Inorganic carbon dominates total dissolved carbon concentrations and fluxes in British rivers: application of the THINCARB model – thermodynamic modelling of inorganic carbon in freshwaters

River water-quality studies rarely measure dissolved inorganic carbon (DIC) routinely, and there is a gap in our knowledge of the contributions of DIC to aquatic carbon fluxes and cycling processes. Here, we present the THINCARB model (THermodynamic modelling of INorganic CARBon), which uses widely-measured determinands (pH, alkalinity and temperature) to calculate DIC concentrations, speciation (bicarbonate, HCO3−; carbonate, CO32 −; and dissolved carbon dioxide, H2CO3⁎) and excess partial pressures of carbon dioxide (EpCO2) in freshwaters. If calcium concentration measurements are available, THINCARB also calculates calcite saturation. THINCARB was applied to the 39-year Harmonised Monitoring Scheme (HMS) dataset, encompassing all the major British rivers discharging to the coastal zone. Model outputs were combined with the HMS dissolved organic carbon (DOC) datasets, and with spatial land use, geology, digital elevation and hydrological datasets. We provide a first national-scale evaluation of: the spatial and temporal variability in DIC concentrations and fluxes in British rivers; the contributions of DIC and DOC to total dissolved carbon (TDC); and the contributions to DIC from HCO3− and CO32 − from weathering sources and H2CO3⁎ from microbial respiration. DIC accounted for > 50% of TDC concentrations in 87% of the HMS samples. In the seven largest British rivers, DIC accounted for an average of 80% of the TDC flux (ranging from 57% in the upland River Tay, to 91% in the lowland River Thames). DIC fluxes exceeded DOC fluxes, even under high-flow conditions, including in the Rivers Tay and Tweed, draining upland peaty catchments. Given that particulate organic carbon fluxes from UK rivers are consistently lower than DOC fluxes, DIC fluxes are therefore also the major source of total carbon fluxes to the coastal zone. These results demonstrate the importance of accounting for DIC concentrations and fluxes for quantifying carbon transfers from land, via rivers, to the coastal zone

Within-river phosphorus retention: accounting for a missing piece in the watershed phosphorus puzzle

The prevailing "puzzle" in watershed phosphorus (P) management is how to account for the nonconservative behavior (retention and remobilization) of P along the land-freshwater continuum. This often hinders our attempts to directly link watershed P sources with their water quality impacts. Here, we examine aspects of within-river retention of wastewater effluent P and its remobilization under high flows. Most source apportionment methods attribute P loads mobilized under high flows (including retained and remobilized effluent P) as nonpoint agricultural sources. We present a new simple empirical method which uses chloride as a conservative tracer of wastewater effluent, to quantify within-river retention of effluent P, and its contribution to river P loads, when remobilized under high flows. We demonstrate that within-river P retention can effectively mask the presence of effluent P inputs in the water quality record. Moreover, we highlight that by not accounting for the contributions of retained and remobilized effluent P to river storm-flow P loads, existing source apportionment methods may significantly overestimate nonpoint agricultural sources and underestimate wastewater sources in mixed land-use watersheds. This has important implications for developing effective watershed remediation strategies, where remediation needs to be equitably and accurately apportioned among point and nonpoint P contributors

Phosphorus mirabilis: illuminating the past and future of phosphorus stewardship

After its discovery in 1669, phosphorus (P) was named Phosphorus mirabilis (“the miraculous bearer of light”), arising from the chemoluminescence when white P is exposed to the atmosphere. The metaphoric association between P and light resonates through history: from the discovery of P at the start of the Enlightenment period to the vital role of P in photosynthetic capture of light in crop and food production through to new technologies, which seek to capitalize on the interactions between novel ultrathin P allotropes and light, including photocatalysis, solar energy production, and storage. In this introduction to the Journal of Environmental Quality special section “Celebrating the 350th Anniversary of Discovering Phosphorus—For Better or Worse,” which brings together 22 paper contributions, we shine a spotlight on the historical and emerging challenges and opportunities in research and understanding of the agricultural, environmental, and societal significance of this vital element. We highlight the role of P in water quality impairment and the variable successes of P mitigation measures. We reflect on the need to improve P use efficiency and on the kaleidoscope of challenges facing efficient use of P. We discuss the requirement to focus on place-based solutions for developing effective and lasting P management. Finally, we consider how cross-disciplinary collaborations in P stewardship offer a guiding light for the future, and we explore the glimmers of hope for reconnecting our broken P cycle and the bright new horizons needed to ensure future food, water, and bioresource security for growing global populations

The role of field-scale management on soil and surface runoff C/N/P stoichiometry

Agricultural runoff is an important contributor to water quality impairment. This study was conducted to evaluate the potential role of field-scale management on carbon (C), nitrogen (N), and phosphorus (P) stoichiometry in soils and runoff from agricultural fields. Cultivated and pasture fields at the Riesel watersheds in central Texas were used for this analysis, and nutrients were transformed to evaluate relative to the Redfield ratio (106 C/16 N/1 P). Using the Redfield ratio, all soil samples were P depleted relative to C and N. The majority of stormflow and baseflow runoff samples contained 9 to 19% Redfield N relative to C and P. Shifting from inorganic fertilizer application to poultry litter as a fertilizer source resulted in increased absolute C, N, and P concentrations in stormflow and baseflow runoff. Increasing rates of poultry litter application increased the Redfield P relative to Redfield C, whereas Redfield N remained relatively constant at roughly 9 to 11% in stormflow runoff from cultivated fields. This study shows how land use and management can affect C/N/P stoichiometry in stormflow and baseflow runoff

High-frequency water quality monitoring in an urban catchment: hydrochemical dynamics, primary production and implications for the Water Framework Directive

This paper describes the hydrochemistry of a lowland, urbanised river-system, The Cut in England, using in situ sub-daily sampling. The Cut receives effluent discharges from four major sewage treatment works serving around 190,000 people. These discharges consist largely of treated water, originally abstracted from the River Thames and returned via the water supply network, substantially increasing the natural flow. The hourly water quality data were supplemented by weekly manual sampling with laboratory analysis to check the hourly data and measure further determinands. Mean phosphorus and nitrate concentrations were very high, breaching standards set by EU legislation. Though 56% of the catchment area is agricultural, the hydrochemical dynamics were significantly impacted by effluent discharges which accounted for approximately 50% of the annual P catchment input loads and, on average, 59% of river flow at the monitoring point. Diurnal dissolved oxygen data demonstrated high in-stream productivity. From a comparison of high frequency and conventional monitoring data, it is inferred that much of the primary production was dominated by benthic algae, largely diatoms. Despite the high productivity and nutrient concentrations, the river water did not become anoxic and major phytoplankton blooms were not observed. The strong diurnal and annual variation observed showed that assessments of water quality made under the Water Framework Directive (WFD) are sensitive to the time and season of sampling. It is recommended that specific sampling time windows be specified for each determinand, and that WFD targets should be applied in combination to help identify periods of greatest ecological risk. This article is protected by copyright. All rights reserved

Future phosphorus: advancing new 2D phosphorus allotropes and growing a sustainable bioeconomy

With more than 40 countries currently proposing to boost their national bioeconomies, there is no better time for a clarion call for a “new” bioeconomy, which, at its core, tackles the current disparities and inequalities in phosphorus (P) availability. Existing biofuel production systems have widened P inequalities and contributed to a linear P economy, impairing water quality and accelerating dependence on P fertilizers manufactured from finite nonrenewable phosphate rock reserves. Here, we explore how the emerging bioeconomy in novel, value-added, bio-based products offers opportunities to rethink our stewardship of P. Development of integrated value chains of new bio-based products offers opportunities for codevelopment of “P refineries” to recover P fertilizer products from organic wastes. Advances in material sciences are exploiting unique semiconductor and opto-electrical properties of new “two-dimensional” (2D) P allotropes (2D black phosphorus and blue phosphorus). These novel P materials offer the tantalizing prospect of step-change innovations in renewable energy production and storage, in biomedical applications, and in biomimetic processes, including artificial photosynthesis. They also offer a possible antidote to the P paradox that our agricultural production systems have engineered us into, as well as the potential to expand the future role of P in securing sustainability across both agroecological and technological domains of the bioeconomy. However, a myriad of social, technological, and commercialization hurdles remains to be crossed before such an advanced circular P bioeconomy can be realized. The emerging bioeconomy is just one piece of a much larger puzzle of how to achieve more sustainable and circular horizons in our future use of P

Phosphorus and nitrogen limitation and impairment of headwater streams relative to rivers in Great Britain: a national perspective on eutrophication

This study provides a first national-scale assessment of the nutrient status of British headwater streams within the wider river network, by joint analysis of the national Countryside Survey Headwater Stream and Harmonised River Monitoring Scheme datasets. We apply a novel Nutrient Limitation Assessment methodology to explore the extent to which nutrients may potentially limit primary production in headwater streams and rivers, by coupling ternary assessment of nitrogen (N), phosphorus (P), and carbon (C) depletion, with N:P stoichiometry, and threshold P and N concentrations. P limitation was more commonly seen in the rivers, with greater prevalence of N limitation in the headwater streams. High levels of potential P and N co-limitation were found in the headwater streams, especially the Upland-Low-Alkalinity streams. This suggests that managing both P and N inputs may be needed to minimise risks of degradation of these sensitive headwater stream environments. Although localised nutrient impairment of headwater streams can occur, there were markedly lower rates of P and N impairment of headwater streams relative to downstream rivers at the national scale. Nutrient source contributions, relative to hydrological dilution, increased with catchment scale, corresponding with increases in the extent of agricultural and urban land-use. The estimated nutrient reductions needed to achieve compliance with Water Framework Directive standards, and to reach limiting concentrations, were greatest for the Lowland-High-Alkalinity rivers and streams. Preliminary assessments suggest that reducing P concentrations in the Lowland-High-Alkalinity headwater streams, and N concentrations in the Upland-Low-Alkalinity rivers, might offer greater overall benefits for water-quality remediation at the national scale, relative to the magnitude of nutrient reductions required. This approach could help inform the prioritisation of nutrient remediation, as part of a directional approach to water quality management based on closing the gaps between current and target nutrient concentrations

Enhanced nitrogen and phosphorus flows in a mixed land use basin: drivers and consequences

Rapid increase in accumulation of phosphorus (P) relative to nitrogen (N) has been observed in human-impacted regions, but the reasons are largely unknown. We developed an Integrated Nutrient Flow Analysis (INFA) model in order to assess the changes in nutrient flows of the Chaohu Lake basin from 1978 to 2015. Results show that the increase in total N input is slower than that of P (3.5-fold versus 4.2-fold) during 1978–2015, while total N loss increases much faster than that of P (3.1-fold versus 2.3-fold). We found a decline trend in the N:P ratio of nutrient input and accumulation since the mid-1990s. The decline in N:P ratio of nutrient loss to waterbodies in the basin is correlated (p < 0.05) with TN:TP of water concentration in Chaohu Lake, which may be related to the frequent algal blooms in the P-limited lake by supplying more P than N. Using an extended STIRPAT model, we found that nutrient use efficiency, urban rate, diet choice and population are key factors driving the change in nutrient flows, which contribute over 90% to the total change. This study confirms that human activities decrease N:P in regional environment and demonstrates the importance of P management to balance nutrient for improving water quality. The method in this study has a wide application for many other mixed land use regions to address nutrient flows imbalance problems and to explore nutrient management options

Phosphorus footprint in China over the 1961–2050 period: historical perspective and future prospect

The phosphorus footprint (PF) is a novel concept to analyze human burdens on phosphorus resources. However, research on PF approach is still limited, and current several PF studies include incomplete phosphorus sources and have limited quantitative interpretation about the drivers of PF changes, which can help understand future trends of PF. This study develops a more comprehensive PF model by considering crop, livestock and aquatic food, and non-food goods, which covers the mainly phosphorus containing products consumed by human. The model is applied to quantify China's PF from 1961 to 2014, and the results of the model are also used to analyze the factors driving the PF changes and explored China's PF scenarios for 2050 using an econometric analysis model (STIRPAT). The result shows that China's PF increased over 11-fold, from 0.9 to 10.6 Tg between 1961 and 2014. The PF of livestock food dominated China's PF, accounting for 57% of the total in 1961 and 45% in 2014. The key factors driving the increase in China's PF are the increase in population and urbanization rate, with contributions of 38% and 33%, respectively. We showed that in the baseline scenario, China's PF would increase by 70% during 2014–2050 and cause the depletion of China's phosphate reserves in 2045. However, in the best case scenario, China's PF would decrease by 15% in 2050 compared with that in 2014, and it would have 50% of current phosphate reserve remaining by 2050. Several mitigation measures are then proposed by considering China's realities from both production and consumption perspective, which can provide valuable policy insights to other rapid developing countries to mitigate the P footprint

Coupling high-frequency stream metabolism and nutrient monitoring to explore biogeochemical controls on downstream nitrate delivery

Instream biogeochemical process measurements are often short-term and localized. Here we use in situ sensors to quantify the net effects of biogeochemical processes on seasonal patterns in baseflow nitrate retention at the river-reach scale. Dual-station high-frequency in situ nitrate measurements, were coupled with high-frequency measurements of stream metabolism and dissolved inorganic carbon, in a tributary of the Buffalo National River, Arkansas. Nitrate assimilation was calculated from net primary production, and combined with mass-balance measurements, to estimate net nitrification and denitrification. The combined net effects of these instream processes (assimilation, denitrification, and nitrification) removed >30–90% of the baseflow nitrate load along a 6.5 km reach. Assimilation of nitrate by photoautotrophs during spring and early summer was buffered by net nitrification. Net nitrification peaked during the spring. After midsummer, there was a pronounced switch from assimilatory nitrate uptake to denitrification. There was clear synchronicity between the switch from nitrate assimilation to denitrification, a reduction in river baseflows, and a shift in stream metabolism from autotrophy to heterotrophy. The results show how instream nitrate retention and downstream delivery is driven by seasonal shifts in metabolic pathways; and how continuous in situ stream sensor networks offer new opportunities for quantifying the role of stream biota in the dynamics, fate, and transport of nitrogen in fluvial systems