Rainfall and runoff water quality of the Pang and Lambourn, tributaries of the River Thames, south-eastern England

The water quality of rainfall and runoff is described for two catchments of two tributaries of the River Thames, the Pang and Lambourn. Rainfall chemistry is variable and concentrations of most determinands decrease with increasing volume of catch probably due to 'wash out' processes. Two rainfall sites have been monitored, one for each catchment. The rainfall site on the Lambourn shows higher chemical concentrations than the one for the Pang which probably reflects higher amounts of local inputs from agricultural activity, Rainfall quality data at a long-term rainfall site on the Pang (UK National Air Quality Archive) shows chemistries similar to that for the Lambourn site. but with some clear differences. Rainfall chemistries show considerable variation on an event-to-event basis. Average water quality concentrations and flow-weighted concentrations as well as fluxes vary across the sites, typically by about 30%. Stream chemistry is much less variable due to the main Source of water coming from aquifer sources of high storage. The relationship between rainfall and runoff chemistry at the catchment outlet is described in terms of the relative proportions of atmospheric and within-catchment sources. Remarkably, in view of the quantity of agricultural and sewage inputs to the streams, the catchments appear to be retaining both P and N.

The water quality of the River Carnon, west Cornwall, November 1992 to March 1994: the impacts of Wheal Jane discharges

In January 1992, there was a major pollutant event for the River Canon and downstream with its confluence to the River Fal and the Fal estuary in the west Cornwall. This incident was associated with the discharge of several million gallons of highly polluted water from the abandoned Wheal Jane tin mine that also extracted Ag, Cu and Zn ore. Later that year, the Centre for Ecology and Hydrology (CBH; then Institute of Hydrology) Wallingford undertook daily monitoring of the River Canon for a range of major, minor and trace elements to assess the nature and the dynamics of the pollutant discharges. These data cover an 18-month period when there remained major water-quality problems after the initial phase of surface water contamination. Here, a summary is provided of the water quality found, as a backdrop to set against subsequent remediation. Two types of water-quality determinant grouping were observed. The first type comprises the determinants B, Cs, Ca, Li, K, Na, SO4, Rb and Sr, and their concentrations are positively correlated with each other but inversely correlated with flow. This type of water-quality determinant shows variations in concentration that broadly link to the normal hydrogeochemical processes within the catchment, with limited confounding issues associated with mine drainage. The second type of water-quality determinant comprises Al, Be, Cd, Ce, Co, Cu, Fe, La, Pb, Pr, Nd, Ni, Si, Sb, U, Y and Zn, and concentrations for all this group are positively correlated. The determinants in this second group all have concentrations that are negatively correlated with pH. This group links primarily to pollutant mine discharge. The water-quality variations in the River Camon are described in relation to these two distinct hydrogeochemical groupings. (C) 2004 Elsevier B.V All rights reserved.

Assessing the sources and magnitude of diurnal nitrate variability in the San Joaquin River (California) with an in-situ optical nitrate sensor and dual nitrate isotopes

We investigated diurnal nitrate (NO3-) concentration variability in the San Joaquin River using an in situ optical NO3- sensor and discrete sampling during a 5-day summer period characterized by high algal productivity. Dual NO3- isotopes (delta N-15(NO3) and delta O-18(NO3)) and dissolved oxygen isotopes (delta O-18(DO)) were measured over 2 days to assess NO3- sources and biogeochemical controls over diurnal time-scales. Concerted temporal patterns of dissolved oxygen (DO) concentrations and delta O-18(DO) were consistent with photosynthesis, respiration and atmospheric O-2 exchange, providing evidence of diurnal biological processes independent of river discharge. Surface water NO3- concentrations varied by up to 22% over a single diurnal cycle and up to 31% over the 5-day study, but did not reveal concerted diurnal patterns at a frequency comparable to DO concentrations. The decoupling of delta N-15(NO3) and delta O-18(NO3) isotopes suggests that algal assimilation and denitrification are not major processes controlling diurnal NO3- variability in the San Joaquin River during the study. The lack of a clear explanation for NO3- variability likely reflects a combination of riverine biological processes and time-varying physical transport of NO3- from upstream agricultural drains to the mainstem San Joaquin River. The application of an in situ optical NO3- sensor along with discrete samples provides a view into the fine temporal structure of hydrochemical data and may allow for greater accuracy in pollution assessment.

Calibration and sensitivity analysis of a river water quality model under unsteady flow conditions

Water quality models generally require a relatively large number of parameters to define their functional relationships, and since prior information on parameter values is limited, these are commonly defined by fitting the model to observed data. In this paper, the identifiability of water quality parameters and the associated uncertainty in model simulations are investigated. A modification to the water quality model `Quality Simulation Along River Systems' is presented in which an improved flow component is used within the existing water quality model framework. The performance of the model is evaluated in an application to the Bedford Ouse river, UK, using a Monte-Carlo analysis toolbox. The essential framework of the model proved to be sound, and calibration and validation performance was generally good. However some supposedly important water quality parameters associated with algal activity were found to be completely insensitive, and hence non-identifiable, within the model structure, while others (nitrification and sedimentation) had optimum values at or close to zero, indicating that those processes were not detectable from the data set examined. (C) 2003 Elsevier Science B.V. All rights reserved.

Evaluation of two hybrid metric-conceptual models, for simulating phosphorus transfer from agricultural land in the river enborne, a lowland UK catchment

Across Europe, elevated phosphorus (P) concentrations in lowland rivers have made them particularly susceptible to eutrophication. This is compounded in southern and central UK by increasing pressures on water resources, which may be further enhanced by the potential effects of climate change. The EU Water Framework Directive requires an integrated approach to water resources management at the catchment scale and highlights the need for modelling tools that can distinguish relative contributions from multiple nutrient sources and are consistent with the information content of the available data. Two such models are introduced and evaluated within a stochastic framework using daily flow and total phosphorus concentrations recorded in a clay catchment typical of many areas of the lowland UK. Both models disaggregate empirical annual load estimates, derived from land use data, as a function of surface/near surface runoff, generated using a simple conceptual rainfall-runoff model. Estimates of the daily load from agricultural land, together with those from baseflow and point sources, feed into an in-stream routing algorithm. The first model assumes constant concentrations in runoff via surface/near surface pathways and incorporates an additional P store in the river-bed sediments, depleted above a critical discharge, to explicitly simulate resuspension. The second model, which is simpler, simulates P concentrations as a function of surface/near surface runoff, thus emphasising the influence of non-point source loads during flow peaks and mixing of baseflow and point sources during low flows. The temporal consistency of parameter estimates and thus the suitability of each approach is assessed dynamically following a new approach based on Monte-Carlo analysis. (c) 2004 Elsevier B.V. All rights reserved.

Water quality and ecology of the River Lee: mass balance and a review of temporal and spatial data

A regional overview of the water quality and ecology of the River Lee catchment is presented. Specifically, data describing the chemical, microbiological and macrobiological water quality and fisheries communities have been analysed, based on a division into river, sewage treatment works, fish-farm, lake and industrial samples. Nutrient enrichment and the highest concentrations of metals and micro-organics were found in the urbanised, lower reaches of the Lee and in the Lee Navigation. Average annual concentrations of metals were generally within environmental quality standards although, oil many occasions, concentrations of cadmium, copper, lead, mercury and zinc were in excess of the standards. Various organic substances (used as herbicides, fungicides, insecticides, chlorination by-products and industrial solvents) were widely detected in the Lee system. Concentrations of ten micro-organic substances were observed in excess of their environmental quality standards, though not in terms of annual averages. Sewage treatment works were the principal point source input of nutrients. metals and micro-organic determinands to the catchment. Diffuse nitrogen sources contributed approximately 60% and 27% of the in-stream load in the upper and lower Lee respectively, whereas approximately 60% and 20% of the in-stream phosphorus load was derived from diffuse sources in the upper and lower Lee. For metals, the most significant source was the urban runoff from North London. In reaches less affected by effluent discharges, diffuse runoff from urban and agricultural areas dominated trends. Flig-h microbiological content, observed in the River Lee particularly in urbanised reaches, was far in excess of the EC Bathing Water Directive standards. Water quality issues and degraded habitat in the lower reaches of the Lee have led to impoverished aquatic fauna but, within the mid-catchment reaches and upper agricultural tributaries, less nutrient enrichment and channel alteration has permitted more diverse aquatic fauna.

Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long-term DOC monitoring data. Intensive sampling across the historically under-sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean.

Eutrophication control in river-systems: an application of INCA-P to the River Lugg

The Integrated Catchments model of Phosphorus dynamics (INCA-P) was applied to the River Lugg to determine the key factors controlling delivery of phosphorus to the main channel and to quantify the relative contribution of diffuse and point sources to the in-stream phosphorus (P) load under varying hydrological conditions. The model is able to simulate the seasonal variations and inter-annual variations in the in-stream total-phosphorus concentrations. However, difficulties in simulating diffuse inputs arise due to equifinality in the model structure and parameters. The River Lugg is split into upper and lower reaches. The upper reaches are dominated by grassland and woodland, so the patterns in the stream-water total-phosphorus concentrations are typical of diffuse source inputs; application of the model leads to estimates of the relative contribution to the in-stream P load from diffuse and point sources as 9:1. In the lower reaches, which are more intensively cultivated and urbanised, the stream-water total-phosphorus concentration dynamics are influenced more by point-sources; the simulated relative diffuse/point contribution to the in-stream P load is 1: 1. The model set-up and simulations are used to identify the key source-areas of P in the catchment, the P contribution of the Lugg to the River Wye during years with contrasting precipitation inputs, and the uptake and release of P from within-reach sediment. In addition, model scenarios are run to identify the impacts of likely P reductions at sewage treatment works on the in-stream soluble-reactive P concentrations and the suitability of this as a management option is assessed for reducing eutrophication.

Towards an improved understanding of the nitrate dynamics in lowland, permeable river-systems: Applications of INCA-N

The Integrated Catchment Model of Nitrogen (INCA-N) was applied to the Lambourn and Pang river-systems to integrate current process-knowledge and available-data to test two hypotheses and thereby determine the key factors and processes controlling the movement of nitrate at the catchment-scale in lowland, permeable river-systems: (i) that the in-stream nitrate concentrations were controlled by two end-members only: groundwater and soil-water, and (ii) that the groundwater was the key store of nitrate in these river-systems. Neither hypothesis was proved true or false. Due to equifinality in the model structure and parameters at least two alternative models provided viable explanations for the observed in-stream nitrate concentrations. One model demonstrated that the seasonal-pattern in the stream-water nitrate concentrations was controlled mainly by the mixing of ground- and soil-water inputs. An alternative model demonstrated that in-stream processes were important. It is hoped further measurements of nitrate concentrations made in the catchment soil- and ground-water and in-stream may constrain the model and help determine the correct structure, though other recent studies suggest that these data may serve only to highlight the heterogeneity of the system. Thus when making model-based assessments and forecasts it is recommend that all possible models are used, and the range of forecasts compared. In this study both models suggest that cereal production contributed approximately 50% the simulated in-stream nitrate toad in the two catchments, and the point-source contribution to the in-stream load was minimal. (c) 2006 Elsevier B.V. All rights reserved.

Nutrient monitoring, simulation and management within a major lowland UK river system: the Kennet

This paper describes an assessment of the nitrogen and phosphorus dynamics of the River Kennet in the south east of England. The Kennet catchment (1200 km(2)) is a predominantly groundwater fed river impacted by agricultural and sewage sources of nutrient (nitrogen and phosphorus) pollution. The results from a suite of simulation models are integrated to assess the key spatial and temporal variations in the nitrogen (N) and phosphorus (P) chemistry, and the influence of changes in phosphorous inputs from a Sewage Treatment Works on the macrophyte and epiphyte growth patterns. The models used are the Export Co-efficient model, the Integrated Nitrogen in Catchments model, and a new model of in-stream phosphorus and macrophyte dynamics: the 'Kennet' model. The paper concludes with a discussion on the present state of knowledge regarding the water quality functioning, future research needs regarding environmental modelling and the use of models as management tools for large, nutrient impacted riverine systems. (C) 2003 IMACS. Published by Elsevier B.V. All rights reserved.

Impacts of forestry on nitrogen in upland and lowland catchments: a comparison of the River Severn at Plynlimon in mid-Wales and the Bedford Ouse in south-east England using the INCA Model

The impacts of afforestation at Plynlimon in the Severn catchment, mid-Wales. and in the Bedford Ouse catchment in south-east England are evaluated using the INCA model to simulate Nitrogen (N) fluxes and concentrations. The INCA model represents the key hydrological and N processes operating in catchments and simulates the daily dynamic behaviour as well as the annual fluxes. INCA has been applied to five years of data front the Hafren and Hore headwater sub-catchments (6.8 km(2) area in total) of the River Severn at Plytilimon and the model was calibrated and validated against field data. Simulation of afforestation is achieved by altering the uptake rate parameters in the model. INCA simulates the daily N behaviour in the catchments with good accuracy as well as reconstructing the annual budgets for N release following clearfelling a four-fold increase in N fluxes was followed by a slow recovery after re-afforestation. For comparison, INCA has been applied to the large (8380 km(2)) Bedford Ouse catchment to investigate the impact of replacing 20% arable land with forestry. The reduction in fertiliser inputs from arable farming and the N uptake by the forest are predicted to reduce the N flux reaching the main river system, leading to a 33% reduction in N-Nitrate concentrations in the river water.