Rui Costa Martins

Abstract
Nutrient quantification in hydroponic systems is essential. Reagent-less spectral quantification of nitrogen, phosphate and potassium faces challenges in accessing information-rich spectral signals and unscrambling interference from each constituent. Herein, we introduce information equivalence between spectra and sample composition, enabling extraction of consistent covariance to isolate nutrient-specific spectral information (N, P or K) in Hoagland nutrient solutions using orthogonal covariance modes. Chemometrics methods quantify nitrogen and potassium, but not phosphate. Orthogonal covariance modes, however, enable quantification of all three nutrients: nitrogen (N) with R = 0.9926 and standard error of 17.22 ppm, phosphate (P) with R = 0.9196 and standard error of 63.62 ppm, and potassium (K) with R = 0.9975 and standard error of 9.51 ppm. Including pH information significantly improves phosphate quantification (R = 0.9638, standard error: 43.16 ppm). Results demonstrate a direct relationship between spectra and Hoagland nutrient solution information, preserving NPK orthogonality and supporting orthogonal covariance modes. These modes enhance detection sensitivity by maximizing information of the constituent being quantified, while minimizing interferences from others. Orthogonal covariance modes predicted nitrogen (R = 0.9474, standard error: 29.95 ppm) accurately. Phosphate and potassium showed strong interference from contaminants, but most extrapolation samples were correctly diagnosed above the reference interval (83.26%). Despite potassium features outside the knowledge base, a significant correlation was obtained (R = 0.6751). Orthogonal covariance modes use unique N, P or K information for quantification, not spurious correlations due to fertilizer composition. This approach minimizes interferences during extrapolation to complex samples, a crucial step towards resilient nutrient management in hydroponics using spectroscopy.

Abstract
The potential of hyperspectral UV–VIS–NIR reflectance for the in-field, non-destructive discrimination of bacterial canker on kiwi leaves caused by Pseudomonas syringae pv. actinidiae (Psa) was analyzed. Spectral data (325–1075 nm) of twenty kiwi plants were obtained in vivo and in situ with a handheld spectroradiometer in two commercial kiwi orchards in northern Portugal over 15 weeks, resulting in 504 spectral measurements. The suitability of different vegetation indexes (VIs) and applied predictive models (based on supervised machine learning algorithms) for classifying non-symptomatic and symptomatic kiwi leaves was evaluated. Eight distinct types of VIs were identified as relevant for disease diagnosis, highlighting the relevance of the Green, Red, Red-Edge, and NIR spectral features. The class prediction was achieved with good model metrics, achieving an accuracy of 0.71, kappa of 0.42, sensitivity of 0.67, specificity of 0.75, and F1 of 0.67. Thus, the present findings demonstrated the potential of hyperspectral UV–VIS–NIR reflectance for the non-destructive discrimination of bacterial canker on kiwi leaves. © 2023 by the authors.

Abstract
Laser-induced breakdown spectroscopy (LIBS) is a technique that leverages atomic emission towards element identification and quantification. While the potential of the technology is vast, it still struggles with obstacles such as the variability of the technique. In recent years, several methods have exploited modifications to the standard implementation to work around this problem, mostly focused on the laser side to increase the signal-to-noise ratio of the emission. In this paper, we explore the effect of pulse duration on the detected signal intensity using a tunable LIBS system that consists of a versatile fiber laser, capable of emitting square-shaped pulses with a duration ranging from 10 to 100 ns. Our results show that, by tuning the duration of the pulse, it is possible to increase the signal-to-noise ratio of relevant elemental emission lines, an effect that we relate with the computed plasma temperature and associated density for the ion species. Despite the limitations of the work due to the low-resolution and small range of the spectrometer used, the preliminary results pave an interesting path towards the design of controllable LIBS systems that can be tailored to increase the signal-to-noise ratio and thus be useful for the deployment of more sensitive instruments both for qualitative and quantitative purposes. © 2022, Universidade do Porto - Faculdade de Engenharia. All rights reserved.

Abstract
This paper focuses on predicting predawn leaf water potential through a self-learning artificial intelligence (SL-AI) algorithm, a novel spectral processing algorithm that is based on the search for covariance modes, providing a direct relationship between spectral information and plant constituents. The SL-AI algorithm was applied in a dataset containing 847 observations obtained with a handheld hyperspectral spectroradiometer (400 -1010 nm), structured as: three grapevine cultivars (Touriga Nacional, Touriga Franca and Tinta Barroca), collected in three years (2014, 2015 and 2017), in two test sites in the renowned Douro Wine Region, northeast of Portugal. The Psi(pd) SL-AI quantification was tested both in regressive (R-2 = 0.97, MAPE = 18.30%) and classification (three classes; overall accuracy = 86.27%) approaches, where the radiation absorption spectrum zones of the chlorophylls, xanthophyll and water were identified along the vegetative growth cycle. The dataset was also tested with Artificial Neural Networks with Principal Component Analysis (ANN-PCA) and Partial Least Square (PLS), which presented worse performance when compared to SL-AI in the regressive (ANN-PCA - R-2 = 0.85, MAPE = 43.64%; PLS - R-2 = 0.94, MAPE = 28.76%) and classification (ANN-PCA - overall accuracy: 72.37%; PLS - overall accuracy: 73.79%) approaches. The Psi(pd) modelled with SL-AI demonstrated, through hyperspectral reflectance, a cause-effect of the grapevine's hydric status with the absorbance of bands related to chlorophyll, xanthophylls and water. This cause-effect interaction could be explored to identify cultivars and cultural practices, hydric, heating and lighting stresses.

Abstract
Pseudomonas syringae pv. actinidiae (Psa) has been responsible for numerous epidemics of bacterial canker of kiwi (BCK), resulting in high losses in kiwi production worldwide. Current diagnostic approaches for this disease usually depend on visible signs of the infection (disease symptoms) to be present. Since these symptoms frequently manifest themselves in the middle to late stages of the infection process, the effectiveness of phytosanitary measures can be compromised. Hyperspectral spectroscopy has the potential to be an effective, non-invasive, rapid, cost-effective, high-throughput approach for improving BCK diagnostics. This study aimed to investigate the potential of hyperspectral UV-VIS reflectance for in-situ, non-destructive discrimination of bacterial canker on kiwi leaves. Spectral reflectance (325-1075 nm) of twenty plants were obtained with a handheld spectroradiometer in two commercial kiwi orchards located in Portugal, for 15 weeks, totaling 504 spectral measurements. Several modeling approaches based on continuous hyperspectral data or specific wavelengths, chosen by different feature selection algorithms, were tested to discriminate BCK on leaves. Spectral separability of asymptomatic and symptomatic leaves was observed in all multi-variate and machine learning models, including the FDA, GLM, PLS, and SVM methods. The combination of a stepwise forward variable selection approach using a support vector machine algorithm with a radial kernel and class weights was selected as the final model. Its overall accuracy was 85%, with a 0.70 kappa score and 0.84 F-measure. These results were coherent with leaves classified as asymptomatic or symptomatic by visual inspection. Overall, the findings herein reported support the implementation of spectral point measurements acquired in situ for crop disease diagnosis.