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Made available in DSpace on 2020-12-12T02:43:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-09-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The determination of N is an important demand for several sectors and the analytical features of laser-induced breakdown spectroscopy (LIBS) are very attractive to accomplish this task. In this work, a novel proposal for nitrogen determination was explored considering molecular diatomic emission lines of CN measured by LIBS. As a proof of concept, a method was developed to determine N in biochar-based fertilizers, a highly recalcitrant matrix. The fertilizers were prepared from biochar of eucalyptus pruning residues, peanut skin and fibers of banana tree and the calibration standards were prepared by matrix matching using eucalyptus biochar. Diatomic emission signals of CN at 388.3 nm showed high correlation with the levels of N in standards and samples, suggesting the molecular emission of CN is little affected by the matrix effect. The developed method is accurate since the N levels determined in the samples do not differ statistically from the expected level, with a 95% confidence level. Furthermore, the method using molecular emission is simple and highlights the potential of LIBS for N determination in complex matrices (e.g. biochar). Department of Analytical Chemistry São Paulo State University – UNESP Department of Chemistry Federal University of São Paulo – UNIFESP Department of Analytical Chemistry São Paulo State University – UNESP FAPESP: 2015/24757-9 FAPESP: 2019/18873-7 CNPq: 302414/2017-7 CNPq: 308200/2018-7

Made available in DSpace on 2018-12-11T17:36:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-06-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) A spark discharge system was coupled to laser-induced breakdown spectroscopy (SD-LIBS) to improve sensitivity in the determination of P in fertilizers. A LIBS system consisting of a Q-switched Nd:YAG laser operating at 1064 nm and emitting pulses at 50 mJ with a fluence of 70 J cm−2 at the focal point was used. Results of preliminary experiments suggested that the most appropriate wavelength to measure P was the P (I) line at 214.9 nm, which did not show interferences by Fe, Cu and Zn. The electrical discharge was provided by a homemade high-voltage electronic circuit consisting of two cylindrical tungsten electrodes at the optimized output voltage of 4.5 kV, with tips arranged at the optimal distances of 4 mm between them and 2 mm above the sample surface. To minimize the expected matrix effects calibration standards of P2O5 in the range of 4.8 and 33.3% were prepared by mixing various amounts of a phosphate rock reference material (SRM-120c) with a mixture of CaCO3, CaSO4, (NH2)2CO and KCl at a 1:1:1:1 mass ratio. The calibration curves obtained at a 4.5 kV SD-LIBS output voltage showed correlation coefficients ≥0.993, RSD ≤8% and LOQ 5.3% (m/m) P2O5. Data obtained by analyzing commercial samples by the proposed system were in good agreement, at 95% confidence level, with those obtained by using high-resolution continuum-source flame atomic absorption spectroscopy. São Paulo State University - UNESP Analytical Chemistry Department, P.O. Box 355 University of São Paulo – USP Department of Electrical and Computer Engineering CNR-Istituto di Nanotecnologia (NANOTEC) – PLasMI Lab, Via Amendola 122/D Federal University of São Paulo - UNIFESP Exact and Earth Sciences Department São Paulo State University - UNESP Analytical Chemistry Department, P.O. Box 355 CNPq: 141977/2016-7 FAPESP: 2004/14212-0 CNPq: 2015/24757-9 CNPq: 303255/2013-7 CNPq: 311085/2014-8

article i nfo A simultaneous optimization strategy based on a neuro-genetic approach is proposed for selection of laser induced breakdown spectroscopy operational conditions for the simultaneous determination of macro- nutrients (Ca, Mg and P), micro-nutrients (B, Cu, Fe, Mn and Zn), Al and Si in plant samples. A laser induced breakdown spectroscopy system equipped with a 10 Hz Q-switched Nd:YAG laser (12 ns, 532 nm, 140 mJ) and an Echelle spectrometer with intensified coupled-charge device was used. Integration time gate, delay time, amplification gain and number of pulses were optimized. Pellets of spinach leaves (NIST 1570a) were employed as laboratory samples. In order to find a model that could correlate laser induced breakdown spectroscopy operational conditions with compromised high peak areas of all elements simultaneously, a Bayesian Regularized Artificial Neural Network approach was employed. Subsequently, a genetic algorithm was applied to find optimal conditions for the neural network model, in an approach called neuro-genetic. A single laser induced breakdown spectroscopy working condition that maximizes peak areas of all elements simultaneously, was obtained with the following optimized parameters: 9.0 µs integration time gate, 1.1 µs delay time, 225 (a.u.) amplification gain and 30 accumulated laser pulses. The proposed approach is a useful and a suitable tool for the optimization process of such a complex analytical problem.

Studies were carried out to investigate the contamination of Piracicaba and Mogi-Guaçu River basins (São Paulo State, Southeastern, Brazil) for heavy metals (Cd and Pb), using the limnic bivalve Anodontites trapesialis as a biological monitor. The results showed that the concentrations of Pb were higher than the control group in both basins, showing the bioavailability of this non-essential element in the basins. The concentrations were higher in the Mogi-Guaçu than in the Piracicaba basin, and in the slightly contaminated sites in both basins. There was no correlation between the degree of human impact and Cd and Pb concentrations, it was not possible to infer about concentrations of these heavy metals in the bivalves based only in a broad evaluation of human impact.O principal objetivo deste estudo foi investigar a contaminação pelos metais pesados Cd e Pb nas bacias dos rios Piracicaba e Mogi-Guaçu (Estado de São Paulo, Brasil), utilizando o bivalve limnico Anodontites trapesialis como indicador biológico. As bacias estudadas apresentam diferentes graus de impacto, sendo a qualidade da água geralmente melhor na bacia do rio Mogi-Guaçu. Os teores de Pb detectados nos bivalves não podem ser considerados críticos, contudo, houve acúmulo em relação ao grupo de controle em ambas as bacias, especialmente na bacia do rio Mogi-Guaçu. As maiores concentrações dos elementos, especialmente Pb, foram observadas nos locais menos poluídos e na bacia menos degradada. Este fato sugere que estas concentrações não estão sendo afetadas apenas pelas atividades antrópicas nas bacias, mas deve-se considerar também fatores que afetem a biodisponibilidade ou fontes específicas e não pontuais.