Performance characteristics of methods of analysis used for regulatory purposes. Part II. Pesticide formulations.

The precision parameters of the method-performance (collaborative) studies published in the AOAC Journal from 1915 through 1990 for pesticide formulations have been recalculated on a uniform basis by the International Union of Pure and Applied Chemistry 1987 protocol. About 93% of the 953 accepted assays, which are predominantly gravimetric (G), volumetric (V), and gas (GC) and liquid (LC) chromatographic methods, exhibit relative standard deviations among laboratories (RSDR) that are generally less than 2 times the values predicted from the Horwitz equation: RSDR (%) = 2 exp (1-0.5 log C), where C is the concentration expressed as a decimal fraction. UV, VIS, and IR spectrophotometric (S) methods are somewhat poorer, with about 80% of the reported RSDR values less than twice the predicted RSDR value. The precision parameters of pesticide formulations analyzed by the older methods (G, V, GC) are equivalent to those previously found for drug preparations in the same concentration range; the precision parameters of pesticide formulations analyzed by LC and S are somewhat poorer. Overall, however, the precision parameters of pesticide formulations are generally independent of analyte, method, and matrix, and are primarily a function of concentration. The method-acceptability decisions of the AOAC for pesticide formulations during the past 75 years can be approximated retrospectively by using a criterion for RSDR that is less than 2 times the RSDR calculated from the Horwitz equation.