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.

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.

Assessing the potential impacts of a revised set of on-farm nutrient and sediment 'basic' control measures for reducing agricultural diffuse pollution across England.

The need for improved abatement of agricultural diffuse water pollution represents cause for concern throughout the world. A critical aspect in the design of on-farm intervention programmes concerns the potential technical cost-effectiveness of packages of control measures. The European Union (EU) Water Framework Directive (WFD) calls for Programmes of Measures (PoMs) to protect freshwater environments and these comprise 'basic' (mandatory) and 'supplementary' (incentivised) options. Recent work has used measure review, elicitation of stakeholder attitudes and a process-based modelling framework to identify a new alternative set of 'basic' agricultural sector control measures for nutrient and sediment abatement across England. Following an initial scientific review of 708 measures, 90 were identified for further consideration at an industry workshop and 63 had industry support. Optimisation modelling was undertaken to identify a shortlist of measures using the Demonstration Test Catchments as sentinel agricultural landscapes. Optimisation selected 12 measures relevant to livestock or arable systems. Model simulations of 95% implementation of these 12 candidate 'basic' measures, in addition to business-as-usual, suggested reductions in the national agricultural nitrate load of 2.5%, whilst corresponding reductions in phosphorus and sediment were 11.9% and 5.6%, respectively. The total cost of applying the candidate 'basic' measures across the whole of England was estimated to be £450 million per annum, which is equivalent to £52 per hectare of agricultural land. This work contributed to a public consultation in 2016.

Understanding the controls on deposited fine sediment in the streams of agricultural catchments.

Excessive sediment pressure on aquatic habitats is of global concern. A unique dataset, comprising instantaneous measurements of deposited fine sediment in 230 agricultural streams across England and Wales, was analysed in relation to 20 potential explanatory catchment and channel variables. The most effective explanatory variable for the amount of deposited sediment was found to be stream power, calculated for bankfull flow and used to index the capacity of the stream to transport sediment. Both stream power and velocity category were highly significant (p ≪ 0.001), explaining some 57% variation in total fine sediment mass. Modelled sediment pressure, predominantly from agriculture, was marginally significant (p<0.05) and explained a further 1% variation. The relationship was slightly stronger for erosional zones, providing 62% explanation overall. In the case of the deposited surface drape, stream power was again found to be the most effective explanatory variable (p<0.001) but velocity category, baseflow index and modelled sediment pressure were all significant (p<0.01); each provided an additional 2% explanation to an overall 50%. It is suggested that, in general, the study sites were transport-limited and the majority of stream beds were saturated by fine sediment. For sites below saturation, the upper envelope of measured fine sediment mass increased with modelled sediment pressure. The practical implications of these findings are that (i) targets for fine sediment loads need to take into account the ability of streams to transport/retain fine sediment, and (ii) where agricultural mitigation measures are implemented to reduce delivery of sediment, river management to mobilise/remove fines may also be needed in order to effect an improvement in ecological status in cases where streams are already saturated with fines and unlikely to self-cleanse.

The changing trend in nitrate concentrations in major aquifers due to historical nitrate loading from agricultural land across England and Wales from 1925 to 2150.

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.

Does fine sediment source as well as quantity affect salmonid embryo mortality and development?

Fine sediments are known to be an important cause of increased mortality in benthic spawning fish. To date, most of the research has focussed on the relationship between embryo mortality and the quantity of fine sediment accumulated in the egg pocket. However, recent evidence suggests a) that the source of fine sediment might also be important, and b) that fitness of surviving embryos post-hatch might also be impacted by the accumulation of fine sediments. In this paper, we report an experiment designed to simulate the incubation environment of brown trout (Salmo trutta) and Atlantic salmon (Salmo salar). During the experiment, the incubating embryos were exposed to different quantities of fine (<63 µm) sediment derived from four different sources; agricultural topsoils, damaged road verges, eroding river channel banks and tertiary level treated sewage. Results showed that mass and source are independently important for determining the mortality and fitness of alevin. Differences between species were observed, such that brown trout are less sensitive to mass and source of accumulated sediment. We demonstrate for the first time that sediment source is an additional control on the impact of fine sediment, and that this is primarily controlled by the organic matter content and oxygen consumption of the catchment source material.

Catchment source contributions to the sediment-bound organic matter degrading salmonid spawning gravels in a lowland river, southern England.

The ingress of particulate material into freshwater spawning substrates is thought to be contributing to the declining success of salmonids reported over recent years for many rivers. Accordingly, the need for reliable information on the key sources of the sediment problem has progressed up the management agenda. Whilst previous work has focussed on apportioning the sources of minerogenic fine sediment degrading spawning habitats, there remains a need to develop procedures for generating corresponding information for the potentially harmful sediment-bound organic matter that represents an overlooked component of interstitial sediment. A source tracing procedure based on composite signatures combining bulk stable (13)C and (15)N isotope values with organic molecular structures detected using near infrared (NIR) reflectance spectroscopy was therefore used to assess the primary sources of sediment-bound organic matter sampled from artificial spawning redds. Composite signatures were selected using a combination of the Kruskal-Wallis H-test, principal component analysis and GA-driven discriminant function analysis. Interstitial sediment samples were collected using time-integrating basket traps which were inserted at the start of the salmonid spawning season and extracted in conjunction with critical phases of fish development (eyeing, hatch, emergence, late spawning). Over the duration of these four basket extractions, the overall relative frequency-weighted average median (±95% confidence limits) source contributions to the interstitial sediment-bound organic matter were estimated to be in the order: instream decaying vegetation (39±<1%; full range 0-77%); damaged road verges (28±<1%; full range 0-77%); septic tanks (22±<1%; full range 0-50%), and; farm yard manures/slurries (11±<1%; full range 0-61%). The reported procedure provides a promising basis for understanding the key sources of interstitial sediment-bound organic matter and can be applied alongside apportionment for the minerogenic component of fine-grained sediment ingressing the benthos. The findings suggest that human septic waste contributes to the interstitial fines ingressing salmonid spawning habitat in the study area.

A novel application of natural fluorescence to understand the sources and transport pathways of pollutants from livestock farming in small headwater catchments.

This paper demonstrates the application of a low-cost and rapid natural fluorescence technique for tracing and quantifying the transport of pollutants from livestock farming through a small headwater catchment. Fluorescence intensities of Dissolved Organic Matter (DOM) present in different pollutant sources and drainage waters in the Den Brook catchment (Devon, UK) were monitored through storm events occurring between January 2007 and June 2008. Contrasting fluorescence signals from different sources confirmed the technique's usefulness as a tracer of pollutants from livestock farming. Changes in fluorescence intensities of drainage waters throughout storm events were used to assess the dynamics of key pollutant sources. The farmyard area of the catchment studied was shown to contribute polluted runoff at the onset of storm events in response to only small amounts of rain, when flows in the Den Brook first-order channel were low. The application of slurry to a field within the catchment did not elevate the fluorescence of drainage waters during storm events suggesting that when slurry is applied to undrained fields the fluorescent DOM may become quickly adsorbed onto soil particles and/or immobilised through bacterial breakdown. Fluorescence intensities of drainage waters were successfully combined with discharge data in a two component mixing model to estimate pollutant fluxes from key sources during the January 2007 storm event. The farmyard was shown to be the dominant source of tryptophan-like material, contributing 61-81% of the total event flux at the catchment outlet. High spatial and temporal resolution measurements of fluorescence, possibly using novel in-situ fluorimeters, may thus have great potential in quickly identifying and quantifying the presence, dynamics and sources of pollutants from livestock farming in catchments.

The influence of storm events on fine sediment transport, erosion and deposition within a reach of the River Swale, Yorkshire, UK.

The spatial and temporal dynamics of suspended sediment fluxes through a 55 km reach of the lowland River Swale, Yorkshire, UK are investigated for the period July 1994-June 1996. Seventeen storm events were monitored, each of which produced significant suspended sediment transport. Variations in sediment flux dynamics and reach sediment storage through events, representing a combination of channel bed erosion and/or deposition, bank erosion and floodplain deposition, were observed. Some, but not all, of this variation can be explained in terms of event size, precipitation distribution and intensity, and antecedent sediment storage conditions. In particular, marked variations in the size of the reach sediment store over the extremely wet 4-month winter period from December 1994 to April 1995 are demonstrated. Net sediment loss from the reach took place over during this winter period. These event-scale and seasonal patterns form a background to annual variations in the catchment sediment budget.

Long term variation in water colour from Yorkshire catchments.

Water colour is a problem in the upland water-gathering grounds of the UK. It has shown considerable variation over recent years and this needs to be put into the longer-term context. In order to do this, factors to convert water colour measured in absorbance units per metre (Au/m) to Hazen units are presented for ten sites in the Yorkshire region using data from August 1997 to June 1998. The conversion factors are site-specific and there is some evidence that they may show seasonal variation. There is also a short-term upward trend in the conversion factor for a number of catchments, which may be related to their recovery following the 1995 drought. Time series of water colour in Hazen from 1980 to 1998 are shown for selected sites. The seasonal variation in colour levels is disrupted at all sites during and following drought periods, notably 1990-1992 and 1995-1998 and, in the case of two sites with long-term colour measurements, the 1975-1976 drought. These periods are followed by enhanced levels of colour and, since the end of the 1995 drought, unprecedented high values have been recorded at some catchments.

Statistical modelling of water colour in the uplands: The Upper Midd catchment 1979-1987.

The increasing colour of raw water from the uplands is a matter of concern to water managers. The colour record for the period 1979-1987 is examined for the catchment of Upper Nidderdale, North Yorkshire. The variation in colour shows a marked seasonality with peaks occurring during the autumn months. No long-term sustained increase in colour is found, although colour levels were high in 1980, 1985 and 1987. Colour is found to be highly correlated with iron and, more particularly, aluminium. There is no relationship between colour and turbidity which suggests that there is no direct link between colour levels and erosion on the catchments. Colour increases appear to relate to large soil moisture deficits in months immediately prior to the colour flush and to high soil moisture deficits in the previous year. Complementary relationships are found between monthly rainfall totals and colour. In the light of these findings, it is suggested that high colour is associated with water table lowering and aerobic decomposition of the upper organic peat layers.