Ana Rua Ibarz

@article{RODLERRORBO2025106122,

title = {Cinnabar for Roman Ephesus: Material quality, processing and provenance},

author = {Alexandra Rodler-Rørbo and Anthony J. Baragona and Eliah J. Verbeemen and Lasse Vilien Sørensen and Berk Çakmakoğlu and Cahit Helvaci and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Frank Vanhaecke and Hilary Becker and Gilberto Artioli and Lilli Zabrana and Vinciane Debaille and Nadine Mattielli and Steven Goderis and Philippe Claeys},

url = {https://www.sciencedirect.com/science/article/pii/S0305440324001900},

doi = {https://doi.org/10.1016/j.jas.2024.106122},

issn = {0305-4403},

year  = {2025},

date = {2025-01-01},

journal = {Journal of Archaeological Science},

volume = {173},

pages = {106122},

abstract = {Ephesus was an important harbor city that flourished during the Roman period and ancient texts mention Almadén in Spain and the Cilbian fields of Ephesus as important cinnabar sources in antiquity. This work investigates whether imported cinnabar was used and whether this could be related to changes in painting activities over time. Microscopic analysis indicates a consistent preparation of cinnabar, hinting at a uniform source material quality or processing technique. However, the use of cinnabar varies among the architectural structures studied, indicating a plurality of painting techniques. A few of the analyzed cinnabar samples overlap with Turkish- and Balkan reference Pb isotope ratios; three samples from tabernas, however, deviate from this. The Hg isotope ratios reveal that cinnabar from carbonate-hosted deposits was likely used, and that processing of cinnabar included heating as suggested by ancient texts. Most notably, a correlation exists between the geochemical data and the painting technique – shifts in sourcing and cinnabar usage are potentially assignable to building chronology and/or usage. Through the lens of material provenance and processing, Ephesian cinnabar brings the organization of pigment trade into focus.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@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%.},

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pubstate = {published},

tppubtype = {article}

}

@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}

}

@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}

}

@article{DEJONGHE2024112013,

title = {An evaluation of the analytical and biological robustness of a method for quantifying iron in individual red blood cells via single-cell tandem ICP-mass spectrometry},

author = {Rinus Dejonghe and Eduardo Bolea-Fernandez and Ana Lores-Padin and Thibaut Van Acker and Ana Rua-Ibarz and Olivier De Wever and Frank Vanhaecke},

url = {https://www.sciencedirect.com/science/article/pii/S0026265X24021258},

doi = {https://doi.org/10.1016/j.microc.2024.112013},

issn = {0026-265X},

year  = {2024},

date = {2024-01-01},

journal = {Microchemical Journal},

volume = {207},

pages = {112013},

abstract = {This work evaluated the analytical and biological robustness of iron (Fe) determination in individual red blood cells (RBCs) via single-cell ICP-MS (SC-ICP-MS). RBCs were separated from other whole blood constituents using Ficoll-Paque™ density gradient centrifugation. While fixation with paraformaldehyde (PFA) led to RBC lysis, the use of glutaraldehyde (GA) left the RBCs intact and permitted storage of RBC suspensions in ultra-pure water for up to 16 months at 4 °C. GA-fixation also rendered the RBCs sufficiently robust to maintain integrity during their introduction into the ICP by means of nebulization of dilute suspensions. Obtaining quantitative data on a cell-per-cell basis required determination of the transport efficiency using the particle size method and external calibration against aqueous Fe standard solutions. The average Fe content per RBC obtained using SC-ICP-MS (103 fg/cell) agreed well with the value obtained using solution-based ICP-MS obtained after cell pellet digestion and with values obtained from literature. Variation of the cell number density in the suspensions analyzed between 1.5 × 105 and 6.0 × 105 cells per mL did not affect the result. Identical results from one-week interval blood drawings from healthy individuals demonstrate biological consistency. Compared to bulk analysis, the SC-ICP-MS approach offers the added value of providing information on the cell-to-cell heterogeneity in Fe content.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}