Discrimination of Genetically Very Close Accessions of Sweet Orange (Citrus sinensis L. Osbeck) by Laser-Induced Breakdown Spectroscopy (LIBS).

The correct recognition of sweet orange (Citrus sinensis L. Osbeck) variety accessions at the nursery stage of growth is a challenge for the productive sector as they do not show any difference in phenotype traits. Furthermore, there is no DNA marker able to distinguish orange accessions within a variety due to their narrow genetic trace. As different combinations of canopy and rootstock affect the uptake of elements from soil, each accession features a typical elemental concentration in the leaves. Thus, the main aim of this work was to analyze two sets of ten different accessions of very close genetic characters of three varieties of fresh citrus leaves at the nursery stage of growth by measuring the differences in elemental concentration by laser-induced breakdown spectroscopy (LIBS). The accessions were discriminated by both principal component analysis (PCA) and a classifier based on the combination of classification via regression (CVR) and partial least square regression (PLSR) models, which used the elemental concentrations measured by LIBS as input data. A correct classification of 95.1% and 80.96% was achieved, respectively, for set 1 and set 2. These results showed that LIBS is a valuable technique to discriminate among citrus accessions, which can be applied in the productive sector as an excellent cost-benefit tool in citrus breeding programs.

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.

Semiquantitative analysis of mercury in landfill leachates using double-pulse laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) is showing to be a promising, quick, accurate, and practical technique to detect and measure metal contaminants and nutrients in urban wastes and landfill leachates. Although conventional LIBS presents some limitations, such as low sensitivity, when used in the single pulse configuration if compared to other spectroscopic techniques, the use of the double-pulse (DP) configuration represents an adequate alternative. In this work DP LIBS has been applied to the qualitative and quantitative analysis of mercury (Hg) in landfill leachates. The correlation analysis performed between each intensified charge-coupled device pixel and the Hg concentration allowed us to choose the most appropriate Hg emission line to be used for its measure. The normalization process applied to LIBS spectra to correct physical matrix effects and small fluctuations increased from 0.82 to 0.98 the linear correlation of the calibration curve between LIBS and the reference data. The limit of detection for Hg estimated using DP LIBS was 76 mg Kg-1. The cross validation (leave-one-out) analysis yielded an absolute average error of about 21%. These values showed that the calibration models were close to the optimization limit and satisfactory for Hg quantification in landfill leachate.

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 (Pearson's 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.