Plasma Time Of Flight Mass Spectrometry Research Articles

Evaluation of Ultraviolet-Femtosecond-Laser Ablation-ICP-TOFMS for fast, sensitive and high-spatially resolved multi-elemental mapping of laser-deposited Hastelloy coated carbon steel

Ultraviolet Femtosecond Laser Ablation-Inductively Coupled Plasma-Time of Flight Mass Spectrometry (UV-fs-LA-ICP-TOFMS) is critically evaluated for fast multi-elemental mapping of Hastelloy coated carbon steel that was immersed in a liquid corrosive environment for two months. The Hastelloy coating, which is a multi-elemental Cr-Fe-Ni-Mo-W matrix, is produced using laser cladding technology. A UV-fs laser is employed to reduce the ablation thermal effects improving the spatial resolution in the elemental analysis of the coating, interface and substrate. Moreover, the TOFMS is equipped with ion beam attenuation grids to expand its linear dynamic range, allowing the determination of major, minor and trace elements. In particular, spatial distribution of major (e.g., Co, Ni, Fe), minor (e.g., Mn, Si) and trace (e.g., Cu, In, Zn) elements from two sequential mapping analysis were determined. Quantification is achieved through Relative Sensitivity Factors calculated using matrix-matched external reference materials and making use of measurements carried out by SEM-EDX to determine the concentration of internal standard elements. Qualitative and quantitative elemental maps highlight diffusion processes at the coating-substrate interface. Moreover, correlated spatial distributions of ion signals from external corrosive elements (e.g., 32S, 138Ba, 202Hg, 205Tl, and 209Bi) were detected in localized regions within the material and on the external surface.

Improving spatially-resolved lithium quantification in drill core samples of spodumene pegmatite by using laser-induced breakdown spectroscopy and pixel-matched reference areas

Laser ablation-inductively coupled plasma-time of flight mass spectrometry (LA-ICP-TOFMS) concentrations were used to develop accurate calibration models for laser-induced breakdown spectroscopy (LIBS) mappings of pegmatitic drill cores samples. Both methods were applied on the same area of drill core samples, providing two spatially-resolved datasets for this area. The datasets were aligned pixel by pixel to create a pixel-matched reference area that covered the heterogeneity of the complete drill core. This way, different matrix effects affecting LIBS intensities could be taken into account and accurate spatial quantification of Li2O, SiO2, Al2O3, Na2O, and K2O from LIBS measurements was enabled.In particular, LIBS intensities and LA-ICP-TOFMS concentrations of individual pixels of the reference area were used as the input for a linear Partial Least Square Regression (PLSR) and a non-linear Least Square Support Vector Machines (LS-SVM) calibration model. Varying numbers between 100 and 2000 pixels were used for model creation, and root mean square error (RMSE) and R2 of each model were compared. Better values were achieved for the LS-SVM calibration model. Based on these results, the PLSR model was discarded and only the LS-SVM model with 1000 train pixels was further validated.For two different validation areas, LA-ICP-TOFMS concentrations were compared to LIBS-based concentrations obtained from the LS-SVM calibration model. The spatially-resolved quantification results of the LIBS data agree very well with the independently analysed LA-ICP-TOFMS concentrations, which is e.g. reflected in R2 values between 0.83 and 0.96 (mean 0.89) for Li2O, SiO2, Al2O3, Na2O, and K2O. In general, it was shown that the combination of LA-ICP-TOFMS and LIBS yields a comprehensive dataset for robust multivariate calibration. This enables spatially-resolved LIBS-based quantification of pegmatite samples that are subject to significant physical and chemical matrix effects.

Fluid-rock interaction, skarn genesis, and hydrothermal alteration within an upper crustal fault zone (Island of Elba, Italy)

The Terranera magnetite-hematite-pyrite deposit of the Island of Elba (Italy) is an historical skarn deposit hosted by a fault zone of regional importance (Zuccale Fault) and by its hanging wall rocks.We combine field observations with petrographic data, electron probe microanalyses (EPMA), XRPD data, fluid inclusion microthermometry, and element imaging by Laser Ablation-Inductively Coupled Plasma-Time of Flight Mass Spectrometry (LA-ICP-TOFMS) to define the ore-forming process at Terranera. We show that in this location the fault is made of four levels of mineralized fault rocks having distinct mineral compositions. In these levels, a mineral association made of diopside, clinozoisite, and other Mg-rich minerals is replaced by magnetite, hematite, pyrite, Mg-hornblende, clinochlore, and other Mg-rich phyllosilicates. This paragenesis is overprinted by goethite and clay minerals. Chlorite-quartz geothermometry and fluid inclusion microthermometry show that ore precipitation occurred at 350–180 °C from fluids of distinct bulk salinities, but goethite and clay mineral overprinting progressed at lower T.We propose that Terranera is a magnesian Fe skarn formed due to the interaction between distinct hydrothermal fluids and a dolomitic protolith, which was preserved within the fault zone. These fluids mixed and cooled during protolith metasomatism, causing ore precipitation due to oxidation and desulfidation. A very similar process was described in a large deposit of Elba (Rio Marina). Argillic alteration was widespread within the fault but met permanently intermediate sulfidation conditions. Trace element composition of hematite shows that Terranera has features that overlap those of skarn and epithermal deposits. In particular, elements that are typical of epithermal deposits (Sb, Ga, Ge, As) occur at mass fractions (50–200 μg/g) that are either unreported or not typical of hematite from skarn deposits. These features identify Terranera as formed in an ore environment that was transitional between that of a skarn and of an epithermal deposit. These features are shared by other historical deposits located at Elba and in the massive pyritic ore district of south Tuscany (e.g., Gavorrano, Fenice Capanne). This indicates that a similar environment might have occurred during the Neogene beyond Elba, in a much larger ore district of south Tuscany.

Detection and correction of matrix interference in inductively coupled plasma – time of flight mass spectrometry by means of aerosol dispersion

The time-dependent ratio of two ion signals is used to indicate and correct for mass-dependent matrix interference in inductively coupled plasma-time of flight mass spectrometry.