Scalable solution for agricultural soil organic carbon measurements using laser-induced breakdown spectroscopy.

Effective verification of soil organic carbon (SOC) improvement interventions through soil carbon sequestration (SCS) requires robust methodologies to measure, report, and verify changes in soil carbon (C) levels. Furthermore, soil C must be monitored over time to ensure that sequestered C is not being re-emitted, thus ensuring the permanence of C removals. The traditional methods for soil C measurement are time-consuming, labor-intensive, and energy-intensive, increasing analysis costs. In this article, we verify the use of a commercially available laser-induced breakdown spectroscopy analyzer, the LaserAg-Quantum, coupled with the recursive feature addition, the gradient-boosted decision trees regression model, and the novelty detection model to predict C in soils. The developed method shows promising performance with an average limit of quantification of 0.75% of C and a precision of 4.10%. Accuracy metrics, including R2, mean absolute error, and root mean square error, yielded values of 0.81, 0.27%, and 0.37% for the validation dataset. Additionally, around 10% of validation samples after the novelty detection model exhibited relative error greater than 30%. Finally, our findings demonstrate the potential of the LaserAg-Quantum process to support measuring SOC in agricultural soils on a large scale.

Carbon quantification in soils with different textures using laser-induced breakdown spectroscopy: spectral interference correction and use of a 3D plane model.

Soil carbon (C) determinations have been widely studied due to soil C sequestration that contributes to the mitigation of greenhouse gas emissions and improves soil quality. However, traditional chemical processes for large-scale analysis generate waste, are time-consuming, and have a high cost per measurement. Laser-induced breakdown spectroscopy (LIBS) is a multi-element spectroanalytical technique that allows fast and low-cost analysis, almost no sample preparation is required, and does not generate hazardous chemical waste. Two emission lines are commonly used for LIBS C determination, 193.03 and 247.85 nm. However, Brazilian soils have a high concentration of aluminum (Al) and iron (Fe), directly interfering in those C emission lines. Furthermore, multiple soil textures increase the difficulty of building calibration models due to matrix effects. In the present work, a mathematical model is proposed to quantify the total C in soil samples having different textures bypassing spectral interferences. A LIBS-specific method for removing outliers has been developed with 6% spectrum removal. From the univariate analysis, it was noticed that some results were projections of a 3D surface in a 2D space, so a 3D plane model was obtained with good fits for the evaluated C emission lines, R2 > 0.91, with limits of detection of 0.11% and 0.13% and limits of quantitation of 0.11% and 0.32% for lines 193.03 and 247.85 nm, respectively. Three repetitions were used to test the robustness of the methods and presented an R2 of 0.95 and 0.93, a mean error of about 20.38% and 24.12% for lines 193.03 and 247.85 nm, respectively, and a root mean square error of prediction lower than 0.40% for both lines.

Metronidazole-loaded gold nanoparticles in natural rubber latex as a potential wound dressing.

Gold nanoparticles (AuNPs) have shown interesting properties and specific biofunctions, providing benefits and new opportunities for controlled release systems. In this research, we demonstrated the use of natural rubber latex (NRL) from Hevea brasiliensis as a carrier of AuNPs and the antibiotic metronidazole (MET). We prepared AuNP-MET-NRL and characterized by physicochemical, biological and in vitro release assays. The effect of AuNPs on MET release was evaluated using UV-Vis and Laser-Induced Breakdown Spectroscopy (LIBS) techniques. AuNPs synthesized by Turkevich and Frens method resulted in a spherical shape with diameters of 34.8 ± 5.5 nm. We verified that there was no emergence or disappearance of new vibrational bands. Qualitatively and quantitatively, we showed that the MET crystals dispersed throughout the NRL. The Young's modulus and elongation values at dressing rupture were in the range appropriate for human skin application. 64.70% of the AuNP-MET complex was released within 100 h, exhibiting a second-order exponential release profile. The LIBS technique allowed monitoring of the AuNP release, indicating the Au emission peak reduction at 267.57 nm over time. Moreover, the dressing displayed an excellent hemocompatibility and fibroblast cell viability. These results demonstrated that the AuNP-MET-NRL wound dressing is a promising approach for dermal applications.

Direct determination of Cu, Cr, and Ni in river sediments using double pulse laser-induced breakdown spectroscopy: Ecological risk and pollution level assessment.

Double pulse laser-induced breakdown spectroscopy (DP LIBS) has attracted much attention for analyzing trace elements due to its higher sensitivity when compared to single pulse laser-induced breakdown spectroscopy (SP LIBS). However, the development of quantitative methods in LIBS for the analysis of complex samples, such as sediments, is a great challenge due to the matrix effects that are very accentuated in this technique. In this study, different spectral treatments and calibration strategies were investigated to obtain calibration models that allow determinations with satisfactory accuracy and precision of Cr, Cu, and Ni in river sediments from different hydrographic basins. The best model developed for Cr was using MMC without spectral normalization and for Cu and Ni it was using MMC with spectral normalization, and using inverse regression, an increase in the accuracy of the determinations of all analytes was obtained. These models showed limit of quantification (LOQ) of 7.87 mg kg-1, 1.62 mg kg-1, and 2.21 mg kg-1 and root mean square error of prediction (RMSEP) of 7.54 mg kg-1, 14.53 mg kg-1, and 8.29 mg kg-1 for Cr, Cu, and Ni, respectively. Therefore, the models have adequate sensitivity and precision for the quantification of the potentially toxic elements (PTEs) evaluated, since, according to Brazilian legislation, the lower concentration of threshold effect level (TEL) for Cr, Cu, and Ni is <37.3 mg kg-1, <35.7 mg kg-1, and <18 mg kg-1, respectively. The concentrations of Cr, Cu, and Ni determined by DP LIBS allowed to obtain a partial ecological risk assessment of the studied sediments. Also, the chemometric tool Kohonen self-organizing map (KSOM) were used for data interpretation.

Direct determination of nutrient elements in plant leaves by double pulse laser-induced breakdown spectroscopy: evaluation of calibration strategies using direct and inverse models for matrix-matching.

This study aims to develop a single calibration model to determine nutrient elements directly (Ca, Mg, Mn, and P) in soybean and sugar cane leaf samples by double pulse laser-induced breakdown spectroscopy (DP LIBS). Matrix-matching calibration (MMC) was evaluated using direct and inverse models. Forty-five samples were used to build the calibration model (23 soybean leaves and 22 sugar cane leaves), and fifteen were used for the prediction test (8 soybean leaves and 7 sugar cane leaves) models. In the direct model, the analyte concentration in the sample is the independent variable, and the analytical signal is the dependent variable. In the inverse model, the analytical signal is the independent variable, and the analyte concentration in the sample is the dependent variable. In general, both models presented satisfactory results; however, the inverse model performed better. Emission lines used to propose calibration models were selected using a linear Pearson's correlation (R) strategy between each spectral point and the Ca, Mg, Mn, and P concentration measured by reference methods using inductively coupled plasma optical emission spectrometry (ICP OES). The root mean square errors of prediction (RMSEP) for the direct models were 0.60 g kg-1 to (Ca), 0.47 g kg-1 (Mg), 9.3 mg kg-1 to (Mn), and 0.28 g kg-1 to (P); for inverse model was 0.55 g kg-1 to (Ca), 0.39 g kg-1 (Mg), 10.5 mg kg-1 to (Mn), and 0.21 g kg-1 to (P). The calibration strategies proposed in this study may minimize matrix effects in direct solid analysis in soybean and sugar cane leaf samples, performing the determination of Ca, Mg, Mn, and P by DP LIBS using a single calibration model.

Laser-induced breakdown spectroscopy determination of K in biochar-based fertilizers in the presence of easily ionizable element.

Laser-induced breakdown spectroscopy is an optical emission technique quite suitable for the analysis of recalcitrant materials as it eliminates complex procedures of sample preparation. However, for some simple LIBS instrumentation the detection limits are still higher compared to those of consolidated spectroscopic techniques. The aim of the present work was to develop a method for the determination of K in new biochar-based fertilizer samples using a simple single pulse LIBS arrangement. Due to the low K detectability, which made impossible to obtain calibration curves, an exploratory qualitative study was performed aiming to evaluate the influence of the addition of easily ionizable elements (EIE) on the sensitivity. To this aim different salts containing EIE (K, Li and Na) and other cations (Cu and Mg) have been evaluated. Results obtained showed that salts containing EIE cations increased the spectral emission signals of some elements in samples previously submitted to charring. In particular, the strategy of using Li+ was applied to the determination of K in biochar-based fertilizers. The addition of Li+ allowed to develop an analytical method for K determination featuring a linear dynamic range from 0.8% to 21.56% K, and limits of detection and quantification of 0.2% and 0.8%, respectively.