Ana Rua Ibarz

@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.},

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pubstate = {published},

tppubtype = {article}

}

@article{BAZO2024343305,

title = {Intensity- and time-based strategies for micro/nano-sizing via single-particle ICP-mass spectrometry: A comparative assessment using Au and SiO2 as model particles},

author = {Antonio Bazo and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Maite Aramendía and Martín Resano},

url = {https://www.sciencedirect.com/science/article/pii/S0003267024011061},

doi = {https://doi.org/10.1016/j.aca.2024.343305},

issn = {0003-2670},

year  = {2024},

date = {2024-01-01},

urldate = {2024-01-01},

journal = {Analytica Chimica Acta},

volume = {1331},

pages = {343305},

abstract = {Background 

Single-particle ICP-mass spectrometry (SP-ICP-MS) is a powerful method for micro/nano-particle (MNP) sizing. Despite the outstanding evolution of the technique in the last decade, most studies still rely on traditional approaches based on (1) the use of integrated intensity as the analytical signal and (2) the calculation of the transport efficiency (TE). However, the increasing availability of MNP standards and advancements in hardware and software have unveiled new venues for MNP sizing, including TE-independent and time-based approaches. This work systematically examines these different methodologies to identify and summarize their strengths and weaknesses, thus helping to determine their preferred application areas. 

Results 

Different SP-ICP-MS methods for MNP sizing were assessed using AuNPs (20–70 nm) and SiO2MNPs (100–1000 nm). Among TE-dependent approaches, the particle frequency method was characterized by larger uncertainties than the particle size method. The results of the latter were dependent on the appropriate selection of the reference MNP, making the use of multiple reference MNPs recommended. TE-independent methods were based on external (linear and polynomial) calibrations and a relative approach. These methods exhibited the lowest uncertainties of all the strategies evaluated. External calibrations benefited from simpler calculations, but their application could be hindered by a lack of reference MNPs within the desired size range or by the need for interpolations outside the calibration range. Finally, transit time signals are directly proportional to the MNP size rather than its mass. The time-based method demonstrated adequate performance for sizing AuNPs but failed when sizing the largest SiO2MNPs (1000 nm). 

Significance and novelty 

This work provides further insights into the application of different SP-ICP-MS methodologies for MNP sizing. Both TE-independent approaches and the monitoring of the transit time as the analytical signal are underused strategies; in this context, a Python script was developed for accurate transit time measurement. After 20 years of development, a quantitative comparison of the different methodologies, including the most novel approaches, is deemed necessary for further growth on solid theoretical ground.},

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pubstate = {published},

tppubtype = {article}

}

@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}

}

@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}

}

@article{BOLEAFERNANDEZ201995,

title = {On the effect of using collision/reaction cell (CRC) technology in single-particle ICP-mass spectrometry (SP-ICP-MS)},

author = {Eduardo Bolea-Fernandez and Diego Leite and Ana Rua-Ibarz and Tong Liu and Glenn Woods and Maite Aramendia and Martín Resano and Frank Vanhaecke},

url = {https://www.sciencedirect.com/science/article/pii/S0003267019306920},

doi = {https://doi.org/10.1016/j.aca.2019.05.077},

issn = {0003-2670},

year  = {2019},

date = {2019-01-01},

journal = {Analytica Chimica Acta},

volume = {1077},

pages = {95-106},

abstract = {In this work, the effects of using collision/reaction cell (CRC) technology in quadrupole-based ICP-MS (ICP-QMS) instrumentation operated in single-particle (SP) mode have been assessed. The influence of (i) various CRC gases, (ii) gas flow rates, (iii) nanoparticle (NP) sizes and (iv) NP types was evaluated using Ag, Au and Pt NPs with both a traditional ICP-QMS instrument and a tandem ICP-mass spectrometer. It has been shown that using CRC technology brings about a significant increase in the NP signal peak width (from 0.5 up to 6 ms). This effect is more prominent for a heavier gas (e.g., NH3) than for a lighter one (e.g., H2 or He). At a higher gas flow rate and/or for larger particle sizes >100 nm), the NP signal duration was prolonged to a larger extent. This effect of using CRC technology has been further demonstrated by characterizing custom-made 50 and 200 nm Fe3O4 NPs (originally strongly affected by the occurrence of spectral overlap) using different CRC approaches (H2 on-mass and NH3 mass-shift). The use of NH3 (monitoring of Fe as the Fe(NH3)2+ reaction product ion at m/z = 90 amu) induces a significant peak broadening compared to that observed when using H2 (6.10 ± 1.60 vs. 0.94 ± 0.49 ms). This extension of transit time can most likely be attributed to the collisions/interactions of the ion cloud generated by a single NP event with the CRC gas and it even precludes 50 nm Fe3O4 NPs to be detected when using the NH3 mass-shift approach. Based on these results, the influence of a longer peak width on the accuracy of SP-ICP-MS measurement data (NP size, particle number density and mass concentration) must be taken into account when using CRC technology as a means to overcome spectral overlap. To mitigate the potential detrimental effect of using CRC technology in the characterization of NPs via SP-ICP-MS(/MS), the use of light gases and low gas flow rates is recommended.},

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pubstate = {published},

tppubtype = {article}

}