Large-scale laboratory- and method-performance studies involving more than
about 30 laboratories may be evaluated by calculating the HORRAT ratio for
each test sample (HORRAT = [experimentally found among-laboratories relativ
e standard deviation] divided by [relative standard deviation calculated fr
om the Horwitz formula]). The chemical analytical method is deemed acceptab
le per se if HORRAT approximate to 1.0 (+/- 0.5). If HORRAT is greater than
or similar to 2.0, the most extreme values are removed successively until
an "acceptable" ratio is obtained. The laboratories responsible for the ext
reme values that are removed should examine their technique and procedures.
If greater than or similar to 15% of the values have to be removed, the in
structions and the methods should be examined. This suggested computation p
rocedure is simple and does not require statistical outlier tables. Propose
d action limits may be adjusted according to experience. Data supporting U.
S. Environmental Protection Agency method 245.1 for mercury in waters (manu
al cold-vapor atomic absorption spectrometry), supplemented by subsequent l
aboratory-performance data, were reexamined in this manner. Method-performa
nce parameters (means and among-laboratories relative standard deviations)
were comparable with results from the original statistical analysis that us
ed a robust biweight procedure for outlier removal. The precision of the cu
rrent controlled performance is better by a factor of 4 than that of estima
tes resulting from the original method-performance study, at the expense of
rejecting more experimental values as outliers.