Phosphate measurement in natural waters: two examples of analytical problems associated with silica interference using phosphomolybdic acid methodologies

Assessment of phosphate species for bicarbonate-bearing lowland rivers of the Thames valley, England and acidic Welsh upland streams (the Plynlimon area, mid-Wales) reveal problems of silica interference when employing standard automated 'phosphomolybdic acid' colorimetric methodologies. The interference occurs under a combination of two conditions: (1) when the reagents and samples are heated to speed up the rate of formation of phosphomolybdic acid; and (2) when the strength of a sulfuric acid reagent is too low. While this paper alerts researchers to potential analytical problems with silica interference within phosphomolybdic acid methodologies to determine soluble reactive phosphorus (SRP) concentrations, it cannot detail whether or not there is a general problem. This lack of specificity occurs because there are a variety of phosphomolybdic acid methodologies available which vary in their reagent recipes and it is not clear which methods will or will not suffer from silica interference. Changing the sulfuric acid reagent strength by a factor of two overcame the problem, in this case, with regards to the determination of soluble reactive phosphorus. However, even here, the method may not be applicable to very high alkalinity waters owing to their potential for reducing the acidity of the analyte. With regard to total dissolved phosphorus (TDP) and total phosphorus (TP) measurements, the importance of undertaking the analysis under ambient conditions is clearly shown. There are many small variants on standard phosphomolybdate methods for determining SRP, TDP and TP in use and it is not always clear which methods will or will not show silica interference for particular water types. It is therefore recommended that individual laboratories check their methodologies for silica interference using phosphate-free solutions with similar silica and alkalinity ranges for the waters being assayed.