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Quaternion principal component analysis (QPCA) was utilized for features extraction and followed by feature crossing among the quaternion principal components to obtain final fusion spectral feature vectors. Support vector regression (SVR) was then used to establish the quantitative model of melamine-contaminated milk samples with seven concentrations (1ppm to 250ppm). Compared with traditional TLC-SERS analysis methods, QPCA method significantly improved the accuracy of quantification by reaching only 7% and 2% quantization errors at 2