In this study, the partial least squares regression (PLSR) models were developed using no pre-processing, traditional preprocessing, multi-preprocessing 5 range, multi-preprocessing 3 range, genetic algorithm (GA), and successive projection algorithm (SPA) to assess the higher heating value (HHV) and ultimate analysis of grounded biomass for energy usage employing near-infrared (NIR) spectroscopy. A novel approach was utilized based on the assumption that using multiple pretreatment methods across different sections in the entire NIR wavenumber range would enhance the performance of the model. The performance of the model obtained from 200 biomass samples for HHV and 120 samples for ultimate analysis was compared, and the best model was selected based on the coefficient of determination of validation set, root mean square error of prediction, and the ratio of prediction to deviation values. Based on model performance results, the proposed HHV model from GA-PLSR, and the N and O models from the mul-ti-preprocessing PLSR 5 range method could be used for most applications, including research, whereas the C and H models from GA-PLSR performance is fair and applicable only for rough screening. The overall findings highlight that the multi-preprocessing 5-range method, which was attempted as a novel approach in this study to develop the PLSR model, demonstrated better accuracy for HHV, C, N, and O, improving by 4.1839%, 8.1842%, 3.7587%, and 35.9404%, respec-tively. Therefore, it can be considered a reliable and non-destructive alternative method for rap-idly assessing biomass properties for energy usage and can also be used effectively in biomass trading. However, due to the smaller number of samples used in the model development, more samples are needed to update the model for a robust application.

A non-destructive analysis of proximate parameters (moisture content, MC; volatile matter, VM; fixed carbon, FC; and ash content) for a variety of chipped and ground biomasses was investigated through a combination of thermogravimetric analysis (TGA) and near-infrared spectroscopy (NIRS) with partial least squares regression (PLSR). In this study, the thermogravimetric method was employed as a tool to determine the proximate analysis data of biomass samples through TG and DTG curves, which were generated by tracking changes in biomass mass loss over time or temperature. NIRS non−destructively scanned the chipped biomass in diffuse reflectance while ground biomass using transflectance mode, covering the wavenumber range of 3594.87 to 12,489.48 cm−1. The PLSR−based models: Full−PLSR, genetic algorithm (GA)−PLSR, successive projection algorithm (SPA)−PLSR, the spectral multi−preprocessing (MP) PLSR− 5 range method, and the MP PLSR−3 range method were developed. Model performance was assessed, compared, and selected based on the coefficient of determination in the prediction set (R2P), root mean square error in the validation set (RMSEP), and the ratio of prediction to deviation (RPD). Based on the comprehensive analysis of model performance, MC and FC models of chip biomass have demonstrated satisfactory performance which makes it applicable cautiously in any application, including research. The optimum models for MC and FC in chip biomass were constructed using GA−PLSR with 2nd derivative and Full−PLSR with a constant offset, resulting in R2P values of 0.8654 and 0.8773, RMSEP values of 0.85% and 2.12%, and RPD values of 2.9 and 3.0, respectively. Other parameters such as MC and FC in ground biomass as well as VM and ash content in both chip and ground biomass were found suitable for rough screening. The sensitivity of the selected model was assessed by calculating the limit of quantification (LOQ), and the results indicated that the calculated LOQ values for VM in both chip and ground biomass and FC in chip biomass are lower than the minimum reference values used during model development, signifying a high level of sensitivity. However, for the remaining parameters, the LOQ values surpass the established minimum reference value, suggesting the model could not predict the future samples with reference value lower than the calibration range. Nevertheless, enhancing the models by incorporation an ample number of representative biomass samples and consistently validating the models with unknown samples is imperative to ensure accurate predictions.

The ultimate analysis parameters including carbon (C), hydrogen (H), nitrogen (N), and oxygen (O) content in biomass was rarely found to be predicted by nondestructive tests until to date. In this research, we developed partial least squares regression (PLSR) models to predict the ultimate analysis parameters of chip biomass using near infrared (NIR) raw spectra of non-wood and wood samples from fast growing tree and agricultural residue and nine different traditional spectral preprocessing techniques. These techniques include first derivative (sd1), second derivative (sd2), constant offset, standard normal variate (SNV), multiplicative scatter correction (MSC), vector normalization, min-max normalization, mean centering, sd1 + vector normalization, and sd1 + MSC. Additionally, we employed a genetic algorithm (GA), successive projection algorithm (SPA), multi-preprocessing (MP) 5−range, and MP 3−range to develop a PLSR model for rapid prediction. A dataset consisting of 120 chip biomass samples was utilized for model development in which the samples was non-wood samples of 65-67% and wood samples was 33-35%, and the model performance were evaluated and compared. The selection of the optimum performing model was mainly based on criteria such as the coefficient of determination in the prediction set (R2P), root mean square error of the prediction set (RMSEP), and the ratio of prediction to deviation values (RPD). The optimal model for weight percentage (wt.%) of C was obtained using GA−PLSR, yielding R2P, RMSEP, and RPD values of 0.6954, 1.1252 wt.%, and 1.8, respectively. Similarly, for wt.% of O, the most effective model was obtained using the multi-preprocessing PLSR−5 range method with R2P of 0.7150, RMSEP of 1.3088 wt.%, and RPD of 1.9. For wt.% of N, the optimal model was obtained using the MP PLSR−3 range method, resulting in R2P, RMSEP, and RPD values of 0.6073, 0.1008 wt.%, and 1.6, respectively. However, wt.% of H model provided R2P, RMSEP, and RPD values of 0.5162, 0.2322 wt.%, and 1.5, respectively. Notably, the limit of quantification (LOQ) values for C, H, and O were lower than the minimum reference values used during model development, indicating a high level of sensitivity. However, the LOQ for N, exceeded the minimum reference value, implying the samples to be predicted by the model must be in the range of reference range in calibration set. By scatter plot analysis, the effect of combined non-wood and wood spectra of biomass chips on rapid prediction of ultimate analysis parameters using NIR spectroscopy was investigated. To include different species in a model, the species have to be not only in the different values of the constituents to make a wider range for robust model but also they must provide their trend line characteristics in the scatter plot i.e. correlation coefficient (R), slope and intercept (same slope and slope approached to 1 and intercept is same (no gap) and approached zero, high R approached to 1). The effect of the R, slope and intercept to obtain the better optimized model were studied. The results show that the different species affected model performance of each parameter prediction in a different manner and by scatter plot analysis which of these species were affecting the model negatively and how the model could be improved was indicated. This is the first time of the effect is studied by the principle of scatter plot.

Nepal, primarily an agricultural country, heavily relies on agricultural residue and fuelwood for daily energy requirements. In 2022, total energy consumption was 640 PJ, with traditional sources accounting for 64.17%, and fuelwood comprising 58.53% of total fuel consumption. The estimated potential supply of agricultural residue is 26 million tonnes, yielding about 442 million GJ of energy in 2021. Biomass trading often emphasizes volume or weight, necessitating a rapid and non-destructive assessment of energy properties for mutual benefit, aiding in the identification, management, and utilization of biomass sources. In this study, 200 biomass samples were collected in two batches (126 and 74 samples) from various locations in Nepal. Using Partial Least Squares Regression (PLSR), a model was developed correlating higher heating value (HHV) from a bomb calorimeter and spectral data from Fourier Transform near-infrared spectroscopy (FT-NIRS) (3595 – 12,489 cm-1) sensor. PLSR models incorporated raw spectra, eight preprocessing techniques, the multi-preprocessing five-range method, and a genetic algorithm. Outliers in the first batch were identified, and the first batch divided into an 80% calibration set and a 20% validation set, while the second batch was designated as an unknown sample set. The optimum PLSR model, utilizing first derivative preprocessing, improved accuracy by 6.77%, with coefficients of determination in the calibration set, validation set, and unknown set as 0.9694, 0.9578, and 0.8089, respectively. Root mean square errors were 132.4790 J/g, 189.4800 J/g, and 360.8845 J/g for the calibration set (RMSEC), validation set (RMSEP), and unknown set (RMSEUN), respectively. The prediction to deviation ratio (RPD) for the validation set and unknown set was 4.9 and 2.4, respectively. The cross validation model of combined sample data of every sets showed the R2CV of 0.95 and RPDCV of 4.6 indicating the model could serve as a reliable and swift non-destructive alternative for evaluating biomass HHV using NIRS and ready for updating for industrial use. However, incorporating a larger number of representative samples is crucial to enhance accuracy and develop a more comprehensive global model for predicting biomass HHV.