Implications of converting native forest areas to agricultural systems on the dynamics of CO2 emission and carbon stock in a Cerrado soil, Brazil.

The conversion of native vegetation to agricultural areas leads to a natural process of carbon loss but these systems can stabilize in terms of carbon dynamics depending on the management and conversion time, presenting potential to both store and stabilize this carbon in the soil, resulting in lower soil respiration rates. In this context, this study aimed to investigate the effect of converting native Cerrado forest areas to agricultural systems with a forest planted with Eucalyptus camaldulensis and silvopastoral systems on the dynamics of CO2 emission and carbon stock at different soil depths. The experimental sites are located in the Midwest of Brazil, in the coordinates 20°22'31″ S and 51°24'12″ W. Were evaluated soil CO2 emission (FCO2), soil organic carbon, the degree of humification of soil organic matter (HLIFS), soil temperature, soil moisture, and soil chemical and physical attributes. The soil of the area is classified as an Oxisol (Haplic Acrustox). Soil samples were collected at depths of 0.00-0.10, 0.10-0.20, 0.20-0.30, and 0.30-0.40 m. The lowest FCO2 values were found in the silvopastoral system (1.05 µmol m-2 s-1), followed by the native forest (1.65 µmol m-2 s-1) and the eucalyptus system (1.96 µmol m-2 s-1), indicating a 36% reduction in FCO2 compared to the conversion of the native forest to the silvopastoral system and an increase of 19% when converting the native forest to the eucalyptus system. The soil chemical attributes (N, K+, Ca2+, H++Al3+, CEC, and organic carbon) showed a decrease along the profile. The shallowest depths (0.00-0.10 and 0.10-0.20 m) presented no differences between systems but the subsequent depths (0.20-0.30 and 0.30-0.40 m) had a difference (95% confidence interval), relative to N, Ca2+, H++Al3, CEC, and organic carbon stock (OCS), and the soil under silvopastoral system showed a higher concentration of these attributes than the native forest. The multivariate analysis showed that the eucalyptus and silvopastoral systems did not differ from the forest in the shallowest soil layer but differed from each other. This behavior changed from the second assessed depth (0.10-0.20 m), in which the silvopastoral system stands out, differing both from the eucalyptus system and from the native forest, and this behavior is maintained at the following depths (0.20-0.30 and 0.30-0.40 m). OCS, H++Al3, CEC, and nitrogen are strongly related to land use change for silvopastoral system. Regarding the behavior/relationship of attributes as a function of depth, the silvopastoral system contributed to soil carbon accumulation and stability over consecutive years.

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.

Laser-Induced Breakdown Spectroscopy Associated with the Design of Experiments and Machine Learning for Discrimination of Brachiaria brizantha Seed Vigor.

Laser-induced breakdown spectroscopy (LIBS) associated with machine learning algorithms (ML) was used to evaluate the Brachiaria seed physiological quality by discriminating the high and low vigor seeds. A 23 factorial design was used to optimize the LIBS experimental parameters for spectral analysis. A total of 120 samples from two distinct cultivars of Brachiaria brizantha seeds exhibiting high vigor (HV) and low vigor (LV) in standard tests were studied. The raw LIBS spectra were normalized and submitted to outlier verification, previously to the reduction data dimensionality from principal component analysis. Supervised machine learning algorithm parameters were chosen by leave-one-out cross-validation in the test samples, and it was tested by external validation using a new set of data. The overall accuracy in external validation achieved 100% for HV and LV discrimination, regardless of the cultivar or the classification algorithm.

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.

Modeling the quenching of fluorescence from organic matter in Amazonian soils.

Knowledge of the interactions of soil organic matter (SOM) with metal species is important in order to obtain information concerning the fates of the metals in environment, whose reactive functional groups present in SOM can provide high complexation capacity. The aim of this study was to evaluate the interactions involving humic acids (HA) and fulvic acids (FA), extracted from Amazonian soils, with Cu(II) and Al(III) ions, using fluorescence quenching spectroscopy. The obtained results showed that the data for the humic fractions of the Amazonian Spodosols could be fitted with one to one complexation model, which provided the best representation of the changes in fluorescence quenching after addition of Cu(II) or Al(III) ions. It was found that the HA presented fewer complexation sites and lower stability constants, compared to the FA samples. Furthermore, the FA showed selective interaction with the metals, while the HA fraction was less selective and could be associated its homogeneous structure. The results showed that the humic acids required 10 times more carbon in their structures than fulvic acids for complexing a metal atom. This behavior can be associated to the fact that the Fulvic Acid fraction has higher mobility and greater interaction during the profile when compare humic acids. Hence, given the diversity of metals to which the HA has affinity, this soil fraction appears to be mainly responsible for soil fertility, while the FA fraction has higher mobility and greater interaction with water.

Prediction of black, immature and sour defective beans in coffee blends by using Laser-Induced Breakdown Spectroscopy.

One of the most important factors that interfere negatively in coffee global quality has been blends with defective beans, especially those called Black, Immature and Sour (BIS). The methods based on visual-manual estimation of defective beans have shown their inefficiency in coffee value chain for large-scale analysis. The lack of fast, accurate and robust analytical methods for BIS determination is still a research gap. Laser-Induced Breakdown Spectroscopy (LIBS) is a fast, low-cost and residue-free technique capable of performing multielemental determination and investigating organic composition of samples. In the present work, LIBS together with spectral processing and variable selection were evaluated to fit linear regression models for predicting BIS in blends. Models showed high capacity of prediction with RMSEP smaller than 3.8% and R2 higher than 80%. Most importantly, measurements are guided by chemical responses, which make LIBS-based methods less susceptible to the visual indistinguishability that occurs in manual inspections.

Fluorescence lifetime evaluation of whole soils from the Amazon rainforest.

Time-resolved fluorescence spectroscopy (TRFS) is a new tool that can be used to investigate processes of interaction between metal ions and organic matter (OM) in soils, providing a specific analysis of the structure and dynamics of macromolecules. To the best of our knowledge, there are no studies in the literature reporting the use of this technique applied to whole/non-fractionated soil samples, making it a potential method for use in future studies. This work describes the use of TRFS to evaluate the fluorescence lifetimes of OM of whole soils from the Amazon region. Analysis was made of pellets of soils from an oxisol-spodosol system, collected in São Gabriel da Cachoeira (Amazonas, Brazil). The fluorescence lifetimes in the oxisol-spodosol system were attributed to two different fluorophores. One was related to complexation of an OM fraction with metals, resulting in a shorter fluorophore lifetime. A short fluorescence lifetime (2-12 ns) could be associated with simpler structures of the OM, while a long lifetime (19-66 ns) was associated with more complex OM structures. This new TRFS technique for analysis of the fluorescence lifetime in whole soil samples complies with the principles of green chemistry.

Double pulse laser induced breakdown spectroscopy: A potential tool for the analysis of contaminants and macro/micronutrients in organic mineral fertilizers.

Organic fertilizers are obtained from waste of plant or animal origin. One of the advantages of organic fertilizers is that, from the composting, it recycles waste-organic of urban and agriculture origin, whose disposal would cause environmental impacts. Fast and accurate analysis of both major and minor/trace elements contained in organic mineral and inorganic fertilizers of new generation have promoted the application of modern analytical techniques. In particular, laser induced breakdown spectroscopy (LIBS) is showing to be a very promising, quick and practical technique to detect and measure contaminants and nutrients in fertilizers. Although, this technique presents some limitations, such as a low sensitivity, if compared to other spectroscopic techniques, the use of double pulse (DP) LIBS is an alternative to the conventional LIBS in single pulse (SP). The macronutrients (Ca, Mg, K, P), micronutrients (Cu, Fe, Na, Mn, Zn) and contaminant (Cr) in fertilizer using LIBS in SP and DP configurations were evaluated. A comparative study for both configurations was performed using optimized key parameters for improving LIBS performance. The limit of detection (LOD) values obtained by DP LIBS increased up to seven times as compared to SP LIBS. In general, the marked improvement obtained when using DP system in the simultaneous LIBS quantitative determination for fertilizers analysis could be ascribed to the larger ablated mass of the sample. The results presented in this study show the promising potential of the DP LIBS technique for a qualitative analysis in fertilizers, without requiring sample preparation with chemical reagents.

The importance of humin in soil characterisation: A study on Amazonian soils using different fluorescence techniques.

Soil organic matter (SOM) is a complex mixture of molecules with different physicochemical properties, with humic substances (HS) being the main component as it represents around 20-50% of SOM structure. Soil of the Amazon region is considered one of the larger carbon pools of the world; thus, studies of the humic fractions are important for understanding the dynamics of organic matter (OM) in these soils. The aim of this study was to use laser-induced fluorescence spectroscopy (LIFS) and a combination of excitation-emission matrix (EEM) fluorescence with Parallel Factor Analysis (CP/PARAFAC) to assess the characteristics of humin (HU) extracted from Amazonian soils. The results obtained using LIFS showed that there was an increasing gradient of humification degree with depth, the deeper horizon presenting a higher amount of aromatic groups in the structure of HU. From the EEM, the contribution of two fluorophores with similar behaviour in the structures of HU and whole soil was assessed. Additionally, the results showed that the HU fraction might represent a larger fraction of SOM than previously thought: about 80-93% of some Amazon soils. Therefore, HU is an important humic fraction, thus indicating its role in environmental analysis, mainly in soil analysis.

Infrared spectroscopy: a potential tool in huanglongbing and citrus variegated chlorosis diagnosis.

Huanglongbing (HLB) and citrus variegated chlorosis (CVC) are serious threats to citrus production and have caused considerable economic losses worldwide, especially in Brazil, which is one of the biggest citrus producers in the world. Neither disease has a cure nor an efficient means of control. They are also generally confused with each other in the field since they share similar initial symptoms, e.g., yellowing blotchy leaves. The most efficient tool for detecting these diseases is by polymerase chain reaction (PCR). However, PCR is expensive, is not high throughput, and is subject to cross reaction and contamination. In this report, a diagnostic method is proposed for detecting HLB and CVC diseases in leaves of sweet orange trees using attenuated total reflectance Fourier transform infrared spectroscopy and the induced classifier via partial least-squares regression. Four different leaf types were considered: healthy, CVC-symptomatic, HLB-symptomatic, and HLB-asymptomatic. The results show a success rate of 93.8% in correctly identifying these different leaf types. In order to understand which compounds are responsible for the spectral differences between the leaf types, samples of carbohydrates starch, sucrose, and glucose, flavonoids hesperidin and naringin, and coumarin umbelliferone were also analyzed. The concentration of these compounds in leaves may vary due to biotic stresses.

Evaluation of laser induced breakdown spectroscopy for multielemental determination in soils under sewage sludge application.

Laser induced breakdown spectroscopy (LIBS) is an atomic emission spectroscopy technique for simple, direct and clean analysis, with great application potential in environmental sustainability studies. In a single LIBS spectrum it is possible to obtain qualitative information on the sample composition. However, quantitative analysis requires a reliable model for analytical calibration. Multilayer perceptron (MLP), an artificial neural network, is a multivariate technique that is capable of learning to recognize features from examples. Therefore MLP can be used as a calibration model for analytical determinations. Accordingly, the present study proposes to evaluate the traditional linear fit and MLP models for LIBS calibration, in order to attain a quantitative multielemental method for contaminant determination in soil under sewage sludge application. Two sets of samples, both composed of two kinds of soils were used for calibration and validation, respectively. The analyte concentrations in these samples, used as reference, were determined by a reference analytical method using inductively coupled plasma optical emission spectrometry (ICP OES). The LIBS-MLP was compared to a LIBS-linear fit method. The values determined by LIBS-MLP showed lower prediction errors, correlation above 98% with values determined by ICP OES, higher accuracy and precision, lower limits of detection and great application potential in the analysis of different kinds of soils.

Solid-phase fluorescence spectroscopy to characterize organic wastes.

The production of solid organic waste (SOW) such as sewage sludge (SS) or municipal solid waste (MSW) has been continuously increasing in Europe since the beginning of the 1990'. Today, the European Union encourages the stabilization of these wastes using biologic processes such as anaerobic digestion and/or composting to produce bio-energy and organic fertilizers. However, the design and management of such biologic processes require knowledge about the quantity and quality of the organic matter (OM) contained in the SOW. The current methods to characterize SOW are tedious, time-consuming and often insufficiently informative. In this paper, we assess the potential of solid-phase fluorescence (SPF) spectroscopy to quickly provide a relevant characterization of SOW. First, we tested well known model compounds (tryptophan, bovine serum albumin, lignin and humic acid) and biologic matrix (Escherichia coli) in three dimensional solid-phase fluorescence (3D-SPF) spectroscopy. We recorded fluorescence spectra from proteinaceous samples but we could not record the fluorescence emitted by lignin and humic acid powders. For SOW samples, fluorescence spectra were successfully recorded for MSW and most of its sub-components (foods, cardboard) but impossible for SS, sludge compost (SC) and ligno-cellulosic wastes. Based on visual observations and additional assays, we concluded that the presence of highly light-absorptive chemical structures in such dark-colored samples was responsible for this limitation. For such samples, i.e. lignin, humic acid, SS, SC and ligno-cellulosic wastes, we show that laser induced fluorescence (LIF) spectroscopy enables the acquisition of 2D fluorescence spectra.

Evaluation of the effects of Candidatus Liberibacter asiaticus on inoculated citrus plants using laser-induced breakdown spectroscopy (LIBS) and chemometrics tools.

This study investigated the organic and inorganic constituents of healthy leaves and Candidatus Liberibacter asiaticus (CLas)-inoculated leaves of citrus plants. The bacteria CLas are one of the causal agents of citrus greening (or Huanglongbing) and its effect on citrus leaves was investigated using laser-induced breakdown spectroscopy (LIBS) combined with chemometrics. The information obtained from the LIBS spectra profiles with chemometrics analysis was promising for the construction of predictive models to identify healthy and infected plants. The major, macro- and microconstituents were relevant for differentiation of the sample conditions. The models were then applied to different inoculation times (from 1 to 8 months). The models were effective in the classification of 82-97% of the diseased samples with a 95% significance level. The novelty of this method was in the fingerprinting of healthy and diseased plants based on their organic and inorganic contents.

Changes in optical properties caused by UV-irradiation of aquatic humic substances from the amazon river basin: seasonal variability evaluation.

Aquatic humic substances (AHS) isolated from two characteristic seasons of the Negro river, winter and summer corresponding to floody and dry periods, were structurally characterized by 13C nuclear magnetic ressonance. Subsequently, AHS aqueous solutions were irradiated with a polychromatic lamp (290-475 nm) and monitored by its total organic carbon (TOC) content, ultraviolet-visible (UV-vis) absorbance, fluorescence, and Fourier transformed infrared spectroscopy (FTIR). As a result, a photobleaching up to 80% after irradiation of 48 h was observed. Conformational rearrangements and formation of low molecular complexity structures were formed during the irradiation, as deduced from the pH decrement and the fluorescence shifting to lower wavelengths. Additionally a significant mineralization with the formation of CO2, CO, and inorganic carbon compounds was registered, as assumed by TOC losses of up to 70%. The differences in photodegradation between samples expressed by photobleaching efficiency were enhanced in the summer sample and related to its elevated aromatic content. Aromatic structures are assumed to have high autosensitization capacity effects mediated by the free radical generation from quinone and phenolic moieties.