Lidiane Cristina Nunes

Optimization and validation of a LIBS method for the determination of macro and micronutrients in sugar cane leaves.

Laser induced breakdown spectrometry (LIBS) was applied for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Cu, Fe, Mn and Zn) in sugar cane leaves, which is one of the most economically important crops in Brazil. Operational conditions were previously optimized by a neuro-genetic approach, by using a laser Nd:YAG at 1064 nm with 110 mJ per pulse focused on a pellet surface prepared with ground plant samples. Emission intensities were measured after 2.0 μs delay time, with 4.5 μs integration time gate and 25 accumulated laser pulses. Measurements of LIBS spectra were based on triplicate and each replicate consisted of an average of ten spectra collected in different sites (craters) of the pellet. Quantitative determinations were carried out by using univariate calibration and chemometric methods, such as PLSR and iPLS. The calibration models were obtained by using 26 laboratory samples and the validation was carried out by using 15 test samples. For comparative purpose, these samples were also microwave-assisted digested and further analyzed by ICP OES. In general, most results obtained by LIBS did not differ significantly from ICP OES data by applying a t-test at 95% confidence level. Both LIBS multivariate and univariate calibration methods produced similar results, except for Fe where better results were achieved by the multivariate approach. Repeatability precision varied from 0.7 to 15% and 1.3 to 20% from measurements obtained by multivariate and univariate calibration, respectively. It is demonstrated that LIBS is a powerful tool for analysis of pellets of plant materials for determination of macro and micronutrients by choosing calibration and validation samples with similar matrix composition.

Evaluation of laser induced breakdown spectrometry for the determination of macro and micronutrients in pharmaceutical tablets

The aim of this work is to demonstrate the feasibility of laser induced breakdown spectrometry (LIBS) for the determination of macro and micronutrients in multielement tablets. The experimental setup was designed by using a laser Q-switch (Nd:YAG, 10 Hz, λ = 1064 nm) and the emission signals were collected by lenses into an optical fiber coupled to an echelle spectrometer equipped with a high-resolution intensified charge coupled device (ICCD). Tablets were cryogenically ground and thereafter pelletized before LIBS analysis. Calibration curves were made by employing samples and mixtures of commercial multielement tablets with binders at different ratios. Best results were achieved by using the following experimental conditions: 29 J cm−2 laser fluence, 165 mm lens to sample distance (f = 200 mm), 2.0 μs delay time, 5.0 μs integration time and 5 accumulated laser pulses. In general, the results obtained by the proposed LIBS procedure were in agreement with those obtained by ICP OES from the corresponding acid digests and coefficients variation of LIBS measurements varied from 2 to 16%. The metrological figures of merit indicate that LIBS fits for the intended purposes, and can be recommended for the analysis of multielement tablets and similar matrices aiming the determination of Ca, Cu, Fe, Mg, Mn, P and Zn.

Evaluation of grinding methods for pellets preparation aiming at the analysis of plant materials by laser induced breakdown spectrometry

It has been demonstrated that laser induced breakdown spectrometry (LIBS) can be used as an alternative method for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Fe, Cu, Mn, Zn) in pellets of plant materials. However, information is required regarding the sample preparation for plant analysis by LIBS. In this work, methods involving cryogenic grinding and planetary ball milling were evaluated for leaves comminution before pellets preparation. The particle sizes were associated to chemical sample properties such as fiber and cellulose contents, as well as to pellets porosity and density. The pellets were ablated at 30 different sites by applying 25 laser pulses per site (Nd:YAG@1064 nm, 5 ns, 10 Hz, 25J cm(-2)). The plasma emission collected by lenses was directed through an optical fiber towards a high resolution echelle spectrometer equipped with an ICCD. Delay time and integration time gate were fixed at 2.0 and 4.5 μs, respectively. Experiments carried out with pellets of sugarcane, orange tree and soy leaves showed a significant effect of the plant species for choosing the most appropriate grinding conditions. By using ball milling with agate materials, 20 min grinding for orange tree and soy, and 60 min for sugarcane leaves led to particle size distributions generally lower than 75 μm. Cryogenic grinding yielded similar particle size distributions after 10 min for orange tree, 20 min for soy and 30 min for sugarcane leaves. There was up to 50% emission signal enhancement on LIBS measurements for most elements by improving particle size distribution and consequently the pellet porosity.

Comparison of analytical performance of benchtop and handheld energy dispersive X-ray fluorescence systems for the direct analysis of plant materials

The analytical performances of benchtop and handheld energy dispersive X-ray fluorescence spectrometry (EDXRF) systems were evaluated aiming at the direct and simultaneous determination of P, K, Ca, S, Fe, Mn, and Si in plant materials. Pressed pellets of comminuted leaves from 23 varieties of sugar cane were used as laboratory samples. Both systems presented similar figures of merit, and were able to provide useful data for plant nutrition diagnosis. Linear correlation between the elemental mass fractions in the test samples and characteristic X-ray intensities was obtained for all analytes with both types of equipment. Correlation coefficients from 0.9601 to 0.9918 and from 0.9094 to 0.9948 were attained for benchtop and handheld EDXRF, respectively. The coefficient of variation of measurements carried out in 3 different test samples was also appropriate, being lower than 13% for all analytes. Limits of detection were comparable for both systems (20 mg kg−1 for Fe and Mn, and approximately 0.1 g kg−1 for P, K, Ca, S and Si) and permit the evaluation of the mineral nutrition status of sugar cane crop taking into account the critical levels of these elements. The handheld system is a cost-effective and appealing option for those who intend to carry out faster in situ and laboratory analysis with equivalent performance of the benchtop equipment.

Identification of Four Wood Species by an Electronic Nose and by LIBS

This paper presents two complementary methods capable of identifying four wood species (Cedrela fissilis, Ocotea porosa, Hymenolobium petraeum, and Aspidosperma subincanum) both by their volatile organic compounds and by the presence of 10 chemical elements: Al, B, Ca, Mg, Zn, Cu, Mn, Fe, Na, and Si. The volatile compounds were detected by an electronic nose formed by an array of three different conductive polymer gas sensors. The elemental determination was made by laser-induced breakdown spectrometry (LIBS). The emissions measured were treated by principal component analysis (PCA). Leave-one-out analysis showed a rate of hits of 100%.

Melted Paraffin Wax as an Innovative Liquid and Solid Extractant for Elemental Analysis by Laser-Induced Breakdown Spectroscopy

This work proposes a new development in the use of melted paraffin wax as a new extractant in a procedure designed to aggregate the advantages of liquid phase extraction (extract homogeneity, fast, and efficient transfer, low cost and simplicity) to solid phase extraction. As proof of concept, copper(II) in aqueous samples was converted into a hydrophobic complex of copper(II) diethyldithiocarbamate and subsequently extracted into paraffin wax. Parameters which affect the complexation and extraction (pH, DDTC, and Triton X-100 concentration, vortex agitation time and complexation time) were optimized in a univariate way. The combination of the extraction proposed procedure with laser-induced breakdown spectroscopy allowed the precise copper determination (coefficient of variation = 3.1%, n = 10) and enhanced detectability because of the concentration factor of 18 times. A calibration curve was obtained with a linear range of 0.50-10.00 mg L-1 (R2 = 0.9990, n = 7), LOD = 0.12 mg L-1, and LOQ = 0.38 mg L-1 under optimized conditions. An extraction procedure efficiency of 94% was obtained. The accuracy of the method was confirmed through the analysis of a reference material of human blood serum, by the spike and recovery trials with seawater, tap water, mineral water, and alcoholic beverages and by comparing with those results obtained by graphite furnace atomic absorption spectrometry.

Exploiting multivariate calibration for compensation of iron interference in the spectrophotometric flow-based catalytic determination of molybdenum

Multivariate calibration involving partial least squares was exploited in the flow-based spectrophotometric determination of molybdenum in river waters relying on the Mo(VI)-catalyzed iodide oxidation by H2O2 under acidic conditions. Two sample aliquots were simultaneously inserted into the carrier stream, and differential pumping was accountable for in-line addition of sulfuric acid to one of them. Pronounced gradients (acidity and reagent concentrations) were established along the complex sample zone formed, and the absorbance-time function was characterized by local maximum and minimum values. As these values were intrinsically more precise, they were used for implementing the PLS multivariate calibration. Mo(VI) and Fe(III) were jointly determined, and Fe(III) interference was straightforwardly circumvented. Influence of reagent concentrations, acidity, available time for reaction development, and nature of the acid was investigated, and this later parameter manifested itself as relevant for discriminating purposes. The calibration set consisted of 6.2 - 50.0μgL-1 Mo(VI) plus 0.5 - 7.0mgL-1 Fe(III) solutions. The PLS model was characterized by good prediction ability [RMSEP = 0.67μgL-1 for Mo(VI)]. The innovation was applied to spiked river waters, and analytical precision, sampling rate, recovery, detection limit and reagent consumption were estimated as 0.5 - 2.4%, 31h-1, 98-114%. 0.88μgL-1 Mo(VI), and 54.0mg KI per determination, respectively. Results were in agreement with ICP OES.

Recent advances in LIBS and XRF for the analysis of plants

The ability to provide a fast and multielemental analytical response directly from a solid sample makes both laser-induced breakdown spectroscopy (LIBS) and X-ray fluorescence spectrometry (XRF) very versatile tools for plant nutrition diagnosis. This review focuses on the main developments and advances in LIBS and XRF in the analysis of plant materials over the last ten years. Fundamental aspects and instrumentation are given for both techniques. The developments in the quantitative analysis of plant leaves are discussed, with special emphasis on the key aspects and challenges concerning field sampling protocols, sample preparation, and calibration strategies. Microchemical imaging applications by LIBS and XRF (including synchrotron radiation) are also presented in a broader selection of plant compartments (e.g., leaves, roots, stems, and seeds). Challenges, expectations and complementarities of LIBS and XRF towards plant nutrition diagnosis are thoroughly discussed.