Paulino R. Villas-Boas

Quantification of total carbon in soil using laser-induced breakdown spectroscopy: a method to correct interference lines

The C cycle in the Brazilian forests is very important, mainly for issues addressed to climate changes and soil management. Assessing and understanding C dynamics in Amazonian soils can help scientists to improve models and anticipate scenarios. New methods that allow soil C measurements in situ are a crucial approach for this kind of region, due to the costs for collecting and sending soil samples from the rainforest to the laboratory. Laser-induced breakdown spectroscopy (LIBS) is a multielemental atomic emission spectroscopy technique that employs a highly energetic laser pulse for plasma production and requires neither sample preparation nor the use of reagents. As LIBS takes less than 10 s per sample measurement, it is considered a promising technique for in situ soil analyses. One of the limitations of portable LIBS systems, however, is the common overlap of the emission lines that cannot be spectrally resolved. In this study a method was developed capable of separating the Al interference from the C emission line in LIBS measurements. Two typical forest Brazilian soils rich in Al were investigated: a spodosol (Amazon Forest) and an oxisol (Atlantic Forest). Fifty-three samples were collected and analyzed using a low-resolution LIBS apparatus to measure the intensities of C lines. In particular, two C lines were evaluated, at 193.03 and 247.86 nm. The line at 247.86 nm showed very strong interference with Fe and Si lines, which made quantitative analysis difficult. The line at 193.03 nm showed interference with atomic and ionic Al emission lines, but this problem could be solved by applying a correction method that was proposed and tested in this work. The line at 247.86 was used to assess the proposed model. The strong correlation (Pearsons coefficient R=0.91) found between the LIBS values and those obtained by a reference technique (dry combustion by an elemental analyzer) supported the validity of the proposed method.

Phosphorus quantification in fertilizers using laser induced breakdown spectroscopy (LIBS): a methodology of analysis to correct physical matrix effects

The aim of this study was to develop a quantitative method to determine phosphorus in fertilizers of different matrix compositions using the laser induced breakdown spectroscopy (LIBS) technique. The LIBS spectra were acquired on 26 samples of organic and inorganic fertilizers by using a low cost, portable, gated CCD system in the atmospheric environment. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used as the reference technique. A method was developed to remove the outlier spectra and perform the baseline correction and peak normalization. By applying the proposed corrections, the linear correlation between LIBS and ICP increased from R = 0.76 to R = 0.95. An average error of 15% found in cross-validation of LIBS quantification appeared feasible for P quantification in fertilizers. Two reference samples with different matrix compositions were also analyzed, and the absolute error in the quantification was below 5%. Further, no significant fluctuation was found in P quantification when LIBS was performed over 150 days.

Structure of Humic Substances from Some Regions of the Amazon Assessed Coupling 3D Fluorescence Spectroscopy and CP/PARAFAC

The Amazon rainforest presents one of the greater biodiversity in the world and a huge and dynamic carbon reservoir, both in the vegetation and in the soil pools, so it is an attractive subject of study. In the present paper, humic acids from a toposequence of an Oxisol-Spodosol system associated with kaolin was studied using fluorescence emission-excitation matrix combined with parallel factor analysis. The combined techniques allowed to assess the intensities of the two different fluorophores associated with humic acid with core consistency diagnoses of 84.2%. The results for the Humiluvic Spodosol seem to corroborate the model of the supramolecular structure of humic acid, because the intensity ratio of fluorophores does not remain in the profile. Therefore, the use of these combined techniques can provide information about the transformation processes of humic substances in soils, becoming an interesting analytical tool for studying these substances of different soils.

Performance evaluation of a portable laser-induced fluorescence spectroscopy system for the assessment of the humification degree of the soil organic matter.

Laser-induced fluorescence spectroscopy (LIFS) has shown advantages for analyses of whole soil, providing results about chemical structure of soil organic matter (SOM) without the need for a chemical fractionating process; thus, allowing direct analysis of soils. Moreover, another advantage is the potential for the development of portable systems, which could be usable in field analyses. The aim of this paper is to evaluate the performance of a portable LIFS system to assess the humification degree (HD) of SOM. A good correlation (R > 0.8) was obtained for results (HD) achieved using the proposed portable system and a conventional fluorescence spectrometric method for humic acid. In addition, the results obtained using the portable LIFS system statistically agreed with the ones achieved using a benchtop LIFS system already described in the literature for such application (R = 0.953). Thus, the portable LIFS system constitutes an affordable option for the in situ characterization of SOM.

Evaluation of the Nutritional Changes Caused by Huanglongbing (HLB) to Citrus Plants Using Laser-Induced Breakdown Spectroscopy

Huanglongbing (HLB) is the most recent and destructive bacterial disease of citrus and has no cure yet. A promising alternative to conventional methods is to use laser-induced breakdown spectroscopy (LIBS), a multi-elemental analytical technique, to identify the nutritional changes provoked by the disease to the citrus leaves and associate the mineral composition profile with its health status. The leaves were collected from adult citrus trees and identified by visual inspection as healthy, HLB-symptomatic, and HLB-asymptomatic. Laser-induced breakdown spectroscopy measurements were done in fresh leaves without sample preparation. Nutritional variations were evaluated using statistical tools, such as Students t-test and analysis of variance applied to LIBS spectra, and the largest were found for Ca, Mg, and K. Considering the nutritional profile changes, a classifier induced by classification via regression combined with partial least squares regression was built resulting in an accuracy of 73% for distinguishing the three categories of leaves.

Determination of Pb in soils by double-pulse laser-induced breakdown spectroscopy assisted by continuum wave-diode laser-induced fluorescence

Laser-induced breakdown spectroscopy (LIBS) has attracted a lot of attention due to its potential to rapidly identify and quantify any chemical element with minimal sample preparation. Despite continuous improvements, the sensitivity of this technique still remains a challenge. In order to increase LIBS intensity, a laser-induced fluorescence (LIF) system can be coupled with LIBS to re-excite a transition of the element in the plasma by employing very expensive optical parametric oscillators (OPO). In this work, a homemade tunable continuum wave-diode laser (CW-DL) has been developed and coupled to a double pulse (DP) LIBS system to enhance the sensitivity of Pb detection in a soil sample at the transition 6s26p2-P32→6s26p7s-P31 at 405.78 nm. Before sample analysis, the production of no scattered light by the plasma was ascertained, and the optimal temperature of 10,000 K was estimated for this transition, feasible to be achieved in DP-LIBS systems. An increase of approximately 100% for the Pb I transition at 405.78 nm was obtained by DP-LIBS-CW-DL-LIF with respect to the DP-LIBS system alone. This result opens a new promising line of research to improve LIBS sensitivity using the CW-DL approach.

Development of a Double-Pulse (DP) Laser-Induced Breakdown Spectroscopy (LIBS) Setup in the Orthogonal Configuration for Environmental Applications

The purpose of this work was to develop and optimize the key parameters that influence the double-pulse laser-induced breakdown spectroscopy technique in the orthogonal beam geometry when applied to the elemental analysis of environmental samples.

Laser Induced Breakdown Spectroscopy as a tool for support to agriculture

In this work, we will present the main results in agriculture researches involving the use of LIBS technique for analysis in soils, plants and fertilizers. All results were achieved using a LIBS single pulse technique.