Comparison of Algorithms for Baseline Correction of LIBS Spectra for Quantifying Total Carbon in Brazilian Soils

LIBS is a promising and versatile technique for multi-element analysis that usually takes less than a minute and requires minimal sample preparation and no reagents. Despite the recent advances in elemental quantification, the LIBS still faces issues regarding the baseline produced by background radiation, which adds non-linear interference to the emission lines. In order to create a calibration model to quantify elements using LIBS spectra, the baseline has to be properly corrected. In this paper, we compared the performance of three filters to remove random noise and five methods to correct the baseline of LIBS spectra for the quantification of total carbon in soil samples. All combinations of filters and methods were tested, and their parameters were optimized to result in the best correlation between the corrected spectra and the carbon content in a training sample set. Then all combinations with the optimized parameters were compared with a separate test sample set. A combination of Savitzky-Golay filter and 4S Peak Filling method resulted in the best correction: Pearson's correlation coefficient of 0.93 with root mean square error of 0.21. The result was better than using a linear regression model with the carbon emission line 193.04 nm (correlation of 0.91 with error of 0.26). The procedure proposed here opens a new possibility to correct the baseline of LIBS spectra and to create multivariate methods based on the a given spectral range.Comment: 13 pages, 5 figure

Fluorescência induzida por laser da matéria orgânica de um Latossolo brasileiro tratado com lodo de esgoto

A aplicação do lodo de esgoto é utilizada como alternativa de conservação e manutenção da fertilidade dos solos sem prejudicar o ecossistema. O objetivo do presente trabalho foi avaliar a influência da aplicação de lodo de esgoto sobre a matéria orgânica (MO) de um Latossolo vermelho amarelo brasileiro, através da fluorescência induzida por laser (LIF). A LIF foi utilizada para analisar a fluorescência do solo intacto e suas frações químicas e físicas. Houve grande contribuição da fração humina à fluorescência do solo intacto, remarcando a importância de estudar a matéria orgânica (MO) associada à matriz mineral do solo. Para cada fração granulométrica foram obtidos espectros com diferentes perfis, indicando diferenças nos compostos orgânicos a elas ligados. A fração 2-20 µm, que apresentou maior conteúdo de carbono (~5%), representa somente 10% do solo mas acumula 34-39 % do conteúdo total de carbono do mesmo e mostrou a maior intensidade de fluorescência. O espectro desta fração mostra sua heterogeneidade e alta concentração de compostos cuja fluorescência é centrada nos 510 nm, o que indica alta concentração de sistemas com ligações insaturadas, com alto grau de ressonância e maior conjugação do sistema de eletrons pi, indicando maior aromaticidade quando comparado as outras frações. Não foram observadas diferenças significativas entre os tratamentos de lodo de esgoto. A LIF é uma técnica promissora para caraterizar a MO de solos intatos, permitindo estudar sua distribuição na matriz mineral do solo, inclusive nos Latossolos.Sludge applications have been used to maintain fertility of agricultural soils without damaging the natural ecosystem. The aim of this study was evaluating the influence of sewage-sludge addition on the quality of organic matter (OM) of a Brazilian Oxisol by Laser Induced Fluorescence (LIF). LIF was used to analyze OM of whole soil and different soil fractions separated by chemical and physical methods. The high fluorescence contribution of humin fraction to the fluorescence of whole soils was shown, stressing the importance of studying OM associated to mineral matrix of soil. Spectra with different shapes were obtained for every particle size fraction, indicating differences in organic compounds bounded to them. The fraction with the higher carbon content was the 2-20 µm, that contains ~5% C and represents only 10% in soil, but stores 34-39 % of total C and shows the highest fluorescence intensity. The spectrum of this fraction shows its heterogeneity and a higher concentration of compounds which fluorescence is centered at 510 nm. This indicates a higher concentration of unsaturated bond systems capable of high degree of resonance, increased conjugation of the electron pi system, and higher aromaticity comparing with other fractions. No differences were detected for treatments of sewage-sludge applications. LIF spectroscopy is a promising technique for OM studies in whole soils, allowing to study spatial distribution of OM within the soil's mineral matrix, including Oxisols

Atributos químicos e qualidade da matéria orgânica do solo em sistemas de colheita de cana-de-açúcar com e sem queima

The objective of this work was to evaluate soil chemical attributes, to quantify soil contents and stocks of C and N, and to evaluate the chemical quality of soil organic matter in sugarcane harvest systems with or without burning. Cultivated sugarcane areas were evaluated with or without burning of the fields at 6 and 12 years after the last renovation of the sugarcane fields. In addition, a native vegetation area and another one cultivated for 19 years without burning were also evaluated. Soil C content in the unburnt areas was higher thanthat of the burnt ones and lower than that of the areas with native vegetation. Carbon stock at the 0.0–0.3-m soil depth in the burnt areas was 22% lower than in the 6-year unburnt area and 43% lower in the 12-year area. The highest humification degrees occurred in the 19-year unburnt area; and the lowest, in the native vegetation area. The cultivated soils showed higher concentration of phenolic and carboxylic groups in humic acids. Soil fertility increases in the unburnt sugarcane areas because of their more humified organic matter and of the higher quantity of carboxylic and phenolic groups.O objetivo deste trabalho foi avaliar atributos químicos do solo, quantificar os teores e os estoques de C e N, e avaliar a qualidade química da matéria orgânica do solo em sistemas de colheita de cana-de-açúcar com ou sem queima da palhada. Áreas cultivadas com cana-de-açúcar foram avaliadas com ou sem queima da palhada, aos 6 e aos 12 anos após a última reforma do canavial. Além disso, também foram avaliadas uma área de vegetação nativa e outra cultivada por 19 anos sem queima. O teor de C no solo das áreas sem queima foi superior ao daquelas queimadas e inferior ao da área com vegetação nativa. O estoque de C a 0,0–0,3 m deprofundidade, na área queimada, foi 22% menor do que o na área sem queima, aos 6 anos, e 43% menor, aos 12 anos. Os maiores graus de humificação ocorreram na área sem queima por 19 anos; e os menores, na área com vegetação nativa. Os solos cultivados apresentaram maior concentração de grupos fenólicos e carboxílicos nos ácidos húmicos. A fertilidade do solo aumenta em áreas de cana-de-açúcar sem queima, em razão da matéria orgânica do solo mais humificada e da maior quantidade de grupamentos carboxílicos e fenólicos

Caracterização química e espectroscópica de solos irrigados com efluente de esgoto tratado

A utilização de efluentes de esgoto tratado na irrigação, ao invés de realizar a disposição deste subproduto nos cursos d'água tem sido uma alternativa antiga, popular e atrativa, com triplo propósito: tratamento complementar do efluente, fonte de água e de nutrientes ao sistema solo-planta. Entretanto, no Brasil, a reciclagem de águas residuárias, particularmente, do efluente de esgoto tratado, não é uma prática comum e, conseqüentemente, trabalhos científicos relacionados a este tema são incipientes. Com a finalidade de fornecer mais informações para subsidiar as pesquisas nesta área, este trabalho visa avaliar, por meio de técnicas química e espectroscópica, o processo de humificação na matéria orgânica dos solos irrigados com efluente de esgoto tratado em experimentos de campo. Os cinco tratamentos estudados foram: TSI (controle) - irrigado com água potável e adição de nitrogênio via fertilizante mineral, T100, T125, T150 e T200 irrigado com efluente de esgoto tratado e adição de nitrogênio via fertilizante mineral. Os resultados obtidos mostram variações no teor de carbono e no grau de humificação, para os solos irrigados com efluente de esgoto tratado, decorrentes do aumento da atividade de decomposição da matéria orgânica, estimulada pelo aumento da quantidade de água no solo.FAPESPCNPqCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES

Soil Organic Matter Quality in Jatropha spp. Plantations in Different Edaphoclimatic Conditions

ABSTRACT: The substitution of native vegetation by agricultural ecosystems can change the quantity and quality of soil organic matter (SOM), and the intensity of these changes depends on the soil type, climate, and land use. The objective of this study was to evaluate the quality of organic matter in chronosequences of Jatropha cultivation in contrasting soil and climatic conditions. Soil samples were evaluated at depths of 0.00-0.10, 0.20-0.30, and 0.80-1.00 m in chronosequences located in Planaltina, Distrito Federal (Cerrado-Pasture-Jatropha), Dourados, Mato Grosso do Sul (Atlantic Forest-Corn-Jatropha), and Araripina, Pernambuco (Caatinga-Jatropha). To assess SOM quality, we determined C contents in the SOM fractions, C stocks, the carbon management index (CMI), the SOM humification index (H LIF ), and the C and N concentrations in the microbial biomass. The conversion of native vegetation to agropastoral systems changed the composition of SOM in the biomes evaluated, especially in the surface layers. The CMI and the C and N contents in the microbial biomass were the most responsive to land use changes in all the biomes studied. The pasture improved SOM quality by increasing the CMI (116) and the C content by 8, 21, and 6 % in the organic, mineral, and organomineral fractions, respectively, while maintaining the SOM humification index and the C and N contents in the microbial biomass in the 0-0.10 m layer. The lowest values of C in the SOM fractions, the CMI (52), and C microbial biomass (136 mg kg -1 ) were observed for annual crops. Jatropha cultivation increased C contents in the SOM fractions, C stocks, the CMI, and C and N in the microbial biomass with an increase in cultivation time, which demonstrates the potential of this long-term system for improving SOM quality

Modeling the quenching of fluorescence from organic matter in Amazonian soils

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Solid-phase fluorescence spectroscopy to characterize organic wastes

International audienceThe 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

Optimization of laser-induced breakdown spectroscopy parameters from the design of experiments for multi-element qualitative analysis in river sediment

International audienceLaser-induced breakdown spectroscopy (LIBS) is a fast, low analytical cost, environmentally clean technique that does not require the use of reagents for sample preparation. However, regardless of the LIBS setup, it has limitations in terms of sensitivity and precision, especially when applied to complex samples, such as river sediment. To overcome these limitations, in this work, different experimental parameters were optimized for multi-element analysis of a river sediment sample using design of experiments (DOE) approaches, i.e., fractional factorial and central composite designs (CCD). The findings demonstrated that DOE applied to the LIBS technique can be used as an efficient tool for optimizing the key parameters affecting sediment analysis by LIBS