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The water quality of 13 rivers in the lowland, agricultural county of Suffolk is investigated using routine monitoring data for the period 1981 to 2006 collected by the Environment Agency of England and Wales (EA), and its predecessors, with particular emphasis on phosphorus (as total reactive phosphorus, TRP) and total (dissolved and particulate) oxidised nitrogen (TOxN--predominantly nitrate NO3). Major ion and flow data are used to outline fundamental hydrochemical characteristics related to the groundwater provenance of base-flow waters. Relative load contributions from point and diffuse sources are approximated using Load Apportionment Modelling for both TRP and TOxN where concurrent flow and concentration data are available. Analyses indicate a mixture of point and diffuse sources of TRP, with the former being dominant during low flow periods, while for TOxN diffuse sources dominate. Out of 59 sites considered, 53 (90%) were found to have annual average TRP concentrations greater than 0.05 mg P l(-1), and 36 (61%) had average concentrations over 0.120 mg P l(-1), the upper thresholds for 'High' and 'Good' ecological status, respectively. Correspondingly, for TOxN, most of the rivers are already within 70% of the 11.3 mg N l(-1) threshold, with two rivers (Wang and Ore) being consistently greater than this. It is suggested that the major challenge is to characterise and control point-source TRP inputs which, being predominant during the late spring and summer low-flow period, coincide with the peak of primary biological production, thus presenting the major challenge to achieving 'good' ecological status under the Water Framework Directive. Results show that considerable effort is still required to ensure appropriate management and develop tools for decision-support.

This paper examines the nutrient chemistry and biological quality indices [Mean Trophic Rank (MTR) and Trophic Diatom Index (TDI)] for rivers within the upper Thames basin. The predominant sources of nitrogen within the rivers monitored were diffuse and agricultural in nature. However, phosphorus showed both diffuse and point source signals. MTR surveys undertaken both upstream and downstream of major STWs indicate that these rivers are 'at risk' of eutrophication or 'badly damaged'. MTR surveys also indicate increased trophic status downstream of STWs, whereas TDI does not indicate such a consistent pattern. Phosphorus treatment at selected major sewage treatment works in the upper Thames basin resulted in significant reductions in in-stream P concentrations and reductions in fluxes by a half to two thirds. However, the effects of P-reduction on in-stream ecology (measured as MTR and TDI) were more difficult to ascribe, owing to: (1) the high variability in river flow rates experienced since P-reduction was introduced; (2) lag effects related to P stores in river bed sediments; and (3) diffuse and smaller point source inputs upstream. The results of this study indicate that control of upstream sources of phosphorus may prove critical in improving the biological quality status of UK lowland rivers, including ecological responses to P-source controls on the major sewage treatment works downstream. Upstream sources include both diffuse (agricultural) sources and small point source inputs which, at present, are not classified as 'qualifying discharges' under the Urban Wastewater Treatment Directive (UWWTD) and are thus not subject to phosphorus control measures. These results are of relevance for integrated, sustainable management and protection of European freshwater resources, particularly in terms of new ecological targets for water quality management under the new Water Framework Directive.

The relationship between calcium carbonate saturation and phosphorus concentrations for seven sites on the upper reaches of the River Kennet are examined. The findings are related to issues of groundwater supplies and the introduction of phosphorus treatment of effluent from the Marlborough sewage treatment works (STW) at part of the way along the study reach. Being supplied from a Cretaceous Chalk aquifer, the Kennet is mainly of a calcium-bicarbonate type and has a relatively constant composition of many major water quality determinands. Typically, the waters average a pH of approximately eight (range approx. 7.5-8.5) during the day with the lowest values occurring at the upstream site. Dissolved carbon dioxide varies from approximately 5 to 35 times atmospheric pressure during the late morning with the highest values occurring at the upstream site. However, in-stream biological activity gives rise to marked diurnal fluctuations in pH and dissolved carbon dioxide concentrations and during the summer months, by mid to late afternoon, pH is at its maximum and dissolved carbon dioxide is at its lowest: this is shown by continuous measurements at one of the river sites. Alkalinity and calcium concentrations remain relatively constant at approximately 4,700 microEq/l (range 3,500-6,000 microEq/l) and 120 mg/l (range 85-150 mg/l), respectively, and the waters are oversaturated with respect to calcium carbonate (calcite) typically by a factor of six (range 2-25). Along the reach, soluble reactive phosphate (SRP) increases from the first to the second site with the introduction of sewage supplies from the Marlborough STW, and then declines further downstream as sewage dilution and uptake by the river bed/aquatic plants increases. The differences in concentration decrease after phosphorus removal from Marlborough STW. Despite this change, there is no clear indication of any calcite solubility control except perhaps at times of extreme baseflow during the growing season when within-stream photosynthesis is maximal and within-stream residence times are longer. A comparison of river and groundwater data shows that the groundwaters have similar alkalinities and calcium concentrations. However, the groundwaters have (a) higher carbon dioxide saturations (a factor of 2-5 times the value for the river), (b) lower pHs (0.5-1.5 units), (c) lower SRP concentrations (a quarter or less of the river values) and (d) waters near calcite saturation (unlike the surface waters which are oversaturated). The findings indicate a river system dominated by the input carbon dioxide laden groundwaters in approximate equilibrium with calcite attenuated by within-channel biological and physical processes. Within the river: (a) the waters degas carbon dioxide increasing the pH, producing oversaturated conditions; and (b) oscillating pH-dissolved carbon dioxide levels occur between day and night due to changing balances between photosynthesis and respiration. It seems that lowering the phosphorus levels have not resulted in calcite precipitation within the water column and that no significant within-stream self-cleansing mechanisms are occurring that might be predicted from theory: other components in the water such as dissolved organic carbon may inhibit calcite nucleation. However, the low SRP levels in the groundwater coupled with calcite saturation, may well indicate that phosphorous concentrations within the groundwater are regulated by such processes: the number of calcite nucleating sites are orders of magnitude higher and the calcite inhibitors may be less prevalent.

This paper provides data from two years of monitoring of the chemical quality of rivers and streams in North West England from the clean headwaters to polluted rivers just above the tidal reach and covers 26 sites including the Ribble, Wyre and the tributary rivers of the Calder and Douglas. Across the basins that include areas of rural, urban and industrial typologies, data is presented for three of the priority substances in the Water Framework Directive i.e., nickel (Ni), cadmium (Cd), and lead (Pb). Average concentrations are low and well below the Environmental Quality Standards values for all three of these substances. Cadmium and Pb appear in approximately equal proportions in the dissolved (<0.45 μm) and in the acid available particulate fractions (>0.45 μm) whilst Ni occurs predominantly in the dissolved form (92%). Regional inputs of these metals arise mostly from diffuse sources as the storm-flow concentrations are generally greater than at base-flow condition. Greater concentrations of Ni are transported at the headwaters and smaller tributary sites under storm flow condition than for the main stream of the Ribble. For Ni, amounts increase as the river proceeds from its headwaters down towards the Ribble and Wyre estuaries, whilst Cd and Pb show consistent values throughout the catchment. There is annual cycling of dissolved concentrations of Cd, Pb and Ni for the clean headwater streams that gives maxima during the latter half of the year when the river flow is greater. For the impacted sites the pattern is less distinct or absent. Our estimates suggest that the Ribble estuary receives 550 t y-1 of dissolved Ni, 16 t y-1 of dissolved Cd and 240 t y-1 of dissolved Pb. [ABSTRACT FROM AUTHOR]

Abstract: Information on a new observatory study of the water quality of two major river basins in northwestern England (the Ribble and Wyre) is presented. It covers upland, intermediate and lowland environments of contrasting pollution history with sufficient detail to examine transitional gradients. The upland rivers drain acidic soils subjected to long-term acidic deposition. Nonetheless, the acidic runoff from the soils is largely neutralised by high alkalinity groundwaters, although the rivers retain, perhaps as colloids, elements such as Al and Fe that are mobilised under acid conditions. The lowland rivers are contaminated and have variable water quality due to variable urban/industrial point and diffuse inputs reflecting local and regional differences in historic and contemporary sources. For most determinands, pollutant concentrations are not a major cause for concern although phosphate levels remain high. Set against earlier studies for other regions, there may be a general decline in pollutant levels and this is most clearly observed for boron where effluent inputs have declined significantly due to reductions in household products that are flushed down the drain. High concentrations of sodium and chloride occurred briefly after a severe cold spell due to flushing of road salts. A major inventory for water quality within rural, urban, industrial and agricultural typologies is provided within data summary attachments for over 50 water quality determinands. Within the next year, the full dataset will be made available from the CEH website. This, with ongoing monitoring, represents a platform for water quality studies across a wide range of catchment typologies pertinent to environmental management of clean and impacted systems within the UK. The study provides a base of research “from source to sea” including extensions to the estuary and open sea for a semi-confined basin, the Irish Sea, where there are many issues of pollution inputs and contamination. [Copyright &y& Elsevier]

The article offers information on a research conducted on phosphorus (P) release and retention in rivers and watersheds. It mentions that the research is done on the basis of extended end-member mixing analysis (E-EMMA) for exploring the role of P in water quality management. According to E-EMMA, 14 percent of the P flux was retained for the Thames river of Great Britain, while up to 48 was retained for the Sandusky River of the U.S. It informs that watershed outlets of both rivers fluxes are strongly influenced by processes that cycle and retain P.

Abstract: The relationship between soluble and particulate phosphorus was examined for 9 major UK rivers including 26 major tributaries and 68 monitoring points, covering wide-ranging rural and agricultural/urban impacted systems with catchment areas varying from 1 to 6000km2 scales. Phosphorus concentrations in Soluble Reactive (SRP), Total Dissolved (TDP), Total (TP), Dissolved Hydrolysable (DHP) and Particulate (PP) forms correlated with effluent markers (sodium and boron) and SRP was generally dominant signifying the importance of sewage sources. Low flows were particularly enriched in SRP, TDP and TP for average SRP>100μg/l indicating low effluent dilution. At particularly low average concentrations, SRP increased with flow but effluent sources were still implicated as the effluent markers (boron in particular) increased likewise. For rural areas, DHP had proportionately high concentrations and SRP+DHP concentrations could exceed environmental thresholds currently set for SRP. Given DHP has a high bioavailability the environmental implications need further consideration. PP concentrations were generally highest at high flows but PP in the suspended solids was generally at its lowest and in general PP correlated with particulate organic carbon and more so than the suspended sediment in total. Separation of pollutant inputs solely between effluent and diffuse (agriculture) components is misleading, as part of the “diffuse” term comprises effluents flushed from the catchments during high flow. Effluent sources of phosphorus supplied directly or indirectly to the river coupled with within-river interactions between water/sediment/biota largely determine pollutant levels. The study flags the fundamental need of placing direct and indirect effluent sources and contaminated storage with interchange to/from the river at the focus for remediation strategies for UK rivers in relation to eutrophication and the WFD. [Copyright &y& Elsevier]

Summary: The water quality along the River Kennet, in the Thames basin of southern England, was examined in terms of the influence of point- and diffuse-nutrient inputs. The river is supplied mainly from a Cretaceous Chalk aquifer and hence the waters are of a calcium bicarbonate type. The nitrate largely comes from agricultural sources, with concentrations decreasing downstream due to plant uptake and probable denitrification. In contrast, soluble reactive phosphorus (SRP) is largely associated with sewage inputs and concentrations increase downstream in line with effluents from major towns such as Newbury and Reading. Adjacent to the river in the lower half of the catchment is the Kennet and Avon Canal and the two are in places hydrologically connected. The canal inputs may influence calcium carbonate (calcite) precipitation and increase suspended sediment and particulate phosphorus concentrations in the river. Monitoring upstream and downstream of Marlborough sewage treatment works (STW) showed that SRP concentrations in the effluent were highly variable due to variable efficiency of P stripping and still sufficiently concentrated to dominate downstream river SRP with potential impacts on stream ecology. Biological recovery in this river following P stripping at STWs is complex and controlling those spikes in SRP that are above a threshold of 100μgl−1 may be a critical requirement. More stringent effluent targets than are currently recommended may be needed (less than 800μgRPl−1) to achieve good ecological status in this river depending on SRP concentrations upstream. [Copyright &y& Elsevier]

Summary: The water quality of rivers in the eastern part of the Humber Basin, north-eastern England is described from a baseflow survey (11–13 August 2006) of a wide range of water quality determinants, and long-term nutrient records of the Environment Agency of England and Wales (EA). The baseflow survey shows that the rivers are oversaturated with respect to dissolved CO2 and calcite. They are sodium, potassium, lithium, boron, chloride, sulphate and fluoride bearing from a combination of atmospheric, within-catchment, agricultural and sewage effluent sources. Nitrate concentrations are uniform for rivers draining permeable bedrock but decrease for clay drainage areas. Soluble reactive phosphorus (SRP) concentrations are variable across the catchments reflecting the importance and variability of point sources and within-river processing. The EA data show annual oscillations for both NO3 and SRP concentrations. Average NO3 concentrations vary between 3.3 and 18.8mgN/l and concentrations are low during the summer months. Average SRP concentrations vary between 23 and 1959μg/l. Highest SRP concentrations generally occur when there is effluent input from sewage treatment works and agricultural point sources (e.g. overflow from slurry tanks, farmyard washings). Despite many of the rivers being nutrient rich, they are generally of good biological quality when point source inputs are not important. [Copyright &y& Elsevier]

Summary: The water quality of the River Dun and associated surface waters (a reservoir, two tributaries of the Dun, the Kennet and Avon Canal and the River Kennet to which the Dun drains) is described for a wide range of major, minor and trace elements. The water quality is determined by inputs from: (a) geologic sources (Ca, Sr concentrations and alkalinity) and (b) contaminant inputs from farming and sewage (Na, Cl, B, soluble reactive phosphorus and nitrate). As river water is mainly supplied from the Chalk aquifer and riparian areas, the water quality variation is damped, but there are occasional storms, where near surface/surface runoff delivers higher nutrient and suspended sediment concentrations, but dilutes determinands derived predominantly from geologic and point sources. River and canal water quality is also modified by in-stream biological processes in spring and summer, which remove nutrients (N, P and Si) and CO2 from the water, bringing about precipitation of calcium carbonate and thus reductions in Ca concentrations and alkalinity. The biological effects are particularly marked for the Kennet and Avon Canal. The River Dun and Kennet and Avon Canal have been subject to episodic fish-kills and concern has been expressed about the role of event-based resuspension of bed sediments and mobilisation of dredged sediments on dissolved oxygen levels within the river. Therefore, fluvarium experiments on sediment–water interactions were undertaken to examine the potential effects of bed sediment disturbance on dissolved oxygen levels. The results of the fluvarium experiments demonstrate an ecologically-significant 30% reduction in dissolved oxygen levels following bed sediment disturbance. This reduction in DO concentrations was greater than expected from calculations using the measured sediment-oxygen demand. However, it is not clear that the bed sediments are mobilized to sufficient extent in the field for deleterious loss of DO. Indeed, much of the resuspended sediments within the canal and the river may well come from runoff from the land. The results also demonstrate key hydrogeochemical processes in Chalk-fed surface waters, with implications for environmental management. [Copyright &y& Elsevier]

Implementation of the Water Framework Directive (WFD) represents a fundamental change in the management of water in Europe with a requirement that member states ensure ‘good ecological status’ for all water bodies by 2015. Agriculture is expected to bear a major share of WFD implementation costs as it is compelled to reduce the emission of diffuse water pollutants. The research outlined here comprises interdisciplinary modelling of agricultural land use, hydrology and consequent water quality effects to consider both agricultural costs and the non-market recreational use (and potentially non-use) values that implementation of the Directive may generate. A theme throughout the research is the spatial distribution of the costs and benefits of WFD implementation, which is addressed through the use of GIS techniques in the modelling of agricultural land use, the integration of land use and hydrological models, and the estimation, aggregation and transfer of the economic value of the benefits. [ABSTRACT FROM AUTHOR]

Abstract: The water quality of the River Thame, a tributary of the River Thames in the Thames basin, is described in relation to point and diffuse contaminant inputs and runoff from permeable and impermeable bedrock geology with their own characteristic water quality. The data is examined to see if the market town of Aylesbury in the upper part of the catchment influences water quality. Previous studies highlighted the influence of Aylesbury sewage treatment works (STW) on soluble reactive phosphorus (SRP) concentrations in the river before and after phosphorus (P) stripping at the STW. Variations in water quality along the river are described and the study indicates that, apart from SRP, water quality determinants seem to be relatively unaffected by Aylesbury. The Thame water quality is compared with other catchment typologies and it is very similar to that of the main stem of the Thames even though the Thames is mainly Chalk groundwater fed. Differences in water quality largely link to the amount of STW effluent within the rivers and to the endmember compositions of the groundwater and near surface water sources. [Copyright &y& Elsevier]

Abstract: The water quality of the River Cherwell and a tributary of it, the Ray, are described in terms of point and diffuse sources of pollution, for this rural area of the upper Thames Basin. Point sources of pollution dominate at the critical ecological low flow periods of high biological activity. Although the surface geology is predominantly clay, base flow is partly supplied from springs in underlying carbonate-bearing strata, which influences the water quality particularly with regards to calcium and alkalinity. The hydrogeochemistry of the river is outlined and the overall importance of urban point sources even in what would normally be considered to be rural catchments is stressed in relation to the European Unions Water Framework Directive. Issues of phosphorus stripping at sewage treatment works are also considered: such stripping on the Cherwell has reduced phosphorus concentrations by about a factor of two, but this is insufficient for the needs of the Water Framework Directive. [Copyright &y& Elsevier]

Abstract: The distribution of dissolved organic carbon (DOC) in rainfall, cloud water, spruce throughfall and stemflow, stream runoff and groundwater is described for the Plynlimon catchments in mid-Wales for up to 20 years of record. Rainfall concentrations average at 0.69mg-Cl−1 while equivalent values in cloud water are over three times higher. Spruce throughfall and stemflow averages are over an order of magnitude higher than rainfall. DOC averages are around 1.5mg-Cl−1 for most streams draining moorland and forested areas but much higher values occur for streams draining from organic-rich gley soils in the forest. Groundwater concentrations typically average about 0.5mg-Cl−1. For forested sites where felling has taken place, this has typically resulted in little change for either the streams or the groundwater, but larger changes can occur for a small stream drainage area with gley soils. For rainfall, DOC concentrations increased from 1983 to 1993 and then declined thereafter to 2003. For the streams draining forest there has been a fairly uniform rise in DOC concentrations over time throughout the period of typically about 0.055mg-Cl−1 year−1. However, when the influence of season, air temperature and flow was filtered out of the ‘raw’ time series, there appeared a residual trend for 1983–1993 and a moderate levelling off from 1983 onwards the streams draining forest. One moorland stream showed a lower gradient barely significant from zero, but this may be partially because data was only available from 1990. The variation in gradient across the sites for the full monitoring period of each of the streams was 0.019–0.146mg-Cl−1 year−1 for the raw and 0–0.113mg-Cl−1 year−1 for the residual time series. [Copyright &y& Elsevier]

Abstract: Data for water quality surveys of effluent from sewage treatment works (STWs) in the rural Kennet/Dun sub-catchments of the upper Thames Basin are presented to characterize treated sewage effluent. Water quality determinand relationships with boron (B) are presented to provide information that can be used, with stream water quality information, to assess the relative inputs of treated sewage effluent pollutants to streams in rural areas. The approach is based on three points: (1) information on sewage effluent and agricultural pollution is of concern in relation to the management of UK lowland river systems in rural environments; (2) the lack of detailed information on sewage runoff chemistry and flow means that direct assessment of sewage effluent pollution to surface waters cannot be gauged; (3) B provides a clear chemically conservative marker of sewage sources in surface and ground waters. Three types of relationship to B were observed. Firstly, determinands such as Na, Cl, soluble reactive phosphorus (SRP) and NO3 showed a positive linear relationship with B and there is a near zero intercept; these components are essentially derived from sewage sources. Secondly, Mg and SO4 show linear relationships with B, but there is a non-zero intercept; these components have both a sewage component and a background component linked to water supplies from surface and groundwater sources. Thirdly, there are determinands that show no relationship with boron. In this study, an erratic pattern was observed for ammonium. This probably reflects the variable removal of this pollutant from sewage sources. Near constant concentrations of components such as Ca and alkalinity, which come from the background aquifer sources, were also found. SRP and B relationships for rivers in the upper Thames Basin showed the potential importance of (a) removal processes in the stream/groundwater for SRP derived from STW effluent inputs and (b) tertiary P stripping at the STWs on river water SRP levels. The importance of agricultural sources of SRP is questioned. [Copyright &y& Elsevier]

Abstract: This paper describes the variations in silicon concentrations in UK waters for a wide range of catchment systems (near pristine, rural, and agricultural and urban impacted systems). The paper largely concerns silicon levels in streams, rivers and lakes based on extensive data collected as part of several research and monitoring initiatives of national and international standing. For a detailed study of an upland catchment in mid-Wales, information on atmospheric inputs and groundwater chemistries is provided to supply background information to cross link to the surface water chemistry. Several hundred streams/rivers and lakes are dealt with within the study, dealing with the main types of freshwater riverine and lacustrine environments. The streams/rivers vary from small ephemeral runoff to the major rivers of the UK. The geographical location of sites vary from local sites in mid-Wales, to regional studies across Scotland, to the major eastern UK rivers entering the North Sea and to acid sensitive upland sites across Wales, the English Lake District, Scotland and Northern Ireland. The surface waters range in silicon concentration from 0 to 19mg-Sil−1 (average for individual sites vary between 0.7 and 7.6mg-Sil−1) and there are some clear variations which link to two primary processes (1) the relative inputs of groundwaters enriched in silicon and near surface waters more depleted in silicon and (2) plankton uptake of silicon during the summer months under baseflow conditions. Thermodynamic analysis reveals that the waters are approximately saturated with respect to either quartz or chalcedony except for two circumstances when undersaturation occurs. Firstly, undersaturation occurs at pH less than 5.5 in the upland areas and this is because the waters are mainly sourced from the acidic organic soils which are depleted in inorganic minerals. Secondly, undersaturation occurs in the lowland rivers when biological activity is at its highest and this leads to silicon removal from the water column. Quartz equilibrium can be approached (at pH>5.5) mainly within the upland systems which are not aquifer recharge dominated. However, for the lowland systems that are groundwater recharge dominated, it is chalcedony saturation which is approached, and such saturation is often observed within groundwaters. Similar patterns of undersaturation in response to biological uptake are seen in lakes and the extent of silicon depletion increases with biological productivity. Chalcedony oversaturation can occur for some UK rivers under baseflow conditions and this probably links to a higher rate of weathering. [Copyright &y& Elsevier]

Abstract: In January 1992, there was a major pollutant event for the River Carnon 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 (CEH; then Institute of Hydrology) Wallingford undertook daily monitoring of the River Carnon 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 Carnon are described in relation to these two distinct hydrogeochemical groupings. [Copyright &y& Elsevier]

Hydrological and hydrochemical data from long-term monitoring stations are vital for inferring travel times and flowpaths of water, and transport of contaminants through catchments. Spectral analysis is particularly powerful for studying the hydrological and chemical dynamics of catchments across a wide range of time scales. Here, recent work is reviewed that illustrates how spectral analyses of long-term monitoring data can be used to infer the travel-time distribution of water through catchments, and to measure the chemical retardation of reactive solutes at the catchment scale. For spectral analysis, it is desirable to have data sets with high sampling frequency and long periods of coverage. Using two data sets, a 3-yr daily data series and a 17-yr weekly data series from the Hafren catchment at Plynlimon, Wales, we demonstrate that high-frequency sampling (e.g., daily or more frequent) is particularly useful for revealing the short-term chemical dynamics that most clearly reflect the interplay of subsurface chemical and hydrological processes. However, data sets that combine high-frequency sampling during storm events with low-frequency sampling between storms can cause spectral artifacts and must be treated with special care. [ABSTRACT FROM AUTHOR]

This paper brings together information on the water quality functioning of the River Kennet and other parts of the upper River Thames in the south east of England. The Kennet represents a groundwater fed riverine environment impacted by agricultural and sewage sources of nutrient pollution. Descriptions of the general water quality of the area, nutrient sources, sinks and within river processes are provided together with biological responses to driving issues of agriculture, sewage treatment and climatic change. Models are developed and applied to assess the key processes involved for a highly dynamic system and to provide initial estimates of the likely responses to environmental change. Furthermore, the economic aspects of pollution control are reviewed, together with legislation issues, which are presented within the context of a landmark case known as the ‘Axford Inquiry’, the implications of which extend to regional and national dimensions. The paper concludes with a discussion on the present state of knowledge, key issues and future research on the science and management of groundwater fed nutrient impacted riverine systems. [Copyright &y& Elsevier]

Continuous pH, dissolved oxygen and temperature information for three sites on the upper portion of the River Kennet, a tributary of the Thames in southern England is presented. A thermodynamic model is developed which links this information to weekly water quality data allowing the estimation of dissolved carbon dioxide and calcite saturation levels within the river on a continuous basis. The results show a dynamic and variable system along the length of the river. Marked diurnal patterns are observed for pH, dissolved oxygen, dissolved carbon dioxide and calcite saturation and the highest fluctuations occur during the summer months. There is also a marked gradient downstream in average pH (7.5–8.0) and dissolved carbon dioxide (30–10 times atmospheric pressure). Dissolved oxygen levels average approximately 100% saturation across all sites, and the diurnal pattern occurring during the summer months declines downstream. The waters are permanently oversaturated with respect to calcite and the diurnal patterns of change are maximal during the summer months. The results are discussed in relation to: (a) the balance between photosynthesis and respiratory processes; (b) the relative interchanges between the sediment/plant interface with the water column; and (c) the rates of degassing of carbon dioxide and oxygen between the river surface and the atmosphere. [Copyright &y& Elsevier]

Concern about acidification in upland areas has brought about the need to model the stream hydrochemical response to deposition and land-use changes and calculate critical loads. Application of dynamic models such as MAGIC are preferable to steady-state methods, since they are able to produce an estimate of the time scale required to meet some water chemistry target given a reduction in acid deposition. These models typically consider annual changes in stream chemistry at one point. However, in order to protect biota from 'acid episodes', quantification of temporal variability needs to encompass event responses; in addition spatial variability across the catchment also needs to be considered. In this paper, modelling of both spatial and temporal variability is combined in a new framework which enables quantification of catchment hydrochemical variability in time and space. Both low and high flow hydro-chemical variability are quantified in terms of statistical distributions of ANC (Acid Neutralisation Capacity). These are then input as stochastic variables to an EMMA (End-Member Mixing Analysis) model which accounts for temporal variability and ANC is hence predicted as a function of time and space across the whole catchment using Monte-Carlo simulation. The method is linked to MAGIC to predict future scenarios and may be used by iteration to calculate critical loads. The model is applied to the headwaters of the River Severn at Plynlimon, Wales, to demonstrate its capabilities. [ABSTRACT FROM AUTHOR]

Analyzes a detailed time series of chloride, a natural tracer, in both rainfall and runoff from headwater catchments at Plynlimon, Wales. Observation that the catchments do not have characteristic flushing times; Observation that contaminants will initially be flushed rapidly, but that low-level contamination will be delivered to streams for a surprisingly long time; Implications for environmental sciences.

Changes in the relationship between soluble reactive phosphorus (SRP) concentration and river flow between 1966 and 2006 were assessed for the River Frome, UK using the recently developed Load Apportionment Model. The resulting source load estimates gave good agreement with known changes within the catchment. The model indicated an increase in point source contribution to the total river load from 46% to 62% between 1970 and 1985. This corresponded with the population increase within the catchment during that time. The predicted mean SRP load was highest between 1996 and 2000 (30 t y−1), with 49% coming from point sources. Despite no lowering in population or major changes in agricultural practice, the model predicted a reduced load of 18.1 t y−1 for the period 2001 to 2005, due mainly to a decrease in point source inputs from 14.6 t y−1 to 6.1 t y−1 (equivalent to 34% of the total load). This prediction matches the major improvements in sewage treatment that occurred within the catchment in 2002. This study thus provides a major validation of the Load Apportionment Model. The model provides an effective and rapid method of determining past changes in phosphorus sources, based entirely on the P concentration – flow relationship: critically, it does not require any historical information on land use, fertiliser application rates, topography, soil types and sewage inputs. Further decreases in SRP concentration in the River Frome during the algal growing season would be best achieved by further reductions of STW inputs. [Copyright &y& Elsevier]