Temporal drivers of tryptophan-like fluorescent dissolved organic matter along a river continuum.

Tryptophan-like fluorescence (TLF) is used to indicate anthropogenic inputs of dissolved organic matter (DOM), typically from wastewater, in rivers. We hypothesised that other sources of DOM, such as groundwater and planktonic microbial biomass can also be important drivers of riverine TLF dynamics. We sampled 19 contrasting sites of the River Thames, UK, and its tributaries. Multivariate mixed linear models were developed for each site using 15 months of weekly water quality observations and with predictor variables selected according to the statistical significance of their linear relationship with TLF following a stepwise procedure. The variables considered for inclusion in the models were potassium (wastewater indicator), nitrate (groundwater indicator), chlorophyll-a (phytoplankton biomass), and Total bacterial Cells Counts (TCC) by flow cytometry. The wastewater indicator was included in the model of TLF at 89 % of sites. Groundwater was included in 53 % of models, particularly those with higher baseflow indices (0.50-0.86). At these sites, groundwater acted as a negative control on TLF, diluting other potential sources. Additionally, TCC was included positively in the models of six (32 %) sites. The models on the Thames itself using TCC were more rural sites with lower sewage inputs. Phytoplankton biomass (Chlorophyll-a) was only used in two (11 %) site models, despite the seasonal phytoplankton blooms. It is also notable that, the wastewater indicator did not always have the strongest evidence for inclusion in the models. For example, there was stronger evidence for the inclusion of groundwater and TCC than wastewater in 32 % and 5 % of catchments, respectively. Our study underscores the complex interplay of wastewater, groundwater, and planktonic microbes, driving riverine TLF dynamics, with their influence determined by site characteristics.

A case study: The deployment of a novel in situ fluorimeter for monitoring biological contamination within the urban surface waters of Kolkata, India.

The quality and health of many of our vital freshwater systems are poor. To tackle this with ever increasing pressures from anthropogenic and climatic changes, we must improve water quality monitoring and devise and implement more appropriate water quality parameters. Recent research has highlighted the potential for Peak T fluorescence (tryptophan-like fluorescence, TLF) to monitor microbial activity in aquatic systems. The VLux TPro (Chelsea Technologies Ltd., UK), an in situ real-time fluorimeter, was deployed in different urban freshwater bodies within Kolkata (West Bengal, India) during March 2019. This study is the first to apply this technology in surface waters within a densely populated urban area. Spot-sampling was also undertaken at 13 sampling locations enabling physicochemical analysis, bacterial enumeration and determination of nutrient (nitrate and phosphate) concentrations. This case study has demonstrated the ability of an in situ fluorimeter, VLux TPro, to successfully identify both biological contamination events and potential elevated microbial activity, related to nutrient loading, in complex surface freshwaters, without the need for expensive and time-consuming laboratory analysis.

Using dissolved organic matter fluorescence to identify the provenance of nutrients in a lowland catchment; the River Thames, England.

Catchment based solutions are being sought to mitigate water quality pressures and achieve multiple benefits but their success depends on a sound understanding of catchment functioning. Novel approaches to monitoring and data analysis are urgently needed. In this paper we explore the potential of river water fluorescence at the catchment scale in understanding nutrient concentrations, sources and pathways. Data were collected from across the River Thames basin from January 2012 to March 2015. Analysing emission excitation matrices (EEMs) using both PARAFAC and optimal area averaging produced consistent results for humic-like component 1 and tryptophan-like component 4 in the absence of a subset of samples that exhibited an unusual peak; illustrating the importance of inspecting the entire EEM before using peak averaging methods. Strong relationships between fluorescence components and dissolved organic carbon (DOC), soluble reactive phosphorus (SRP), and ammonium clearly demonstrated its potential, in this study basin, as a field based surrogate for nutrients. Analysing relationships between fluorescence, catchment characteristics and boron from across the basin enabled new insights into the provenance of nutrients. These include evidence for diffuse sources of DOC from near surface hydrological pathways (i.e. soil horizons); point source inputs of nutrients from sewage effluent discharges; and diffuse contributions of nutrients from agriculture and/or sewage (e.g. septic tanks). The information gained by broad scale catchment wide monitoring of fluorescence could support catchment managers in (a) prioritising subcatchments for nutrient mitigation; (b) providing information on relative nutrient source contributions; and (c) providing evidence of the effectiveness of investment in pollution mitigation measures. The collection of high resolution fluorescence data at the catchment scale and, in particular, over shorter event timescales would complement broad scale assessments by enhancing our hydro-biogeochemical process understanding.

A novel application of remote sensing for modelling impacts of tree shading on water quality.

Uncertainty in capturing the effects of riparian tree shade for assessment of algal growth rates and water temperature hinders the predictive capability of models applied for river basin management. Using photogrammetry-derived tree canopy data, we quantified hourly shade along the River Thames (UK) and used it to estimate the reduction in the amount of direct radiation reaching the water surface. In addition we tested the suitability of freely-available LIDAR data to map ground elevation. Following removal of buildings and objects other than trees from the LIDAR dataset, results revealed considerable differences between photogrammetry- and LIDAR-derived methods in variables including mean canopy height (10.5 m and 4.0 m respectively), percentage occupancy of riparian zones by trees (45% and 16% respectively) and mid-summer fractional penetration of direct radiation (65% and 76% respectively). The generated data on daily direct radiation for 2010 were used as input to a river network water quality model (QUESTOR). Impacts of tree shading were assessed in terms of upper quartile levels, revealing substantial differences in indicators such as biochemical oxygen demand (BOD) (1.58-2.19 mg L-1 respectively) and water temperature (20.1 and 21.2 °C respectively) between 'shaded' and 'non-shaded' radiation inputs. Whilst the differences in canopy height and extent derived by the two methods are appreciable they only make small differences to water quality in the Thames. However such differences may prove more critical in smaller rivers. We highlight the importance of accurate estimation of shading in water quality modelling and recommend use of high resolution remotely sensed spatial data to characterise riparian canopies. Our paper illustrates how it is now possible to make better reach scale estimates of shade and make aggregations of these for use at river basin scale. This will allow provision of more effective guidance for riparian management programmes than currently possible. This is important to support adaptation to future warming and maintenance of water quality standards.

Phosphorus fluxes to the environment from mains water leakage: Seasonality and future scenarios.

Accurate quantification of sources of phosphorus (P) entering the environment is essential for the management of aquatic ecosystems. P fluxes from mains water leakage (MWL-P) have recently been identified as a potentially significant source of P in urbanised catchments. However, both the temporal dynamics of this flux and the potential future significance relative to P fluxes from wastewater treatment works (WWT-P) remain poorly constrained. Using the River Thames catchment in England as an exemplar, we present the first quantification of both the seasonal dynamics of current MWL-P fluxes and future flux scenarios to 2040, relative to WWT-P loads and to P loads exported from the catchment. The magnitude of the MWL-P flux shows a strong seasonal signal, with pipe burst and leakage events resulting in peak P fluxes in winter (December, January, February) that are >150% of fluxes in either spring (March, April, May) or autumn (September, October, November). We estimate that MWL-P is equivalent to up to 20% of WWT-P during peak leakage events. Winter rainfall events control temporal variation in both WWT-P and riverine P fluxes which consequently masks any signal in riverine P fluxes associated with MWL-P. The annual average ratio of MWL-P flux to WWT-P flux is predicted to increase from 15 to 38% between 2015 and 2040, associated with large increases in P removal at wastewater treatment works by 2040 relative to modest reductions in mains water leakage. However, further research is required to understand the fate of MWL-P in the environment. Future P research and management programmes should more fully consider MWL-P and its seasonal dynamics, alongside the likely impacts of this source of P on water quality.

Characterisation of a major phytoplankton bloom in the River Thames (UK) using flow cytometry and high performance liquid chromatography.

Recent river studies have observed rapid phytoplankton dynamics, driven by diurnal cycling and short-term responses to storm events, highlighting the need to adopt new high-frequency characterisation methods to understand these complex ecological systems. This study utilised two such analytical methods; pigment analysis by high performance liquid chromatography (HPLC) and cell counting by flow cytometry (FCM), alongside traditional chlorophyll spectrophotometry and light microscopy screening, to characterise the major phytoplankton bloom of 2015 in the River Thames, UK. All analytical techniques observed a rapid increase in chlorophyll a concentration and cell abundances from March to early June, caused primarily by a diatom bloom. Light microscopy identified a shift from pennate to centric diatoms during this period. The initial diatom bloom coincided with increased HPLC peridinin concentrations, indicating the presence of dinoflagellates which were likely to be consuming the diatom population. The diatom bloom declined rapidly in early June, coinciding with a storm event. There were low chlorophyll a concentrations (by both HPLC and spectrophotometric methods) throughout July and August, implying low biomass and phytoplankton activity. However, FCM revealed high abundances of pico-chlorophytes and cyanobacteria through July and August, showing that phytoplankton communities remain active and abundant throughout the summer period. In combination, these techniques are able to simultaneously characterise a wider range of phytoplankton groups, with greater certainty, and provide improved understanding of phytoplankton functioning (e.g. production of UV inhibiting pigments by cyanobacteria in response to high light levels) and ecological status (through examination of pigment degradation products). Combined HPLC and FCM analyses offer rapid and cost-effective characterisation of phytoplankton communities at appropriate timescales. This will allow a more-targeted use of light microscopy to capture phytoplankton peaks or to investigate periods of rapid community succession. This will lead to greater system understanding of phytoplankton succession in response to biogeochemical drivers.

Identifying multiple stressor controls on phytoplankton dynamics in the River Thames (UK) using high-frequency water quality data.

River phytoplankton blooms can pose a serious risk to water quality and the structure and function of aquatic ecosystems. Developing a greater understanding of the physical and chemical controls on the timing, magnitude and duration of blooms is essential for the effective management of phytoplankton development. Five years of weekly water quality monitoring data along the River Thames, southern England were combined with hourly chlorophyll concentration (a proxy for phytoplankton biomass), flow, temperature and daily sunlight data from the mid-Thames. Weekly chlorophyll data was of insufficient temporal resolution to identify the causes of short term variations in phytoplankton biomass. However, hourly chlorophyll data enabled identification of thresholds in water temperature (between 9 and 19°C) and flow (<30m(3)s(-1)) that explained the development of phytoplankton populations. Analysis showed that periods of high phytoplankton biomass and growth rate only occurred when these flow and temperature conditions were within these thresholds, and coincided with periods of long sunshine duration, indicating multiple stressor controls. Nutrient concentrations appeared to have no impact on the timing or magnitude of phytoplankton bloom development, but severe depletion of dissolved phosphorus and silicon during periods of high phytoplankton biomass may have contributed to some bloom collapses through nutrient limitation. This study indicates that for nutrient enriched rivers such as the Thames, manipulating residence time (through removing impoundments) and light/temperature (by increasing riparian tree shading) may offer more realistic solutions than reducing phosphorus concentrations for controlling excessive phytoplankton biomass.

Riparian shading controls instream spring phytoplankton and benthic algal growth.

Dissolved oxygen (DO) concentrations showed a striking pattern in a multi-year study of the River Enborne, a small river in SE England. In each of three years (2010-2012), maximum DO concentrations were attained in mid-April, preceded by a period of steadily increasing diurnal amplitudes, followed by a steady reduction in both amplitude and concentration. Flow events during the reduction period reduce DO to low concentrations until the following spring. Evidence is presented that this pattern is mainly due to benthic algal growth which is eventually suppressed by the growth of the riparian tree canopy. Nitrate and silicate concentrations are too high to inhibit the growth of either benthic algae or phytoplankton, but phosphate concentrations might have started to reduce growth if the tree canopy development had been delayed. This interpretation is supported by evidence from weekly flow cytometry measurements and analysis of the diurnal, seasonal and annual patterns of nutrient concentrations. As the tree canopy develops, the river switches from an autotrophic to a heterotrophic state. The results support the use of riparian shading to help control algal growth, and highlight the risks of reducing riparian shade.

Characterising phosphorus and nitrate inputs to a rural river using high-frequency concentration-flow relationships.

The total reactive phosphorus (TRP) and nitrate concentrations of the River Enborne, southern England, were monitored at hourly interval between January 2010 and December 2011. The relationships between these high-frequency nutrient concentration signals and flow were used to infer changes in nutrient source and dynamics through the annual cycle and each individual storm event, by studying hysteresis patterns. TRP concentrations exhibited strong dilution patterns with increasing flow, and predominantly clockwise hysteresis through storm events. Despite the Enborne catchment being relatively rural for southern England, TRP inputs were dominated by constant, non-rain-related inputs from sewage treatment works (STW) for the majority of the year, producing the highest phosphorus concentrations through the spring-summer growing season. At higher river flows, the majority of the TRP load was derived from within-channel remobilisation of phosphorus from the bed sediment, much of which was also derived from STW inputs. Therefore, future phosphorus mitigation measures should focus on STW improvements. Agricultural diffuse TRP inputs were only evident during storms in the May of each year, probably relating to manure application to land. The nitrate concentration-flow relationship produced a series of dilution curves, indicating major inputs from groundwater and to a lesser extent STW. Significant diffuse agricultural inputs with anticlockwise hysteresis trajectories were observed during the first major storms of the winter period. The simultaneous investigation of high-frequency time series data, concentration-flow relationships and hysteresis behaviour through multiple storms for both phosphorus and nitrate offers a simple and innovative approach for providing new insights into nutrient sources and dynamics.

A cost-effectiveness analysis of water security and water quality: impacts of climate and land-use change on the River Thames system.

The catchment of the River Thames, the principal river system in southern England, provides the main water supply for London but is highly vulnerable to changes in climate, land use and population. The river is eutrophic with significant algal blooms with phosphorus assumed to be the primary chemical indicator of ecosystem health. In the Thames Basin, phosphorus is available from point sources such as wastewater treatment plants and from diffuse sources such as agriculture. In order to predict vulnerability to future change, the integrated catchments model for phosphorus (INCA-P) has been applied to the river basin and used to assess the cost-effectiveness of a range of mitigation and adaptation strategies. It is shown that scenarios of future climate and land-use change will exacerbate the water quality problems, but a range of mitigation measures can improve the situation. A cost-effectiveness study has been undertaken to compare the economic benefits of each mitigation measure and to assess the phosphorus reductions achieved. The most effective strategy is to reduce fertilizer use by 20% together with the treatment of effluent to a high standard. Such measures will reduce the instream phosphorus concentrations to close to the EU Water Framework Directive target for the Thames.

Spatial and temporal changes in chlorophyll-a concentrations in the River Thames basin, UK: are phosphorus concentrations beginning to limit phytoplankton biomass?

Chlorophyll-a and nutrient concentrations were monitored at weekly intervals across 21 river sites throughout the River Thames basin, southern England, between 2009 and 2011. Despite a 90% decrease in soluble reactive phosphorus (SRP) concentration of the lower River Thames since the 1990s, very large phytoplankton blooms still occur. Chlorophyll concentrations were highest in the mid and lower River Thames and the larger tributaries. Lowest chlorophyll concentrations were observed in the smaller tributaries, despite some having very high phosphorus concentrations of over 300 µg l(-1). There was a strong positive correlation between river length and mean chlorophyll concentration (R(2)=0.82), and rivers connected to canals had ca. six times greater chlorophyll concentration than 'natural' rivers with similar phosphorus concentrations, indicating the importance that residence time has on determining phytoplankton biomass. Phosphorus concentration did have some influence, with phosphorus-enriched rivers having much larger phytoplankton blooms than nutrient-poor rivers of a similar length. Water quality improvements may now be capping chlorophyll peaks in the Rivers Thames and Kennet, due to SRP depletion during the spring/early summer phytoplankton bloom period. Dissolved reactive silicon was also depleted to potentially-limiting concentrations for diatom growth in the River Thames during these phytoplankton blooms, but nitrate remained in excess for all rivers throughout the study period. Other potential mitigation measures, such as increasing riparian shading and reducing residence times by removing impoundments may be needed, alongside phosphorus mitigation, to reduce the magnitude of phytoplankton blooms in the future.

Nutrient and light limitation of periphyton in the River Thames: implications for catchment management.

Soluble reactive phosphorus (SRP) concentrations in the River Thames, south east England, have significantly decreased from an annual maximum of 2100 µg l(-1) in 1997 to 344 in 2010, primarily due to the introduction of phosphorus (P) removal at sewage treatment works within the catchment. However, despite this improvement in water quality, phytoplankton biomass in the River Thames has greatly increased in recent years, with peak chlorophyll concentrations increasing from 87 µg l(-1) in the period 1997 to 2002, to 328 µg l(-1) in 2009. A series of within-river flume mesocosm experiments were performed to determine the effect of changing nutrient concentrations and light levels on periphyton biomass accrual. Nutrient enrichment experiments showed that phosphorus, nitrogen and silicon were not limiting or co-limiting periphyton growth in the Thames at the time of the experiment (August-September 2010). Decreasing ambient SRP concentration from 225 µg l(-1) to 173 µg l(-1) had no effect on periphyton biomass accrual rate or diatom assemblage. Phosphorus limitation became apparent at 83 µg SRP l(-1), at which point a 25% reduction in periphyton biomass was observed. Diatom assemblage significantly changed when the SRP concentration was reduced to 30 µg l(-1). Such stringent phosphorus targets are costly and difficult to achieve for the River Thames, due to the high population density and intensive agriculture within the Thames basin. Reducing light levels by shading reduced the periphyton accrual rate by 50%. Providing shading along the River Thames by planting riparian tree cover could be an effective measure to reduce the risk of excessive algal growth. If the ecology of the Thames is to reach the WFD's "good ecological status", then both SRP concentration reductions (probably to below 100 µg l(-1)) and increased shading will be required.

Can we use medical examiners' records for suicide surveillance and prevention research in Nova Scotia?

INTRODUCTION: Medical examiners' records can contribute to our understanding of the extent of suicide in a population, as well as associated sociodemographic and other factors. METHODS: Using a mixed methods approach, the key objective of this pilot study was to determine the sources and types of information found in the Nova Scotia Medical Examiner Service (NSMES) records that might inform suicide surveillance and targeted prevention efforts. A secondary objective was to describe the one-year cohort of 108 individuals who died by suicide in 2006 in terms of available sociodemographic information and health care use in the year prior to death. RESULTS: Data extraction revealed inconsistencies both across and within files in terms of the types and amounts of sociodemographic and other data collected, preventing correlational analyses. However, linkage of the records to administrative databases revealed frequent health care use in the month prior to death. CONCLUSION: The introduction of systematic data collection to NSMES investigations may yield a comprehensive dataset useful for policy development and population level research.

Changes in water quality of the River Frome (UK) from 1965 to 2009: is phosphorus mitigation finally working?

The water quality of the River Frome, Dorset, southern England, was monitored at weekly intervals from 1965 until 2009. Determinands included phosphorus, nitrogen, silicon, potassium, calcium, sodium, magnesium, pH, alkalinity and temperature. Nitrate-N concentrations increased from an annual average of 2.4 mg l⁻¹ in the mid to late 1960s to 6.0 mg l⁻¹ in 2008-2009, but the rate of increase was beginning to slow. Annual soluble reactive phosphorus (SRP) concentrations increased from 101 µg l⁻¹ in the mid 1960s to a maximum of 190 µg l⁻¹ in 1989. In 2002, there was a step reduction in SRP concentration (average=88 µg l⁻¹ in 2002-2005), with further improvement in 2007-2009 (average=49 µg l⁻¹), due to the introduction of phosphorus stripping at sewage treatment works. Phosphorus and nitrate concentrations showed clear annual cycles, related to the timing of inputs from the catchment, and within-stream bioaccumulation and release. Annual depressions in silicon concentration each spring (due to diatom proliferation) reached a maximum between 1980 and 1991, (the period of maximum SRP concentration) indicating that algal biomass had increased within the river. The timing of these silicon depressions was closely related to temperature. Excess carbon dioxide partial pressures (EpCO2) of 60 times atmospheric CO2 were also observed through the winter periods from 1980 to 1992, when phosphorus concentration was greatest, indicating very high respiration rates due to microbial decomposition of this enhanced biomass. Declining phosphorus concentrations since 2002 reduced productivity and algal biomass in the summer, and EpCO2 through the winter, indicating that sewage treatment improvements had improved riverine ecology. Algal blooms were limited by phosphorus, rather than silicon concentration. The value of long-term water quality data sets is discussed. The data from this monitoring programme are made freely available to the wider science community through the CEH data portal (http://gateway.ceh.ac.uk/).

A review and model assessment of (32)P and (33)P uptake to biota in freshwater systems.

Bioaccumulation of key short-lived radionuclides such as (131)I and (32,33)P may be over-estimated since concentration ratios (CRs) are often based on values for the corresponding stable isotope which do not account for radioactive decay during uptake via the food chain. This study presents estimates for bioaccumulation of radioactive phosphorus which account for both radioactive decay and varying ambient levels of stable P in the environment. Recommended interim CR values for radioactive forms of P as a function of bioavailable stable phosphorus in the water body are presented. Values of CR are presented for three different trophic levels of the aquatic food chain; foodstuffs from all three trophic levels may potentially be consumed by humans. It is concluded that current recommended values of the CR are likely to be significantly over-estimated for radioactive phosphorus in many freshwater systems, particularly lowland rivers. Further research is recommended to field-validate these models and assess their uncertainty. The relative importance of food-chain uptake and direct uptake from water are also assessed from a review of the literature. It can be concluded that food-chain uptake is the dominant accumulation pathway in fish and hence accumulation factors for radioactive phosphorus in farmed fish are likely to be significantly lower than those for wild fish.

Are groundwater nitrate concentrations reaching a turning point in some chalk aquifers?

In past decades, there has been much scientific effort dedicated to the development of models for simulation and prediction of nitrate concentrations in groundwaters, but producing truly predictive models remains a major challenge. A time-series model, based on long-term variations in nitrate fertiliser applications and average rainfall, was calibrated against measured concentrations from five boreholes in the River Frome catchment of Southern England for the period spanning from the mid-1970s to 2003. The model was then used to "blind" predict nitrate concentrations for the period 2003-2008. To our knowledge, this represents the first "blind" test of a model for predicting nitrate concentrations in aquifers. It was found that relatively simple time-series models could explain and predict a significant proportion of the variation in nitrate concentrations in these groundwater abstraction points (R(2)=0.6-0.9 and mean absolute prediction errors 4.2-8.0%). The study highlighted some important limitations and uncertainties in this, and other modelling approaches, in particular regarding long-term nitrate fertiliser application data. In three of the five groundwater abstraction points (Hooke, Empool and Eagle Lodge), once seasonal variations were accounted for, there was a recent change in the generally upward historical trend in nitrate concentrations. This may be an early indication of a response to levelling-off (and declining) fertiliser application rates since the 1980s. There was no clear indication of trend change at the Forston and Winterbourne Abbas sites nor in the trend of nitrate concentration in the River Frome itself from 1965 to 2008.

Modelling the dispersion of radionuclides following short duration releases to rivers: Part 1. Water and sediment.

This paper evaluates and generalises state-of-the-art approaches for modelling short duration liquid discharges of radionuclides ((3)H, (14)C, (60)Co, (134)Cs, (137)Cs, (65)Zn, (89)Sr, (90)Sr, (125)I, (131)I, (241)Am, isotopes of Pu and U) to rivers. An advection-dispersion model was parameterised and used to predict the concentrations of radionuclides in the river environment, i.e. in river water, river bed sediment and fish (Part II of this paper covers uptake to fish). The coupled transport and bio-uptake model was used to predict the concentrations of radionuclides in the River Thames, UK, and one of its tributaries as a result of hypothetical short duration discharges. A simplified version of this model was developed and presented as "look-up" graphs. The influence of various environmental parameters on model output was evaluated by sensitivity analysis. Time-integrated water and sediment concentrations and maximum sediment concentrations may be predicted for all rivers on the basis of the river volumetric flow rate only. Maximum concentration in water is, however, also dependent on other river characteristics. For this latter case, generalised modelling approaches are tested for use in situations where detailed hydrological and dispersion data are not available.

Seasonal nutrient dynamics in a chalk stream: the River Frome, Dorset, UK.

Chalk streams provide unique, environmentally important habitats, but are particularly susceptible to human activities, such as water abstraction, fish farming and intensive agricultural activity on their fertile flood-meadows, resulting in increased nutrient concentrations. Weekly phosphorus, nitrate, dissolved silicon, chloride and flow measurements were made at nine sites along a 32 km stretch of the River Frome and its tributaries, over a 15 month period. The stretch was divided into two sections (termed the middle and lower reach) and mass balances were calculated for each determinand by totalling the inputs from upstream, tributaries, sewage treatment works and an estimate of groundwater input, and subtracting this from the load exported from each reach. Phosphorus and nitrate were retained within the river channel during the summer months, due to bioaccumulation into river biota and adsorption of phosphorus to bed sediments. During the autumn to spring periods, there was a net export, attributed to increased diffuse inputs from the catchment during storms, decomposition of channel biomass and remobilisation of phosphorus from the bed sediment. This seasonality of retention and remobilisation was higher in the lower reach than the middle reach, which was attributed to downstream changes in land use and fine sediment availability. Silicon showed much less seasonality, but did have periods of rapid retention in spring, due to diatom uptake within the river channel, and a subsequent release from the bed sediments during storm events. Chloride did not produce a seasonal pattern, indicating that the observed phosphorus and nitrate seasonality was a product of annual variation in diffuse inputs and internal riverine processes, rather than an artefact of sampling, flow gauging and analytical errors.