Call: +34 976 761 175
Email: maiteam@unizar.es
Address: c/Pedro Cerbuna 12, Universidad de Zaragoza, Facultad de Ciencias, Departamento de Química Analítica – Zaragoza (Spain)
ABOUT ME
PUBLICATIONS
2027
Mataloni, Matilde; Bazo, Antonio; Bolea-Fernandez, Eduardo; Rua-Ibarz, Ana; Aramendía, Maite; Güemes, Lucas; Téllez, Carlos; Coronas, Joaquín; Grotti, Marco; Resano, Martín
En: Talanta, vol. 312, pp. 130379, 2027, ISSN: 0039-9140.
@article{MATALONI2027130379,
title = {Determining Si/Al atomic ratios in particulate matter via quadrupole single-particle ICP-MS with combined unit-mass and bandpass resolution modes: a proof-of-concept study on Antarctic snow},
author = {Matilde Mataloni and Antonio Bazo and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Maite Aramendía and Lucas Güemes and Carlos Téllez and Joaquín Coronas and Marco Grotti and Martín Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0039914026010350},
doi = {https://doi.org/10.1016/j.talanta.2026.130379},
issn = {0039-9140},
year = {2027},
date = {2027-01-01},
urldate = {2027-01-01},
journal = {Talanta},
volume = {312},
pages = {130379},
abstract = {Micrometer-scale mineral dust deposited in Antarctica represents a valuable archive for reconstructing atmospheric variability and for improving our understanding of dust-climate interactions. Among the various types of particle-specific information available, elemental ratios, such as the Si/Al atomic ratio, are especially useful as geochemical indicators of particle composition and provenance. However, the nature of these samples, characterized by coexisting particle populations and limited particle numbers, makes this determination particularly challenging. In this work, a novel quadrupole-based single-particle ICP-mass spectrometry (SP-ICP-QMS) approach to determine population-specific Si/Al atomic ratios containing chemically heterogeneous particle populations is presented. To overcome the sequential acquisition inherent to ICP-QMS instrumentation, Al and Si measurements at unit-mass resolution (m/z 27 and 28, respectively) were combined with bandpass acquisition centered at m/z 27 (2.47 ± 0.06 amu resolution at 10% peak height), enabling simultaneous collection of 27Al+ and 28Si + signals. This strategy was first used to identify the Al and Si distributions belonging to the same particle population and, consequently, to determine the corresponding atomic ratios in a suspension containing SiO2 microparticles (MPs) and two different types of synthesized zeolite MPs with different Si/Al atomic ratios. The reliability and accuracy of the method were confirmed by comparing the results with those obtained from individual Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDX) and SP-ICP-MS characterization of the zeolite samples. As a proof-of-concept, the analysis of an Antarctic snow sample demonstrated the potential of the developed method to provide population-specific information – Si/Al atomic ratios – essential for environmental assessments based on high-resolution short-term records.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Micrometer-scale mineral dust deposited in Antarctica represents a valuable archive for reconstructing atmospheric variability and for improving our understanding of dust-climate interactions. Among the various types of particle-specific information available, elemental ratios, such as the Si/Al atomic ratio, are especially useful as geochemical indicators of particle composition and provenance. However, the nature of these samples, characterized by coexisting particle populations and limited particle numbers, makes this determination particularly challenging. In this work, a novel quadrupole-based single-particle ICP-mass spectrometry (SP-ICP-QMS) approach to determine population-specific Si/Al atomic ratios containing chemically heterogeneous particle populations is presented. To overcome the sequential acquisition inherent to ICP-QMS instrumentation, Al and Si measurements at unit-mass resolution (m/z 27 and 28, respectively) were combined with bandpass acquisition centered at m/z 27 (2.47 ± 0.06 amu resolution at 10% peak height), enabling simultaneous collection of 27Al+ and 28Si + signals. This strategy was first used to identify the Al and Si distributions belonging to the same particle population and, consequently, to determine the corresponding atomic ratios in a suspension containing SiO2 microparticles (MPs) and two different types of synthesized zeolite MPs with different Si/Al atomic ratios. The reliability and accuracy of the method were confirmed by comparing the results with those obtained from individual Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDX) and SP-ICP-MS characterization of the zeolite samples. As a proof-of-concept, the analysis of an Antarctic snow sample demonstrated the potential of the developed method to provide population-specific information – Si/Al atomic ratios – essential for environmental assessments based on high-resolution short-term records.
2026
Souza, André L. M.; Aramendía, Maite; García-Ruiz, Esperanza; Nakadi, Flávio V.; Resano, Javier; Resano, Martín
En: J. Anal. At. Spectrom., vol. 41, pp. 1951-1963, 2026.
@article{D6JA00062B,
title = {Single- and dual-isotopic analysis using high-resolution continuum-source graphite-furnace molecular absorption. Strategies for data selection, processing, and modeling},
author = {André L. M. Souza and Maite Aramendía and Esperanza García-Ruiz and Flávio V. Nakadi and Javier Resano and Martín Resano},
url = {http://dx.doi.org/10.1039/D6JA00062B},
doi = {10.1039/D6JA00062B},
year = {2026},
date = {2026-01-01},
urldate = {2026-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {41},
pages = {1951-1963},
publisher = {The Royal Society of Chemistry},
abstract = {This work evaluates different strategies for data processing, aiming at achieving isotopic information via high-resolution continuum-source graphite-furnace molecular absorption. For this purpose, two different molecules are investigated: CaF and CaCl. In the first case, only the measurement of 44Ca and 40Ca is pursued, whereas in the second case, isotopic variations affect both elements present in the molecule (44Ca and 40Ca, but also 37Cl and 35Cl). Thus, two different approaches are proposed. For Ca isotopic analysis through the monitoring of CaF, the effects of selecting the number of detection pixels and the number of molecular spectra, as well as of using a regression approach for temporal data, are discussed. Overall, using three detector pixels and using this regression approach tend to produce the best results (0.5–1.0% RSD) for isotopic analysis via HR CS GFMAS in those situations in which the signal can be derived from two separate peaks. On the other hand, to perform simultaneous Ca and Cl isotopic analysis by monitoring CaCl, a machine-learning strategy is proposed. The performance of such a model is promising for isotopic abundances of at least 10% (median absolute percentage error of 1.21%), while the error escalates when one of the isotopes shows a lower abundance. To detect such underperforming situations in real-world settings, it is recommended to monitor the prediction uncertainty to set thresholds and flag results with poor reliability.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work evaluates different strategies for data processing, aiming at achieving isotopic information via high-resolution continuum-source graphite-furnace molecular absorption. For this purpose, two different molecules are investigated: CaF and CaCl. In the first case, only the measurement of 44Ca and 40Ca is pursued, whereas in the second case, isotopic variations affect both elements present in the molecule (44Ca and 40Ca, but also 37Cl and 35Cl). Thus, two different approaches are proposed. For Ca isotopic analysis through the monitoring of CaF, the effects of selecting the number of detection pixels and the number of molecular spectra, as well as of using a regression approach for temporal data, are discussed. Overall, using three detector pixels and using this regression approach tend to produce the best results (0.5–1.0% RSD) for isotopic analysis via HR CS GFMAS in those situations in which the signal can be derived from two separate peaks. On the other hand, to perform simultaneous Ca and Cl isotopic analysis by monitoring CaCl, a machine-learning strategy is proposed. The performance of such a model is promising for isotopic abundances of at least 10% (median absolute percentage error of 1.21%), while the error escalates when one of the isotopes shows a lower abundance. To detect such underperforming situations in real-world settings, it is recommended to monitor the prediction uncertainty to set thresholds and flag results with poor reliability.
2025
Bazo, Antonio; Bolea-Fernandez, Eduardo; Rua-Ibarz, Ana; Aramendía, Maite; Resano, Martín
En: Analytical Chemistry, vol. 97, pp. 13922-13929, 2025, ISSN: 1520-6882.
@article{,
title = {Ions with Ions, Entities with Entities: A Proof-of-Concept Study Using the SELM-1 Yeast Certified Reference Material for Intra- and Extracellular Se Quantification via Single-Cell ICP-Mass Spectrometry},
author = {Antonio Bazo and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Maite Aramendía and Martín Resano},
url = {https://pubs.acs.org/doi/10.1021/acs.analchem.5c01588},
doi = {https://doi.org/10.1021/acs.analchem.5c01588},
issn = {1520-6882},
year = {2025},
date = {2025-06-07},
urldate = {2025-06-07},
journal = {Analytical Chemistry},
volume = {97},
pages = {13922-13929},
abstract = {In this work, two novel nanoparticle (NP)-based calibration strategies, external calibration and a relative method, have been explored for single-cell ICP-mass spectrometry (SC-ICP-MS) analysis. The fundamental principle of these methods is to rely on individual entities (well-characterized NPs of the target analyte) for calibration rather than on ionic standard solutions. The performance of the NP-based calibration approaches has been compared to that of the reference method (particle size with AuNP standards). In addition to the intracellular Se content (mass per individual cell), the extracellular Se (dissolved fraction) was also determined directly and simultaneously using the average background from the SC-ICP-MS time-resolved signal. The figures-of-merit of the methods developed have been evaluated by relying on the analysis of the SELM-1 cell-certified reference material, consisting of Se-enriched yeast cells, and certified for its total Se content (intracellular + extracellular Se). All methods successfully determined the Se elemental contents, but an improvement in accuracy and precision was observed for the NP-based methods compared to the reference one. Furthermore, the NP-based methods were found to be less time-consuming, more straightforward, and more user-friendly in terms of calculations. These results open new avenues for calibration in quantitative SC-ICP-MS analysis and call for a fundamental change in the methodology, where the determination of ionic contents is based on the use of ionic standard solutions for calibration, while the determination of elemental contents in discrete micro/nanoentities, such as cells, should ideally be based on calibration using standard entities, thus avoiding the need to calculate a transport efficiency coefficient.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
In this work, two novel nanoparticle (NP)-based calibration strategies, external calibration and a relative method, have been explored for single-cell ICP-mass spectrometry (SC-ICP-MS) analysis. The fundamental principle of these methods is to rely on individual entities (well-characterized NPs of the target analyte) for calibration rather than on ionic standard solutions. The performance of the NP-based calibration approaches has been compared to that of the reference method (particle size with AuNP standards). In addition to the intracellular Se content (mass per individual cell), the extracellular Se (dissolved fraction) was also determined directly and simultaneously using the average background from the SC-ICP-MS time-resolved signal. The figures-of-merit of the methods developed have been evaluated by relying on the analysis of the SELM-1 cell-certified reference material, consisting of Se-enriched yeast cells, and certified for its total Se content (intracellular + extracellular Se). All methods successfully determined the Se elemental contents, but an improvement in accuracy and precision was observed for the NP-based methods compared to the reference one. Furthermore, the NP-based methods were found to be less time-consuming, more straightforward, and more user-friendly in terms of calculations. These results open new avenues for calibration in quantitative SC-ICP-MS analysis and call for a fundamental change in the methodology, where the determination of ionic contents is based on the use of ionic standard solutions for calibration, while the determination of elemental contents in discrete micro/nanoentities, such as cells, should ideally be based on calibration using standard entities, thus avoiding the need to calculate a transport efficiency coefficient.
Bazo, Antonio; López-Villellas, Lorién; Mataloni, Matilde; Bolea-Fernandez, Eduardo; Rua-Ibarz, Ana; Grotti, Marco; Aramendía, Maite; Resano, Martín
Improving detection and figures of merit in single-particle inductively coupled plasma-mass spectrometry via transient event heights Journal Article
En: Analytica Chimica Acta, vol. 1378, pp. 344694, 2025, ISSN: 0003-2670.
@article{BAZO2025344694,
title = {Improving detection and figures of merit in single-particle inductively coupled plasma-mass spectrometry via transient event heights},
author = {Antonio Bazo and Lorién López-Villellas and Matilde Mataloni and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Marco Grotti and Maite Aramendía and Martín Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0003267025010888},
doi = {https://doi.org/10.1016/j.aca.2025.344694},
issn = {0003-2670},
year = {2025},
date = {2025-01-01},
urldate = {2025-01-01},
journal = {Analytica Chimica Acta},
volume = {1378},
pages = {344694},
abstract = {Background
Single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is a powerful method for characterizing micro- and nanoparticulate materials. The technique primarily relies on the linear relationship between the integrated intensities of individual events (peak areas) and the analyte mass, though transit times (peak widths) have also been used for quantitative purposes. This work (1) evaluates the potential of using peak heights as analytical signals in SP-ICP-MS, (2) introduces a new method for determining peak heights, and (3) explores scenarios in which peak height offers added value over the commonly used SP-ICP-MS signals.
Results
A new method was proposed to estimate peak height values in SP-ICP-MS accurately. The cumulative intensity across consecutive dwell times was modeled using a third-degree polynomial, from which the adjusted peak height was derived. This approach reduces the uncertainty associated with using raw maximum intensity values, yielding NP distributions comparable to those obtained via integrated intensities. The effect of dwell time on peak height was also evaluated. An optimal range (50 μs–200 μs) was identified, where a linear relationship was observed between the peak height and the square of the NP diameter. Within this range, peak height showed the lowest bias when characterizing smaller NPs, indicating the potential to improve the limit of quantification (LoQ). Additionally, peak heights proved helpful in determining the limit of detection (LoD) and setting appropriate threshold values for data processing, thereby helping to flag incorrect resultsand addressing a challenge in SP-ICP-MS analysis.
Significance
This is the first study to evaluate peak height as an analytical signal in SP-ICP-MS. The results highlight its advantages in specific applications, such as sizing NPs near the LoD, and in supporting the more reliable use of other signals, such as peak areas, by helping to identify incorrect threshold selection that could lead to biased distributions. Finally, monitoring peak heights allows for a more realistic and assumption-free determination of the LoD.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Background
Single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is a powerful method for characterizing micro- and nanoparticulate materials. The technique primarily relies on the linear relationship between the integrated intensities of individual events (peak areas) and the analyte mass, though transit times (peak widths) have also been used for quantitative purposes. This work (1) evaluates the potential of using peak heights as analytical signals in SP-ICP-MS, (2) introduces a new method for determining peak heights, and (3) explores scenarios in which peak height offers added value over the commonly used SP-ICP-MS signals.
Results
A new method was proposed to estimate peak height values in SP-ICP-MS accurately. The cumulative intensity across consecutive dwell times was modeled using a third-degree polynomial, from which the adjusted peak height was derived. This approach reduces the uncertainty associated with using raw maximum intensity values, yielding NP distributions comparable to those obtained via integrated intensities. The effect of dwell time on peak height was also evaluated. An optimal range (50 μs–200 μs) was identified, where a linear relationship was observed between the peak height and the square of the NP diameter. Within this range, peak height showed the lowest bias when characterizing smaller NPs, indicating the potential to improve the limit of quantification (LoQ). Additionally, peak heights proved helpful in determining the limit of detection (LoD) and setting appropriate threshold values for data processing, thereby helping to flag incorrect resultsand addressing a challenge in SP-ICP-MS analysis.
Significance
This is the first study to evaluate peak height as an analytical signal in SP-ICP-MS. The results highlight its advantages in specific applications, such as sizing NPs near the LoD, and in supporting the more reliable use of other signals, such as peak areas, by helping to identify incorrect threshold selection that could lead to biased distributions. Finally, monitoring peak heights allows for a more realistic and assumption-free determination of the LoD.
Single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is a powerful method for characterizing micro- and nanoparticulate materials. The technique primarily relies on the linear relationship between the integrated intensities of individual events (peak areas) and the analyte mass, though transit times (peak widths) have also been used for quantitative purposes. This work (1) evaluates the potential of using peak heights as analytical signals in SP-ICP-MS, (2) introduces a new method for determining peak heights, and (3) explores scenarios in which peak height offers added value over the commonly used SP-ICP-MS signals.
Results
A new method was proposed to estimate peak height values in SP-ICP-MS accurately. The cumulative intensity across consecutive dwell times was modeled using a third-degree polynomial, from which the adjusted peak height was derived. This approach reduces the uncertainty associated with using raw maximum intensity values, yielding NP distributions comparable to those obtained via integrated intensities. The effect of dwell time on peak height was also evaluated. An optimal range (50 μs–200 μs) was identified, where a linear relationship was observed between the peak height and the square of the NP diameter. Within this range, peak height showed the lowest bias when characterizing smaller NPs, indicating the potential to improve the limit of quantification (LoQ). Additionally, peak heights proved helpful in determining the limit of detection (LoD) and setting appropriate threshold values for data processing, thereby helping to flag incorrect resultsand addressing a challenge in SP-ICP-MS analysis.
Significance
This is the first study to evaluate peak height as an analytical signal in SP-ICP-MS. The results highlight its advantages in specific applications, such as sizing NPs near the LoD, and in supporting the more reliable use of other signals, such as peak areas, by helping to identify incorrect threshold selection that could lead to biased distributions. Finally, monitoring peak heights allows for a more realistic and assumption-free determination of the LoD.
Bazo, Antonio; Bolea-Fernandez, Eduardo; Billimoria, Kharmen; Rua-Ibarz, Ana; Aramendía, Maite; Menero-Valdés, Paula; Morley, Jack; Neves, Sara; Sánchez-Cachero, Armando; Goenaga-Infante, Heidi; Resano, Martín
En: J. Anal. At. Spectrom., vol. 40, pp. 2673-2681, 2025.
@article{D5JA00253B,
title = {A novel particle mass calibration strategy for the quantification of AuNPs in single cancer cells via laser ablation ICP-mass spectrometry. A case study},
author = {Antonio Bazo and Eduardo Bolea-Fernandez and Kharmen Billimoria and Ana Rua-Ibarz and Maite Aramendía and Paula Menero-Valdés and Jack Morley and Sara Neves and Armando Sánchez-Cachero and Heidi Goenaga-Infante and Martín Resano},
url = {http://dx.doi.org/10.1039/D5JA00253B},
doi = {10.1039/D5JA00253B},
year = {2025},
date = {2025-01-01},
urldate = {2025-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {40},
pages = {2673-2681},
publisher = {The Royal Society of Chemistry},
abstract = {Laser ablation ICP-mass spectrometry (LA-ICP-MS) has developed as a powerful tool for elemental quantitative analysis of individual cells, assuring that the content of each cell is analyzed individually. However, this technique is still limited by the difficulties associated with calibration using solid standards. This work proposes a particle mass calibration strategy that is independent of both the properties and thickness of the gelatin films used for calibration, overcoming a significant drawback of previously established methods. The fundamental principle of this strategy relies on the individual ablation of nanoparticles (NPs) of well-characterized size that are embedded in the films, so that their mass can be directly used for calibration without the need to calculate their exact concentration within the gelatin. The performance of the newly developed method was compared to that of the previously reported approaches (ionic and particle number calibration) in terms of linearity and homogeneity between different films prepared from the same gelatin solution. As a case study, the three calibration strategies were used for the quantitative analysis of HeLa cancer cells exposed to AuNPs. In parallel, in-suspension single-cell (SC) ICP-MS Au data were obtained and used as reference for comparison with the three LA-SC-ICP-MS strategies. The results obtained with the novel particle mass approach demonstrated better accuracy and repeatability over three different working sessions, addressing key limitations and providing a robust and reliable method for quantitative LA-SC-ICP-MS analysis. The particle mass method holds promise for quantitative LA-ICP-MS analysis of samples beyond NP-exposed cells, such as biological tissues.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Laser ablation ICP-mass spectrometry (LA-ICP-MS) has developed as a powerful tool for elemental quantitative analysis of individual cells, assuring that the content of each cell is analyzed individually. However, this technique is still limited by the difficulties associated with calibration using solid standards. This work proposes a particle mass calibration strategy that is independent of both the properties and thickness of the gelatin films used for calibration, overcoming a significant drawback of previously established methods. The fundamental principle of this strategy relies on the individual ablation of nanoparticles (NPs) of well-characterized size that are embedded in the films, so that their mass can be directly used for calibration without the need to calculate their exact concentration within the gelatin. The performance of the newly developed method was compared to that of the previously reported approaches (ionic and particle number calibration) in terms of linearity and homogeneity between different films prepared from the same gelatin solution. As a case study, the three calibration strategies were used for the quantitative analysis of HeLa cancer cells exposed to AuNPs. In parallel, in-suspension single-cell (SC) ICP-MS Au data were obtained and used as reference for comparison with the three LA-SC-ICP-MS strategies. The results obtained with the novel particle mass approach demonstrated better accuracy and repeatability over three different working sessions, addressing key limitations and providing a robust and reliable method for quantitative LA-SC-ICP-MS analysis. The particle mass method holds promise for quantitative LA-ICP-MS analysis of samples beyond NP-exposed cells, such as biological tissues.