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.

Characterization of para-Nitrophenol-degrading bacterial communities in river water by using functional markers and stable isotope probing

Microbial degradation is a major determinant of the fate of pollutants in the environment. para-Nitrophenol (PNP) is an EPA listed priority pollutant with a wide environmental distribution, but little is known about the microorganisms that degrade it in the environment. We studied the diversity of active PNP-degrading bacterial populations in river water using a novel functional marker approach coupled with [13C6]PNP stable isotope probing (SIP). Culturing together with culture-independent terminal restriction fragment length polymorphism analysis of 16S rRNA gene amplicons identified Pseudomonas syringae to be the major driver of PNP degradation in river water microcosms. This was confirmed by SIP-pyrosequencing of amplified 16S rRNA. Similarly, functional gene analysis showed that degradation followed the Gram-negative bacterial pathway and involved pnpA from Pseudomonas spp. However, analysis of maleylacetate reductase (encoded by mar), an enzyme common to late stages of both Gram-negative and Gram-positive bacterial PNP degradation pathways, identified a diverse assemblage of bacteria associated with PNP degradation, suggesting that mar has limited use as a specific marker of PNP biodegradation. Both the pnpA and mar genes were detected in a PNP-degrading isolate, P. syringae AKHD2, which was isolated from river water. Our results suggest that PNP-degrading cultures of Pseudomonas spp. are representative of environmental PNP-degrading populations.

The water quality of the River Enborne, UK: observations from high-frequency Monitoring in a rural, lowland river system

This paper reports the results of a 2-year study of water quality in the River Enborne, a rural river in lowland England. Concentrations of nitrogen and phosphorus species and other chemical determinands were monitored both at high-frequency (hourly), using automated in situ instrumentation, and by manual weekly sampling and laboratory analysis. The catchment land use is largely agricultural, with a population density of 123 persons km−2. The river water is largely derived from calcareous groundwater, and there are high nitrogen and phosphorus concentrations. Agricultural fertiliser is the dominant source of annual loads of both nitrogen and phosphorus. However, the data show that sewage effluent discharges have a disproportionate effect on the river nitrogen and phosphorus dynamics. At least 38% of the catchment population use septic tank systems, but the effects are hard to quantify as only 6% are officially registered, and the characteristics of the others are unknown. Only 4% of the phosphorus input and 9% of the nitrogen input is exported from the catchment by the river, highlighting the importance of catchment process understanding in predicting nutrient concentrations. High-frequency monitoring will be a key to developing this vital process understanding.

Distribution of selected heavy metals in sediments of the Agueda river (Central Portugal)

The state of river water deterioration in the Agueda hydrographic basin, mostly in the western part, partly reflects the high rate of housing and industrial development in this area in recent years. The streams have acted as a sink for organic and inorganic loads from several origins: domestic and industrial sewage and agricultural waste. The contents of the heavy metals Cr, Cd, Ni, Cu, Pb, and Zn were studied by sequential chemical extraction of the principal geochemical phases of streambed sediments, in the <63 mum fraction, in order to assess their potential availability to the environment, investigating, the metal concentrations, assemblages, and trends. The granulometric and mineralogical characteristics of this sediment fraction were also studied. This study revealed clear pollution by Cr, Cd, Ni, Cu, Zn, and Pb, as a result from both natural and anthropogenic origins. The chemical transport of metals appears to be essentially by the following geochemical phases, in decreasing order of significance: (exchangeable + carbonates) much greater than (organics) much greater than (Mn and Fe oxides and hydroxides). The (exchangeable + carbonate) phase plays an important part in the fixation of Cu, Ni, Zn, and Cd. The organic phase is important in the fixation of Cr, Pb, and also Cu and Ni. Analyzing the metal contents in the residual fraction, we conclude that Zn and Cd are the most mobile, and Cr and Pb are less mobile than Cu and Ni. The proximity of the pollutant sources and the timing of the influx of contaminated material control the distribution of the contaminant-related sediments locally and on the network scale.

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.

Water quality trends in the Windrush catchment: Nitrogen speciation and sediment interactions

For the predominantly agricultural River Windrush catchment, spatial variations in concentrations of nitrogen species and suspended sediment were strongly related to geology and land use. Temporal patterns of NO3- and NO2- concentrations during the three year study were highly correlated with seasonal variations in baseflow. Suspended sediment concentrations were mainly controlled by storm discharge. Variations in total ammonium concentrations reflected both flow controls. Suspended sediment effects total ammonium and organic nitrogen transport to the aquatic system, and in-stream cycling processes. Organic nitrogen did not display consistent seasonal variations, but concentrations occasionally exceeding those of NO3-. Overall, NO3- and organic nitrogen were the most important at 60% and -40%, of total nitrogen load, respectively. Future assessments of agriculture impact on river water quality should consider the total nitrogen load, and not solely that of NO3-.

High-frequency water quality monitoring in an urban catchment: hydrochemical dynamics, primary production and implications for the Water Framework Directive

This paper describes the hydrochemistry of a lowland, urbanised river-system, The Cut in England, using in situ sub-daily sampling. The Cut receives effluent discharges from four major sewage treatment works serving around 190,000 people. These discharges consist largely of treated water, originally abstracted from the River Thames and returned via the water supply network, substantially increasing the natural flow. The hourly water quality data were supplemented by weekly manual sampling with laboratory analysis to check the hourly data and measure further determinands. Mean phosphorus and nitrate concentrations were very high, breaching standards set by EU legislation. Though 56% of the catchment area is agricultural, the hydrochemical dynamics were significantly impacted by effluent discharges which accounted for approximately 50% of the annual P catchment input loads and, on average, 59% of river flow at the monitoring point. Diurnal dissolved oxygen data demonstrated high in-stream productivity. From a comparison of high frequency and conventional monitoring data, it is inferred that much of the primary production was dominated by benthic algae, largely diatoms. Despite the high productivity and nutrient concentrations, the river water did not become anoxic and major phytoplankton blooms were not observed. The strong diurnal and annual variation observed showed that assessments of water quality made under the Water Framework Directive (WFD) are sensitive to the time and season of sampling. It is recommended that specific sampling time windows be specified for each determinand, and that WFD targets should be applied in combination to help identify periods of greatest ecological risk. This article is protected by copyright. All rights reserved.

Fe-sulphate-rich evaporative mineral precipitates from the Rio Tinto, southwest Spain

The soluble metal sulphate salts melanterite, rozenite, rhomboclase, szornolnokite, copiapite, coquimbite, hexahydrite and halotrichite, together with gypsum, have been identified, some for the first time oil the banks of the Rio Tinto, SW Spain. Secondary Fe-sulphate minerals call form directly from evaporating acid, sulphate-rich Solutions as a result of pyrite oxidation. Chemical analyses of mixtures of these salt minerals indicate concentrations of Fe (up to 31 wt.%), Mg (up to 4 wt.%), Cu (up to 2 wt.%) and Zn (up to wt.%). These minerals are shown to act as transient storage Cor metals and can store on average up to 10% (9.5 - 11%) and 22% (20-23%) Zn and Cu respectively, of the total discharge of the Rio Tinto during the summer period. Melanterite and rozenite precipitates at Rio Tinto are only found in association with very acidic drainage waters (pH <1.0) draining directly from pyritic waste piles. Copiapite precipitates abundantly oil the banks of the Rio Tinto by (1) direct evaporation of the river water; or (2) as part of a paragenetic sequence with the inclusion of minor halotrichite, indicating natural dehydration and decomposition. The natural occurrences are comparable with the process of paragenesis from the evaporation of Rio Tinto river water under laboratory experiments resulting in the formation of aluminocopiapite, halotrichite, coquimbite, voltaite and gypsum.

Seasonally resolved growth of freshwater bivalves determined by oxygen and carbon isotope shell chemistry

By means of a monitoring experiment in two rivers in the Netherlands, we establish a relationship between seasonally resolved growth rates in unionid freshwater bivalves and their environment. We reconstructed these seasonally resolved growth rates by using relationships of stable isotopes in the shells and their ambient river water. The reconstructed growth rates reveal that shells grow fastest in spring-early summer, when highest food availability occurs in the rivers. In addition, the reconstructed growth rates show that onset and cessation of growth are mainly influenced by water temperature.

A procedure for the simultaneous determination of total nitrogen and total phosphorus in freshwater samples using persulphate microwave digestion

In the absence of a suitable method for routine analysis of large numbers of natural river water samples for organic nitrogen and phosphorus fractions, a new simultaneous digestion technique was developed, based on a standard persulphate digestion procedure. This allows rapid analysis of river, lake and groundwater samples from a range of environments for total nitrogen and phosphorus. The method was evaluated using a range of organic nitrogen and phosphorus structures tested at low, mid and high range concentrations from 2 to 50 mg l-1 nitrogen and 0.2 to 10 mg l-1 phosphorus. Mean recoveries for nitrogen ranged from 94.5% (2 mg I-1) to 92.7% (50 mg I-1) and for phosphorus were 98.2% (0.2 mg l-1) to 100.2% (10 mg l-1). The method is precise in its ability m reproduce results from replicate digestions, and robust in its ability to handle a variety of natural water samples in the pH range 5-8.

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.

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.

Integrated modelling of climate change impacts on water resources and quality in a lowland catchment: River Kennet, UK

An integrated approach to climate change impact assessment is explored by linking established models of regional climate (SDSM), water resources (CATCHMOD) and water quality (INCA) within a single framework. A case study of the River Kennet illustrates how the system can be used to investigate aspects of climate change uncertainty, deployable water resources, and water quality dynamics in upper and lower reaches of the drainage network. The results confirm the large uncertainty in climate change scenarios and freshwater impacts due to the choice of general circulation model (GCM). This uncertainty is shown to be greatest during summer months as evidenced by large variations between GCM-derived projections of future tow river flows, deployable yield from groundwater, severity of nutrient flushing episodes, and Long-term trends in surface water quality. Other impacts arising from agricultural land-use reform or delivery of EU Water Framework Directive objectives under climate change could be evaluated using the same framework. (c) 2006 Elsevier B.V. All rights reserved.