Performances of analytical methods for freshwater analysis assessed through intercomparison exercises. II. Major ions.

From 1991 to 1997, nine intercomparison exercises on rainwater and freshwater samples were held in the framework of an activity connecting laboratories participating in different projects (Environmental studies in the Mediterranean basin, Italian network for the study of wet deposition, Acidification of mountain lakes, Limnological studies of Lake Léman, Monitoring of atmospheric deposition in forests). The number of participants increased from 72 in 1991 to 177 in 1997. Among the measured variables (pH, conductivity, alkalinity, major ions and nutrients), Ca, Mg, Na, K, ammonium, sulphate, chloride and nitrate are considered in this paper. The methods commonly used by the laboratories involved in the exercises are compared for precision, and an estimate of the performance of each method at different concentrations is made. The results show that some of the participating laboratories use analytical methods which are not reliable for the concentration values occurring in freshwater and/or in rainwater. However, outliers are also produced by laboratories using well-performing methods, indicating the importance of introducing analytical control procedures.