Phosphorus-calcium carbonate saturation relationships in a lowland chalk river impacted by sewage inputs and phosphorus remediation: an assessment of phosphorus self-cleansing mechanisms in natural waters.

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.