Coal Discrimination Analysis Using Tandem Laser-Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

The contribution and impact of combined laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS) and laser-induced breakdown spectroscopy (LIBS) were evaluated for the discrimination analysis of different coal samples. This tandem approach allows simultaneous determination of major and minor elements (C, H, Si, Ca, Al, Mg, etc.) and trace elements (V, Ba, Pb, U, etc.) in the coal. The research focused on coal-classification strategies based on principle component analysis (PCA) combined with K-means clustering, partial least-squares discrimination analysis (PLS-DA), and support vector machine (SVM) for analytical performance. Correlation analyses performed from TOF mass and LIBS emission spectra from the coal samples showed that most major, minor, and trace element emissions had negative correlation with the volatile content. Suitable variables for the classification models were determined from these data. The individual TOF data, LIBS data, and combined data of TOF and LIBS as the inputs for different models were analyzed and compared. In all cases, the results obtained with the combined TOF and LIBS data were found to be superior to those obtained with the individual TOF or LIBS data. The nonlinear SVM model combined with TOF and LIBS data provided the best coal-classification performance, with a classification accuracy of up to 98%.

Elemental Analysis of Asphaltenes Using Simultaneous Laser-Induced Breakdown Spectroscopy (LIBS)-Laser Ablation Inductively Coupled Plasma Optical Emission Spectrometry (LA-ICP-OES).

Laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma optical emission spectrometry (LA-ICP-OES) were used simultaneously for the elemental analysis of asphaltene samples using minimum sample pretreatment in combination with low laser energy to reduce the amount of removed particles and avoid carbon deposits in the ablation cell. Quantitative analyses of S, Ni, and V were accomplished with LA-ICP-OES using external calibration with the C line as internal standard. The aromatic/paraffinic nature of the asphaltenes was also obtained throughout the H/C ratio using LIBS and partial least square regression model. The results showed very good agreement (±10%) between the concentration obtained by LA-ICP-OES and microwave-assisted acid digestion values.

Analysis of Plant Leaves Using Laser Ablation Inductively Coupled Plasma Optical Emission Spectrometry: Use of Carbon to Compensate for Matrix Effects.

Direct solid sampling by laser ablation into an inductively coupled plasma synchronous vertical dual view optical emission spectroscope (LA-SVDV-ICP-OES) was used for the elemental analysis of nutrient elements Ca, B, Mn, Mg, K, and Zn and essential (non-metallic) elements P and S in plant materials. The samples were mixed with paraffin as a binder, an approach that provides better cohesion of the particles in the pellets in addition to supplying carbon to serve as an internal standard (atomic line C I 193.027 nm) as a way to compensate for matrix effects, and/or variations in the ablation process. Precision was in the range of 1-8% relative standard deviation (RSD) with limit of detection in the range of 0.4-1 mg/kg-1 and 25-640 mg/kg-1 for metallic and non-metallic elements, respectively.

Laser-Ablation Sampling for Accurate Analysis of Sulfur in Edible Salts.

We evaluated the performance of laser ablation analysis techniques such as laser-induced breakdown spectroscopy (LIBS), laser ablation inductively coupled optical emission spectrometry (LA-ICP-OES), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), in comparison with that of ICP-OES using aqueous solutions for the quantification of sulfur (S) in edible salts from different geographical origins. We found that the laser ablation based sampling techniques were not influenced by loss of S, which was observed in ICP-OES with aqueous solutions for a certain salt upon their dissolution in aqueous solutions, originating from the formation of volatile species and precipitates upon their dilution in water. Although detection of S using direct laser sampling with LA-ICP-MS has well-known isobaric and polyatomic interferences, LIBS and LA-ICP-OES showed good accuracy in the detection of S for all salts. LIBS also provided the ability to identify the dominant chemical form in which S is present in salts. Correlation between S and oxygen, observed in LIBS spectra, provided chemical information about the presence of S2- or [Formula: see text], which are associated with the origin and quality of edible salts.