Abstract
Fertilization is paramount for agriculture productivity and food security. Plant nutrition pre-established recipes and nutrient uptake are rarely managed by changing the fertilizer composition at the different stages of the plant life cycle. Herein we perform a literature review analysis - since the year 2000 and onwards - of the state-of-the-art capabilities of Nitrogen, Phosphorous, and Potassium (NPK) sensors for liquid fertilizers ( e.g. , hydroponics). From the initial search hits of 1660 results, only 53 publications had relevant information for this topic; from these, only 9 had NPK quantitative information. Qualitative analysis was performed by determining the number of publications for each nutrient, according to sample complexity and existing single, multiplexed or hybrid technologies. Quantitative assessment was performed by extracting the bias and linearity, the limit of detection and concentration ranges of sensor operation, framed into the context of the sensor technology development stage and sample compositional complexity. The most common technologies are colorimetry, ionselective electrodes, optrodes, chemosensors, and optical spectroscopy. The most abundant technologies are for nitrate quantification, from which ion-selective electrodes are the most widely used technology, and sensors for phosphate quantification are the less developed. Most are at low technological levels of development, not dealing with the complexity of agriculture samples due to matrix effects and interference. Measuring the fertilizer composition, nutrient uptake, the state of the chemical network, and controlling the release of nutrients using new functional materials, is one of the most important challenges ahead for the existence of precision fertilization. Intelligent sensing and smart materials are today the most successful strategy for dealing with matrix effects and interferences, being led by ion-selective electrodes and spectroscopy technologies.

Abstract
Data scarcity is a hurdle for physiology-based precision agriculture. Measuring nutrient uptake by visible-near infrared spectroscopy implies collecting spectral and compositional data from low-throughput, such as inductively coupled plasma optical emission spectroscopy. This paper introduces data augmentation in spectroscopy by hybridisation for expanding real-world data into synthetic datasets statistically representative of the real data, allowing the quantification of macronutrients (N, P, K, Ca, Mg, and S) and micronutrients (Fe, Mn, Zn, Cu, and B). Partial least squares (PLS), local partial least squares (LocPLS), and self-learning artificial intelligence (SLAI) were used to determine the capacity to expand the knowledge base. PLS using only real-world data (RWD) cannot quantify some nutrients (N and Cu in grapevine leaves and K, Ca, Mg, S, and Cu in apple tree leaves). The synthetic dataset of the study allowed predicting real-world leaf composition of macronutrients (N, P, K, Ca, Mg and S) (Pearson coefficient correlation (R) 0.61-0.94 and standard error (SE) 0.04-0.05%) and micronutrients (Fe, Mn, Zn, Cu and B) (R 0.66-0.91 and SE 0.88-3.98 ppm) in grapevine leaves using LocPLS and SLAI. The synthetic dataset loses significance if the real-world counterpart has low representativity, resulting in poor quantifications of macronutrients (R 0.51-0.72 and SE 0.02-0.13%) and micronutrients (R 0.53-0.76 and SE 8.89-37.89 ppm), and not allowing S quantification (R = 0.37, SE = 0.01) in apple tree leaves. Representative real-world sampling makes data augmentation in spectroscopy very efficient in expanding the knowledge base and nutrient quantifications.

Abstract
Spectral point-of-care technology is reagentless with minimal sampling (<10 mu L) and can be performed in real-time. White blood cells are non-dominant in blood and in spectral information, suffering significant interferences from dominant constituents such as red blood cells, hemoglobin and billirubin. White blood cells of a bigger size can account for 0.5% to 22.5% of blood spectra information. Knowledge expansion was performed using data augmentation through the hybridization of 94 real-world blood samples into 300 synthetic data samples. Synthetic data samples are representative of real-world data, expanding the detailed spectral information through sample hybridization, allowing us to unscramble the spectral white blood cell information from spectra, with correlations of 0.7975 to 0.8397 and a mean absolute error of 32.25% to 34.13%; furthermore, we achieved a diagnostic efficiency between 83% and 100% inside the reference interval (5.5 to 19.5 x 10(9) cell/L), and 85.11% for cases with extreme high white blood cell counts. At the covariance mode level, white blood cells are quantified using orthogonal information on red blood cells, maximizing sensitivity and specificity towards white blood cells, and avoiding the use of non-specific natural correlations present in the dataset; thus, the specifity of white blood cells spectral information is increased. The presented research is a step towards high-specificity, reagentless, miniaturized spectral point-of-care hematology technology for Veterinary Medicine.

Abstract
The Phenobot platform is comprised by an autonomous robot, instrumentation, artificial intelligence, and digital twin diagnosis at the molecular level, marking the transition from pure data-driven to knowledge-driven agriculture 4.0, towards a physiology-based approach to precision viticulture. Such is achieved by measuring the plant metabolome 'in vivo' and 'in situ', using spectroscopy and artificial intelligence for quantifying metabolites, e.g.: i. grapes: chlorophylls a and b, pheophytins a and b, anthocyanins, carotenoids, malic and tartaric acids, glucose and fructose; ii. foliage: chlorophylls a and b, pheophytins a and b, anthocyanins, carotenoids, nitrogen, phosphorous, potassium, sugars, and leaf water potential; and iii. soil nutrients (NPK). The geo-referenced metabolic information of each plant (organs and tissues) is the basis of multi-scaled analysis: i. geo-referenced metabolic maps of vineyards at the macroscopic field level, and ii. genome-scale 'in-silico' digital twin model for inferential physiology (phenotype state) and omics diagnosis at the molecular and cellular levels (transcription, enzyme efficiency, and metabolic fluxes). Genome-scale 'in-silico' Vitis vinifera numerical network relationships and fluxes comprise the scientific knowledge about the plant's physiological response to external stimuli, being the comparable mechanisms between laboratory and field experimentation - providing a causal and interpretable relationship to a complex system subjected to external spurious interactions (e.g., soil, climate, and ecosystem) scrambling pure data-driven approaches. This new approach identifies the molecular and cellular targets for managing plant physiology under different stress conditions, enabling new sustainable agricultural practices and bridging agriculture with plant biotechnology, towards faster innovations (e.g. biostimulants, anti-microbial compounds/mechanisms, nutrition, and water management). Phenobot is a project under the Portuguese emblematic initiative in Agriculture 4.0, part of the Recovery and Resilience Plan (Ref. PRR: 190 Ref. 09/C05-i03/2021 - PRR-C05-i03-I-000134). © The Authors, published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution License 4.0 (https://creativecommons.org/licenses/by/4.0/).

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.