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.

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.

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.

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/).

The management of perforation of the duodenum following endoscopic sphincterotomy: a proposal for selective therapy.

The successful non-surgical management of retroduodenal perforation following endoscopic sphincterotomy is reported and the literature reviewed. Two patients are described who developed gas in the retroperitoneum following endoscopic sphincterotomy. One patient developed retroperitoneal emphysema and cervical emphysema, while the second patient developed retroperitoneal emphysema and a pneumothorax following endoscopic sphincterotomy. Both patients were treated conservatively and made uneventful recoveries. An algorithm for assessment and treatment is proposed based on the authors' experience and a literature review. Patients with confirmed ongoing duodenal leakage, sepsis or collection should have expeditious surgery.

Computer aided diagnosis of acute abdominal pain at Middlesbrough General Hospital.

This presentation reports the experience of the surgical house staff and registrars at Middlesbrough General Hospital who used a desk-top computer system to support their clinical diagnosis of acute abdominal pain. The results cover a two year period and are compared with a baseline period of one year. Substantial benefits followed the introduction of the computer-aided diagnostic support system; increased diagnostic accuracy of the whole surgical team, reduction in negative laparotomy rates, earlier surgical intervention for acute appendicitis, reduction in the number of cases of perforated appendicitis and more efficient use of resources. The reasons for these improvements include more thorough collection of data, use of common terminology and an educational element provided by detailed feedback from the computer system.