The generalized rank annihilation method (CRAM) is a method for curve resol
ution and calibration that uses two bilinear matrices simultaneously, i.e.,
one for the unknown and one for the calibration sample. A GRAM calculation
amounts to solving an eigenvalue problem for which the eigenvalues are rel
ated to the predicted analyte concentrations. Previous studies have shown t
hat random measurement errors bring about a bias in the eigenvalues, which
directly translates into prediction bias. In this paper, accurate formulas
are derived that enable removing most of this bias. Two bias correction met
hods are investigated. While the first method directly subtracts bias from
the eigenvalues obtained by the original GRAM, the second method first appl
ies a weight to the data matrices to reduce bias. These weights are specifi
c for the analyte of interest and must be determined iteratively from the d
ata. Consequently, the proposed modification is called iteratively reweight
ed GRAM (IRGRAM). The results of Monte Carlo simulations show that both met
hods are effective in the sense that the standard error in the bias-correct
ed prediction compares favourably with the root mean squared error (RMSE) t
hat accompanies the original quantity. However, IRGRAM is found to perform
best because the increase of variance caused by subtracting bias is minimis
ed, In the original formulation of GRAM only a single calibration sample is
exploited. The error analysis is extended to cope with multiple calibratio
n samples. (C) 2001 Elsevier Science B.V. All rights reserved.