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.

A simple model for predicting soil temperature in snow-covered and seasonally frozen soil: model description and testing

Microbial processes in soil are moisture, nutrient and temperature dependent and, consequently, accurate calculation of soil temperature is important for modelling nitrogen processes. Microbial activity in soil occurs even at sub-zero temperatures so that, in northern latitudes, a method to calculate soil temperature under snow cover and in frozen soils is required. This paper describes a new and simple model to calculate daily values for soil temperature at various depths in both frozen and unfrozen soils. The model requires four parameters average soil thermal conductivity, specific beat capacity of soil, specific heat capacity due to freezing and thawing and an empirical snow parameter. Precipitation, air temperature and snow depth (measured or calculated) are needed as input variables. The proposed model was applied to five sites in different parts of Finland representing different climates and soil types. Observed soil temperatures at depths of 20 and 50 cm (September 1981-August 1990) were used for model calibration. The calibrated model was then tested using observed soil temperatures from September 1990 to August 2001. R-2-values of the calibration period varied between 0.87 and 0.96 at a depth of 20 cm and between 0.78 and 0.97 at 50 cm. R-2 -values of the testing period were between 0.87 and 0.94 at a depth of 20cm. and between 0.80 and 0.98 at 50cm. Thus, despite the simplifications made, the model was able to simulate soil temperature at these study sites. This simple model simulates soil temperature well in the uppermost soil layers where most of the nitrogen processes occur. The small number of parameters required means, that the model is suitable for addition to catchment scale models.

Adaptation of the Integrated Nitrogen Model for Catchments (INCA) to seasonally snow-covered catchments

Testing of the Integrated Nitrogen model for Catchments (INCA) in a wide range of ecosystem types across Europe has shown that the model underestimates N transformation processes to a large extent in northern catchments of Finland and Norway in winter and spring. It is found, and generally assumed, that microbial activity in soils proceeds at low rates at northern latitudes during winter, even at sub-zero temperatures. The INCA model was modified to improve the simulation of N transformation rates in northern catchments, characterised by cold climates and extensive snow accumulation and insulation in winter, by introducing an empirical function to simulate soil temperatures below the seasonal snow pack, and a degree-day model to calculate the depth of the snow pack. The proposed snow-correction factor improved the simulation of soil temperatures at Finnish and Norwegian field sites in winter, although soil temperature was still underestimated during periods with a thin snow cover. Finally, a comparison between the modified INCA version (v. 1.7) and the former version (v. 1.6) was made at the Simojoki river basin in northern Finland and at Dalelva Brook in northern Norway. The new modules did not imply any significant changes in simulated NO3- concentration levels in the streams but improved the timing of simulated higher concentrations. The inclusion of a modified temperature response function and an empirical snow-correction factor improved the flexibility and applicability of the model for climate effect studies.

Integrated Nitrogen CAtchment model (INCA) applied to a tropical catchment in the Atlantic Forest, Sao Paulo, Brazil

Stream-water flows and in-stream nitrate and ammonium concentrations in a small (36.7 ha) Atlantic Forest catchment were simulated using the Integrated Nitrogen in CAtchments (INCA) model version 1.9.4. The catchment, at Cunha, is in the Serra do Mar State Park, SE Brazil and is nearly pristine because the nearest major conurbations, Sao Paulo and Rio, are some 450 km distant. However, intensive farming may increase nitrogen (N) deposition and there are growing pressures for urbanisation. The mean-monthly discharges and NO3-N concentration dynamics were simulated adequately for the calibration and validation periods with (simulated) loss rates of 6.55 kg.ha(-1) yr(-1) for NO3-N and 3.85 kg.ha(-1) yr(-1) for NH4-N. To investigate the effects of elevated levels of N deposition in the future, various scenarios for atmospheric deposition were simulated; the highest value corresponded to that in a highly polluted area of Atlantic Forest in Sao Paulo City. It was found that doubling the atmospheric deposition generated a 25% increase in the N leaching rate, while at levels approaching the highly polluted Sao Paulo deposition rate, five times higher than the current rate, leaching increased by 240%, which would create highly eutrophic conditions, detrimental to downstream water quality. The results indicate that the INCA model can be useful for estimating N concentration and fluxes for different atmospheric deposition rates and hydrological conditions.

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.

The diurnal course of soil moisture as measured by various dielectric sensors: Effects of soil temperature and the implications for evaporation estimates

Soil moisture content, theta, of a bare and vegetated UK gravelly sandy loam soil (in situ and repacked in small lysimeters) was measured using various dielectric instruments (single-sensor ThetaProbes, multi-sensor Profile Probes, and Aquaflex Sensors), at depths ranging between 0.03 and I m, during the summers of 2001 (in situ soil) and 2002 (mini-lysimeters). Half-hourly values of evaporation, E, were calculated from diurnal changes in total soil profile water content, using the soil water balance equation. For the bare soil field, Profile Probes and ML2x ThetaProbes indicated a diurnal course of theta that did not concur with typical soil physical observations: surface layer soil moisture content increased from early morning until about midday, after which theta declined, generally until the early evening. The unexpected course of theta was positively correlated to soil temperature, T-s, also at deeper depths. Aquaflex and ML1 ThetaProbe (older models) outputs, however, reflected common observations: 0 increased slightly during the night (capillary rise) and decreased from the morning until late afternoon (as a result of evaporation). For the vegetated plot, the spurious diurnal theta fluctuations were less obvious, because canopy shading resulted in lower amplitudes of T-s. The unrealistic theta profiles measured for the bare and vegetated field sites caused diurnal estimates of E to attain downward daytime and upward night-time values. In the mini-lysimeters, at medium to high moisture contents, theta values measured by (ML2x) ThetaProbes followed a relatively realistic course, and predictions of E from diurnal changes in vertically integrated theta generally compared well with lysimeter estimates of E. However, time courses of theta and E became comparable to those observed for the field plots when the soil in the lysimeters reached relatively low values of theta. Attempts to correct measured theta for fluctuations in T, revealed that no generally applicable formula could be derived. (c) 2005 Elsevier B.V. All rights reserved.

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.

Assessing nitrogen dynamics in European ecosystems, integrating measurement and modelling: conclusions

This contribution closes this special issue of Hydrology and Earth System Sciences concerning the assessment of nitrogen dynamics in catchments across Europe within a semi-distributed Integrated Nitrogen model for multiple source assessment in Catchments (INCA). New developments in the understanding of the factors and processes determining the concentrations and loads of nitrogen are outlined. The ability of the INCA model to simulate the hydrological and nitrogen dynamics of different European ecosystems is assessed and the results of the first scenario analyses investigating the impacts of deposition, climatic and land-use change on the nitrogen dynamics are summarised. Consideration is given as to how well the model has performed as a generic too] for describing the nitrogen dynamics of European ecosystems across Arctic, Maritime. Continental and Mediterranean climates, its role in new research initiatives and future research requirements.

Modelling nitrogen fluxes from the land surface to the coastal zone in European systems: the perspective of the INCA project

This paper describes the results and conclusions of the INCA (Integrated Nitrogen Model for European CAtchments) project and sets the findings in the context of the ELOISE (European Land-Ocean Interaction Studies) programme. The INCA project was concerned with the development of a generic model of the major factors and processes controlling nitrogen dynamics in European river systems, thereby providing a tool (a) to aid the scientific understanding of nitrogen transport and retention in catchments and (b) for river-basin management and policy-making. The findings of the study highlight the heterogeneity of the factors and processes controlling nitrogen dynamics in freshwater systems. Nonetheless, the INCA model was able to simulate the in-stream nitrogen concentrations and fluxes observed at annual and seasonal timescales in Arctic, Continental and Maritime-Temperate regimes. This result suggests that the data requirements and structural complexity of the INCA model are appropriate to simulate nitrogen fluxes across a wide range of European freshwater environments. This is a major requirement for the production of coupled fiver-estuary-coastal shelf models for the management of our aquatic environment. With regard to river-basin management, to achieve an efficient reduction in nutrient fluxes from the land to the estuarine and coastal zone, the model simulations suggest that management options must be adaptable to the prevailing environmental and socio-economic factors in individual catchments: 'Blanket approaches' to environmental policy appear too simple. (c) 2004 Elsevier B.V. All rights reserved.