Alkalinity measurements within natural waters: towards a standardised approach

A discussion on the measurement of alkalinity in bicarbonate bearing and acidic waters is presented as a move towards developing a standardised approach within the aquatic sciences. The discussion is based on theoretical and practical considerations. Practical illustrations are provided from measurements of calcium bicarbonate bearing waters (River Thames) and acidic to near neutral waters from acidic soil systems with calcium bearing groundwater sources (the mid-Wales region and the Scottish Dee basin). A comparison of single endpoint and Gran procedures is made and the various error terms assessed. It is concluded that single endpoint and Gran methodologies are applicable in the standard pH titration used in aquatic research (pH 4.5-4.0). However, analytical errors increase, particularly for the single endpoint titration, the lower the endpoint/endpoint-range in pH. For the Thames, the value of a single endpoint over a Gran procedure is illustrated. The Thames results show that some buffering components may still be titrated out within the Gran titration range used: this leads to an underestimate in the alkalinity. Indeed, by making a comparison between single endpoint and Gran alkalinity measurements, the Thames results indicated the presence of unexpected buffering components: the interrogative nature of this type of analysis is highlighted. A standardised approach is outlined.