Trade-offs in nutrient and sediment losses in tile drainage from no-till versus conventional conservation-till cropping systems.

Nutrient and soil loss from agricultural areas impairs surface water quality globally. In the Great Lakes region, increases in the frequency and magnitude of harmful and nuisance algal blooms in freshwater lakes have been linked to elevated phosphorus (P) losses from agricultural fields, some of which are transported via tile drainage. This study examined whether concentrations and loads of P fractions, total suspended sediments (TSS), nitrate (NO3 - ), and ammonium (NH4 + ) in tile drainage in a clay soil differed between a continuous no-till system combining cover crops and surface broadcast fertilizer (no-till cover crop [NTCC]), and a more conventional tillage system with shallow tillage, fertilizer incorporation and limited use of cover crops (conventional conservation-till, CT). Both sites had modest soil fertility levels. Year-round, high-frequency observations of tile drainage flow and chemistry are described over 4 full water years and related to management practices on the associated fields. There were similar water yields in tile drainage between the two systems; however, losses of TSS, particulate P (PP), and NO3 - were consistently greater from the CT site, which received larger quantities of fertilizer. In contrast, dissolved reactive P (DRP) losses were considerably greater from the NTCC site, offsetting the lower PP losses, such that there was little difference in TP losses between sites. Approximately 60% of the DRP losses from the NTCC site over the 4 years were associated with incidental losses following surface application of fertilizer in fall. This study provides insight into trade-offs in controlling losses of different nutrient fractions using different management systems.

The Latitudes, Attitudes, and Platitudes of Watershed Phosphorus Management in North America.

Phosphorus (P) plays a crucial role in agriculture as a primary fertilizer nutrient-and as a cause of the eutrophication of surface waters. Despite decades of efforts to keep P on agricultural fields and reduce losses to waterways, frequent algal blooms persist, triggering not only ecological disruption but also economic, social, and political consequences. We investigate historical and persistent factors affecting agricultural P mitigation in a transect of major watersheds across North America: Lake Winnipeg, Lake Erie, the Chesapeake Bay, and Lake Okeechobee/Everglades. These water bodies span 26 degrees of latitude, from the cold climate of central Canada to the subtropics of the southeastern United States. These water bodies and their associated watersheds have tracked trajectories of P mitigation that manifest remarkable similarities, and all have faced challenges in the application of science to agricultural management that continue to this day. An evolution of knowledge and experience in watershed P mitigation calls into question uniform solutions as well as efforts to transfer strategies from other arenas. As a result, there is a need to admit to shortcomings of past approaches, plotting a future for watershed P mitigation that accepts the sometimes two-sided nature of Hennig Brandt's "Devil's Element."

Phosphorus fluxes to the environment from mains water leakage: Seasonality and future scenarios.

Accurate quantification of sources of phosphorus (P) entering the environment is essential for the management of aquatic ecosystems. P fluxes from mains water leakage (MWL-P) have recently been identified as a potentially significant source of P in urbanised catchments. However, both the temporal dynamics of this flux and the potential future significance relative to P fluxes from wastewater treatment works (WWT-P) remain poorly constrained. Using the River Thames catchment in England as an exemplar, we present the first quantification of both the seasonal dynamics of current MWL-P fluxes and future flux scenarios to 2040, relative to WWT-P loads and to P loads exported from the catchment. The magnitude of the MWL-P flux shows a strong seasonal signal, with pipe burst and leakage events resulting in peak P fluxes in winter (December, January, February) that are >150% of fluxes in either spring (March, April, May) or autumn (September, October, November). We estimate that MWL-P is equivalent to up to 20% of WWT-P during peak leakage events. Winter rainfall events control temporal variation in both WWT-P and riverine P fluxes which consequently masks any signal in riverine P fluxes associated with MWL-P. The annual average ratio of MWL-P flux to WWT-P flux is predicted to increase from 15 to 38% between 2015 and 2040, associated with large increases in P removal at wastewater treatment works by 2040 relative to modest reductions in mains water leakage. However, further research is required to understand the fate of MWL-P in the environment. Future P research and management programmes should more fully consider MWL-P and its seasonal dynamics, alongside the likely impacts of this source of P on water quality.

Riparian shading controls instream spring phytoplankton and benthic algal growth.

Dissolved oxygen (DO) concentrations showed a striking pattern in a multi-year study of the River Enborne, a small river in SE England. In each of three years (2010-2012), maximum DO concentrations were attained in mid-April, preceded by a period of steadily increasing diurnal amplitudes, followed by a steady reduction in both amplitude and concentration. Flow events during the reduction period reduce DO to low concentrations until the following spring. Evidence is presented that this pattern is mainly due to benthic algal growth which is eventually suppressed by the growth of the riparian tree canopy. Nitrate and silicate concentrations are too high to inhibit the growth of either benthic algae or phytoplankton, but phosphate concentrations might have started to reduce growth if the tree canopy development had been delayed. This interpretation is supported by evidence from weekly flow cytometry measurements and analysis of the diurnal, seasonal and annual patterns of nutrient concentrations. As the tree canopy develops, the river switches from an autotrophic to a heterotrophic state. The results support the use of riparian shading to help control algal growth, and highlight the risks of reducing riparian shade.

Characterising phosphorus and nitrate inputs to a rural river using high-frequency concentration-flow relationships.

The total reactive phosphorus (TRP) and nitrate concentrations of the River Enborne, southern England, were monitored at hourly interval between January 2010 and December 2011. The relationships between these high-frequency nutrient concentration signals and flow were used to infer changes in nutrient source and dynamics through the annual cycle and each individual storm event, by studying hysteresis patterns. TRP concentrations exhibited strong dilution patterns with increasing flow, and predominantly clockwise hysteresis through storm events. Despite the Enborne catchment being relatively rural for southern England, TRP inputs were dominated by constant, non-rain-related inputs from sewage treatment works (STW) for the majority of the year, producing the highest phosphorus concentrations through the spring-summer growing season. At higher river flows, the majority of the TRP load was derived from within-channel remobilisation of phosphorus from the bed sediment, much of which was also derived from STW inputs. Therefore, future phosphorus mitigation measures should focus on STW improvements. Agricultural diffuse TRP inputs were only evident during storms in the May of each year, probably relating to manure application to land. The nitrate concentration-flow relationship produced a series of dilution curves, indicating major inputs from groundwater and to a lesser extent STW. Significant diffuse agricultural inputs with anticlockwise hysteresis trajectories were observed during the first major storms of the winter period. The simultaneous investigation of high-frequency time series data, concentration-flow relationships and hysteresis behaviour through multiple storms for both phosphorus and nitrate offers a simple and innovative approach for providing new insights into nutrient sources and dynamics.

Climate change and coupling of macronutrient cycles along the atmospheric, terrestrial, freshwater and estuarine continuum.

This paper provides an introduction to the Special Issue on "Climate Change and Coupling of Macronutrient Cycles along the Atmospheric, Terrestrial, Freshwater and Estuarine Continuum", dedicated to Colin Neal on his retirement. It is not intended to be a review of this vast subject, but an attempt to synthesize some of the major findings from the 22 contributions to the Special Issue in the context of what is already known. The major research challenges involved in understanding coupled macronutrient cycles in these environmental media are highlighted, and the difficulties of making credible predictions of the effects of climate change are discussed. Of particular concern is the possibility of interactions which will enhance greenhouse gas concentrations and provide positive feedback to global warming.

Role of riverine colloids in macronutrient and metal partitioning and transport, along an upland-lowland land-use continuum, under low-flow conditions.

An assessment is made of the role of riverine colloids in macronutrient (nitrogen, phosphorus and carbon), metal and trace element partitioning and transport, for five rivers in the Ribble and Wyre catchments in north-western England, under baseflow/near-baseflow conditions. Cross-flow ultrafiltration was used to separate colloidal (<0.45 µm >1 kDa) and truly dissolved (<1 kDa) fractions from river water. Clear patterns were observed, along the upland-lowland land use continuum, in the partitioning and transport of macronutrients and metals between the colloidal, truly dissolved and acid-available particulate (>0.45 µm, suspended) fractions. Of these operationally-defined fractions measured, colloids were generally more important for both macronutrient and metal transport in the upland than in the lowland rivers. The results suggest that organic moieties in truly dissolved form from sewage effluent may have a greater capacity to chelate metals. Organic-rich colloids in the upland moorlands and metal oxide colloidal precipitates in the industrial rivers had a higher capacity for binding metals than the colloidal fractions in the urban and agricultural lowland rivers. Aggregation of these colloids may provide an important mechanism for formation of larger suspended particulates, accounting for a higher degree of metal enrichment in the acid-available particulate fractions of the upland moorland and lowland industrial rivers, than in the lowland agricultural and urban rivers. This mechanism of transfer of contaminants to larger aggregates via colloidal intermediates, known as 'colloidal pumping' may also provide a mechanism for particulate P formation and the high proportion of P being transported in the particulate fraction in the uplands. The cross-flow ultrafiltration data also allowed refinement of partition coefficients, by accounting for colloids within the solids phase and replacing the filtered (<0.45 µm) fraction with the truly dissolved (<1 kDa) concentrations. These provided a clearer description of the controls on metal and P partitioning along the upland-lowland continuum.

Modelling phosphorus dynamics in multi-branch river systems: a study of the Black River, Lake Simcoe, Ontario, Canada.

High rates of nutrient loading from agricultural and urban development have resulted in surface water eutrophication and groundwater contamination in regions of Ontario. In Lake Simcoe (Ontario, Canada), anthropogenic nutrient contributions have contributed to increased algal growth, low hypolimnetic oxygen concentrations, and impaired fish reproduction. An ambitious programme has been initiated to reduce phosphorus loads to the lake, aiming to achieve at least a 40% reduction in phosphorus loads by 2045. Achievement of this target necessitates effective remediation strategies, which will rely upon an improved understanding of controls on nutrient export from tributaries of Lake Simcoe as well as improved understanding of the importance of phosphorus cycling within the lake. In this paper, we describe a new model structure for the integrated dynamic and process-based model INCA-P, which allows fully-distributed applications, suited to branched river networks. We demonstrate application of this model to the Black River, a tributary of Lake Simcoe, and use INCA-P to simulate the fluxes of P entering the lake system, apportion phosphorus among different sources in the catchment, and explore future scenarios of land-use change and nutrient management to identify high priority sites for implementation of watershed best management practises.

The biogeochemistry of arsenic in a remote UK upland site: trends in rainfall and runoff, and comparisons with urban rivers.

Ten years of monitoring of rainfall and streams in the remote acidic and acid sensitive moorland and afforested moorland of upland mid-Wales reveals concentrations of arsenic (As) typically <1 µg L(-1). On average, the lowest concentrations occur within rainfall and they have declined over time probably in response to reductions in global emissions. There is a corresponding reduction within the streams except for forested systems where concentrations up to doubled following clear-fell. Within the streams there are both annual cycling and diurnal cycling of As. The annual cycling gives maxima during the summer months and this probably reflects the importance of groundwater inputs and mineralisation/desorption from the surface soil layers. Correspondingly, the diurnal cycling occurs during the summer months at low flow periods with As concentrations highest in the afternoon/evening. For the urban/industrial basins of northern England with historically a much higher As deposition, land contamination and effluent discharges, comparative data indicate As concentrations around three fold higher: strong seasonal patterns are observed for the same reasons as with the uplands. Across the sites, the As concentrations are over an order of magnitude lower than that of environmental concern. Nonetheless, the results clearly show the effects of declining emissions on rainfall deposition and some indication of areas of historic contamination. Arsenic is mainly present in the <0.45 fraction, but cross-flow filtration indicates that approx. 43% is in the colloidal phase at the clean water sites, and 16% in the colloidal phase at the contaminated sites. Part of this colloidal component may well be associated with organic carbon.

Quantifying the impact of septic tank systems on eutrophication risk in rural headwaters.

Septic tank systems (STS) are a potential source of nutrient emissions to surface waters but few data exist in the UK to quantify their significance for eutrophication. We monitored the impact of STS on nutrient concentrations in a stream network around a typical English village over a 1-year period. Septic tank effluent discharging via a pipe directly into one stream was highly concentrated in soluble N (8-63mgL(-1)) and P (<1-14mgL(-1)) and other nutrients (Na, K, Cl, B and Mn) typical of detergent and household inputs. Ammonium-N (NH(4)N) and soluble reactive P (SRP) fractions were dominant (70-85% of total) and average concentrations of nitrite-N (NO(2)N) were above levels considered harmful to fish (0.1mgL(-1)). Lower nutrient concentrations were recorded at a ditch and a stream site, but range and average values downstream of rural habitation were still 4 to 10-fold greater than those in upstream sections. At the ditch site, where flow volumes were low, annual flow-weighted concentrations of NH(4)N and SRP increased from 0.04 and 0.07mgL(-1), respectively upstream to 0.55 and 0.21mgL(-1) downstream. At the stream site, flow volumes were twice as large and flow-weighted concentrations increased much less; from 0.04 to 0.21mgL(-1) for NH(4)N and from 0.06 to 0.08mgL(-1) for SRP. At all sites, largest nutrient concentrations were recorded under low flow and stream discharge was the most important factor determining the eutrophication impact of septic tank systems. The very high concentrations, intercorrelation and dilution patterns of SRP, NH(4)-N and the effluent markers Na and B suggested that soakaways in the heavy clay catchment soils were not retaining and treating the septic tank effluents efficiently, with profound implications for stream biodiversity. Water companies, water regulators and rural communities therefore need to be made more aware of the potential impacts of STS on water quality so that their management can be optimised to reduce the risk of potential eutrophication and toxicity to aquatic ecosystems during summer low flow periods.

Characterization of phosphorus sources in rural watersheds.

Correct identification of P sources in rural watersheds is critical for the development of cost-effective measures to combat agriculturally-driven eutrophication. The chemical composition of various storm runoff types (field surface runoff, field drain outfalls, roads, farmyards, and septic tanks) and the receiving streams in three micro (<10 km(2)) watersheds of varying agricultural intensity were monitored over a 2-yr period. Mean weekly stream soluble reactive phosphorus (SRP) and total phosphorus (TP) concentrations increased from 29 and 69 microg L(-1), respectively in the watershed with the lowest intensity agriculture to 382 and 503 microg L(-1), respectively in the watershed with high intensity agriculture and a village sewage treatment works. Concentrations of TP in storm runoff varied by up to two orders of magnitude reflecting the complex origins, routing, and composition of contributing source areas. Application of the DESPRAL test suggested field runoff TP concentrations were influenced by both P and organic matter in soil. However, runoff from impervious surfaces (farmyard and roads), and/or influenced by septic tank discharges, was significantly more concentrated (0.08-16 mg TP L(-1), mean >>1 mg L(-1)) than surface and subsurface runoff from cultivated land and pasture (0.02-3.6 mg TP L(-1), mean <1 mg L(-1)), and/or contained a significantly greater proportion (>50% vs. <50%) of P in dissolved forms. It is concluded that P sources associated with the functioning of rural communities (impervious surfaces, detergents, and wastewater) may be more ecologically relevant than those associated with agriculture and should be better quantified and controlled to avoid localized eutrophication impacts.

Delivery and cycling of phosphorus in rivers: a review.

Phosphorus (P) supply (concentration and flux) is an important driver for biological activity in flowing waters and needs to be managed to avoid eutrophication impacts associated with urbanisation and agricultural intensification. This paper examines the role of in-stream retention and cycling in regulating river P concentrations in order to better understand the links between P sources and their ecological impacts. In terms of their composition (solubility and concentration), patterns of delivery (mode and timing) and therefore ecological relevance, P sources entering rivers are best grouped into wastewater discharges > runoff from impervious surfaces (roads, farmyards) > runoff from pervious surfaces (forestry, cultivated land and pasture). The localized impacts of soluble P discharges during ecologically sensitive periods can be distinguished from the downstream impacts associated with particulate P discharges under high flows due to the different processes by which these sources are retained, transformed and assimilated within the river channel. The range of physico-chemical processes involved in P cycling and the variable importance of these processes in different river environments according to stream size, stream geomorphology and anthropogenic pressures are summarised. It is concluded that the capacity to retain (process) P within the river channel, and hence regulate the downstream delivery of P without stressing the aquatic communities present, is considerable, especially in headwaters. To help achieve good water quality, there is scope to better manage this ecosystem service through regulation of P supply whilst optimising in-stream P retention according to subsidy-stress theory. Further research is needed to develop in-stream management options for maximising P subsidies and to demonstrate that regulation of downstream P delivery will reduce the incidence of eutrophication in connected waterbodies.

Measuring in-stream productivity: the potential of continuous chlorophyll and dissolved oxygen monitoring for assessing the ecological status of surface waters.

Continuous (hourly) measurements of dissolved oxygen and chlorophyll (determined by fluorimetry) were made for an inter-linked lowland river and canal system. The dissolved oxygen data were used to estimate daily rates of re-aeration, photosynthesis and respiration, using a process-based analytical technique (the Delta method). In-situ fluorimeter measurements of chlorophyll were ground-truthed on a fortnightly basis using laboratory methanol extraction of chlorophyll and spectrophotometric analysis. Water samples were also analysed for algal species on a fortnightly basis. The river and canal exhibited very similar rates of photosynthesis and respiration during the summer of 2001, despite much higher chlorophyll concentrations and total algal counts, indicating that benthic algae and/or aquatic macrophytes may be making an important contribution to photosynthesis rates in the river. Suspended algal populations in the canal are dominated by planktonic species, whereas the river has a higher proportion of species which are predominantly benthic in habitat. The river exhibited higher rates of respiration, reflecting a higher organic loading from external (e.g. sewage effluent) sources.

Macrophyte and periphyton dynamics in a UK Cretaceous Chalk stream: the river Kennet, a tributary of the Thames.

An initial study to observe the seasonal trends and to determine the factors influencing macrophyte and periphyton growth patterns was undertaken on a representative reach of the River Kennet (UK) over a 2-year period (1998-2000). Maximum average macrophyte and average periphyton dry matter biomass recorded during the growing season were 200 and 21 g m(-2), respectively. The relationships between macrophyte and periphyton percentage cover and biomass data with physico-chemical variables were investigated. Regression analysis indicated that of the parameters measured, flow, and in the case of the dominant Ranunculus spp., solar radiation, were best able to predict macrophyte biomass and cover. The periphytic biomass within the reach was low, possibly as a result of relatively high flows and low phosphorus concentrations following the introduction of effluent treatment at the sewage works immediately upstream of the reach. Periphytic biomass was poorly correlated with the physical variables measured. This indicates that biomass is regulated by complex interactions between the physical and chemical factors, such as flow, solar radiation and phosphorus concentration. These interrelationships require further investigation.

On modelling the impacts of phosphorus stripping at sewage works on in-stream phosphorus and macrophyte/epiphyte dynamics: a case study for the River Kennet.

A new model of in-stream phosphorus and macrophyte dynamics, 'The Kennet model', was applied to a reach of the River Kennet, southern England. The reach, which is 1.5 km long, is immediately downstream of Marlborough sewage treatment works, where phosphorus reduction by tertiary effluent treatment began in September 1997. The model is used to simulate the flow, water chemistry and macrophyte biomass within the reach, both before and after phosphorus removal from the effluent. Monte Carlo experiments coupled with a general sensitivity analysis indicate that the model offers a feasible explanation for the salient aspects of the system behaviour. Model simulations indicate that epiphyte smothering is an important limitation to macrophyte growth, and that higher stream and pore water soluble reactive phosphorus (SRP) concentrations allow the earlier onset of growth for the epiphytes and macrophytes, respectively. Higher flow conditions are shown to reduce the simulated peak epiphyte biomass; though at present, the effect of flow on the macrophyte biomass is unclear. Another simulation result suggests that phosphorus will not be released from the bed sediments in this reach following phosphorus removal from the effluent.

Use of continuous water quality records for hydrograph separation and to assess short-term variability and extremes in acidity and dissolved carbon dioxide for the River Dee, Scotland.

A combination of continuous (15-min) pH, conductivity and temperature measurements and fortnightly spot-sampled water quality data were used to examine temporal variability and extremes in river water quality in an upland Scottish river: the River Dee at Mar Lodge. An empirical relationship was established for Gran-alkalinity by multiple regression against flow and conductivity for the fortnightly data. Applying this relationship to the continuous data, an estimate of continuous Gran-alkalinity was calculated. The continuous Gran-alkalinity record was used as (1) a conservative tracer in a simple two-component mixing model to determine the relative proportions of near-surface runoff and deeper groundwater contributing to stream flow; (2) to deconvolute the contribution of weathering and sea-salt contributions to stream conductivity; and (3) to calculate the excess partial pressure of carbon dioxide in stream water. The episodic variations in pH, weathering and sea-salt conductivity and excess partial pressures of carbon dioxide (EpCO2) associated with high flow events in the River Dee suggest that hydrological pathways play an important role in determining stream chemistry. The results of the hydrograph separation indicate that groundwater provides an important contribution to stream flow, and that there are large and hydrologically active stores of groundwater within the upper River Dee catchment. Sea-salts have an important influence on stream conductivity, particularly with the onset of storm runoff following summer drought periods. This suggests that sea-salts are concentrated in the upper soil horizons by dry deposition and/or evapotranspiration. EpCO2 behaves non-conservatively and shows marked diurnal variability under low-flow conditions during summer, inducing diurnal pH variations, and indicating the importance of within-river biological processes. This study emphasises the very intermittent nature of water quality extremes with stream spates and the diurnal nature of biologically-induced responses. Fortnightly sampling programmes do not capture the range of high flow extremes, and with sampling undertaken during the working day, biological extremes occurring at night are also missed, introducing bias. This study shows the value of continuous measurements for infilling aspects of these intermittent extremes. However, it is also noted that the relatively simple patterns of response observed from the continuous measurements may well belie a much more varied response at the sub-catchment and hillslope scales, as local chemical and hydrological heterogeneities do occur. Thus, the two-component mixing model used is, in practice, based on catchment integrated values for a range of soil water and groundwater endmembers.

Riverine inputs of major ions and trace elements to the tidal reaches of the River Tweed, UK.

This paper examines spatial and temporal variability in freshwater inputs of trace elements and major ions to the tidal reaches of the River Tweed. The relationships between concentrations of major ions and trace elements (in dissolved and acid-available particulate forms) and flow are examined, and a simple two-component endmember mixing analysis performed to link river water chemistry to catchment sources, and to identify whether within-river processes modify concentrations to produce non-conservative behaviour. The results indicate that most dissolved major ions and trace elements behave conservatively in the lower reaches of the River Tweed, the variability in concentrations being dominated by hydrology and the existence of different high-flow and low-flow endmember runoff chemistries. This suggests that the variability in concentration of most dissolved trace elements and major ions in the lower Tweed can be modelled using simple mixing relationships. However, the relationships between pH, Ca, Mg and Gran alkalinity show pronounced non-conservative behaviour, indicating the importance of understanding within-river process for modelling these determinants. The non-conservative behaviour identified is related to biological controls and the resultant diurnal variations in pH which promote daytime removal of Ca from solution by precipitation of calcium carbonate (and corresponding removal of Mg by co-precipitation) during extreme low-flow conditions and algal blooms during the summer.

The water quality of the River Kennet: initial observations on a lowland chalk stream impacted by sewage inputs and phosphorus remediation.

The water quality of seven sites on the upper reaches of the River Kennet round the market town of Marlborough is described and related to the introduction of phosphorus treatment of effluent from Marlborough sewage treatment works (STW). The River Kennet is mainly groundwater-fed from a Cretaceous chalk aquifer and hence the river water is calcium- and bicarbonate-bearing and has a relatively constant composition of many major water quality determinants. In-stream biological activity gives rise to marked diurnal fluctuations in pH (of approx. 0.8 units). Dissolved carbon dioxide and dissolved oxygen also show marked diurnal fluctuations. Dissolved carbon dioxide varies from approximately 10 to 70 times atmospheric pressure, indicating net release of carbon dioxide and the dominance of heterotrophic (respiratory) processes over autotrophic processes (photosynthesis). Much of the excess carbon dioxide is probably associated with carbon dioxide laden groundwater inputs and the relatively short within-stream residence times ensures only limited degassing to the atmosphere. Diurnal fluctuations in dissolved oxygen vary from approximately 20% to 200% saturation. For both dissolved carbon dioxide and dissolved oxygen, the amplitude of fluctuations is much lower during the winter period, when biological activity is at its lowest. The concentrations of soluble reactive phosphorus (SRP), total phosphorus (TP) and boron increase markedly just downstream of the sewage works as a result of this point source input. These concentrations slowly decline further downstream as additional groundwater inputs dilute the effluent further. The introduction of chemical treatment of sewage effluent for phosphorus reduction at Marlborough STW resulted in a marked decrease in within-river SRP and TP concentrations to levels approximately the same as those upstream of the STW. A comparison of SRP and boron concentrations reveals a reduction in in-stream SRP concentrations by approximately 75% following effluent treatment. In terms of within-river processes controlling in-stream phosphorus concentrations, previous studies have indicated that one potentially important mechanism within calcium bicarbonate bearing rivers may be related to co-precipitation of phosphorus with calcium carbonate (calcite). The present study shows that the waters are oversaturated with respect to calcium carbonate, that no equilibrium conditions exist and that phosphorus removal has led to undetectable changes in calcium carbonate oversaturation. Hence, it is concluded that the primary changes in phosphorus levels within the river is directly associated with changing point source contributions from the STW and physical dilution within the river. However (1) the results relate to only the first year of study and subsequent differences may become apparent and (2) reactions between the water column and plant and bottom sediment interfaces may be important in regulating phosphorus fluxes within the river. The results presented in this paper mark a pilot phase of a longer-term initiative and this paper provides a background setting. The paper discusses the longer-term objectives and important gaps in knowledge of the system that requires further address.