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Multidimensional
Benchmarking for Analytical Methods: The Horwitz
Curve

Oct 1, 2005
By: Desir L. Massart, Johanna Smeyers-Verbeke, Yvan Vander Heyden
LCGC Europe

The Horwitz curve gives an indication of the precision to be expected of a newly
developed method as a function of the concentration of the analyte. It is named after W.
Horwitz, a respected statistician, now retired from the FDA and very active in the AOAC,
The Association of Official Analytical Chemists. Before describing the Horwitz curve, let
us consider some different types of precision. The precision is a measure for the size of
random errors. It measures the dispersion around the mean result and, therefore, it
requires the calculation of the standard deviation of the measurement results. Precision
can be determined at several levels. Repeatability is measured under repeatability
conditions, meaning that the operator, the instrument and the laboratory are the same,
and the time interval is kept short. These are the most favourable conditions possible and
they yield the best precision, (i.e., the smallest standard deviation).
Reproducibility is defined as measured under "conditions where test results are obtained
with the same method on identical test material in different laboratories with different
operators using different equipment."
1
It takes into account many more sources of
variation than the repeatability does. These are the worst precision conditions that can
occur when studying the precision of a method. It can be determined only with inter-
laboratory method performance studies, colloquially known as collaborative trials.
Intermediate situations occur and give rise to an intermediate precision. They take into
account more within-laboratory variations than when the precision is measured under
repeatability conditions, such as the additional variation due to the measurements being
performed over a longer period of time. The intermediate precision can then be seen as a
measure of long-term precision in a given laboratory.
A fourth somewhat different level is the determination of robustness (sometimes also
called ruggedness). It measures to what extent a procedure is affected by small,
deliberate variations introduced in the procedure. If one or more of these variations are
found to be responsible for a significant difference in the results, the procedure must be
adapted and more strictly controlled. If not, the method is considered robust, but the
variations still lead to less precise measurements and robustness can therefore be seen
as a measure of the intermediate precision or the reproducibility that might be expected.
ISO uses the symbol r for repeatability and R for reproducibility. Repeatability and
reproducibility are measured as the repeatability standard deviation, s
r
, and the
reproducibility standard deviation, s
R
. For the intermediate precision ISO proposes the
symbol I
( )
with additional symbols inside the parentheses referring to the intermediate
precision conditions. In this way s
(TO)
, for example, means that the intermediate precision
includes variability due to the time elapsed between measurements as well as due to the
operator.
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Reproducibility as a Function of Concentration
Horwitz et al.
2
initially examined results of a few thousand interlaboratory collaborative
studies on various commodities ranging in concentration from a few percent (salt in
foods) to the ppb (ng/g) level (aflatoxin M1 in foods) but also including studies on, for
example, drug formulations, antibiotics in feeds and pesticide residues. They concluded
that the predicted RSD
R
(%) as a function of concentration is approximated by the
following relationship:









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Pagina 2 de 2 Benchmarking Ior Analytical Methods: The Horwitz Curve - LC-GC Europe
29/07/2006 http://www.lcgceurope.com/lcgceurope/article/articleDetail.jsp?id183844