Gustavo Nicolodelli

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.

Double pulse laser induced breakdown spectroscopy: A potential tool for the analysis of contaminants and macro/micronutrients in organic mineral fertilizers.

Organic fertilizers are obtained from waste of plant or animal origin. One of the advantages of organic fertilizers is that, from the composting, it recycles waste-organic of urban and agriculture origin, whose disposal would cause environmental impacts. Fast and accurate analysis of both major and minor/trace elements contained in organic mineral and inorganic fertilizers of new generation have promoted the application of modern analytical techniques. In particular, laser induced breakdown spectroscopy (LIBS) is showing to be a very promising, quick and practical technique to detect and measure contaminants and nutrients in fertilizers. Although, this technique presents some limitations, such as a low sensitivity, if compared to other spectroscopic techniques, the use of double pulse (DP) LIBS is an alternative to the conventional LIBS in single pulse (SP). The macronutrients (Ca, Mg, K, P), micronutrients (Cu, Fe, Na, Mn, Zn) and contaminant (Cr) in fertilizer using LIBS in SP and DP configurations were evaluated. A comparative study for both configurations was performed using optimized key parameters for improving LIBS performance. The limit of detection (LOD) values obtained by DP LIBS increased up to seven times as compared to SP LIBS. In general, the marked improvement obtained when using DP system in the simultaneous LIBS quantitative determination for fertilizers analysis could be ascribed to the larger ablated mass of the sample. The results presented in this study show the promising potential of the DP LIBS technique for a qualitative analysis in fertilizers, without requiring sample preparation with chemical reagents.

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.

The importance of humin in soil characterisation: A study on Amazonian soils using different fluorescence techniques

Soil organic matter (SOM) is a complex mixture of molecules with different physicochemical properties, with humic substances (HS) being the main component as it represents around 20-50% of SOM structure. Soil of the Amazon region is considered one of the larger carbon pools of the world; thus, studies of the humic fractions are important for understanding the dynamics of organic matter (OM) in these soils. The aim of this study was to use laser-induced fluorescence spectroscopy (LIFS) and a combination of excitation-emission matrix (EEM) fluorescence with Parallel Factor Analysis (CP/PARAFAC) to assess the characteristics of humin (HU) extracted from Amazonian soils. The results obtained using LIFS showed that there was an increasing gradient of humification degree with depth, the deeper horizon presenting a higher amount of aromatic groups in the structure of HU. From the EEM, the contribution of two fluorophores with similar behaviour in the structures of HU and whole soil was assessed. Additionally, the results showed that the HU fraction might represent a larger fraction of SOM than previously thought: about 80-93% of some Amazon soils. Therefore, HU is an important humic fraction, thus indicating its role in environmental analysis, mainly in soil analysis.

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.

Depth profile investigations of surface modifications of limestone artifacts by laser-induced breakdown spectroscopy

The study of the degradation mechanisms of materials constituting historical buildings is very relevant in the context of cultural heritage preservation. In this work, a limestone sample collected from the masonry blocks of the entrance gate of historic Castello Svevo, Bari, Italy, was subjected to depth profile elemental analysis of the ablated black crust and the underlying limestone by double pulse laser-induced breakdown spectroscopy. The specific elemental components were identified and their concentrations along the sample profile analyzed, so allowing to identify the boundary between the weathered and unaltered rock. The laser-induced plasma stability, i.e., the absence of parameter changes during ablation, was verified to be constant and not to affect the elemental peak sizes during the entire depth analysis process when the plasma is confined in the ablation crater.

Direct solid surface fluorescence spectroscopy of standard chemicals and humic acid in ternary system

The front face fluorescence spectroscopy is often used to quantify chemicals in well-known matrices as it is a rapid and powerful technique, with no sample preparation. However it was not used to investigate extracted organic matter like humic substances. This work aims to fully investigate for the first time front face fluorescence spectroscopy response of a ternary system including boric acid, tryptophan and humic substances, and two binaries system containing quinine sulfate or humic substance in boric acid. Pure chemicals, boric acid, tryptophan, quinine sulfate and humic acid were mixed together in solid pellet at different contents from 0 to 100% in mass. The measurement of excitation emission matrix of fluorescence (3D fluorescence) and laser induced fluorescence were then done in the front face mode. Fluorescence matrices were decomposed using the CP/PARAFAC tools after scattering treatments. Results show that for 3D fluorescence there is no specific component for tryptophan and quinine sulfate, and that humic substances lead to a strong extinction effect for mixture containing quinine sulfate. Laser induced fluorescence gives a very good but non-specific related response for both quinine sulfate and tryptophan. No humic substances fluorescence response was found, but extinction effect is observed as for 3D fluorescence. This effect is stronger for quinine sulfate than for tryptophan. These responses were modeled using a simple absorbance versus emission model.

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.

Soil organic matter in podzol horizons of the Amazon region: Humification, recalcitrance, and dating

Characteristics of soil organic matter (SOM) are important, especially in the Amazon region, which represents one of the worlds most relevant carbon reservoirs. In this work, the concentrations of carbon and differences in its composition (humification indexes) were evaluated and compared for several horizons (0 to 390cm) of three typical Amazonian podzol profiles. Fluorescence spectroscopy was used to investigate the humic acid (HA) fractions of SOM isolated from the different samples. Simple and labile carbon structures appeared to be accumulated in surface horizons, while more complex humified compounds were leached and accumulated in intermediate and deeper Bh horizons. The results suggested that the humic acids originated from lignin and its derivatives, and that lignin could accumulate in some Bh horizons. The HA present in deeper Bh horizons appeared to originate from different formation pathways, since these horizons showed different compositions. There were significant compositional changes of HA with depth, with four types of organic matter: recalcitrant, humified, and old dating; labile and young dating; humified and young dating; and little humified and old dating. Therefore, the humification process had no direct relation with the age of the organic matter in the Amazonian podzols.