Comparative near Infrared (NIR) spectroscopy calibrations performance of dried and undried forage on dry and wet matter bases.

The application of Near Infrared (NIR) spectroscopy for analyzing wet feed directly on farms is increasingly recognized for its role in supporting harvest-time decisions and refining the precision of animal feeding practices. This study aims to evaluate the accuracy of NIR spectroscopy calibrations for both undried, unprocessed samples and dried, ground samples. Additionally, it investigates the influence of the bases of reference data (wet vs. dry basis) on the predictive capabilities of the NIR analysis. The study utilized 492 Corn Whole Plant (CWP) and 405 High Moisture Corn (HMC) samples, sourced from various farms across Italy. Spectral data were acquired from both undried, unground and dried, ground samples using laboratory bench NIR instruments, covering a spectral range of 1100 to 2498 nm. The reference chemical composition of these samples was analyzed and presented in two formats: on a wet matter basis and on a dry matter basis. The study revealed that calibrations based on undried samples generally exhibited lower predictive accuracy for most traits, with the exception of Dry Matter (DM). Notably, the decline in predictive performance was more pronounced in highly moist products like CWP, where the average error increased by 60-70%. Conversely, this reduction in accuracy was relatively contained (10-15%) in drier samples such as HMC. The Standard Error of Cross-Validation (SECV) values for DMres, Ash, CP, and EE were notably low, at 0.39, 0.30, 0.29, 0.21% for CWP and 0.49, 0.14, 0.25, 0.14% for HMC, respectively. These results align with previous studies, indicating the reliability of NIR spectroscopy in diverse moisture contexts. The study attributes this variance to the interference caused by water in 'as is' samples, where the spectral features predominantly reflect water content, thereby obscuring the spectral signatures of other nutrients. In terms of calibration development strategies, the study concludes that there is no significant difference in predictive performance between undried calibrations based on either 'dry matter' or 'as is' basis. This finding emphasizes the potential of NIR spectroscopy in diverse moisture contexts, although with varying degrees of accuracy contingent upon the moisture content of the analyzed samples. Overall, this research provides valuable insights into the calibration strategies of NIR spectroscopy and its practical applications in agricultural settings, particularly for on-farm forage analysis.

Exploring the use of NIR and Raman spectroscopy for the prediction of quality traits in PDO cheeses.

The aims of this proof of principle study were to compare two different chemometric approaches using a Bayesian method, Partial Least Square (PLS) and PLS-discriminant analysis (DA), for the prediction of the chemical composition and texture properties of the Grana Padano (GP) and Parmigiano Reggiano (PR) PDO cheeses by using NIR and Raman spectra and quantify their ability to distinguish between the two PDO and among their ripening periods. For each dairy chain consortium, 9 cheese samples from 3 dairy industries were collected for a total of 18 cheese samples. Three seasoning times were chosen for each dairy industry: 12, 20, and 36 months for GP and 12, 24, and 36 months for PR. A portable NIR instrument (spectral range: 950-1,650 nm) was used on 3 selected spots on the paste of each cheese sample, for a total of 54 spectra collected. An Alpha300 R confocal Raman microscope was used to collect 10 individual spectra for each cheese sample in each spot for a total of 540 Raman spectra collected. After the detection of eventual outliers, the spectra were also concatenated together (NIR + Raman). All the cheese samples were assessed in terms of chemical composition and texture properties following the official reference methods. A Bayesian approach and PLS-DA were applied to the NIR, Raman, and fused spectra to predict the PDO type and seasoning time. The PLS-DA reached the best performances, with 100% correctly identified PDO type using Raman only. The fusion of the data improved the results in 60% of the cases with the Bayesian and of 40% with the PLS-DA approach. A Bayesian approach and a PLS procedure were applied to the NIR, Raman, and fused spectra to predict the chemical composition of the cheese samples and their texture properties. In this case, the best performance in validation was reached with the Bayesian method on Raman spectra for fat (R2VAL = 0.74). The fusion of the data was not always helpful in improving the prediction accuracy. Given the limitations associated with our sample set, future studies will expand the sample size and incorporate diverse PDO cheeses.

The use of milk Fourier-transform infrared spectra for predicting cheesemaking traits in Grana Padano Protected Designation of Origin cheese.

The prediction of the cheese yield (%CY) traits for curd, solids, and retained water and the amount of fat, protein, solids, and energy recovered from the milk into the curd (%REC) by Bayesian models, using Fourier-transform infrared spectroscopy (FTIR), can be of significant economic interest to the dairy industry and can contribute to the improvement of the cheese process efficiency. The yields give a quantitative measure of the ratio between weights of the input and output of the process, whereas the nutrient recovery allows to assess the quantitative transfer of a component from milk to cheese (expressed in % of the initial weight). The aims of this study were: (1) to investigate the feasibility of using bulk milk spectra to predict %CY and %REC traits, and (2) to quantify the effect of the dairy industry and the contribution of single-spectrum wavelengths on the prediction accuracy of these traits using vat milk samples destined to the production of Grana Padano Protected Designation of Origin cheese. Information from 72 cheesemaking days (in total, 216 vats) from 3 dairy industries were collected. For each vat, the milk was weighed and analyzed for composition (total solids [TS], lactose, protein, and fat). After 48 h from cheesemaking, each cheese was weighed, and the resulting whey was sampled for composition as well (TS, lactose, protein, and fat). Two spectra from each milk sample were collected in the range between 5,011 and 925 cm-1 and averaged before the data analysis. The calibration models were developed via a Bayesian approach by using the BGLR (Bayesian Generalized Linear Regression) package of R software. The performance of the models was assessed by the coefficient of determination (R2VAL) and the root mean squared error (RMSEVAL) of validation. Random cross-validation (CVL) was applied [80% calibration and 20% validation set] with 10 replicates. Then, a stratified cross-validation (SCV) was performed to assess the effect of the dairy industry on prediction accuracy. The study was repeated using a selection of informative wavelengths to assess the necessity of using whole spectra to optimize prediction accuracy. Results showed the feasibility of using FTIR spectra and Bayesian models to predict cheesemaking traits. The R2VAL values obtained with the CVL procedure were promising in particular for the %CY and %REC for protein, ranging from 0.44 to 0.66 with very low RMSEVAL (from 0.16 to 0.53). Prediction accuracy obtained with the SCV was strongly influenced by the dairy factory industry. The general low values gained with the SCV do not permit a practical application of this approach, but they highlight the importance of building calibration models with a dataset covering the largest possible sample variability. This study also demonstrated that the use of the full FTIR spectra may be redundant for the prediction of the cheesemaking traits and that a specific selection of the most informative wavelengths led to improved prediction accuracy. This could lead to the development of dedicated spectrometers using selected wavelengths with built-in calibrations for the online prediction of these innovative traits.

Invited review: A comprehensive review of visible and near-infrared spectroscopy for predicting the chemical composition of cheese.

Substantial research has been carried out on rapid, nondestructive, and inexpensive techniques for predicting cheese composition using spectroscopy in the visible and near-infrared radiation range. Moreover, in recent years, new portable and handheld spectrometers have been used to predict chemical composition from spectra captured directly on the cheese surface in dairies, storage facilities, and food plants, removing the need to collect, transport, and process cheese samples. For this review, we selected 71 papers (mainly dealing with prediction of the chemical composition of cheese) and summarized their results, focusing our attention on the major sources of variation in prediction accuracy related to cheese variability, spectrometer and spectra characteristics, and chemometrics techniques. The average coefficient of determination obtained from the validation samples ranged from 86 to 90% for predicting the moisture, fat, and protein contents of cheese, but was lower for predicting NaCl content and cheese pH (79 and 56%, respectively). There was wide variability with respect to all traits in the results of the various studies (standard deviation: 9-30%). This review draws attention to the need for more robust equations for predicting cheese composition in different situations; the calibration data set should consist of representative cheese samples to avoid bias due to an overly specific field of application and ensure the results are not biased for a particular category of cheese. Different spectrometers have different accuracies, which do not seem to depend on the spectrum extension. Furthermore, specific areas of the spectrum-the visible, infrared-A, or infrared-B range-may yield similar results to broad-range spectra; this is because several signals related to cheese composition are distributed along the spectrum. Small, portable instruments have been shown to be viable alternatives to large bench-top instruments. Last, chemometrics (spectra pre-treatment and prediction models) play an important role, especially with regard to difficult-to-predict traits. A proper, fully independent, validation strategy is essential to avoid overoptimistic results.

Accuracy and biases in predicting the chemical and physical traits of many types of cheeses using different visible and near-infrared spectroscopic techniques and spectrum intervals.

Near-infrared spectroscopy (NIRS) has been widely used to determine various composition traits of many dairy products in the industry. In the last few years, near-infrared (NIR) instruments have become more and more accessible, and now, portable devices can be easily used in the field, allowing the direct measurement of important quality traits. However, the comparison of the predictive performances of different NIR instruments is not simple, and the literature is lacking. These instruments may use different wavelength intervals and calibration procedures, making it difficult to establish whether differences are due to the spectral interval, the chemometric approach, or the instrument's technology. Hence, the aims of this study were (1) to evaluate the prediction accuracy of chemical contents (5 traits), pH, texture (2 traits), and color (5 traits) of 37 categories of cheese; (2) to compare 3 instruments [2 benchtop, working in reflectance (R) and transmittance (T) mode (NIRS-R and NIRS-T, respectively) and 1 portable device (VisNIRS-R)], using their entire spectral ranges (1100-2498, 850-1048, and 350-1830 nm, respectively, for NIRS-R, NIRS-T and VisNIRS-R); (3) to examine different wavelength intervals of the spectrum within instrument, comparing also the common intervals among the 3 instruments; and (4) to determine the presence of bias in predicted traits for specific cheese categories. A Bayesian approach was used to develop 8 calibration models for each of 13 traits. This study confirmed that NIR spectroscopy can be used to predict the chemical composition of a large number of different cheeses, whereas pH and texture traits were poorly predicted. Color showed variable predictability, according to the trait considered, the instrument used, and, within instrument, according to the wavelength intervals. The predictive performance of the VisNIRS-R portable device was generally better than the 2 laboratory NIRS instruments, whether with the entire spectrum or selected intervals. The VisNIRS-R was found suitable for analyzing chemical composition in real time, without the need for sample uptake and processing. Our results also indicated that instrument technology is much more important than the NIR spectral range for accurate prediction equations, but the visible range is useful when predicting color traits, other than lightness. Specifically for certain categories (i.e., caprine, moldy, and fresh cheeses), dedicated calibrations seem to be needed to obtain unbiased and more accurate results.

Identification of Lipid Biomarkers To Discriminate between the Different Production Systems for Asiago PDO Cheese.

The lipid fraction of Asiago Protected Designation of Origin (PDO) cheese was analyzed to identify specific biomarkers of its main production systems through a canonical discriminant analysis. The three main production systems of the cheese were considered. Two were located in the upland (UL): pasture-based (P-UL) vs hay-based total mixed rations (H-UL). The third was located in the lowland (LL) and processed milk from cows fed maize silage-based rations (maize silage lowland: MS-LL). The discriminant analysis selected nine fatty acids and vitamin A as lipid biomarkers useful to separate the three production systems. High contents of conjugated linoleic acids, anteiso-C15:0, and vitamin A were discriminant factors for P-UL cheese. The separation between H-UL and MS-LL cheese was less marked with the former having the higher content of conjugated linoleic acids and some polyunsaturated n-6 fatty acids and with the latter being identified by cyclopropane fatty acid and C9:0.

Discrimination between Shiraz wines from different Australian regions: the role of spectroscopy and chemometrics.

This study reports the use of UV-visible (UV-vis), near-infrared (NIR), and midinfrared (MIR) spectroscopy combined with chemometrics to discriminate among Shiraz wines produced in five Australian regions. In total, 98 commercial Shiraz samples (vintage 2006) were analyzed using UV-vis, NIR, and MIR wavelength regions. Spectral data were interpreted using principal component analysis (PCA), linear discriminant analysis (LDA), and soft independent model of class analogy (SIMCA) to classify the wine samples according to region. The results indicated that wine samples from Western Australia and Coonawarra can be separated from the other wines based on their MIR spectra. Classification results based on MIR spectra also indicated that LDA achieved 73% overall correct classification, while SIMCA 95.3%. This study demonstrated that IR spectroscopy combined with chemometric methods can be a useful tool for wine region discrimination.