Protected Geographical Indication Discrimination of Zhejiang and Non-Zhejiang Ophiopogonis japonicus by Near-Infrared (NIR) Spectroscopy Combined with Chemometrics: The Influence of Different Stoichiometric and Spectrogram Pretreatment Methods.

This paper presents a method for the protected geographical indication discrimination of Ophiopogon japonicus from Zhejiang and elsewhere using near-infrared (NIR) spectroscopy combined with chemometrics. A total of 3657 Ophiopogon japonicus samples from five major production areas in China were analyzed by NIR spectroscopy, and divided into 2127 from Zhejiang and 1530 from other areas ('non-Zhejiang'). Principal component analysis (PCA) was selected to screen outliers and eliminate them. Monte Carlo cross validation (MCCV) was introduced to divide the training set and test set according to a ratio of 3:7. The raw spectra were preprocessed by nine single and partial combination methods such as the standard normal variable (SNV) and derivative, and then modeled by partial least squares regression (PLSR), a support vector machine (SVM), and soft independent modeling of class analogies (SIMCA). The effects of different pretreatment and chemometrics methods on the model are discussed. The results showed that the three pattern recognition methods were effective in geographical origin tracing, and selecting the appropriate preprocessing method could improve the traceability accuracy. The accuracy of PLSR after the standard normal variable was better, with R2 reaching 0.9979, while that of the second derivative was the lowest with an R2 of 0.9656. After the SNV pretreatment, the accuracy of the training set and test set of SVM reached the highest values, which were 99.73% and 98.40%, respectively. The accuracy of SIMCA pretreated with SNV and MSC was the highest for the origin traceability of Ophiopogon japonicus, which could reach 100%. The distance between the two classification models of SIMCA-SNV and SIMCA-MSC is greater than 3, indicating that the SIMCA model has good performance.

Fingerprint Approaches Coupled with Chemometrics to Discriminate Geographic Origin of Imported Salmon in China's Consumer Market.

Of the salmon sold in China's consumer market, 92% was labelled as Norwegian salmon, but was in fact was mainly imported from Chile. The aim of this study was to establish an effective method for discriminating the geographic origin of imported salmon using two fingerprint approaches, Near-infrared (NIR) spectroscopy and mineral element fingerprint (MEF). In total, 80 salmon (40 from Norway and 40 from Chile) were tested, and data generated by NIR and MEF were analysed via various chemometrics. Four spectral preprocessing methods, including vector normalization (VN), Savitzky Golay (SG) smoothing, first derivative (FD) and second derivative (SD), were employed on the raw NIR data, and a partial least squares (PLS) model based on the FD + SG9 pretreatment could successfully differentiate Norwegian salmons from Chilean salmons, with a R2 value of 98.5%. Analysis of variance (ANOVA) and multiple comparative analysis were employed on the contents of 16 mineral elements including Pb, Fe, Cu, Zn, Al, Sr, Ni, As, Cr, V, Se, Mn, K, Ca, Na and Mg. The results showed that Fe, Zn, Al, Ni, As, Cr, V, Se, Ca and Na could be used as characteristic elements to discriminate the geographical origin of the imported salmon, and the discrimination rate of the linear discriminant analysis (LDA) model, trained on the above 10 elements, could reach up to 98.8%. The results demonstrate that both NIR and MEF could be effective tools for the rapid discrimination of geographic origin of imported salmon in China's consumer market.

Tracing Geographical Origins of Teas Based on FT-NIR Spectroscopy: Introduction of Model Updating and Imbalanced Data Handling Approaches.

This work presents a reliable approach to trace teas' geographical origins despite changes in teas caused by different harvest years. A total of 1447 tea samples collected from various areas in 2014 (660 samples) and 2015 (787 samples) were detected by FT-NIR. Seven classifiers trained on the 2014 dataset all succeeded to trace origins of samples collected in 2014; however, they all failed to predict origins for the 2015 samples due to different data distributions and imbalanced dataset. Three outlier detection based undersampling approaches-one-class SVM (OC-SVM), isolation forest and elliptic envelope-were then proposed; as a result, the highest macro average recall (MAR) for the 2015 dataset was improved from 56.86% to 73.95% (by SVM). A model updating approach was also applied, and the prediction MAR was significantly improved with increase in the updating rate. The best MAR (90.31%) was first achieved by the OC-SVM combined SVM classifier at a 50% rate.

Ripeness Prediction of Postharvest Kiwifruit Using a MOS E-Nose Combined with Chemometrics.

Postharvest kiwifruit continues to ripen for a period until it reaches the optimal "eating ripe" stage. Without damaging the fruit, it is very difficult to identify the ripeness of postharvest kiwifruit by conventional means. In this study, an electronic nose (E-nose) with 10 metal oxide semiconductor (MOS) gas sensors was used to predict the ripeness of postharvest kiwifruit. Three different feature extraction methods (the max/min values, the difference values and the 70th s values) were employed to discriminate kiwifruit at different ripening times by linear discriminant analysis (LDA), and results showed that the 70th s values method had the best performance in discriminating kiwifruit at different ripening stages, obtaining a 100% original accuracy rate and a 99.4% cross-validation accuracy rate. Partial least squares regression (PLSR), support vector machine (SVM) and random forest (RF) were employed to build prediction models for overall ripeness, soluble solids content (SSC) and firmness. The regression results showed that the RF algorithm had the best performance in predicting the ripeness indexes of postharvest kiwifruit compared with PLSR and SVM, which illustrated that the E-nose data had high correlations with overall ripeness (training: R² = 0.9928; testing: R² = 0.9928), SSC (training: R² = 0.9749; testing: R² = 0.9143) and firmness (training: R² = 0.9814; testing: R² = 0.9290). This study demonstrated that E-nose could be a comprehensive approach to predict the ripeness of postharvest kiwifruit through aroma volatiles.

Tracing internal quality and aroma of a red-fleshed kiwifruit during ripening by means of GC-MS and E-nose.

'Hongyang' kiwifruit is a new breed of red-fleshed cultivar that has become broadly popular with consumers in recent years. In this study, the internal quality and aroma of this kiwifruit during ripening were investigated by means of gas chromatography-mass spectrometry (GC-MS) and electronic nose (E-nose). Results showed that the green note aldehydes declined, the main fruity esters increased, and the terpenes had no obvious changes during ripening. Correlations between quality indices, volatile compounds, and E-nose data were analyzed by ANOVA partial least squares regression (APLSR), and the results showed that firmness and titratable acidity (TA) had highly positive correlations with (E)-2-hexenal and hexanal, while soluble solids content (SSC) and SSC/TA ratio had positive correlations with ester compounds. The E-nose sensors of S7, S10, S8, S6, S9, and S2 were positively correlated with ester compounds, S1, S3, and S5 were mainly correlated with hexanal, and S4 was correlated with terpene compounds. Partial least squares regression (PLSR) and support vector machine (SVM) were employed to predict the quality indices by E-nose data, and SVM presented a better performance in predicting firmness, SSC, TA, and SSC/TA ratio (R 2 > 0.98 in the training set and R 2 > 0.94 in the testing set). This study demonstrated that the E-nose technique could be used as an alternative to trace the flavor quality of kiwifruit during ripening.