Call: +34 876 553 503
Email: garciae@unizar.es
Address: c/Pedro Cerbuna 12, Universidad de Zaragoza, Facultad de Ciencias, Departamento de Química Analítica – Zaragoza (Spain)
ABOUT ME
PUBLICATIONS
2017
Guarda, Ananda; Aramendía, Maite; Andrés, Irene; García-Ruiz, Esperanza; Nascimento, Paulo Cícero; Resano, Martín
En: Talanta, vol. 162, pp. 354-361, 2017, ISSN: 0039-9140.
@article{GUARDA2017354,
title = {Determination of chlorine via the CaCl molecule by high-resolution continuum source graphite furnace molecular absorption spectrometry and direct solid sample analysis},
author = {Ananda Guarda and Maite Aramendía and Irene Andrés and Esperanza García-Ruiz and Paulo Cícero Nascimento and Martín Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0039914016307913},
doi = {https://doi.org/10.1016/j.talanta.2016.10.039},
issn = {0039-9140},
year = {2017},
date = {2017-01-01},
journal = {Talanta},
volume = {162},
pages = {354-361},
abstract = {This work investigates the possibilities of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of Cl in solid samples via the CaCl molecule and measurement of its molecular absorption. The method proposed is based on addition of 400µg Ca as molecule-forming reagent and of 20µgPd as chemical modifier, which helps to stabilize the analyte and enhances sensitivity. The molecular spectrum for CaCl offers different lines with different limits of detection and linear ranges, which permitted to analyze solid samples with different Cl contents. The lowest limit of detection (0.75ng Cl, corresponding to 0.75µgg−1 for a typical sample mass of 1mg) could be achieved by combination of three of the most sensitive lines in the vicinity of 620.862nm, while the amplest linear range (up to 860ng Cl) was achieved by selection of the less sensitive line at 377.501nm. The method developed enabled the direct determination of Cl in solid samples using simple external calibration with aqueous standards. Good precision (5–9% RSD) and accuracy was attained in a series of certified samples of very different nature (i.e. coal, iron oxide, polyethylene, human hair, pine needles, rice flour and milk) and with very different Cl contents, ranging from about 50µgg−1 to 1% (w/w) Cl. The method appears as particularly useful for Cl determination in samples with elevated Ca contents, for which biased results with other diatomic molecules, such as AlCl or SrCl, may be obtained.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work investigates the possibilities of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of Cl in solid samples via the CaCl molecule and measurement of its molecular absorption. The method proposed is based on addition of 400µg Ca as molecule-forming reagent and of 20µgPd as chemical modifier, which helps to stabilize the analyte and enhances sensitivity. The molecular spectrum for CaCl offers different lines with different limits of detection and linear ranges, which permitted to analyze solid samples with different Cl contents. The lowest limit of detection (0.75ng Cl, corresponding to 0.75µgg−1 for a typical sample mass of 1mg) could be achieved by combination of three of the most sensitive lines in the vicinity of 620.862nm, while the amplest linear range (up to 860ng Cl) was achieved by selection of the less sensitive line at 377.501nm. The method developed enabled the direct determination of Cl in solid samples using simple external calibration with aqueous standards. Good precision (5–9% RSD) and accuracy was attained in a series of certified samples of very different nature (i.e. coal, iron oxide, polyethylene, human hair, pine needles, rice flour and milk) and with very different Cl contents, ranging from about 50µgg−1 to 1% (w/w) Cl. The method appears as particularly useful for Cl determination in samples with elevated Ca contents, for which biased results with other diatomic molecules, such as AlCl or SrCl, may be obtained.
2016
Nakadi, F. V.; Veiga, M. A. M. S.; Aramendía, M.; García-Ruiz, E.; Resano, M.
En: J. Anal. At. Spectrom., vol. 31, iss. 7, pp. 1381-1390, 2016.
@article{C6JA00114A,
title = {Br isotope determination via the monitoring of CaBr transitions using high-resolution continuum source graphite furnace molecular absorption spectrometry. Potential for direct determination of Br in solid samples using isotope dilution},
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/C6JA00114A},
doi = {10.1039/C6JA00114A},
year = {2016},
date = {2016-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {31},
issue = {7},
pages = {1381-1390},
publisher = {The Royal Society of Chemistry},
abstract = {This work investigates the possibility of obtaining Br isotopic information by generating a gaseous diatomic molecule in a graphite furnace and monitoring its absorption spectrum using a high-resolution continuum source device (HR CS GFMAS). Different metals (Al, Ba, and Ca) were investigated to produce this diatomic molecule and the most promising results, both in terms of isotopic shift and sensitivity, were obtained with Ca, thus leaving CaBr as the target species. The results demonstrate that, unlike what occurs when monitoring atomic spectra, which are characterized by very small isotopic shifts that can hardly be detected, using HR CS GFMAS it is feasible to observe several molecular transitions corresponding to Ca79Br and Ca81Br that are spectrally resolved (i.e. they act like two different molecules absorbing at different wavelengths), and can be simultaneously quantified. The method developed relies on the addition of both Pd and Ca (as a chemical modifier and molecule forming agent, respectively), the selection of peak height values and the use of IBC-m (iterative baseline correction for the monitoring of molecules) for setting the baseline. This method enables accurate Br isotopic analysis in 10 mg L−1 solutions with precision values around 2.5% RSD, without requiring any method for mass bias correction. Moreover, it is also demonstrated how the use of isotope dilution for calibration can help in circumventing severe chemical interferences (e.g., deriving from the presence of high amounts of Cl) when aiming at the direct determination of Br in solid samples by HR CS GFMAS. The accuracy of the method was evaluated via analysis of two different reference materials, poly(vinyl chloride) and tomato leaves.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work investigates the possibility of obtaining Br isotopic information by generating a gaseous diatomic molecule in a graphite furnace and monitoring its absorption spectrum using a high-resolution continuum source device (HR CS GFMAS). Different metals (Al, Ba, and Ca) were investigated to produce this diatomic molecule and the most promising results, both in terms of isotopic shift and sensitivity, were obtained with Ca, thus leaving CaBr as the target species. The results demonstrate that, unlike what occurs when monitoring atomic spectra, which are characterized by very small isotopic shifts that can hardly be detected, using HR CS GFMAS it is feasible to observe several molecular transitions corresponding to Ca79Br and Ca81Br that are spectrally resolved (i.e. they act like two different molecules absorbing at different wavelengths), and can be simultaneously quantified. The method developed relies on the addition of both Pd and Ca (as a chemical modifier and molecule forming agent, respectively), the selection of peak height values and the use of IBC-m (iterative baseline correction for the monitoring of molecules) for setting the baseline. This method enables accurate Br isotopic analysis in 10 mg L−1 solutions with precision values around 2.5% RSD, without requiring any method for mass bias correction. Moreover, it is also demonstrated how the use of isotope dilution for calibration can help in circumventing severe chemical interferences (e.g., deriving from the presence of high amounts of Cl) when aiming at the direct determination of Br in solid samples by HR CS GFMAS. The accuracy of the method was evaluated via analysis of two different reference materials, poly(vinyl chloride) and tomato leaves.
Flórez, M. R.; García-Ruiz, E.; Bolea-Fernández, E.; Vanhaecke, F.; Resano, M.
En: J. Anal. At. Spectrom., vol. 31, iss. 1, pp. 245-251, 2016.
@article{C5JA00298B,
title = {A simple dilute-and-shoot approach for the determination of ultra-trace levels of arsenic in biological fluids via ICP-MS using CH3F/He as a reaction gas},
author = {M. R. Flórez and E. García-Ruiz and E. Bolea-Fernández and F. Vanhaecke and M. Resano},
url = {http://dx.doi.org/10.1039/C5JA00298B},
doi = {10.1039/C5JA00298B},
year = {2016},
date = {2016-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {31},
issue = {1},
pages = {245-251},
publisher = {The Royal Society of Chemistry},
abstract = {The performance of a mixture of CH3F/He (1/9) as a reaction gas for the determination of As in biological fluids using a quadrupole ICP-MS instrument has been explored. A simple (dilute-and-shoot) interference-free method has been developed to quantify As concentrations at trace and ultra-trace levels in matrices with a high Cl content. As+ reacts with CH3F (through CH3F addition, followed by HF elimination) with high efficiency forming AsCH2+ as the primary reaction product, which can be monitored at a mass-to-charge ratio of 89, free from the Cl-based interferents (e.g., 40Ar35Cl+ and 40Ca35Cl+) that hamper the monitoring of 75As+. Matrix effects are overcome by the use of Te as an internal standard and the addition of 3% v/v ethanol to all samples and calibration standard solutions. The method presented was validated by analysing a set of reference materials (blood, serum and urine) and by assessing As recovery from a set of real blood samples. With this method, the limit of detection was calculated to be 0.8 ng L−1 As, favourably comparable to the vast majority of values reported in the literature, even with those obtained using more sophisticated sector-field instrumentation.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The performance of a mixture of CH3F/He (1/9) as a reaction gas for the determination of As in biological fluids using a quadrupole ICP-MS instrument has been explored. A simple (dilute-and-shoot) interference-free method has been developed to quantify As concentrations at trace and ultra-trace levels in matrices with a high Cl content. As+ reacts with CH3F (through CH3F addition, followed by HF elimination) with high efficiency forming AsCH2+ as the primary reaction product, which can be monitored at a mass-to-charge ratio of 89, free from the Cl-based interferents (e.g., 40Ar35Cl+ and 40Ca35Cl+) that hamper the monitoring of 75As+. Matrix effects are overcome by the use of Te as an internal standard and the addition of 3% v/v ethanol to all samples and calibration standard solutions. The method presented was validated by analysing a set of reference materials (blood, serum and urine) and by assessing As recovery from a set of real blood samples. With this method, the limit of detection was calculated to be 0.8 ng L−1 As, favourably comparable to the vast majority of values reported in the literature, even with those obtained using more sophisticated sector-field instrumentation.
Resano, Martín; Garcia-Ruiz, Esperanza; Garde, Raul
High-resolution continuum source graphite furnace atomic absorption spectrometry for the monitoring of Au nanoparticles Journal Article
En: J. Anal. At. Spectrom., vol. 31, iss. 11, pp. 2233-2241, 2016.
@article{C6JA00280C,
title = {High-resolution continuum source graphite furnace atomic absorption spectrometry for the monitoring of Au nanoparticles},
author = {Martín Resano and Esperanza Garcia-Ruiz and Raul Garde},
url = {http://dx.doi.org/10.1039/C6JA00280C},
doi = {10.1039/C6JA00280C},
year = {2016},
date = {2016-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {31},
issue = {11},
pages = {2233-2241},
publisher = {The Royal Society of Chemistry},
abstract = {This work investigates the possibility of obtaining information on the chemical form (ionic or as Au nanoparticles (NPs)) in which Au is found in solutions by means of high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS), without the need to use any additional separation step or any extra technique. It is demonstrated that proper optimization of the temperature program, using a very slow heating ramp (150 °C s−1) during the atomization step and a sufficiently high atomization temperature (2200 °C) in the absence of chemical modifiers, enables a fast and simple screening to be performed, since the signal profiles obtained for solutions/suspensions of ionic Au and AuNPs are very dissimilar. Moreover, in the case of finding NPs, it is possible to estimate the average particle size, because this parameter appears to be directly related with the time of appearance of the maximum peak height (a value of 27.7 nm ± 8.8 nm was estimated for NIST Reference Material 8012 Gold nanoparticles, nominal 30 nm diameter). The proposed procedure offers a limit of detection of 5.5 pg (0.55 μg L−1) and a linear range up to 10 ng (1000 μg L−1), and was further validated by spiking a natural water certified reference material (CRM KEJIM 02). The occurrence of mixtures of ionic Au and AuNPs seems to be more complicated to resolve if quantitative information is aimed at (e.g., calculating the exact amount found in each form) because, even though the mixture behaves as predicted by summing the individual signals of ionic Au and AuNPs, signal overlaps can be anticipated and, thus, proper signal deconvolution should be carried out.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work investigates the possibility of obtaining information on the chemical form (ionic or as Au nanoparticles (NPs)) in which Au is found in solutions by means of high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS), without the need to use any additional separation step or any extra technique. It is demonstrated that proper optimization of the temperature program, using a very slow heating ramp (150 °C s−1) during the atomization step and a sufficiently high atomization temperature (2200 °C) in the absence of chemical modifiers, enables a fast and simple screening to be performed, since the signal profiles obtained for solutions/suspensions of ionic Au and AuNPs are very dissimilar. Moreover, in the case of finding NPs, it is possible to estimate the average particle size, because this parameter appears to be directly related with the time of appearance of the maximum peak height (a value of 27.7 nm ± 8.8 nm was estimated for NIST Reference Material 8012 Gold nanoparticles, nominal 30 nm diameter). The proposed procedure offers a limit of detection of 5.5 pg (0.55 μg L−1) and a linear range up to 10 ng (1000 μg L−1), and was further validated by spiking a natural water certified reference material (CRM KEJIM 02). The occurrence of mixtures of ionic Au and AuNPs seems to be more complicated to resolve if quantitative information is aimed at (e.g., calculating the exact amount found in each form) because, even though the mixture behaves as predicted by summing the individual signals of ionic Au and AuNPs, signal overlaps can be anticipated and, thus, proper signal deconvolution should be carried out.
2015
Nakadi, F. V.; Veiga, M. A. M. S.; Aramendía, M.; García-Ruiz, E.; Resano, M.
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.