2015
Artículos de revista
Rello, Luis; Aramendía, Maite; Belarra, Miguel A; Resano, Martín
Lead screening in DBS by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry: application to newborns and pregnant women Artículo de revista
En: Bioanalysis, vol. 7, no 16, pp. 2057–2070, 2015, ISSN: 1757-6199.
@article{pmid26327185,
title = {Lead screening in DBS by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry: application to newborns and pregnant women},
author = {Luis Rello and Maite Aramendía and Miguel A Belarra and Martín Resano},
doi = {10.4155/bio.15.124},
issn = {1757-6199},
year = {2015},
date = {2015-01-01},
journal = {Bioanalysis},
volume = {7},
number = {16},
pages = {2057--2070},
abstract = {BACKGROUND: DBS have become a clinical specimen especially adequate for establishing home-based collection protocols. In this work, high-resolution continuum source graphite furnace atomic absorption spectrometry is evaluated for the direct monitoring of Pb in DBS, both as a quantitative tool and a screening method.
METHODOLOGY: The development of the screening model is based on the establishment of the unreliability region around the threshold limits, 100 or 50 μg l(-1). More than 500 samples were analyzed to validate the model.
CONCLUSION: The screening method demonstrated high sensitivity (the rate of true positives detected was always higher than 95%), an excellent LOD (1 µg l(-1)) and high throughput (10 min per sample).},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
BACKGROUND: DBS have become a clinical specimen especially adequate for establishing home-based collection protocols. In this work, high-resolution continuum source graphite furnace atomic absorption spectrometry is evaluated for the direct monitoring of Pb in DBS, both as a quantitative tool and a screening method.
METHODOLOGY: The development of the screening model is based on the establishment of the unreliability region around the threshold limits, 100 or 50 μg l(-1). More than 500 samples were analyzed to validate the model.
CONCLUSION: The screening method demonstrated high sensitivity (the rate of true positives detected was always higher than 95%), an excellent LOD (1 µg l(-1)) and high throughput (10 min per sample).
METHODOLOGY: The development of the screening model is based on the establishment of the unreliability region around the threshold limits, 100 or 50 μg l(-1). More than 500 samples were analyzed to validate the model.
CONCLUSION: The screening method demonstrated high sensitivity (the rate of true positives detected was always higher than 95%), an excellent LOD (1 µg l(-1)) and high throughput (10 min per sample).
Nakadi, F. V.; Veiga, M. A. M. S.; Aramendía, M.; García-Ruiz, E.; Resano, M.
Chlorine isotope determination via the monitoring of the AlCl molecule by high-resolution continuum source graphite furnace molecular absorption spectrometry – a case study Artículo de revista
En: J. Anal. At. Spectrom., vol. 30, iss. 7, pp. 1531-1540, 2015.
@article{C5JA00055F,
title = {Chlorine isotope determination via the monitoring of the AlCl molecule by high-resolution continuum source graphite furnace molecular absorption spectrometry – a case study},
author = {F. V. Nakadi and M. A. M. S. Veiga and M. Aramendía and E. García-Ruiz and M. Resano},
url = {http://dx.doi.org/10.1039/C5JA00055F},
doi = {10.1039/C5JA00055F},
year = {2015},
date = {2015-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {30},
issue = {7},
pages = {1531-1540},
publisher = {The Royal Society of Chemistry},
abstract = {This work investigates the possibility of obtaining isotopic information via the monitoring of the absorption spectra of a gaseous diatomic molecule generated in a graphite furnace and using a high-resolution (approx. 1.5 pm per pixel) monochromator (HR CS GFMAS). To test this concept, Cl was chosen as the analyte and AlCl as the target species. The results demonstrate that, unlike what occurs with atomic spectra, under optimum conditions it is possible to acquire isotopic information by HR CS GFMAS in a straightforward way, as it is feasible to observe band heads for each Cl isotope (actually, for Al35Cl and Al37Cl) that are separated, i.e., they act like two different molecules absorbing at different wavelengths. The method proposed, based upon the addition of both Pd and Al and the selection of peak height values, enables Cl isotopic analysis with precision values around 2% RSD for solutions with Cl contents at the mg L−1 level. Accurate values, within this uncertainty, can be directly obtained without requiring any method for mass bias correction. The potential of isotope dilution for calibration is also explored, and it is proven how this approach can help in providing accurate results in situations where the occurrence of chemical interferences, a case frequently encountered for the HR CS GFMAS technique, hampers the use of other calibration approaches, as demonstrated for water analysis.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work investigates the possibility of obtaining isotopic information via the monitoring of the absorption spectra of a gaseous diatomic molecule generated in a graphite furnace and using a high-resolution (approx. 1.5 pm per pixel) monochromator (HR CS GFMAS). To test this concept, Cl was chosen as the analyte and AlCl as the target species. The results demonstrate that, unlike what occurs with atomic spectra, under optimum conditions it is possible to acquire isotopic information by HR CS GFMAS in a straightforward way, as it is feasible to observe band heads for each Cl isotope (actually, for Al35Cl and Al37Cl) that are separated, i.e., they act like two different molecules absorbing at different wavelengths. The method proposed, based upon the addition of both Pd and Al and the selection of peak height values, enables Cl isotopic analysis with precision values around 2% RSD for solutions with Cl contents at the mg L−1 level. Accurate values, within this uncertainty, can be directly obtained without requiring any method for mass bias correction. The potential of isotope dilution for calibration is also explored, and it is proven how this approach can help in providing accurate results in situations where the occurrence of chemical interferences, a case frequently encountered for the HR CS GFMAS technique, hampers the use of other calibration approaches, as demonstrated for water analysis.
Aramendía, M.; Rello, L.; Bérail, S.; Donnard, A.; Pécheyran, C.; Resano, M.
En: J. Anal. At. Spectrom., vol. 30, iss. 1, pp. 296-309, 2015.
@article{C4JA00313F,
title = {Direct analysis of dried blood spots by femtosecond-laser ablation-inductively coupled plasma-mass spectrometry. Feasibility of split-flow laser ablation for simultaneous trace element and isotopic analysis},
author = {M. Aramendía and L. Rello and S. Bérail and A. Donnard and C. Pécheyran and M. Resano},
url = {http://dx.doi.org/10.1039/C4JA00313F},
doi = {10.1039/C4JA00313F},
year = {2015},
date = {2015-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {30},
issue = {1},
pages = {296-309},
publisher = {The Royal Society of Chemistry},
abstract = {This work describes a novel procedure based on the use of a 1030 nm femtosecond (fs) laser ablation (LA) device operating at a high repetition rate (30 000 Hz) coupled to a sector field-inductively coupled plasma-mass spectrometer (ICP-MS), enabling the complete ablation of dried blood spot (DBS) specimens in a reasonable time (200 s for samples of 5 μL). The integration of the complete signal obtained, in combination with the use of Pt as an internal standard (which can be added to the clinical filter paper prior to the blood deposition, ensuring compatibility with unsupervised sample collection schemes), permits obtaining an analytical response that is independent of the particular characteristics of every sample. On the basis of this methodology, an analytical method was developed for the direct determination of several elements (Cd, Co, Cu and Pb) in four blood reference materials as well as in three real samples, providing accurate results in all cases evaluated, at concentration levels ranging from 0.1 to hundreds of μg L−1. Detection limits of 0.043 (Cd), 0.42 (Co), 0.54 (Cu), and 0.040 (Pb) μg L−1 are achieved, and precision values most often range between 3 and 9% RSD. Finally, the potential to couple the LA device simultaneously to a multicollector-ICP-MS and a sector field-ICP-MS unit by split-flow is also demonstrated, thus allowing us to obtain both elemental (Co, Cu, Cd and Pb) and isotopic (Cu isotopic composition) information from every particular DBS, and therefore maximizing the amount of information that can be drawn from a single DBS specimen. Still, the precision of the approach is limited at this point, as RSD values of approx. 1500 ppm and delta variations of almost 4‰ were observed for five DBS specimens created from the same blood sample.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work describes a novel procedure based on the use of a 1030 nm femtosecond (fs) laser ablation (LA) device operating at a high repetition rate (30 000 Hz) coupled to a sector field-inductively coupled plasma-mass spectrometer (ICP-MS), enabling the complete ablation of dried blood spot (DBS) specimens in a reasonable time (200 s for samples of 5 μL). The integration of the complete signal obtained, in combination with the use of Pt as an internal standard (which can be added to the clinical filter paper prior to the blood deposition, ensuring compatibility with unsupervised sample collection schemes), permits obtaining an analytical response that is independent of the particular characteristics of every sample. On the basis of this methodology, an analytical method was developed for the direct determination of several elements (Cd, Co, Cu and Pb) in four blood reference materials as well as in three real samples, providing accurate results in all cases evaluated, at concentration levels ranging from 0.1 to hundreds of μg L−1. Detection limits of 0.043 (Cd), 0.42 (Co), 0.54 (Cu), and 0.040 (Pb) μg L−1 are achieved, and precision values most often range between 3 and 9% RSD. Finally, the potential to couple the LA device simultaneously to a multicollector-ICP-MS and a sector field-ICP-MS unit by split-flow is also demonstrated, thus allowing us to obtain both elemental (Co, Cu, Cd and Pb) and isotopic (Cu isotopic composition) information from every particular DBS, and therefore maximizing the amount of information that can be drawn from a single DBS specimen. Still, the precision of the approach is limited at this point, as RSD values of approx. 1500 ppm and delta variations of almost 4‰ were observed for five DBS specimens created from the same blood sample.
Resano, Martín; Flórez, María Rosario; Queralt, Ignasi; Marguí, Eva
En: Spectrochimica Acta Part B: Atomic Spectroscopy, vol. 105, pp. 38-46, 2015, ISSN: 0584-8547, (Dedicated to James A. Holcombe on the occasion of his retirement).
@article{RESANO201538,
title = {Determination of palladium, platinum and rhodium in used automobile catalysts and active pharmaceutical ingredients using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sample analysis},
author = {Martín Resano and María Rosario Flórez and Ignasi Queralt and Eva Marguí},
url = {https://www.sciencedirect.com/science/article/pii/S058485471400264X},
doi = {https://doi.org/10.1016/j.sab.2014.09.013},
issn = {0584-8547},
year = {2015},
date = {2015-01-01},
journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},
volume = {105},
pages = {38-46},
abstract = {This work investigates the potential of high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct determination of Pd, Pt and Rh in two samples of very different nature. While analysis of active pharmaceutical ingredients is straightforward and it is feasible to minimize matrix effects, to the point that calibration can be carried out against aqueous standard solutions, the analysis of used automobile catalysts is more challenging requiring the addition of a chemical modifier (NH4F·HF) to help in releasing the analytes, a more vigorous temperature program and the use of a solid standard (CRM ERM®-EB504) for calibration. However, in both cases it was possible to obtain accurate results and precision values typically better than 10% RSD in a fast and simple way, while only two determinations are needed for the three analytes, since Pt and Rh can be simultaneously monitored in both types of samples. Overall, the methods proposed seem suited for the determination of these analytes in such types of samples, offering a greener and faster alternative that circumvents the traditional problems associated with sample digestion, requiring a small amount of sample only (0.05mg per replicate for catalysts, and a few milligrams for the pharmaceuticals) and providing sufficient sensitivity to easily comply with regulations. The LODs achieved were 6.5μgg−1 (Pd), 8.3μgg−1 (Pt) and 9.3μgg−1 (Rh) for catalysts, which decreased to 0.08μgg−1 (Pd), 0.15μgg−1 (Pt) and 0.10μgg−1 (Rh) for pharmaceuticals.},
note = {Dedicated to James A. Holcombe on the occasion of his retirement},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work investigates the potential of high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct determination of Pd, Pt and Rh in two samples of very different nature. While analysis of active pharmaceutical ingredients is straightforward and it is feasible to minimize matrix effects, to the point that calibration can be carried out against aqueous standard solutions, the analysis of used automobile catalysts is more challenging requiring the addition of a chemical modifier (NH4F·HF) to help in releasing the analytes, a more vigorous temperature program and the use of a solid standard (CRM ERM®-EB504) for calibration. However, in both cases it was possible to obtain accurate results and precision values typically better than 10% RSD in a fast and simple way, while only two determinations are needed for the three analytes, since Pt and Rh can be simultaneously monitored in both types of samples. Overall, the methods proposed seem suited for the determination of these analytes in such types of samples, offering a greener and faster alternative that circumvents the traditional problems associated with sample digestion, requiring a small amount of sample only (0.05mg per replicate for catalysts, and a few milligrams for the pharmaceuticals) and providing sufficient sensitivity to easily comply with regulations. The LODs achieved were 6.5μgg−1 (Pd), 8.3μgg−1 (Pt) and 9.3μgg−1 (Rh) for catalysts, which decreased to 0.08μgg−1 (Pd), 0.15μgg−1 (Pt) and 0.10μgg−1 (Rh) for pharmaceuticals.
Bolea-Fernandez, Eduardo; Balcaen, Lieve; Resano, Martín; Vanhaecke, Frank
Interference-free determination of ultra-trace concentrations of arsenic and selenium using methyl fluoride as a reaction gas in ICP-MS/MS Artículo de revista
En: Anal Bioanal Chem, vol. 407, no 3, pp. 919–929, 2015, ISSN: 1618-2650.
@article{pmid25260411,
title = {Interference-free determination of ultra-trace concentrations of arsenic and selenium using methyl fluoride as a reaction gas in ICP-MS/MS},
author = {Eduardo Bolea-Fernandez and Lieve Balcaen and Martín Resano and Frank Vanhaecke},
doi = {10.1007/s00216-014-8195-8},
issn = {1618-2650},
year = {2015},
date = {2015-01-01},
journal = {Anal Bioanal Chem},
volume = {407},
number = {3},
pages = {919--929},
abstract = {Interference-free conditions, allowing straightforward As and Se determination, can be obtained by using CH3F (a mixture of 10% CH3F and 90% He) as a reaction gas in tandem ICP-mass spectrometry (ICP-MS/MS). Both target elements react via CH3F addition and subsequent HF elimination, rendering AsCH2 (+) and SeCH2 (+) the respective favored reaction product ions. Instrumental limits of detection were 0.2 ng L(-1) for As and below 10 ng L(-1) for Se, using either (77)Se, (78)Se, or (80)Se. Neither addition of carbon to the solutions, nor admixing of additional He into the octopole reaction cell resulted in a further improvement of the LoDs, despite the increase in analyte signal intensity. By using synthetic matrices, containing elements giving rise to ions interfering at either the original mass-to-charge ratios or those of the reaction products, absence of spectral overlap could be demonstrated. This conclusion was corroborated by successful As and Se determination in a collection of reference materials from plant, animal, or environmental origin, displaying a considerable range of As and Se contents. These accurate results were obtained via external calibration using Te as an internal standard. The high efficiency reaction between As and CH3F and the possibility to use the major isotope of Se provides enhanced detection power versus other techniques, such as sector-field ICP-mass spectrometry, while the possibility to monitor at least three Se isotopes interference-free also enables isotopic analysis.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Interference-free conditions, allowing straightforward As and Se determination, can be obtained by using CH3F (a mixture of 10% CH3F and 90% He) as a reaction gas in tandem ICP-mass spectrometry (ICP-MS/MS). Both target elements react via CH3F addition and subsequent HF elimination, rendering AsCH2 (+) and SeCH2 (+) the respective favored reaction product ions. Instrumental limits of detection were 0.2 ng L(-1) for As and below 10 ng L(-1) for Se, using either (77)Se, (78)Se, or (80)Se. Neither addition of carbon to the solutions, nor admixing of additional He into the octopole reaction cell resulted in a further improvement of the LoDs, despite the increase in analyte signal intensity. By using synthetic matrices, containing elements giving rise to ions interfering at either the original mass-to-charge ratios or those of the reaction products, absence of spectral overlap could be demonstrated. This conclusion was corroborated by successful As and Se determination in a collection of reference materials from plant, animal, or environmental origin, displaying a considerable range of As and Se contents. These accurate results were obtained via external calibration using Te as an internal standard. The high efficiency reaction between As and CH3F and the possibility to use the major isotope of Se provides enhanced detection power versus other techniques, such as sector-field ICP-mass spectrometry, while the possibility to monitor at least three Se isotopes interference-free also enables isotopic analysis.
2014
Artículos de revista
Bolea-Fernandez, Eduardo; Balcaen, Lieve; Resano, Martín; Vanhaecke, Frank
En: Anal Chem, vol. 86, no 15, pp. 7969–7977, 2014, ISSN: 1520-6882.
@article{pmid25062450,
title = {Potential of methyl fluoride as a universal reaction gas to overcome spectral interference in the determination of ultratrace concentrations of metals in biofluids using inductively coupled plasma-tandem mass spectrometry},
author = {Eduardo Bolea-Fernandez and Lieve Balcaen and Martín Resano and Frank Vanhaecke},
doi = {10.1021/ac502023h},
issn = {1520-6882},
year = {2014},
date = {2014-08-01},
journal = {Anal Chem},
volume = {86},
number = {15},
pages = {7969--7977},
abstract = {Methyl fluoride (a mixture of 10% CH3F and 90% of He) was evaluated as a reaction gas in inductively coupled plasma-tandem mass spectrometry (ICPMS/MS) in the context of the determination of ultratrace concentrations of medically relevant metals (Al, Co, Cr, Mn, Ni, Ti, and V) in blood serum and urine. Via product ion scanning, whereby only ions of the mass-to-charge ratio of the target nuclide were admitted into the octopole reaction cell, the various reaction product ions formed for each of the target elements were identified at different CH3F gas flow rates. Limits of detection (LODs) and of quantification (LOQs) and linearity of the calibration curve were documented under (i) optimized ICPMS/MS conditions for single-element monitoring and (ii) compromise conditions, allowing for multielement determination. Even under compromise settings, instrumental LODs were below 10 ng/L for all target elements, while the use of CH3F provided interference-free conditions for their determination in the biofluids of interest. Quantitative data obtained for Seronorm blood serum and urine reference materials were in excellent agreement with the corresponding reference values and/or results obtained using double-focusing sector-field ICPMS (for those elements for which no certified values were available or that were affected during reconstitution), proving the potential of this reaction gas for multielement ultratrace analysis via ICPMS/MS. },
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Methyl fluoride (a mixture of 10% CH3F and 90% of He) was evaluated as a reaction gas in inductively coupled plasma-tandem mass spectrometry (ICPMS/MS) in the context of the determination of ultratrace concentrations of medically relevant metals (Al, Co, Cr, Mn, Ni, Ti, and V) in blood serum and urine. Via product ion scanning, whereby only ions of the mass-to-charge ratio of the target nuclide were admitted into the octopole reaction cell, the various reaction product ions formed for each of the target elements were identified at different CH3F gas flow rates. Limits of detection (LODs) and of quantification (LOQs) and linearity of the calibration curve were documented under (i) optimized ICPMS/MS conditions for single-element monitoring and (ii) compromise conditions, allowing for multielement determination. Even under compromise settings, instrumental LODs were below 10 ng/L for all target elements, while the use of CH3F provided interference-free conditions for their determination in the biofluids of interest. Quantitative data obtained for Seronorm blood serum and urine reference materials were in excellent agreement with the corresponding reference values and/or results obtained using double-focusing sector-field ICPMS (for those elements for which no certified values were available or that were affected during reconstitution), proving the potential of this reaction gas for multielement ultratrace analysis via ICPMS/MS.
Resano, M; Flórez, M R; García-Ruiz, E
Progress in the determination of metalloids and non-metals by means of high-resolution continuum source atomic or molecular absorption spectrometry. A critical review Artículo de revista
En: Anal Bioanal Chem, vol. 406, no 9-10, pp. 2239–2259, 2014, ISSN: 1618-2650.
@article{pmid24317519,
title = {Progress in the determination of metalloids and non-metals by means of high-resolution continuum source atomic or molecular absorption spectrometry. A critical review},
author = {M Resano and M R Flórez and E García-Ruiz},
doi = {10.1007/s00216-013-7522-9},
issn = {1618-2650},
year = {2014},
date = {2014-04-01},
journal = {Anal Bioanal Chem},
volume = {406},
number = {9-10},
pages = {2239--2259},
abstract = {This work examines the new possibilities introduced with the arrival of commercially available high-resolution continuum source atomic absorption spectrometers for the determination of metalloids (B, Si, Ge, As, Se, Sb and Te) and non-metals (P, S, F, Cl, Br, I and N-based species), such as the improved potential to detect and correct for spectral overlaps and the strategies available to correct for matrix effects. In particular, and considering the increasing number of papers reporting on the use of molecular absorption spectrometry using graphite furnaces and flames as vaporizers, the work discusses in detail the advantages and limitations derived from the monitoring of molecular spectra from a practical point of view, in an attempt to guide future users of the technique. },
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work examines the new possibilities introduced with the arrival of commercially available high-resolution continuum source atomic absorption spectrometers for the determination of metalloids (B, Si, Ge, As, Se, Sb and Te) and non-metals (P, S, F, Cl, Br, I and N-based species), such as the improved potential to detect and correct for spectral overlaps and the strategies available to correct for matrix effects. In particular, and considering the increasing number of papers reporting on the use of molecular absorption spectrometry using graphite furnaces and flames as vaporizers, the work discusses in detail the advantages and limitations derived from the monitoring of molecular spectra from a practical point of view, in an attempt to guide future users of the technique.
Balcaen, Lieve; Bolea-Fernandez, Eduardo; Resano, Martín; Vanhaecke, Frank
Accurate determination of ultra-trace levels of Ti in blood serum using ICP-MS/MS Artículo de revista
En: Analytica Chimica Acta, vol. 809, pp. 1-8, 2014, ISSN: 0003-2670.
@article{BALCAEN20141,
title = {Accurate determination of ultra-trace levels of Ti in blood serum using ICP-MS/MS},
author = {Lieve Balcaen and Eduardo Bolea-Fernandez and Martín Resano and Frank Vanhaecke},
url = {https://www.sciencedirect.com/science/article/pii/S0003267013013251},
doi = {https://doi.org/10.1016/j.aca.2013.10.017},
issn = {0003-2670},
year = {2014},
date = {2014-01-01},
journal = {Analytica Chimica Acta},
volume = {809},
pages = {1-8},
abstract = {Ti is frequently used in implants and prostheses and it has been shown before that the presence of these in the human body can lead to elevated Ti concentrations in body fluids such as serum and urine. As identification of the exact mechanisms responsible for this increase in Ti concentrations, and the risks associated with it, are not fully understood, it is important to have sound analytical methods that enable straightforward quantification of Ti levels in body fluids (for both implanted and non-implanted individuals). Until now, only double-focusing sector field ICP-mass spectrometry (SF-ICP-MS) offered limits of detection that are good enough to deal with the very low basal levels of Ti in human serum. This work reports on the development of a novel method for the accurate and precise determination of trace levels of Ti in human serum samples, based on the use of ICP-MS/MS. O2 and NH3/He have been compared as reaction gases. While the use of O2 did not enable to overcome all spectral interferences, it has been shown that conversion of Ti+ ions into Ti(NH3)6+ cluster ions by using NH3/He as a reaction gas in an ICP-QQQ-MS system, operated in MS/MS mode, provided interference-free conditions and sufficiently low limits of detection, down to 3ngL−1 (instrumental detection limit obtained for the most abundant Ti isotope). The accuracy of the method proposed was evaluated by analysis of a Seronorm Trace Elements Serum L-1 reference material and by comparing the results obtained with those achieved by means of SF-ICP-MS. As a proof-of-concept, the newly developed method was successfully applied to the determination of Ti in serum samples obtained from individuals with and without Ti-based implants. All results were found to be in good agreement with those obtained by means of SF-ICP-MS. The typical basal Ti level in human serum was found to be <1μgL−1, while values in the range of 2–6μgL−1 were observed for implanted patients.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Ti is frequently used in implants and prostheses and it has been shown before that the presence of these in the human body can lead to elevated Ti concentrations in body fluids such as serum and urine. As identification of the exact mechanisms responsible for this increase in Ti concentrations, and the risks associated with it, are not fully understood, it is important to have sound analytical methods that enable straightforward quantification of Ti levels in body fluids (for both implanted and non-implanted individuals). Until now, only double-focusing sector field ICP-mass spectrometry (SF-ICP-MS) offered limits of detection that are good enough to deal with the very low basal levels of Ti in human serum. This work reports on the development of a novel method for the accurate and precise determination of trace levels of Ti in human serum samples, based on the use of ICP-MS/MS. O2 and NH3/He have been compared as reaction gases. While the use of O2 did not enable to overcome all spectral interferences, it has been shown that conversion of Ti+ ions into Ti(NH3)6+ cluster ions by using NH3/He as a reaction gas in an ICP-QQQ-MS system, operated in MS/MS mode, provided interference-free conditions and sufficiently low limits of detection, down to 3ngL−1 (instrumental detection limit obtained for the most abundant Ti isotope). The accuracy of the method proposed was evaluated by analysis of a Seronorm Trace Elements Serum L-1 reference material and by comparing the results obtained with those achieved by means of SF-ICP-MS. As a proof-of-concept, the newly developed method was successfully applied to the determination of Ti in serum samples obtained from individuals with and without Ti-based implants. All results were found to be in good agreement with those obtained by means of SF-ICP-MS. The typical basal Ti level in human serum was found to be <1μgL−1, while values in the range of 2–6μgL−1 were observed for implanted patients.
Resano, Martín; Aramendía, Maite; Belarra, Miguel A.
High-resolution continuum source graphite furnace atomic absorption spectrometry for direct analysis of solid samples and complex materials: a tutorial review Artículo de revista
En: J. Anal. At. Spectrom., vol. 29, iss. 12, pp. 2229-2250, 2014.
@article{C4JA00176A,
title = {High-resolution continuum source graphite furnace atomic absorption spectrometry for direct analysis of solid samples and complex materials: a tutorial review},
author = {Martín Resano and Maite Aramendía and Miguel A. Belarra},
url = {http://dx.doi.org/10.1039/C4JA00176A},
doi = {10.1039/C4JA00176A},
year = {2014},
date = {2014-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {29},
issue = {12},
pages = {2229-2250},
publisher = {The Royal Society of Chemistry},
abstract = {The purpose of this review is to examine the literature devoted to direct sample analysis using high-resolution continuum source atomic absorption spectrometry in a tutorial way, in an attempt to provide guidelines on the most critical issues to consider when developing a new method. This review discusses in detail the advantages and limitations of this technique, highlighting its benefits in comparison with classic line source atomic absorption spectrometry instrumentation in the context of direct analysis of solid samples, slurries and complex liquid samples, trying to establish in which situations the use of this technique can be particularly beneficial. Some of the aspects that are addressed comprise: (i) the improved potential to detect and correct for spectral interferences; (ii) the different options to adjust the sensitivity to the analyte content; (iii) strategies to minimize matrix effects and calibrate with aqueous standard solutions; (iv) possibilities to carry out multi-element analysis.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The purpose of this review is to examine the literature devoted to direct sample analysis using high-resolution continuum source atomic absorption spectrometry in a tutorial way, in an attempt to provide guidelines on the most critical issues to consider when developing a new method. This review discusses in detail the advantages and limitations of this technique, highlighting its benefits in comparison with classic line source atomic absorption spectrometry instrumentation in the context of direct analysis of solid samples, slurries and complex liquid samples, trying to establish in which situations the use of this technique can be particularly beneficial. Some of the aspects that are addressed comprise: (i) the improved potential to detect and correct for spectral interferences; (ii) the different options to adjust the sensitivity to the analyte content; (iii) strategies to minimize matrix effects and calibrate with aqueous standard solutions; (iv) possibilities to carry out multi-element analysis.
Rocha, Hugo; Castiñeiras, Daisy; Delgado, Carmen; Egea, José; Yahyaoui, Raquel; González, Yolanda; Conde, Manuel; González, Inmaculada; Rueda, Inmaculada; Rello, Luis; Vilarinho, Laura; Cocho, José
Birth Prevalence of Fatty Acid β-Oxidation Disorders in Iberia Artículo de revista
En: JIMD Rep, vol. 16, pp. 89–94, 2014, ISSN: 2192-8304.
@article{pmid25012579,
title = {Birth Prevalence of Fatty Acid β-Oxidation Disorders in Iberia},
author = {Hugo Rocha and Daisy Castiñeiras and Carmen Delgado and José Egea and Raquel Yahyaoui and Yolanda González and Manuel Conde and Inmaculada González and Inmaculada Rueda and Luis Rello and Laura Vilarinho and José Cocho},
doi = {10.1007/8904_2014_324},
issn = {2192-8304},
year = {2014},
date = {2014-01-01},
journal = {JIMD Rep},
volume = {16},
pages = {89--94},
abstract = {Mitochondrial fatty acid β-oxidation disorders (FAOD) are main targets for newborn screening (NBS) programs, which are excellent data sources for accurate estimations of disease birth prevalence. Epidemiological data is of key importance for the understanding of the natural history of the disorders as well as to define more effective public health strategies. In order to estimate FAOD birth prevalence in Iberia, the authors collected data from six NBS programs from Portugal and Spain, encompassing the screening of more than 1.6 million newborns by tandem mass spectrometry (MS/MS), and compared it with available data from other populations. The participating NBS programs are responsible for the screening of about 46% of all Iberian newborns. Data reveals that Iberia has one of the highest FAOD prevalence in Europe (1:7,914) and that Portugal has the highest birth prevalence of FAOD reported so far (1:6,351), strongly influenced by the high prevalence of medium-chain acyl-CoA dehydrogenase deficiency (MCADD; 1:8,380), one of the highest ever reported. This is justified by the fact that more than 90% of Portuguese MCADD patients are of Gypsy origin, a community characterized by a high degree of consanguinity. From the comparative analysis of various populations with comparable data other differences emerge, which points to the existence of significant variations in FAOD prevalences among different populations, but without any clear European variation pattern. Considering that FAOD are one of the justifications for MS/MS NBS, the now estimated birth prevalences stress the need to screen all Iberian newborns for this group of inherited metabolic disorders. },
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Mitochondrial fatty acid β-oxidation disorders (FAOD) are main targets for newborn screening (NBS) programs, which are excellent data sources for accurate estimations of disease birth prevalence. Epidemiological data is of key importance for the understanding of the natural history of the disorders as well as to define more effective public health strategies. In order to estimate FAOD birth prevalence in Iberia, the authors collected data from six NBS programs from Portugal and Spain, encompassing the screening of more than 1.6 million newborns by tandem mass spectrometry (MS/MS), and compared it with available data from other populations. The participating NBS programs are responsible for the screening of about 46% of all Iberian newborns. Data reveals that Iberia has one of the highest FAOD prevalence in Europe (1:7,914) and that Portugal has the highest birth prevalence of FAOD reported so far (1:6,351), strongly influenced by the high prevalence of medium-chain acyl-CoA dehydrogenase deficiency (MCADD; 1:8,380), one of the highest ever reported. This is justified by the fact that more than 90% of Portuguese MCADD patients are of Gypsy origin, a community characterized by a high degree of consanguinity. From the comparative analysis of various populations with comparable data other differences emerge, which points to the existence of significant variations in FAOD prevalences among different populations, but without any clear European variation pattern. Considering that FAOD are one of the justifications for MS/MS NBS, the now estimated birth prevalences stress the need to screen all Iberian newborns for this group of inherited metabolic disorders.
2013
Artículos de revista
Vanaelst, Barbara; Michels, Nathalie; Huybrechts, Inge; Clays, Els; Flórez, Maria R; Balcaen, Lieve; Resano, Martin; Aramendia, Maite; Vanhaecke, Frank; Rivet, Noellie; Raul, Jean-Sebastien; Lanfer, Anne; Henauw, Stefaan De
Cross-sectional relationship between chronic stress and mineral concentrations in hair of elementary school girls Artículo de revista
En: Biol Trace Elem Res, vol. 153, no 1-3, pp. 41–49, 2013, ISSN: 1559-0720.
@article{pmid23546894,
title = {Cross-sectional relationship between chronic stress and mineral concentrations in hair of elementary school girls},
author = {Barbara Vanaelst and Nathalie Michels and Inge Huybrechts and Els Clays and Maria R Flórez and Lieve Balcaen and Martin Resano and Maite Aramendia and Frank Vanhaecke and Noellie Rivet and Jean-Sebastien Raul and Anne Lanfer and Stefaan De Henauw},
doi = {10.1007/s12011-013-9647-2},
issn = {1559-0720},
year = {2013},
date = {2013-06-01},
journal = {Biol Trace Elem Res},
volume = {153},
number = {1-3},
pages = {41--49},
abstract = {Chronic stress exposure is associated with diverse negative health outcomes. It has been hypothesised that stress may also negatively affect the body's mineral status. This study investigates the association between chronic stress and long-term mineral concentrations of calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), phosphorus (P) and zinc (Zn) in scalp hair among elementary school girls. Complete information on child-reported stress estimates (Coddington Life Events Scale (CLES)), hair cortisone and hair mineral concentrations, and predefined confounders in the stress-mineral relationship (i.e. age, body mass index, physical activity, diet, hair colour and parental education) was provided cross-sectionally for 140 girls (5-10 years old). The relationship between childhood stress measures (predictor) and hair minerals (outcome) was studied using linear regression analysis, adjusted for the abovementioned confounders. Hair cortisone concentrations were inversely associated with hair mineral concentrations of Ca, Mg, Zn and the Ca/P ratio. Children at risk by life events (CLES) presented an elevated Ca/Mg ratio. These findings were persistent after adjustment for confounders. This study demonstrated an independent association between chronic stress measures and hair mineral levels in young girls, indicating the importance of physiological stress-mineral pathways independently from individual or behavioural factors. Findings need to be confirmed in a more heterogeneous population and on longitudinal basis. The precise mechanisms by which stress alters hair mineral levels should be further elucidated.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Chronic stress exposure is associated with diverse negative health outcomes. It has been hypothesised that stress may also negatively affect the body’s mineral status. This study investigates the association between chronic stress and long-term mineral concentrations of calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), phosphorus (P) and zinc (Zn) in scalp hair among elementary school girls. Complete information on child-reported stress estimates (Coddington Life Events Scale (CLES)), hair cortisone and hair mineral concentrations, and predefined confounders in the stress-mineral relationship (i.e. age, body mass index, physical activity, diet, hair colour and parental education) was provided cross-sectionally for 140 girls (5-10 years old). The relationship between childhood stress measures (predictor) and hair minerals (outcome) was studied using linear regression analysis, adjusted for the abovementioned confounders. Hair cortisone concentrations were inversely associated with hair mineral concentrations of Ca, Mg, Zn and the Ca/P ratio. Children at risk by life events (CLES) presented an elevated Ca/Mg ratio. These findings were persistent after adjustment for confounders. This study demonstrated an independent association between chronic stress measures and hair mineral levels in young girls, indicating the importance of physiological stress-mineral pathways independently from individual or behavioural factors. Findings need to be confirmed in a more heterogeneous population and on longitudinal basis. The precise mechanisms by which stress alters hair mineral levels should be further elucidated.
Mattsson, Niklas; Andreasson, Ulf; Persson, Staffan; Carrillo, Maria C; Collins, Steven; Chalbot, Sonia; Cutler, Neal; Dufour-Rainfray, Diane; Fagan, Anne M; Heegaard, Niels H H; Hsiung, Ging-Yuek Robin; Hyman, Bradley; Iqbal, Khalid; Kaeser, Stephan A; Lachno, D Richard; Lleó, Alberto; Lewczuk, Piotr; Molinuevo, José L; Parchi, Piero; Regeniter, Axel; Rissman, Robert A; Rosenmann, Hanna; Sancesario, Giuseppe; Schröder, Johannes; Shaw, Leslie M; Teunissen, Charlotte E; Trojanowski, John Q; Vanderstichele, Hugo; Vandijck, Manu; Verbeek, Marcel M; Zetterberg, Henrik; and, Kaj Blennow
CSF biomarker variability in the Alzheimer’s Association quality control program Artículo de revista
En: Alzheimers Dement, vol. 9, no 3, pp. 251–261, 2013, ISSN: 1552-5279.
@article{pmid23622690,
title = {CSF biomarker variability in the Alzheimer's Association quality control program},
author = {Niklas Mattsson and Ulf Andreasson and Staffan Persson and Maria C Carrillo and Steven Collins and Sonia Chalbot and Neal Cutler and Diane Dufour-Rainfray and Anne M Fagan and Niels H H Heegaard and Ging-Yuek Robin Hsiung and Bradley Hyman and Khalid Iqbal and Stephan A Kaeser and D Richard Lachno and Alberto Lleó and Piotr Lewczuk and José L Molinuevo and Piero Parchi and Axel Regeniter and Robert A Rissman and Hanna Rosenmann and Giuseppe Sancesario and Johannes Schröder and Leslie M Shaw and Charlotte E Teunissen and John Q Trojanowski and Hugo Vanderstichele and Manu Vandijck and Marcel M Verbeek and Henrik Zetterberg and Kaj Blennow and },
doi = {10.1016/j.jalz.2013.01.010},
issn = {1552-5279},
year = {2013},
date = {2013-05-01},
journal = {Alzheimers Dement},
volume = {9},
number = {3},
pages = {251--261},
abstract = {BACKGROUND: The cerebrospinal fluid (CSF) biomarkers amyloid beta 1-42, total tau, and phosphorylated tau are used increasingly for Alzheimer's disease (AD) research and patient management. However, there are large variations in biomarker measurements among and within laboratories.
METHODS: Data from the first nine rounds of the Alzheimer's Association quality control program was used to define the extent and sources of analytical variability. In each round, three CSF samples prepared at the Clinical Neurochemistry Laboratory (Mölndal, Sweden) were analyzed by single-analyte enzyme-linked immunosorbent assay (ELISA), a multiplexing xMAP assay, or an immunoassay with electrochemoluminescence detection.
RESULTS: A total of 84 laboratories participated. Coefficients of variation (CVs) between laboratories were around 20% to 30%; within-run CVs, less than 5% to 10%; and longitudinal within-laboratory CVs, 5% to 19%. Interestingly, longitudinal within-laboratory CV differed between biomarkers at individual laboratories, suggesting that a component of it was assay dependent. Variability between kit lots and between laboratories both had a major influence on amyloid beta 1-42 measurements, but for total tau and phosphorylated tau, between-kit lot effects were much less than between-laboratory effects. Despite the measurement variability, the between-laboratory consistency in classification of samples (using prehoc-derived cutoffs for AD) was high (>90% in 15 of 18 samples for ELISA and in 12 of 18 samples for xMAP).
CONCLUSIONS: The overall variability remains too high to allow assignment of universal biomarker cutoff values for a specific intended use. Each laboratory must ensure longitudinal stability in its measurements and use internally qualified cutoff levels. Further standardization of laboratory procedures and improvement of kit performance will likely increase the usefulness of CSF AD biomarkers for researchers and clinicians.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
BACKGROUND: The cerebrospinal fluid (CSF) biomarkers amyloid beta 1-42, total tau, and phosphorylated tau are used increasingly for Alzheimer’s disease (AD) research and patient management. However, there are large variations in biomarker measurements among and within laboratories.
METHODS: Data from the first nine rounds of the Alzheimer’s Association quality control program was used to define the extent and sources of analytical variability. In each round, three CSF samples prepared at the Clinical Neurochemistry Laboratory (Mölndal, Sweden) were analyzed by single-analyte enzyme-linked immunosorbent assay (ELISA), a multiplexing xMAP assay, or an immunoassay with electrochemoluminescence detection.
RESULTS: A total of 84 laboratories participated. Coefficients of variation (CVs) between laboratories were around 20% to 30%; within-run CVs, less than 5% to 10%; and longitudinal within-laboratory CVs, 5% to 19%. Interestingly, longitudinal within-laboratory CV differed between biomarkers at individual laboratories, suggesting that a component of it was assay dependent. Variability between kit lots and between laboratories both had a major influence on amyloid beta 1-42 measurements, but for total tau and phosphorylated tau, between-kit lot effects were much less than between-laboratory effects. Despite the measurement variability, the between-laboratory consistency in classification of samples (using prehoc-derived cutoffs for AD) was high (>90% in 15 of 18 samples for ELISA and in 12 of 18 samples for xMAP).
CONCLUSIONS: The overall variability remains too high to allow assignment of universal biomarker cutoff values for a specific intended use. Each laboratory must ensure longitudinal stability in its measurements and use internally qualified cutoff levels. Further standardization of laboratory procedures and improvement of kit performance will likely increase the usefulness of CSF AD biomarkers for researchers and clinicians.
METHODS: Data from the first nine rounds of the Alzheimer’s Association quality control program was used to define the extent and sources of analytical variability. In each round, three CSF samples prepared at the Clinical Neurochemistry Laboratory (Mölndal, Sweden) were analyzed by single-analyte enzyme-linked immunosorbent assay (ELISA), a multiplexing xMAP assay, or an immunoassay with electrochemoluminescence detection.
RESULTS: A total of 84 laboratories participated. Coefficients of variation (CVs) between laboratories were around 20% to 30%; within-run CVs, less than 5% to 10%; and longitudinal within-laboratory CVs, 5% to 19%. Interestingly, longitudinal within-laboratory CV differed between biomarkers at individual laboratories, suggesting that a component of it was assay dependent. Variability between kit lots and between laboratories both had a major influence on amyloid beta 1-42 measurements, but for total tau and phosphorylated tau, between-kit lot effects were much less than between-laboratory effects. Despite the measurement variability, the between-laboratory consistency in classification of samples (using prehoc-derived cutoffs for AD) was high (>90% in 15 of 18 samples for ELISA and in 12 of 18 samples for xMAP).
CONCLUSIONS: The overall variability remains too high to allow assignment of universal biomarker cutoff values for a specific intended use. Each laboratory must ensure longitudinal stability in its measurements and use internally qualified cutoff levels. Further standardization of laboratory procedures and improvement of kit performance will likely increase the usefulness of CSF AD biomarkers for researchers and clinicians.
Vanaelst, Barbara; Huybrechts, Inge; Michels, Nathalie; Flórez, Maria R; Aramendía, Maite; Balcaen, Lieve; Resano, Martin; Vanhaecke, Frank; Bammann, Karin; Bel-Serrat, Silvia; Henauw, Stefaan De
Hair minerals and metabolic health in Belgian elementary school girls Artículo de revista
En: Biol Trace Elem Res, vol. 151, no 3, pp. 335–343, 2013, ISSN: 1559-0720.
@article{pmid23254772,
title = {Hair minerals and metabolic health in Belgian elementary school girls},
author = {Barbara Vanaelst and Inge Huybrechts and Nathalie Michels and Maria R Flórez and Maite Aramendía and Lieve Balcaen and Martin Resano and Frank Vanhaecke and Karin Bammann and Silvia Bel-Serrat and Stefaan De Henauw},
doi = {10.1007/s12011-012-9573-8},
issn = {1559-0720},
year = {2013},
date = {2013-03-01},
journal = {Biol Trace Elem Res},
volume = {151},
number = {3},
pages = {335--343},
abstract = {Literature has repeatedly shown a relationship between hair minerals and metabolic health, although studies in children are currently lacking. This study aims to investigate hair levels of calcium (Ca), copper (Cu), magnesium (Mg), iron (Fe), phosphorus (P), and zinc (Zn) and their association with (1) overweight/obesity and (2) metabolic health in Flemish elementary school girls between 5 and 10 years old. Two hundred eighteen girls participated in this study as part of the baseline ChiBS project. Children were subjected to physical examinations, blood and hair sampling. Hair minerals were quantitatively determined via inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion. Body mass index (BMI) and body fat percentage (BF%) were studied as anthropometric parameters, and a metabolic score (including systolic and diastolic blood pressure, insulin resistance and non-high-density lipoprotein (non-HDL) cholesterol as parameters) was calculated, with higher scores indicating a more unhealthy metabolic profile. Hair Ca, Ca/Mg, and Ca/P positively correlated with the anthropometric parameters. An inverse correlation was observed between Ca, Mg, and Ca/P in hair and the metabolic score. Inverse correlations were also observed for individual metabolic parameters (i.e., diastolic blood pressure, homeostasis model assessment for insulin resistance, non-HDL cholesterol). In particular, girls with a total number of three or more metabolic parameters above the age-specific 75th percentile showed significantly reduced hair Ca, Mg, and Ca/P concentrations. This study showed reduced hair mineral concentrations in young girls with a more unhealthy metabolic profile. Positive associations were observed between some minerals and BMI and BF%.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Literature has repeatedly shown a relationship between hair minerals and metabolic health, although studies in children are currently lacking. This study aims to investigate hair levels of calcium (Ca), copper (Cu), magnesium (Mg), iron (Fe), phosphorus (P), and zinc (Zn) and their association with (1) overweight/obesity and (2) metabolic health in Flemish elementary school girls between 5 and 10 years old. Two hundred eighteen girls participated in this study as part of the baseline ChiBS project. Children were subjected to physical examinations, blood and hair sampling. Hair minerals were quantitatively determined via inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion. Body mass index (BMI) and body fat percentage (BF%) were studied as anthropometric parameters, and a metabolic score (including systolic and diastolic blood pressure, insulin resistance and non-high-density lipoprotein (non-HDL) cholesterol as parameters) was calculated, with higher scores indicating a more unhealthy metabolic profile. Hair Ca, Ca/Mg, and Ca/P positively correlated with the anthropometric parameters. An inverse correlation was observed between Ca, Mg, and Ca/P in hair and the metabolic score. Inverse correlations were also observed for individual metabolic parameters (i.e., diastolic blood pressure, homeostasis model assessment for insulin resistance, non-HDL cholesterol). In particular, girls with a total number of three or more metabolic parameters above the age-specific 75th percentile showed significantly reduced hair Ca, Mg, and Ca/P concentrations. This study showed reduced hair mineral concentrations in young girls with a more unhealthy metabolic profile. Positive associations were observed between some minerals and BMI and BF%.
Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank
Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology Artículo de revista
En: Anal Bioanal Chem, vol. 405, no 9, pp. 2973–2986, 2013, ISSN: 1618-2650.
@article{pmid23180083,
title = {Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology},
author = {Eleonora Balliana and Maite Aramendía and Martin Resano and Carlo Barbante and Frank Vanhaecke},
doi = {10.1007/s00216-012-6542-1},
issn = {1618-2650},
year = {2013},
date = {2013-03-01},
journal = {Anal Bioanal Chem},
volume = {405},
number = {9},
pages = {2973--2986},
abstract = {Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of “non-traditional” isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.
Flórez, M. R.; Resano, M.
Direct determination of bromine in plastic materials by means of solid sampling high-resolution continuum source graphite furnace molecular absorption spectrometry Artículo de revista
En: Spectrochimica Acta Part B: Atomic Spectroscopy, vol. 88, pp. 32-39, 2013, ISSN: 0584-8547.
@article{FLOREZ201332,
title = {Direct determination of bromine in plastic materials by means of solid sampling high-resolution continuum source graphite furnace molecular absorption spectrometry},
author = {M. R. Flórez and M. Resano},
url = {https://www.sciencedirect.com/science/article/pii/S058485471300222X},
doi = {https://doi.org/10.1016/j.sab.2013.07.013},
issn = {0584-8547},
year = {2013},
date = {2013-01-01},
journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},
volume = {88},
pages = {32-39},
abstract = {This work investigates the potential of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers, which could be interesting in view of the current regulations restricting the use of organobrominated compounds. The method developed is based on the addition of Ca (300μg) and Pd (30μg) to favor the formation of CaBr, which is monitored at the main molecular “lines” (rotational spectra) found in the vicinity of 625.315nm. It was found that accurate results could be obtained for all the samples investigated (polyethylene, polypropylene and acrylonitrile butadiene styrene certified reference materials) using any of the lines studied and constructing the calibration curve with aqueous standards. Furthermore, the combined use of the main four CaBr lines available in the spectral area simultaneously monitored permits to easily expand the linear range up to 2000ng, provides a limit of detection of 1.8ng (1.8μgg−1 for a mass of 1mg) and further improves precision to values between 3–7% RSD. Overall, the method proposed seems suited for the fast and simple control of these types of samples (approximately 10min for sample are required), circumventing the traditional problems associated with sample digestion (e.g., losses of volatile compounds), and providing sufficient sensitivity to easily comply with regulations.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work investigates the potential of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers, which could be interesting in view of the current regulations restricting the use of organobrominated compounds. The method developed is based on the addition of Ca (300μg) and Pd (30μg) to favor the formation of CaBr, which is monitored at the main molecular “lines” (rotational spectra) found in the vicinity of 625.315nm. It was found that accurate results could be obtained for all the samples investigated (polyethylene, polypropylene and acrylonitrile butadiene styrene certified reference materials) using any of the lines studied and constructing the calibration curve with aqueous standards. Furthermore, the combined use of the main four CaBr lines available in the spectral area simultaneously monitored permits to easily expand the linear range up to 2000ng, provides a limit of detection of 1.8ng (1.8μgg−1 for a mass of 1mg) and further improves precision to values between 3–7% RSD. Overall, the method proposed seems suited for the fast and simple control of these types of samples (approximately 10min for sample are required), circumventing the traditional problems associated with sample digestion (e.g., losses of volatile compounds), and providing sufficient sensitivity to easily comply with regulations.
Rello, L.; Lapeña, A. C.; Aramendía, M.; Belarra, M. A.; Resano, M.
A dried urine spot test to simultaneously monitor Mo and Ti levels using solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry Artículo de revista
En: Spectrochimica Acta Part B: Atomic Spectroscopy, vol. 81, pp. 11-19, 2013, ISSN: 0584-8547.
@article{RELLO201311,
title = {A dried urine spot test to simultaneously monitor Mo and Ti levels using solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry},
author = {L. Rello and A. C. Lapeña and M. Aramendía and M. A. Belarra and M. Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0584854712003734},
doi = {https://doi.org/10.1016/j.sab.2012.12.001},
issn = {0584-8547},
year = {2013},
date = {2013-01-01},
journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},
volume = {81},
pages = {11-19},
abstract = {Home-based collection protocols for clinical specimens are actively pursued as a means of improving life quality of patients that require frequent controls, such as patients with metallic prosthesis, for whom monitoring the evolution of Mo and Ti in biological fluids may play a decisive role to detect prosthesis mal-functioning. The collection of biological fluids on clinical filter papers provides a simple way to implement these protocols. This work explores the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the simultaneous and direct determination of Mo and Ti in urine, after its deposition onto clinical filter paper, giving rise to a dried urine spot. The approach used for depositing the sample was found crucial to develop a quantitative method, since the filter paper acts as a chromatographic support and produces a differential distribution of the target analytes. Furthermore, the high spreading of urine onto a filter paper results in a small amount of urine per surface unit, and thus, ultimately, in lack of sensitivity. In order to circumvent these problems, the use of an alternative approach based on the use of pre-cut 17×19mm filter paper pieces onto which larger amounts of sample (500μL) can be retained by single deposition was proposed and evaluated. In this way, an approximately 12-fold increase in sensitivity and a more homogeneous distribution of the target analytes were obtained, permitting the development of a quantification strategy based on the use of matrix-matched urine samples of known analyte concentrations, which were subjected to the same procedure as the samples. Accuracy of this method, which provides LODs of 1.5μgL−1 for Mo and 6.5μgL−1 for Ti, was demonstrated after analysis of urine reference materials. Overall, the performance of the method developed is promising, being likely suitable for determination of other analytes in dried urine spots.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Home-based collection protocols for clinical specimens are actively pursued as a means of improving life quality of patients that require frequent controls, such as patients with metallic prosthesis, for whom monitoring the evolution of Mo and Ti in biological fluids may play a decisive role to detect prosthesis mal-functioning. The collection of biological fluids on clinical filter papers provides a simple way to implement these protocols. This work explores the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the simultaneous and direct determination of Mo and Ti in urine, after its deposition onto clinical filter paper, giving rise to a dried urine spot. The approach used for depositing the sample was found crucial to develop a quantitative method, since the filter paper acts as a chromatographic support and produces a differential distribution of the target analytes. Furthermore, the high spreading of urine onto a filter paper results in a small amount of urine per surface unit, and thus, ultimately, in lack of sensitivity. In order to circumvent these problems, the use of an alternative approach based on the use of pre-cut 17×19mm filter paper pieces onto which larger amounts of sample (500μL) can be retained by single deposition was proposed and evaluated. In this way, an approximately 12-fold increase in sensitivity and a more homogeneous distribution of the target analytes were obtained, permitting the development of a quantification strategy based on the use of matrix-matched urine samples of known analyte concentrations, which were subjected to the same procedure as the samples. Accuracy of this method, which provides LODs of 1.5μgL−1 for Mo and 6.5μgL−1 for Ti, was demonstrated after analysis of urine reference materials. Overall, the performance of the method developed is promising, being likely suitable for determination of other analytes in dried urine spots.
Flórez, María R.; Aramendía, Maite; Resano, Martín; Lapeña, Ana C.; Balcaen, Lieve; Vanhaecke, Frank
Isotope ratio mapping by means of laser ablation-single collector-ICP-mass spectrometry: Zn tracer studies in thin sections of Daphnia magna Artículo de revista
En: J. Anal. At. Spectrom., vol. 28, iss. 7, pp. 1005-1015, 2013.
@article{C3JA50087J,
title = {Isotope ratio mapping by means of laser ablation-single collector-ICP-mass spectrometry: Zn tracer studies in thin sections of Daphnia magna},
author = {María R. Flórez and Maite Aramendía and Martín Resano and Ana C. Lapeña and Lieve Balcaen and Frank Vanhaecke},
url = {http://dx.doi.org/10.1039/C3JA50087J},
doi = {10.1039/C3JA50087J},
year = {2013},
date = {2013-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {28},
issue = {7},
pages = {1005-1015},
publisher = {The Royal Society of Chemistry},
abstract = {In this paper, the possibilities of LA-single collector-ICP-mass spectrometry for obtaining isotope ratio images of thin sections of Daphnia magna specimens exposed to isotopically enriched Zn tracers were evaluated. Zn was selected considering its importance in ecotoxicological studies. All aspects of the analytical methodology deployed were carefully studied and optimized for obtaining the best isotope ratio precision and accuracy. The development of this methodological approach consisted of: (i) evaluation of the performance of two different medium mass resolution exit slits, a conventional one providing a mass resolution of m/Δm ≈ 4000 and triangular shaped peaks, and another (wider) one, offering a lower mass resolution (m/Δm ≈ 2000), but providing enhanced ion transmission and flat-topped peaks; (ii) the use of a wet plasma for improving plasma robustness; (iii) thorough optimization of the ablation conditions (such as laser spot size, repetition rate, scan speed and laser fluence) and data acquisition parameters (such as scan mode, the number of nuclides monitored, mass window, the number of samples per peak and dwell times); and (iv) adequate data treatment including the use of the moving average of 5 individual values. With the methodology developed, isotope ratio images with 30 micrometer spatial resolution scale were obtained for exposed and unexposed Daphnia magna individuals. The typical overall uncertainty of the measurements was approximately 5% RSD for the 66Zn/64Zn and 68Zn/64Zn ratios, which can be considered as satisfactory taking into account that the amount of Zn present per 30 μm × 30 μm pixel only reached a few picograms in the most favourable cases (giving rise to 10 000–20 000 counts per s for 64Zn). These results open the possibility for tracer studies with stable isotopes to be carried out using single collector instrumentation, a much more widespread analytical technique than multi-collector ICP-MS.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
In this paper, the possibilities of LA-single collector-ICP-mass spectrometry for obtaining isotope ratio images of thin sections of Daphnia magna specimens exposed to isotopically enriched Zn tracers were evaluated. Zn was selected considering its importance in ecotoxicological studies. All aspects of the analytical methodology deployed were carefully studied and optimized for obtaining the best isotope ratio precision and accuracy. The development of this methodological approach consisted of: (i) evaluation of the performance of two different medium mass resolution exit slits, a conventional one providing a mass resolution of m/Δm ≈ 4000 and triangular shaped peaks, and another (wider) one, offering a lower mass resolution (m/Δm ≈ 2000), but providing enhanced ion transmission and flat-topped peaks; (ii) the use of a wet plasma for improving plasma robustness; (iii) thorough optimization of the ablation conditions (such as laser spot size, repetition rate, scan speed and laser fluence) and data acquisition parameters (such as scan mode, the number of nuclides monitored, mass window, the number of samples per peak and dwell times); and (iv) adequate data treatment including the use of the moving average of 5 individual values. With the methodology developed, isotope ratio images with 30 micrometer spatial resolution scale were obtained for exposed and unexposed Daphnia magna individuals. The typical overall uncertainty of the measurements was approximately 5% RSD for the 66Zn/64Zn and 68Zn/64Zn ratios, which can be considered as satisfactory taking into account that the amount of Zn present per 30 μm × 30 μm pixel only reached a few picograms in the most favourable cases (giving rise to 10 000–20 000 counts per s for 64Zn). These results open the possibility for tracer studies with stable isotopes to be carried out using single collector instrumentation, a much more widespread analytical technique than multi-collector ICP-MS.
Resano, M.; Flórez, M. R.; García-Ruiz, E.
High-resolution continuum source atomic absorption spectrometry for the simultaneous or sequential monitoring of multiple lines. A critical review of current possibilities Artículo de revista
En: Spectrochimica Acta Part B: Atomic Spectroscopy, vol. 88, pp. 85-97, 2013, ISSN: 0584-8547.
@article{RESANO201385,
title = {High-resolution continuum source atomic absorption spectrometry for the simultaneous or sequential monitoring of multiple lines. A critical review of current possibilities},
author = {M. Resano and M. R. Flórez and E. García-Ruiz},
url = {https://www.sciencedirect.com/science/article/pii/S0584854713001596},
doi = {https://doi.org/10.1016/j.sab.2013.06.004},
issn = {0584-8547},
year = {2013},
date = {2013-01-01},
journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},
volume = {88},
pages = {85-97},
abstract = {This work examines the capabilities and limitations of commercially available high-resolution continuum source atomic absorption spectrometry instrumentation for multi-line monitoring, discussing in detail the possible strategies to develop multi-element methodologies that are truly simultaneous, or else sequential, but from the same sample aliquot. Moreover, the simultaneous monitoring of various atomic or molecular lines may bring other important analytical advantages, such as: i) expansion of the linear range by monitoring multiplets; ii) improvements in the limit of detection and in precision by summing the signals from different lines of the same element or molecule; iii) simple correction for matrix-effects by selecting a suitable internal standard; or iv) accurate mathematical correction of spectral overlaps by simultaneous monitoring of free lines of the interfering molecule or element. This work discusses how authors have made use of these strategies to develop analytical methodologies that permit the straightforward analysis of complex samples.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work examines the capabilities and limitations of commercially available high-resolution continuum source atomic absorption spectrometry instrumentation for multi-line monitoring, discussing in detail the possible strategies to develop multi-element methodologies that are truly simultaneous, or else sequential, but from the same sample aliquot. Moreover, the simultaneous monitoring of various atomic or molecular lines may bring other important analytical advantages, such as: i) expansion of the linear range by monitoring multiplets; ii) improvements in the limit of detection and in precision by summing the signals from different lines of the same element or molecule; iii) simple correction for matrix-effects by selecting a suitable internal standard; or iv) accurate mathematical correction of spectral overlaps by simultaneous monitoring of free lines of the interfering molecule or element. This work discusses how authors have made use of these strategies to develop analytical methodologies that permit the straightforward analysis of complex samples.
Resano, Martín; Lapeña, Ana C.; Belarra, Miguel A.
En: Anal. Methods, vol. 5, iss. 5, pp. 1130-1139, 2013.
@article{C2AY26456K,
title = {Potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry to monitor the Ag body burden in individual Daphnia magna specimens exposed to Ag nanoparticles},
author = {Martín Resano and Ana C. Lapeña and Miguel A. Belarra},
url = {http://dx.doi.org/10.1039/C2AY26456K},
doi = {10.1039/C2AY26456K},
year = {2013},
date = {2013-01-01},
journal = {Anal. Methods},
volume = {5},
issue = {5},
pages = {1130-1139},
publisher = {The Royal Society of Chemistry},
abstract = {This work evaluates the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) for the direct determination of the Ag body burden in individual specimens of Daphnia magna (a small aquatic invertebrate of approx. 2 mm length typically used in ecotoxicological studies) exposed to different Ag species, and particularly to Ag nanoparticles (NPs). It is shown that this technique offers unique features for this type of application, permitting the direct analysis of these organisms in a very straightforward way (only approx. 2–3 min are required for the analysis of every individual) and constructing the calibration curve with aqueous standards. Moreover, appropriate selection of the detector pixels used for signal quantification makes it feasible to achieve a very broad linear range for any set of experimental conditions, contrary to what occurs for traditional line source-GFAAS. This feature is particularly important for this application, as every Daphnia magna specimen can be measured only once and its Ag content is not known in advance. In this case, the use of central and/or side pixels permits achieving a working range between 3 pg and 1 μg for the 328.068 nm Ag line, thus allowing analysis of all the samples of interest with the same experimental settings.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work evaluates the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) for the direct determination of the Ag body burden in individual specimens of Daphnia magna (a small aquatic invertebrate of approx. 2 mm length typically used in ecotoxicological studies) exposed to different Ag species, and particularly to Ag nanoparticles (NPs). It is shown that this technique offers unique features for this type of application, permitting the direct analysis of these organisms in a very straightforward way (only approx. 2–3 min are required for the analysis of every individual) and constructing the calibration curve with aqueous standards. Moreover, appropriate selection of the detector pixels used for signal quantification makes it feasible to achieve a very broad linear range for any set of experimental conditions, contrary to what occurs for traditional line source-GFAAS. This feature is particularly important for this application, as every Daphnia magna specimen can be measured only once and its Ag content is not known in advance. In this case, the use of central and/or side pixels permits achieving a working range between 3 pg and 1 μg for the 328.068 nm Ag line, thus allowing analysis of all the samples of interest with the same experimental settings.
Resano, Martín; Bolea-Fernández, Eduardo; Mozas, Engracia; Flórez, María R.; Grinberg, Patricia; Sturgeon, Ralph E.
Simultaneous determination of Co, Fe, Ni and Pb in carbon nanotubes by means of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry Artículo de revista
En: J. Anal. At. Spectrom., vol. 28, iss. 5, pp. 657-665, 2013.
@article{C3JA30377B,
title = {Simultaneous determination of Co, Fe, Ni and Pb in carbon nanotubes by means of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry},
author = {Martín Resano and Eduardo Bolea-Fernández and Engracia Mozas and María R. Flórez and Patricia Grinberg and Ralph E. Sturgeon},
url = {http://dx.doi.org/10.1039/C3JA30377B},
doi = {10.1039/C3JA30377B},
year = {2013},
date = {2013-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {28},
issue = {5},
pages = {657-665},
publisher = {The Royal Society of Chemistry},
abstract = {This work explores the possibilities of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct analysis of carbon nanotubes. In particular, the simultaneous determination of Co, Fe, Ni and Pb is intended, as these elements are typically found in these samples as impurities. The results demonstrate that it is possible to find spectral (monitoring of the region between 283.168 and 283.481 nm), furnace (2500 °C for atomization; use of 100 ng Pd as a chemical modifier) and detector (use of side pixels to expand the linear range) conditions that permit the development of a fast and straightforward method for the simultaneous determination of the target elements at the levels at which they are typically found (mg g−1 for Co, Fe and Ni; μg g−1 for Pb) in carbon nanotubes. Limits of detection of 23 pg (Pb), 6 ng (Fe), 65 ng (Ni) and 86 ng (Co) were obtained, which are suitable for this type of sample. In this way, it was feasible to carry out the analysis of the samples investigated (one candidate reference material and three commercially available samples) and achieve accurate results when constructing the calibration curve with aqueous standards. Precision values for 5 solid sample replicates varied between 7 and 15% RSD in most cases. Overall, the proposed method shows important benefits for the cost-effective analysis of such complex samples in routine labs.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work explores the possibilities of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct analysis of carbon nanotubes. In particular, the simultaneous determination of Co, Fe, Ni and Pb is intended, as these elements are typically found in these samples as impurities. The results demonstrate that it is possible to find spectral (monitoring of the region between 283.168 and 283.481 nm), furnace (2500 °C for atomization; use of 100 ng Pd as a chemical modifier) and detector (use of side pixels to expand the linear range) conditions that permit the development of a fast and straightforward method for the simultaneous determination of the target elements at the levels at which they are typically found (mg g−1 for Co, Fe and Ni; μg g−1 for Pb) in carbon nanotubes. Limits of detection of 23 pg (Pb), 6 ng (Fe), 65 ng (Ni) and 86 ng (Co) were obtained, which are suitable for this type of sample. In this way, it was feasible to carry out the analysis of the samples investigated (one candidate reference material and three commercially available samples) and achieve accurate results when constructing the calibration curve with aqueous standards. Precision values for 5 solid sample replicates varied between 7 and 15% RSD in most cases. Overall, the proposed method shows important benefits for the cost-effective analysis of such complex samples in routine labs.