Universal fractal scaling in stream chemistry and its implications for solute transport and water quality trend detection.

The chemical dynamics of lakes and streams affect their suitability as aquatic habitats and as water supplies for human needs. Because water quality is typically monitored only weekly or monthly, however, the higher-frequency dynamics of stream chemistry have remained largely invisible. To illuminate a wider spectrum of water quality dynamics, rainfall and streamflow were sampled in two headwater catchments at Plynlimon, Wales, at 7-h intervals for 1-2 y and weekly for over two decades, and were analyzed for 45 solutes spanning the periodic table from H(+) to U. Here we show that in streamflow, all 45 of these solutes, including nutrients, trace elements, and toxic metals, exhibit fractal 1/f(α) scaling on time scales from hours to decades (α = 1.05 ± 0.15, mean ± SD). We show that this fractal scaling can arise through dispersion of random chemical inputs distributed across a catchment. These 1/f time series are non-self-averaging: monthly, yearly, or decadal averages are approximately as variable, one from the next, as individual measurements taken hours or days apart, defying naive statistical expectations. (By contrast, stream discharge itself is nonfractal, and self-averaging on time scales of months and longer.) In the solute time series, statistically significant trends arise much more frequently, on all time scales, than one would expect from conventional t statistics. However, these same trends are poor predictors of future trends-much poorer than one would expect from their calculated uncertainties. Our results illustrate how 1/f time series pose fundamental challenges to trend analysis and change detection in environmental systems.

Phosphorus retention and remobilization along hydrological pathways in karst terrain.

Karst landscapes are often perceived as highly vulnerable to agricultural phosphorus (P) loss, via solution-enlarged conduits that bypass P retention processes. Although attenuation of P concentrations has been widely reported within karst drainage, the extent to which this results from hydrological dilution, rather than P retention, is poorly understood. This is of strategic importance for understanding the resilience of karst landscapes to P inputs, given increasing pressures for intensified agricultural production. Here hydrochemical tracers were used to account for dilution of P, and to quantify net P retention, along transport pathways between agricultural fields and emergent springs, for the karst of the Ozark Plateau, midcontinent USA. Up to ∼ 70% of the annual total P flux and ∼ 90% of the annual soluble reactive P flux was retained, with preferential retention of the most bioavailable (soluble reactive) P fractions. Our results suggest that, in some cases, karst drainage may provide a greater P sink than previously considered. However, the subsequent remobilization and release of the retained P may become a long-term source of slowly released "legacy" P to surface waters.

Phosphorus mitigation to control river eutrophication: murky waters, inconvenient truths, and "postnormal" science.

This commentary examines an "inconvenient truth" that phosphorus (P)-based nutrient mitigation, long regarded as the key tool in eutrophication management, in many cases has not yet yielded the desired reductions in water quality and nuisance algal growth in rivers and their associated downstream ecosystems. We examine why the water quality and aquatic ecology have not recovered, in some case after two decades or more of reduced P inputs, including (i) legacies of past land-use management, (ii) decoupling of algal growth responses to river P loading in eutrophically impaired rivers; and (iii) recovery trajectories, which may be nonlinear and characterized by thresholds and alternative stable states. It is possible that baselines have shifted and that some disturbed river environments may never return to predisturbance conditions or may require P reductions below those that originally triggered ecological degradation. We discuss the practical implications of setting P-based nutrient criteria to protect and improve river water quality and ecology, drawing on a case study from the Red River Basin in the United States. We conclude that the challenges facing nutrient management and eutrophication control bear the hallmarks of "postnormal" science, where uncertainties are large, management intervention is urgently required, and decision stakes are high. We argue a case for a more holistic approach to eutrophication management that includes more sophisticated regime-based nutrient criteria and considers other nutrient and pollutant controls and river restoration (e.g., physical habitat and functional food web interactions) to promote more resilient water quality and ecosystem functioning along the land-freshwater continuum.

Linking groundwaters of high CO2 to aluminium levels in rivers: the case for the upper Severn in mid-Wales.

Al is a critical ecotoxicant in surface waters impacted by acidic deposition. Apart from the most acidic surface waters, Al concentrations are often considered to be controlled by Al(OH)(3) or aluminosilicate (clay) solubility for modelling studies. For many UK rivers there is no clear evidence for such solubility controls even though there is the potential under moderately acidic/alkaline conditions. Here, Al solubility in ground and river water is compared for acid sensitive catchments in mid-Wales. The results reveal that there may be a solubility control within the groundwater but a more complex state of affairs within the river. The groundwater is of high CO(2) content and once in the river it degasses to raise pH. However, there is limited change in Al concentration and hence the solubility relationship is lost. The results flag the potential importance of groundwater solubility controls for Al and the potential for the groundwater zone to act as an Al filter. For positive alkalinity groundwaters, the high CO(2) levels depress the pH to near the value for minimum Al solubility. However, there is no simple groundwater end-member. Examining Al solubility controls solely within the rivers provides cryptic and misleading clues to the hydrogeological controls for Al within catchments. Assessing the within-catchment processes requires direct measurement with full consideration of both inorganic and organic attenuation.

Quantifying phosphorus retention and release in rivers and watersheds using extended end-member mixing analysis (E-EMMA).

Extended end-member mixing analysis (E-EMMA) is presented as a novel empirical method for exploring phosphorus (P) retention and release in rivers and watersheds, as an aid to water-quality management. E-EMMA offers a simple and versatile tool that relies solely on routinely measured P concentration and flow data. E-EMMA was applied to two river systems: the Thames (U.K.) and Sandusky River (U.S.), which drain similar watershed areas but have contrasting dominant P sources and hydrology. For both the Thames and Sandusky, P fluxes at the watershed outlets were strongly influenced by processes that retain and cycle P. However, patterns of P retention were markedly different for the two rivers, linked to differences in P sources and speciation, hydrology and land use. On an annual timescale, up to 48% of the P flux was retained for the Sandusky and up to 14% for the Thames. Under ecologically critical low-flow periods, up to 93% of the P flux was retained for the Sandusky and up to 42% for the Thames. In the main River Thames and the Sandusky River, in-stream processes under low flows were capable of regulating the delivery of P and modifying the timing of delivery in a way that may help to reduce ecological impacts to downstream river reaches, by reducing ambient P concentrations at times of greatest river eutrophication risk. The results also suggest that by moving toward cleaner rivers and improved ecosystem health, the efficiency of P retention may actually increase.

Aluminium in UK rivers: a need for integrated research related to kinetic factors, colloidal transport, carbon and habitat.

Dissolved aluminium concentrations ([Al]) in the <0.45 µm filtered fraction are described for 54 UK river sites covering rural, acidic/acid sensitive, agricultural and urban typologies, and wide pH range (4 to 11). High [Al] occurred under acidic conditions and for acid runoff neutralised by bicarbonate rich groundwater. Thermodynamic analysis indicates Al hydroxide/hydroxy-silicate oversaturation at circumneutral pH across the rivers, but undersaturation at lower/higher pH. The oversaturation reflects in part the presence of Al bearing colloids as indicated by (1) [Al] being correlated with components associated with both lithogenic (Fe, Ti and lanthanides) colloids and organic carbon, (2) baseflow studies using cross-flow ultrafiltration and (3) comparison of our data with Acid Waters Monitoring Network (AWMN) information on labile and non-labile Al. Tree harvesting and emission reductions of SO(x) in acidic and acid sensitive catchments in mid-Wales led to acidification reversal, lower [Al] and changing [H(+)] - [Al] relationships. The [Al] decline was confined to acidic conditions while [Al] increased during the later part of the monitoring period with a peak around 2002 for moorland and forested systems. Colloidal production across the flow range was indicated late in the record by comparison of our data with information collected by the AWMN for a site in mid-Wales. This production seems interlinked with organic carbon and with dissolved CO(2) changes. In order for further understanding of Al hydrogeochemistry in river systems there is a need to integrate research that moves from equilibrium to kinetic and colloidal consideration including the critical issues of organic and inorganic controls within the context of bioavailability and aquatic stress. The colloidal Al may well be of low environmental concern to fish and other factors such as habitat may well be critical.

Changes in point and diffuse source phosphorus inputs to the River Frome (Dorset, UK) from 1966 to 2006.

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.

Water quality, nutrients and the European union's Water Framework Directive in a lowland agricultural region: Suffolk, south-east England.

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.

Modelling of phosphorus inputs to rivers from diffuse and point sources.

The difference in timing of point and diffuse phosphorus (P) delivery to a river produces clear differences in the P concentration-flow relationship. Point inputs decrease in concentration with increasing river flow, due to dilution of a relatively constant input, whereas diffuse (non-point) load usually increases with river flow. This study developed a simple model, based on this fundamental difference, which allowed point and diffuse inputs to be quantified by modelling their contribution to river P concentration as a power-law function of flow. The relationships between total phosphorus (TP) concentration and river flow were investigated for three contrasting UK river catchments; the Swale (Yorkshire), the Frome (Dorset) and the Avon (Warwickshire). A load apportionment model was fitted to this empirical data to give estimates of point and diffuse load inputs at each monitoring site, at high temporal resolution. The model produced TP source apportionments that were similar to those derived from an export coefficient approach. For many diffuse-dominated sites within this study (with up to 75% of the annual TP load derived from diffuse sources), the model showed that reductions of point inputs would be most effective in order to reduce eutrophication risk, due to point source dominance during the plant and algae growing period. This modelling approach should provide simple, robust and rapid TP source apportionment from most concentration-flow datasets. It does not require GIS, information on land use, catchment size, population or livestock density, and could provide a valuable and versatile tool to catchment managers for determining suitable river mitigation options.

Inorganic carbon dominates total dissolved carbon concentrations and fluxes in British rivers: Application of the THINCARB model - Thermodynamic modelling of inorganic carbon in freshwaters.

River water-quality studies rarely measure dissolved inorganic carbon (DIC) routinely, and there is a gap in our knowledge of the contributions of DIC to aquatic carbon fluxes and cycling processes. Here, we present the THINCARB model (THermodynamic modelling of INorganic CARBon), which uses widely-measured determinands (pH, alkalinity and temperature) to calculate DIC concentrations, speciation (bicarbonate, HCO3-; carbonate, CO32-; and dissolved carbon dioxide, H2CO3⁎) and excess partial pressures of carbon dioxide (EpCO2) in freshwaters. If calcium concentration measurements are available, THINCARB also calculates calcite saturation. THINCARB was applied to the 39-year Harmonised Monitoring Scheme (HMS) dataset, encompassing all the major British rivers discharging to the coastal zone. Model outputs were combined with the HMS dissolved organic carbon (DOC) datasets, and with spatial land use, geology, digital elevation and hydrological datasets. We provide a first national-scale evaluation of: the spatial and temporal variability in DIC concentrations and fluxes in British rivers; the contributions of DIC and DOC to total dissolved carbon (TDC); and the contributions to DIC from HCO3- and CO32- from weathering sources and H2CO3⁎ from microbial respiration. DIC accounted for >50% of TDC concentrations in 87% of the HMS samples. In the seven largest British rivers, DIC accounted for an average of 80% of the TDC flux (ranging from 57% in the upland River Tay, to 91% in the lowland River Thames). DIC fluxes exceeded DOC fluxes, even under high-flow conditions, including in the Rivers Tay and Tweed, draining upland peaty catchments. Given that particulate organic carbon fluxes from UK rivers are consistently lower than DOC fluxes, DIC fluxes are therefore also the major source of total carbon fluxes to the coastal zone. These results demonstrate the importance of accounting for DIC concentrations and fluxes for quantifying carbon transfers from land, via rivers, to the coastal zone.

River water quality of the River Cherwell: an agricultural clay-dominated catchment in the upper Thames Basin, southeastern England.

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.

The water quality of the River Thame in the Thames Basin of south/south-eastern England.

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.

Sewage-effluent phosphorus: a greater risk to river eutrophication than agricultural phosphorus?

Phosphorus (P) concentrations from water quality monitoring at 54 UK river sites across seven major lowland catchment systems are examined in relation to eutrophication risk and to the relative importance of point and diffuse sources. The over-riding evidence indicates that point (effluent) rather than diffuse (agricultural) sources of phosphorus provide the most significant risk for river eutrophication, even in rural areas with high agricultural phosphorus losses. Traditionally, the relative importance of point and diffuse sources has been assessed from annual P flux budgets, which are often dominated by diffuse inputs in storm runoff from intensively managed agricultural land. However, the ecological risk associated with nuisance algal growth in rivers is largely linked to soluble reactive phosphorus (SRP) concentrations during times of ecological sensitivity (spring/summer low-flow periods), when biological activity is at its highest. The relationships between SRP and total phosphorus (TP; total dissolved P+suspended particulate P) concentrations within UK rivers are evaluated in relation to flow and boron (B; a tracer of sewage effluent). SRP is the dominant P fraction (average 67% of TP) in all of the rivers monitored, with higher percentages at low flows. In most of the rivers the highest SRP concentrations occur under low-flow conditions and SRP concentrations are diluted as flows increase, which is indicative of point, rather than diffuse, sources. Strong positive correlations between SRP and B (also TP and B) across all the 54 river monitoring sites also confirm the primary importance of point source controls of phosphorus concentrations in these rivers, particularly during spring and summer low flows, which are times of greatest eutrophication risk. Particulate phosphorus (PP) may form a significant proportion of the phosphorus load to rivers, particularly during winter storm events, but this is of questionable relevance for river eutrophication. Although some of the agriculturally derived PP is retained as sediment on the river bed, in most cases this bed sediment showed potential for removal of SRP from the overlying river water during spring and summer low flows. Thus, bed sediments may well be helping to reduce SRP concentrations within the river at times of eutrophication risk. These findings have important implications for targeting environmental management controls for phosphorus more efficiently, in relation to the European Union Water Framework Directive requirements to maintain/improve the ecological quality of impacted lowland rivers. For the UK rivers examined here, our results demonstrate that an important starting point for reducing phosphorus concentrations to the levels approaching those required for ecological improvement, is to obtain better control over point source inputs, particularly small point sources discharging to ecologically sensitive rural/agricultural tributaries.

Chlorophyll-a in the rivers of eastern England.

Chlorophyll-a concentration variations are described for two major river basins in England, the Humber and the Thames and related to catchment characteristics and nutrient concentrations across a range of rural, agricultural and urban/industrial settings. For all the rivers there are strong seasonal variations, with concentrations peaking in the spring and summer time when biological activity is at its highest. However, there are large variations in the magnitude of the seasonal effects across the rivers. For the spring-summer low-flow periods, average concentrations of chlorophyll-a correlate with soluble reactive phosphorus (SRP). Chlorophyll-a is also correlated with particulate nitrogen (PN), organic carbon (POC) and suspended sediments. However, the strongest relationships are with catchment area and flow, where two straight line relationships are observed. The results indicate the importance of residence times for determining planktonic growth within the rivers. This is also indicated by the lack of chlorophyll-a response to lowering of SRP concentrations in several of the rivers in the area due to phosphorus stripping of effluents at major sewage treatment works. A key control on chlorophyll-a concentration may be the input of canal and reservoir waters during the growing period: this too relates to issues of residence times. However, there may well be a complex series of factors influencing residence time across the catchments due to features such as inhomogeneous flow within the catchments, a fractal distribution of stream channels that leads to a distribution of residence times and differences in planktonic inoculation sources. Industrial pollution on the Aire and Calder seems to have affected the relationship of chlorophyll-a with PN and POC. The results are discussed in relation to the Water Framework Directive.

Nitrate concentrations in river waters of the upper Thames and its tributaries.

The spatial and temporal patterns of in-stream nitrate concentrations for the upper Thames and selected tributaries are described in relation to point and diffuse sources for these rural catchments. The rivers associated with catchments dominated by permeable (Cretaceous Chalk) bedrock show a smaller range in nitrate concentrations than those associated with clay and mixed sedimentary bedrock of lower permeability. The differences reflect the contrasting nature of water storage within the catchments and the influence of point and diffuse sources of nitrate. Nitrate concentrations often increase in a gradual way as a function of flow for the rivers draining the permeable catchments, although there is usually a minor dip in nitrate concentrations at low to intermediate flow due to (1) within-river uptake of nitrate during the spring and the summer when biological activity is particularly high and (2) a seasonal fall in the water table and a change in preferential flow-pathway in the Chalk. There is also a decrease in the average nitrate concentration downstream for the Kennet where average concentrations decrease from around 35 to 25 mg NO(3) l(-1). For the lower permeability catchments, when point source inputs are not of major significance, nitrate concentrations in the rivers increase strongly with increasing flow and level off and in some cases then decline at higher flows. When point source inputs are important, the initial increase in nitrate concentrations do not always occur and there can even be an initial dilution, since the dilution of point sources of nitrate will be lowest under low-flow conditions. For the only two tributaries of the Thames which we have monitored for over 5 years (the Pang and the Kennet), nitrate concentrations have increased over time. For the main stem of the Thames, which was also monitored for over 5 years, there is no clear increase over time. As the Pang and the Kennet river water is mainly supplied from the Chalk, the increasing nitrate concentrations over time clearly reflect increasing nitrate concentrations within the groundwater. It primarily reflects long-term trends for agricultural fertilizer inputs and significant aquifer storage and long water residence times. The results are discussed in terms of hydrogeochemical processes and the Water Framework Directive and are compared with data from other eastern UK rivers. The importance of diffuse sources of nitrate contamination is highlighted. On a flow weighted basis, the average diffuse component of nitrate is around 95% for the Thames Basin rivers draining Chalk and for the corresponding rivers draining less permeable strata, there is a more significant but not major point source component (at least in terms of flux); the average diffuse component is 79% in this case. These data fit well with earlier assessments of agricultural sources to UK surface waters. Under baseflow conditions the diffuse sources remain dominant for the Chalk fed Thames Basin rivers, but point sources can be dominant for the low permeability cases. On a proportionate basis, the Thames Basin rivers are similar to the rural rivers of the Tweed and Humber Basins in terms of percentage diffuse components although the lower intensity agriculture occurring for the rivers monitored means that the average nitrate concentrations are lower for the rural rivers of central and northern England and the borders with Scotland: the Humber and Tweed.

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 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.

Phosphorus concentrations in the River Dun, the Kennet and Avon Canal and the River Kennet, southern England.

Variations in phosphorus (P) concentrations in an agriculturally impacted river draining a Chalk aquifer and an associated canal in the west of the Thames Basin, southern England are examined and linked to agricultural and sewage sources and within river/canal process controls. The study area comprises the River Dun, the adjacent River Kennet and the Kennet and Avon (K&A) Canal. Large seasonal variations are observed for soluble reactive phosphorus (SRP) and dissolved silicon (Si) with low concentrations in the spring and summer times when biological activity is high. The K&A Canal shows the largest SRP and Si concentration declines. This reflects high biological activity coupled with higher temperatures and higher water residence times. The extent of SRP removal is examined in relation to organic (uptake/release with phytoplankton growth/decay) and, to a lesser extent, inorganic (SRP coprecipitation with calcite) mechanisms. Boron (B) is used as a tracer of sewage sources. Agricultural inputs of both dissolved and particulate P (PP) can be important particularly under conditions where the catchment is wet and near surface/overland flow is important: sewage treatment works effluent and septic tank discharges to groundwater also probably provide a major component of the SRP occurring within the water column. The canal, and to a lesser extent the river, acts as sink for P in sewage effluent sources due to the high biological activity especially during the spring and summer. The aquifer probably acts as a major sink for agricultural and septic tank inputs of P.

Nutrient hydrochemistry for a groundwater-dominated catchment: the Hampshire Avon, UK.

The patterns in nitrate and phosphorus sources, loads and concentrations in a groundwater-dominated lowland catchment, the Hampshire Avon, are examined and water quality signatures are used to identify a typology of headwater stream types. The major separations in water quality are linked to geology and groundwater chemistry as modified by the impacts of point source sewage effluents. The water quality of the major tributaries and the main stem of the River Avon are linked to the relative contributions of these source types, the impact of further direct effluent inputs to the main channel and in-stream processing. The tributaries and main stem of the Avon act as net sinks for total reactive phosphorus (TRP). Low concentrations of TRP were found in the Chalk groundwater and the groundwater system acts as an efficient buffer, removing and retaining TRP from water draining from the catchment surface into the aquifer. Thermodynamic analysis of calcium carbonate (CaCO3) solubility controls indicates that this natural 'self-cleansing mechanism' system within the groundwater may be directly linked to CaCO3-P co-precipitation within the aquifer matrix.

Calcite saturation in eastern UK rivers.

Calcite saturation in eastern UK rivers is assessed in relation to the potential kinetic inhibition of calcite precipitation. Two well established inhibitors are considered: soluble reactive phosphorus (SRP, i.e. inorganic monomeric phosphorus); and dissolved organic carbon (DOC). The rivers show a range of calcite saturation levels from approximately 1hundredth to approximately 100-fold. The greatest range occurs for the northernmost river considered, the Tweed, where the waters range from highly unsaturated to highly oversaturated. The lowest range occurs for the most southerly rivers (the Great Ouse and the Thames) where the waters are consistently oversaturated with respect to calcite. The contrasting patterns relate to a greater diversity of water quality within the northern regions. Thus, during the winter, the main waters are derived from the upland areas with acidic soils and low weathering rates. During the summer baseflow periods, groundwater inputs are more important and high photosynthesis results in particularly high pHs and calcite oversaturation. In contrast, for the southern rivers, the main source of water during both the summer baseflow and the winter highflow periods comes from calcium carbonate rich aquifer sources. Statistical analysis of pH vs. the logarithm of the calcite saturation index for each river indicates strong linear features with individual gradients of approximately 1. This linearity results from an autocorrelation (the logarithm of the saturation index is calculated from the pH) and this indicates that calcite solubility controls are not operative in any of the rivers examined. A comparison of calcite saturation levels and SRP and DOC concentrations show a pattern inconsistent with kinetic hindrance, although some structure is observed, probably due to the mixing reactions between point and diffuse sources of water with contrasting chemistry.

Interception and attenuation of atmospheric pollution in a lowland ash forested site, Old Pond Close, Northamptonshire, UK.

A study of interception of chemicals at an ash plantation forest in southern-central England shows the modification of acidic pollution as it passes from precipitation, through the vegetation cover and the soil to generate surface runoff. Precipitation is highly acidic (pH 3.7-4.8, alkalinity -16 to -200 microEq/l) and it is enriched in the strong acid anions associated with acidification (sulfate and nitrate) as well as ammonium and the trace elements aluminium and zinc. The concentration of both sea-salt and pollutant components varies considerably over time and this is linked to washout from the atmosphere during precipitation events as marked by an inverse relationship between concentration and volume of catch. The catchment is also supplied by sea-salt and pollutant additions as dry deposition: gaseous inputs of SO(x) may also increase sulfate deposition. Through the vegetation, much of the acidity is neutralised and, particularly during the growth period, calcium, magnesium and potassium is cycled, while sodium and nitrate are partially removed. Within the catchment, weathering ensures that further base cation production occurs leading to enhanced neutralisation of acidity and the generation of positive alkalinities. As a result, surface runoff becomes buffered with alkalinity approximately 490 microEq/l and pH approximately 7.9. Thus, although the acidification input from the atmosphere is high, this does not translate to acidic runoff due to within-canopy and within-soil processes.