Call: +34 876 553 510
Email: arua@unizar.es
Address: c/Pedro Cerbuna 12, Universidad de Zaragoza, Facultad de Ciencias, Departamento de Química Analítica – Zaragoza (Spain)
ABOUT ME
Ana María Rua Ibarz obtained her Bachelor and Master degrees in Chemistry from the University of Zaragoza (Zaragoza, Spain). She carried out her PhD research at Ghent University (Ghent, Belgium) focused on method development and applications of high-precision isotopic analysis of Hg using cold-vapor generation multi-collector ICP-mass spectrometry instrumentation (CVG-MC-ICP-MS), and he obtained her PhD degree in 2018. In May 2018, after a competitive selection procedure held among international researchers, Ana obtained a postdoctoral position at the Flemish Institute for Technological Research (VITO) in Mol (Belgium), for carrying out a research project intended to explore new analytical strategies for nanoparticle characterization. In March 2020, she started working as postdoctoral researcher at Ghent University on a project in collaboration with TotalEnergies (Feluy, Belgium). The project was based on method development for quantitative elemental and spatially resolved analysis of relevant samples in petrochemistry, such as catalysts, polymers and rocks via laser ablation ICP-MS (LA-ICP-MS). Since November 2022, she is working as postdoctoral researcher at the University of Zaragoza (Spain) after she was awarded a Marie Sklodowska-Curie (MSCA)-COFUND International Fellowship Programme for Talent Attraction to the Campus of International Excellence Campus Iberus. Her research project is entitled “Exploring new venues for the characterization of nanomaterials and microplastics via plasma spectroscopy”.
PUBLICATIONS
2024
Rua-Ibarz, Ana; Acker, Thibaut Van; Bolea-Fernandez, Eduardo; Boccongelli, Marina; Vanhaecke, Frank
A comparison of calibration strategies for quantitative laser ablation ICP-mass spectrometry (LA-ICP-MS) analysis of fused catalyst samples Journal Article
En: J. Anal. At. Spectrom., vol. 39, iss. 3, pp. 888-899, 2024.
@article{D3JA00271C,
title = {A comparison of calibration strategies for quantitative laser ablation ICP-mass spectrometry (LA-ICP-MS) analysis of fused catalyst samples},
author = {Ana Rua-Ibarz and Thibaut Van Acker and Eduardo Bolea-Fernandez and Marina Boccongelli and Frank Vanhaecke},
url = {http://dx.doi.org/10.1039/D3JA00271C},
doi = {10.1039/D3JA00271C},
year = {2024},
date = {2024-01-01},
urldate = {2024-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {39},
issue = {3},
pages = {888-899},
publisher = {The Royal Society of Chemistry},
abstract = {In the field of petrochemistry, the quantitative determination of trace elements in catalysts is crucial for optimizing various types of processes. Catalyst poisoning, resulting from the presence of contaminants, can lead to decreased performance and efficiency, even when these are present at trace level only. Inductively coupled plasma-mass spectrometry (ICP-MS) is a powerful technique for trace elemental analysis, but its application to catalysts is challenging due to their physicochemical characteristics challenging straightforward dissolution. Laser ablation (LA) coupled to ICP-MS (LA-ICP-MS) has emerged as a valuable approach for direct analysis of solid samples. However, developing an appropriate calibration strategy for reliable quantitative LA-ICP-MS analysis of catalyst samples remains a challenge. In this work, different calibration strategies for quantitative LA-ICP-MS analysis of fused catalyst samples were evaluated. The traditional strategy relied on external calibration against certified reference materials (CRMs) combined with internal standardization and was considered the reference approach. When using this approach, the relative bias with respect to the reference value was found to be <15%. Two novel calibration strategies were introduced and compared: a so-called multi-signal calibration approach and a solution-based calibration approach. The multi-signal calibration strategy involved varying the laser repetition rate (20, 30, 40 and 50 Hz) or laser beam diameter (10, 12, 15 and 20 μm), allowing a calibration curve to be constructed by comparing the analytical signal intensity for a single solid CRM with that for the sample, thus partially overcoming the shortage of CRMs for quantitative LA-ICP-MS analysis. The solution-based calibration approach was used for quantitative multi-element analysis without the need for any solid standard and required only minor hardware modifications to accommodate the introduction of aqueous standard solutions for calibration. Various glass certified reference materials were used for method development, calibration, and validation purposes. Furthermore, two fused alumina catalyst samples (used in the context of petroleum refining processes) were successfully analyzed as a proof-of-concept application. For both the multi-signal (matrix-matched conditions) and the solution-based calibration approaches, the average relative bias between the experimentally determined and certified/reference concentrations varied between −9% and +7%.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Bolea-Fernandez, Eduardo; Rua-Ibarz, Ana; Anjos, Jorge Alves; Vanhaecke, Frank
En: Talanta, vol. 276, pp. 126210, 2024, ISSN: 0039-9140.
@article{BOLEAFERNANDEZ2024126210,
title = {Development and initial evaluation of a combustion-based sample introduction system for direct isotopic analysis of mercury in solid samples via multi-collector ICP-mass spectrometry},
author = {Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Jorge Alves Anjos and Frank Vanhaecke},
url = {https://www.sciencedirect.com/science/article/pii/S0039914024005897},
doi = {https://doi.org/10.1016/j.talanta.2024.126210},
issn = {0039-9140},
year = {2024},
date = {2024-01-01},
urldate = {2024-01-01},
journal = {Talanta},
volume = {276},
pages = {126210},
abstract = {High-precision isotopic analysis of mercury (Hg) using multi-collector ICP-mass spectrometry (MC-ICP-MS) is a powerful method for obtaining insight into the sources, pathways and sinks of this toxic metal. Modification of a commercially available mercury analyzer (Teledyne Leeman Labs, Hydra IIc – originally designed for quantification of Hg through sample combustion, collection of the Hg vapor on a gold amalgamator, subsequent controlled release of Hg and detection using cold vapor atomic absorption spectrometry CVAAS) enabled the system to be used for the direct high-precision Hg isotopic analysis of solid samples using MC-ICP-MS – i.e., without previous sample digestion and subsequent dilution. The changes made to the mercury analyzer did not compromise its (simultaneous) use for Hg quantification via CVAAS. The Hg vapor was mixed with a Tl-containing aerosol produced via pneumatic nebulization, creating wet plasma conditions, and enabling the use of Tl as an internal standard for correction of instrumental mass discrimination. Accurate and precise (0.10 ‰ 2SD, δ202Hg},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Freire, Bruna Moreira; Rua-Ibarz, Ana; Nakadi, Flávio Venâncio; Bolea-Fernandez, Eduardo; Barriuso-Vargas, Juan J.; Lange, Camila Neves; Aramendía, Maite; Batista, Bruno Lemos; Resano, Martín
Tracing isotopically labeled selenium nanoparticles in plants via single-particle ICP-mass spectrometry Journal Article
En: Talanta, vol. 277, pp. 126417, 2024, ISSN: 0039-9140.
@article{FREIRE2024126417,
title = {Tracing isotopically labeled selenium nanoparticles in plants via single-particle ICP-mass spectrometry},
author = {Bruna Moreira Freire and Ana Rua-Ibarz and Flávio Venâncio Nakadi and Eduardo Bolea-Fernandez and Juan J. Barriuso-Vargas and Camila Neves Lange and Maite Aramendía and Bruno Lemos Batista and Martín Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0039914024007963},
doi = {https://doi.org/10.1016/j.talanta.2024.126417},
issn = {0039-9140},
year = {2024},
date = {2024-01-01},
journal = {Talanta},
volume = {277},
pages = {126417},
abstract = {Abstract
Agronomic biofortification using selenium nanoparticles (SeNPs) shows potential for addressing selenium deficiency but further research on SeNPs-plants interaction is required before it can be effectively used to improve nutritional quality. In this work, single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) was used for tracing isotopically labeled SeNPs (82SeNPs) in Oryza sativa L. tissues. For this purpose, SeNPs with natural isotopic abundance and 82SeNPs were synthesized by a chemical method. The NPs characterization by transmission electron microscopy (TEM) confirmed that enriched NPs maintained the basic properties of unlabeled NPs, showing spherical shape, monodispersity, and sizes in the nano-range (82.8 ± 6.6 nm and 73.2 ± 4.4 nm for SeNPs and 82SeNPs, respectively). The use of 82SeNPs resulted in an 11-fold enhancement in the detection power for ICP-MS analysis, accompanied by an improvement in the signal-to-background ratio and a reduction of the size limits of detection from 89.9 to 39.9 nm in SP-ICP-MS analysis. This enabled 82SeNPs to be tracked in O. sativa L. plants cultivated under foliar application of 82SeNPs. Tracing studies combining SP-ICP-MS and TEM-energy-dispersive X-ray spectroscopy data confirmed the uptake of intact 82SeNPs by rice leaves, with most NPs remaining in the leaves and very few particles translocated to shoots and roots. Translocation of Se from leaves to roots and shoots was found to be lower when applied as NPs compared to selenite application. From the size distributions, as obtained by SP-ICP-MS, it can be concluded that a fraction of the 82SeNPs remained within the same size range as that of the applied NP suspension, while other fraction underwent an agglomeration process in the leaves, as confirmed by TEM images. This illustrates the potential of SP-ICP-MS analysis of isotopically enriched 82SeNPs for tracing NPs in the presence of background elements within complex plant matrices, providing important information about the uptake, accumulation, and biotransformation of SeNPs in rice plants.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Agronomic biofortification using selenium nanoparticles (SeNPs) shows potential for addressing selenium deficiency but further research on SeNPs-plants interaction is required before it can be effectively used to improve nutritional quality. In this work, single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) was used for tracing isotopically labeled SeNPs (82SeNPs) in Oryza sativa L. tissues. For this purpose, SeNPs with natural isotopic abundance and 82SeNPs were synthesized by a chemical method. The NPs characterization by transmission electron microscopy (TEM) confirmed that enriched NPs maintained the basic properties of unlabeled NPs, showing spherical shape, monodispersity, and sizes in the nano-range (82.8 ± 6.6 nm and 73.2 ± 4.4 nm for SeNPs and 82SeNPs, respectively). The use of 82SeNPs resulted in an 11-fold enhancement in the detection power for ICP-MS analysis, accompanied by an improvement in the signal-to-background ratio and a reduction of the size limits of detection from 89.9 to 39.9 nm in SP-ICP-MS analysis. This enabled 82SeNPs to be tracked in O. sativa L. plants cultivated under foliar application of 82SeNPs. Tracing studies combining SP-ICP-MS and TEM-energy-dispersive X-ray spectroscopy data confirmed the uptake of intact 82SeNPs by rice leaves, with most NPs remaining in the leaves and very few particles translocated to shoots and roots. Translocation of Se from leaves to roots and shoots was found to be lower when applied as NPs compared to selenite application. From the size distributions, as obtained by SP-ICP-MS, it can be concluded that a fraction of the 82SeNPs remained within the same size range as that of the applied NP suspension, while other fraction underwent an agglomeration process in the leaves, as confirmed by TEM images. This illustrates the potential of SP-ICP-MS analysis of isotopically enriched 82SeNPs for tracing NPs in the presence of background elements within complex plant matrices, providing important information about the uptake, accumulation, and biotransformation of SeNPs in rice plants.
2023
Acker, Thibaut Van; Rua-Ibarz, Ana; Vanhaecke, Frank; Bolea-Fernandez, Eduardo
Laser Ablation for Nondestructive Sampling of Microplastics in Single-Particle ICP-Mass Spectrometry Journal Article
En: Anal. Chem., vol. 95, iss. 50, pp. 18579-18586, 2023.
@article{nokey,
title = {Laser Ablation for Nondestructive Sampling of Microplastics in Single-Particle ICP-Mass Spectrometry},
author = {Thibaut Van Acker and Ana Rua-Ibarz and Frank Vanhaecke and Eduardo Bolea-Fernandez},
url = {https://doi.org/10.1021/acs.analchem.3c04473},
doi = {10.1021/acs.analchem.3c04473},
year = {2023},
date = {2023-12-05},
urldate = {2023-12-05},
journal = {Anal. Chem.},
volume = {95},
issue = {50},
pages = {18579-18586},
abstract = {In this work, laser ablation (LA) was characterized as a method for sampling and introducing microplastic particles (MPs) into an inductively coupled plasma (ICP) for subsequent 13C+ monitoring using an ICP-mass spectrometer operated in single-event mode. MPs of different types (PS, PMMA, and PVC) and sizes (2–20 μm) were introduced intactly. The laser energy density did not affect the particle sampling across a wide range (0.25–6.00 J cm–2). Single-shot analysis separated clustered MPs (2–7 MPs per cluster) during the LA and particle transport processes, allowing the temporally resolved analysis of the individual constituting MPs. Line scanning showed superior performance when using a small laser beam diameter combined with a high repetition rate. The 13C+ signal intensity correlated linearly (R2 >0.9945) with the absolute C mass in a 2–10 μm size range, while the use of He in the collision-reaction cell (CRC) allowed extension of the linear range to 20 μm. The LA approach generated narrower 13C+ signal distributions than the traditional solution-based approach (dry versus wet plasma conditions) and proved successful for the analysis of a mixed suspension (containing four sizes of PS MPs in a 2–5 μm size range) and for sampling MPs from PVDF and glass microfiber filters, with the latter offering a lower background.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
2021
Bolea-Fernandez, Eduardo; Rua-Ibarz, Ana; Resano, Martín; Vanhaecke, Frank
To shift, or not to shift: adequate selection of an internal standard in mass-shift approaches using tandem ICP-mass spectrometry (ICP-MS/MS) Journal Article
En: J. Anal. At. Spectrom., vol. 36, iss. 6, pp. 1135-1149, 2021.
@article{D0JA00438C,
title = {To shift, or not to shift: adequate selection of an internal standard in mass-shift approaches using tandem ICP-mass spectrometry (ICP-MS/MS)},
author = {Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Martín Resano and Frank Vanhaecke},
url = {http://dx.doi.org/10.1039/D0JA00438C},
doi = {10.1039/D0JA00438C},
year = {2021},
date = {2021-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {36},
issue = {6},
pages = {1135-1149},
publisher = {The Royal Society of Chemistry},
abstract = {The use of an internal standard to correct for potential matrix effects and instrument instability is common practice in ICP-MS. However, with the introduction of a new generation of ICP-MS instrumentation with a tandem mass spectrometry configuration (ICP-MS/MS), the use of chemical resolution in a mass-shift approach has become much more popular, suggesting that the appropriate selection of an internal standard needs revision. In this particular case, it needs to be decided whether the internal standard should also be subjected to a mass-shift or can simply be monitored on-mass (“to shift, or not to shift”). In this work, 17 elements covering a wide range of masses (24–205 amu) and ionization energies (3.89–9.39 eV) were measured via on-mass and/or mass-shift strategies, and the corresponding atomic ions and reaction product ions were monitored during various systematic experiments. For mass-shifting, an NH3/He gas mixture was used to obtain NH3-based reaction product ions (cluster formation). Product ion scanning (PIS) was used for assessing the differences in reactivity between the different analytes and for the identification of the best suited reaction product ions. It was found that the use of chemical resolution can significantly affect the short-term signal stability and that ion signals measured on-mass are not affected in the same way as those measured mass-shifted. Variations affecting the signal intensities of both atomic and reaction product ions can be attributed to the ion–molecule chemistry occurring within the collision/reaction cell and were found to be related with some degree of initial instability in the cell and differences in reactivity. The use of a sufficiently long stabilization time, however, avoids or at least mitigates such differences in the behavior between signals monitored on-mass and after mass-shifting, respectively. Furthermore, the introduction of cell disturbances, such as those generated after quickly switching between different sets of operating conditions in a multi-tune method, revealed significant differences in signal behavior between atomic and reaction product ions, potentially hampering the use of an internal standard monitored on-mass when the analysis is based on an analyte monitored after mass-shifting. However, the use of a reasonable waiting time again greatly mitigates such differences, with the duration of this stabilization time depending on the magnitude of the cell disturbances (e.g., switch between vented and pressurized mode or only between pressurized modes using different gas flow rates). In addition, also the effect of varying different instrument settings (plasma power, torch position, and gas and liquid flow rates) was evaluated, but no remarkable differences were found between signals monitored on-mass and those mass-shifted. Interestingly, a statistical evaluation of the influence of the different settings on the signal intensities of all ions monitored did not reveal the a priori important role of some properties traditionally suggested for adequate selection of analyte/internal standard pairs, such as mass number or ionization energy, as also suggested in other recent studies.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}