river water on P release to solution using sediment columns taken from a riparian wetland. The mesocosm incubation results showed that rather than retaining nutrients, sediments in the riparian zone may be a significant source of P. Concentrations of dissolved P in porewater reached more than 3 mg L(-1) and in surface water over 0.8 mg L(-1) within a month of sediment inundation. The reductive dissolution of P-bearing iron (Fe) oxides was the likely mechanism responsible for P release. Dissolved P to Fe molar ratios in anaerobic samples were approximately 0.45 when columns were flooded with water that simulated the chemistry of the adjacent river. This suggests there was insufficient Fe in the anaerobic samples to precipitate all P if the solutions were oxygenated or transported to an aerobic environment. If the anaerobic wetland solutions were delivered to oxygenated rivers and streams adjacent to the riparian zone, the equilibrium concentration of P in these systems could rise. The timing of P release was inversely related to the nitrate (NO3-) concentration in floodwater. This indicates that in riparian zones receiving low nitrate loads, or where NO3- loads are being progressively reduced, the risk of dissolved P release may increase. These findings present particular challenges for restoration and management in riparian areas.