2017
Journal Articles
Bolea-Fernandez, Eduardo; Balcaen, Lieve; Resano, Martín; Vanhaecke, Frank
Overcoming spectral overlap via inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). A tutorial review Journal Article
En: J. Anal. At. Spectrom., vol. 32, iss. 9, pp. 1660-1679, 2017.
@article{C7JA00010C,
title = {Overcoming spectral overlap via inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). A tutorial review},
author = {Eduardo Bolea-Fernandez and Lieve Balcaen and Martín Resano and Frank Vanhaecke},
url = {http://dx.doi.org/10.1039/C7JA00010C},
doi = {10.1039/C7JA00010C},
year = {2017},
date = {2017-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {32},
issue = {9},
pages = {1660-1679},
publisher = {The Royal Society of Chemistry},
abstract = {This work reviews the operating principles of ICP-tandem mass spectrometry (ICP-MS/MS) and the key applications reported on since the introduction of the technique in 2012. The main differences between single quadrupole ICP-MS and ICP-MS/MS are elucidated and the tools available for method development are addressed. Examples of real-life applications are given to demonstrate the capabilities of this novel setup in the context of elemental, speciation and isotopic analysis. Attention has been paid to the different approaches (on-mass and mass-shift) allowing interference-free conditions to be obtained.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work reviews the operating principles of ICP-tandem mass spectrometry (ICP-MS/MS) and the key applications reported on since the introduction of the technique in 2012. The main differences between single quadrupole ICP-MS and ICP-MS/MS are elucidated and the tools available for method development are addressed. Examples of real-life applications are given to demonstrate the capabilities of this novel setup in the context of elemental, speciation and isotopic analysis. Attention has been paid to the different approaches (on-mass and mass-shift) allowing interference-free conditions to be obtained.
Patočka, Jan; Bendakovská, Lenka; Krejčová, Anna; Černohorský, Tomáš; Resano, Martín; Bělina, Petr
Thallium in spruce needles: a comparison of the analytical capabilities of spectrochemical methods Journal Article
En: Anal. Methods, vol. 9, iss. 4, pp. 705-715, 2017.
@article{C6AY02760A,
title = {Thallium in spruce needles: a comparison of the analytical capabilities of spectrochemical methods},
author = {Jan Patočka and Lenka Bendakovská and Anna Krejčová and Tomáš Černohorský and Martín Resano and Petr Bělina},
url = {http://dx.doi.org/10.1039/C6AY02760A},
doi = {10.1039/C6AY02760A},
year = {2017},
date = {2017-01-01},
journal = {Anal. Methods},
volume = {9},
issue = {4},
pages = {705-715},
publisher = {The Royal Society of Chemistry},
abstract = {Four spectrochemical methods are employed for the determination of Tl in spruce needles: ICP-MS (inductively coupled plasma mass spectrometry), ETV-ICP-MS (electrothermal vaporisation coupled to ICP-MS) analysis of decomposed and slurry samples (SlS), and SS-HR-CS-GFAAS (solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry). The methods are compared considering practical laboratory aspects (sample pretreatment, optimisation, validation, time-consumption), as well as their analytical performance. For this specific case of Tl in spruce needles, all the methods had similar requirements regarding the time required for sample pretreatment (1–2 hours, ETV-ICP-MS, SS-HR-CS-GFAAS < ICP-MS < SlS-ETV-ICP-MS). The method optimisation can be considered as routine for ICP-MS and more complicated for slurry and solid sampling, due to the differences in the matrix of standards and samples. ICP-MS optimisation required a several dozen minutes and dozens of hours for the ETV methods, which increases operational costs. ETV-ICP-MS requires a well experienced operator, skilled in both techniques (graphite furnace and ICP-MS). The order of complexity can be classified as follows: ICP-MS < SS-HR-CS-GFAAS < ETV-ICP-MS, SlS-ETV-ICP-MS. Requirements for validation in terms of the chemicals, calibration standards, and reference and control materials are similar. Major differences were evident in time demands. The procedural LODs were found typically below 1 μg kg−1 of Tl (in μg kg−1): 0.18 ICP-MS, 0.010 ETV-ICP-MS, 0.024 SlS-ETV-ICP-MS and 1.2 SS-HR-CS-GFAAS, which are appropriate for the Tl levels found in environmental samples. The range of recoveries did not differ significantly for the different methods used (in %): ICP-MS 92–107, ETV-ICP-MS 90–114, SlS-ETV-ICP-MS 94.5–117 and SS-HR-CS-GFAAS 90–115. ICP-MS revealed better repeatabilities (1.9–6.2%) than the others (ETV-ICP-MS 5.2–19%, SlS-ETV-ICP-MS 6.3–17% and SS-HR-CS-GFAAS 0.17–15%), as expected. In practice, ICP-MS shows significant advantages for analysis of Tl in spruce needles. However, it is necessary to consider all of the factors discussed. ETV techniques may have a justified place in special routine applications, in which the difficult development and validation of methods is much more convenient than the daily preparation of highly resistant or otherwise complicated samples.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Four spectrochemical methods are employed for the determination of Tl in spruce needles: ICP-MS (inductively coupled plasma mass spectrometry), ETV-ICP-MS (electrothermal vaporisation coupled to ICP-MS) analysis of decomposed and slurry samples (SlS), and SS-HR-CS-GFAAS (solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry). The methods are compared considering practical laboratory aspects (sample pretreatment, optimisation, validation, time-consumption), as well as their analytical performance. For this specific case of Tl in spruce needles, all the methods had similar requirements regarding the time required for sample pretreatment (1–2 hours, ETV-ICP-MS, SS-HR-CS-GFAAS < ICP-MS < SlS-ETV-ICP-MS). The method optimisation can be considered as routine for ICP-MS and more complicated for slurry and solid sampling, due to the differences in the matrix of standards and samples. ICP-MS optimisation required a several dozen minutes and dozens of hours for the ETV methods, which increases operational costs. ETV-ICP-MS requires a well experienced operator, skilled in both techniques (graphite furnace and ICP-MS). The order of complexity can be classified as follows: ICP-MS < SS-HR-CS-GFAAS < ETV-ICP-MS, SlS-ETV-ICP-MS. Requirements for validation in terms of the chemicals, calibration standards, and reference and control materials are similar. Major differences were evident in time demands. The procedural LODs were found typically below 1 μg kg−1 of Tl (in μg kg−1): 0.18 ICP-MS, 0.010 ETV-ICP-MS, 0.024 SlS-ETV-ICP-MS and 1.2 SS-HR-CS-GFAAS, which are appropriate for the Tl levels found in environmental samples. The range of recoveries did not differ significantly for the different methods used (in %): ICP-MS 92–107, ETV-ICP-MS 90–114, SlS-ETV-ICP-MS 94.5–117 and SS-HR-CS-GFAAS 90–115. ICP-MS revealed better repeatabilities (1.9–6.2%) than the others (ETV-ICP-MS 5.2–19%, SlS-ETV-ICP-MS 6.3–17% and SS-HR-CS-GFAAS 0.17–15%), as expected. In practice, ICP-MS shows significant advantages for analysis of Tl in spruce needles. However, it is necessary to consider all of the factors discussed. ETV techniques may have a justified place in special routine applications, in which the difficult development and validation of methods is much more convenient than the daily preparation of highly resistant or otherwise complicated samples.
Cañabate, Águeda; García-Ruiz, Esperanza; Resano, Martín; Todolí, José-Luis
Analysis of whole blood by ICP-MS equipped with a high temperature total sample consumption system Journal Article
En: J. Anal. At. Spectrom., vol. 32, iss. 1, pp. 78-87, 2017.
@article{C6JA00374E,
title = {Analysis of whole blood by ICP-MS equipped with a high temperature total sample consumption system},
author = {Águeda Cañabate and Esperanza García-Ruiz and Martín Resano and José-Luis Todolí},
url = {http://dx.doi.org/10.1039/C6JA00374E},
doi = {10.1039/C6JA00374E},
year = {2017},
date = {2017-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {32},
issue = {1},
pages = {78-87},
publisher = {The Royal Society of Chemistry},
abstract = {In this work, the performance of a high temperature torch Integrated Sample Introduction System (hTISIS) using inductively coupled plasma mass spectrometry (ICP-MS) for the multi-element analysis of whole blood is evaluated. Two different quadrupole-based spectrometers were tested and the optimization studies were performed with a reference whole blood material. Sample dilution factor and hTISIS temperature were taken as the variables. The sample was introduced following two different procedures: continuous aspiration and air-segmentation. The optimum performance of the system in terms of both analytical figures of merit and accuracy was obtained for a hTISIS temperature of 200 °C and for either 1 : 10 or 1 : 25 dilution factors depending on the ICP-MS device used. An improvement in terms of sensitivity and detection limits was obtained with the hTISIS as compared to the conventional cyclonic spray chamber. Thus, for 1 : 25 diluted blood samples, the hTISIS improved the sensitivity by a factor ranging 2.0–4.5. Moreover, at 200 °C, the limits of detection for hTISIS at 200 °C were 1.1 to 8.4 times lower than those for the cyclonic spray chamber. This analytical parameter was in the ng L−1 range for the detected elements. Matrix effects in turn became less severe as the hTISIS temperature increased (from room temperature to 80 °C). All these results were obtained without a severe degradation of the fundamental plasma parameters. In fact, under optimum conditions BaO+/Ba+ and Ba2+/Ba+ signal ratios were 1.2% and 2.0%, respectively. The developed method was applied for the analysis of low volumes (ca. 2.5 μL) of real blood samples after a minimally invasive collection by volumetric absorptive microsampling. The hTISIS is an easy-to-implement sample introduction system that can be employed for the routine analysis using ICP-MS.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
In this work, the performance of a high temperature torch Integrated Sample Introduction System (hTISIS) using inductively coupled plasma mass spectrometry (ICP-MS) for the multi-element analysis of whole blood is evaluated. Two different quadrupole-based spectrometers were tested and the optimization studies were performed with a reference whole blood material. Sample dilution factor and hTISIS temperature were taken as the variables. The sample was introduced following two different procedures: continuous aspiration and air-segmentation. The optimum performance of the system in terms of both analytical figures of merit and accuracy was obtained for a hTISIS temperature of 200 °C and for either 1 : 10 or 1 : 25 dilution factors depending on the ICP-MS device used. An improvement in terms of sensitivity and detection limits was obtained with the hTISIS as compared to the conventional cyclonic spray chamber. Thus, for 1 : 25 diluted blood samples, the hTISIS improved the sensitivity by a factor ranging 2.0–4.5. Moreover, at 200 °C, the limits of detection for hTISIS at 200 °C were 1.1 to 8.4 times lower than those for the cyclonic spray chamber. This analytical parameter was in the ng L−1 range for the detected elements. Matrix effects in turn became less severe as the hTISIS temperature increased (from room temperature to 80 °C). All these results were obtained without a severe degradation of the fundamental plasma parameters. In fact, under optimum conditions BaO+/Ba+ and Ba2+/Ba+ signal ratios were 1.2% and 2.0%, respectively. The developed method was applied for the analysis of low volumes (ca. 2.5 μL) of real blood samples after a minimally invasive collection by volumetric absorptive microsampling. The hTISIS is an easy-to-implement sample introduction system that can be employed for the routine analysis using ICP-MS.
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.
García-González, Elena; Rello, Luis; Lalaguna, Paula; Conde, Santiago; García-Jiménez, Inmaculada; Castejón, Esperanza; Izquierdo, Beatriz; Haddad, María
Utilidad de la determinación de cobre en periodo neonatal. Enfermedad de Menkes Journal Article
En: Revista del Laboratorio Clínico, vol. 10, no. 2, pp. 95-99, 2017, ISSN: 1888-4008.
@article{GARCIAGONZALEZ201795,
title = {Utilidad de la determinación de cobre en periodo neonatal. Enfermedad de Menkes},
author = {Elena García-González and Luis Rello and Paula Lalaguna and Santiago Conde and Inmaculada García-Jiménez and Esperanza Castejón and Beatriz Izquierdo and María Haddad},
url = {https://www.sciencedirect.com/science/article/pii/S1888400817300041},
doi = {https://doi.org/10.1016/j.labcli.2016.11.003},
issn = {1888-4008},
year = {2017},
date = {2017-01-01},
journal = {Revista del Laboratorio Clínico},
volume = {10},
number = {2},
pages = {95-99},
abstract = {Resumen
Bajas concentraciones séricas de Cu en neonatos pueden ser la primera señal de una ingesta deficiente de este elemento o, alternativamente, de enfermedades genéticas que afectan su metabolismo. Desgraciadamente, es difícil la interpretación de las concentraciones de Cu en esta población, ya que están influenciadas por distintos factores, entre ellos la prematuridad, el tipo de alimentación y la presencia de un estado inflamatorio. Sin embargo, en el caso que aquí se describe fue la baja concentración sérica de Cu la primera pista para el diagnóstico de enfermedad de Menkes. Se demuestra así la utilidad de la determinación de Cu dentro de protocolos neurometabólicos y de retraso psicomotor en población neonatal y lactante.
Low serum Cu concentrations in newborns can be the first indication of a severe Cu deficient intake or, alternatively, of genetic diseases affecting Cu metabolism. Unfortunately, interpretation of serum Cu concentrations in this population is difficult because they also influenced by several variables, such as, prematurity, type of feeding and inflammatory conditions. However, in the case described in this paper was a low serum Cu concentration the first clue for diagnosing Menkes disease. It is so demonstrated the usefulness of Cu determination within neurometabolic or psychomotor retardation protocols for newborn and infant populations.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Resumen
Bajas concentraciones séricas de Cu en neonatos pueden ser la primera señal de una ingesta deficiente de este elemento o, alternativamente, de enfermedades genéticas que afectan su metabolismo. Desgraciadamente, es difícil la interpretación de las concentraciones de Cu en esta población, ya que están influenciadas por distintos factores, entre ellos la prematuridad, el tipo de alimentación y la presencia de un estado inflamatorio. Sin embargo, en el caso que aquí se describe fue la baja concentración sérica de Cu la primera pista para el diagnóstico de enfermedad de Menkes. Se demuestra así la utilidad de la determinación de Cu dentro de protocolos neurometabólicos y de retraso psicomotor en población neonatal y lactante.
Low serum Cu concentrations in newborns can be the first indication of a severe Cu deficient intake or, alternatively, of genetic diseases affecting Cu metabolism. Unfortunately, interpretation of serum Cu concentrations in this population is difficult because they also influenced by several variables, such as, prematurity, type of feeding and inflammatory conditions. However, in the case described in this paper was a low serum Cu concentration the first clue for diagnosing Menkes disease. It is so demonstrated the usefulness of Cu determination within neurometabolic or psychomotor retardation protocols for newborn and infant populations.
Bajas concentraciones séricas de Cu en neonatos pueden ser la primera señal de una ingesta deficiente de este elemento o, alternativamente, de enfermedades genéticas que afectan su metabolismo. Desgraciadamente, es difícil la interpretación de las concentraciones de Cu en esta población, ya que están influenciadas por distintos factores, entre ellos la prematuridad, el tipo de alimentación y la presencia de un estado inflamatorio. Sin embargo, en el caso que aquí se describe fue la baja concentración sérica de Cu la primera pista para el diagnóstico de enfermedad de Menkes. Se demuestra así la utilidad de la determinación de Cu dentro de protocolos neurometabólicos y de retraso psicomotor en población neonatal y lactante.
Low serum Cu concentrations in newborns can be the first indication of a severe Cu deficient intake or, alternatively, of genetic diseases affecting Cu metabolism. Unfortunately, interpretation of serum Cu concentrations in this population is difficult because they also influenced by several variables, such as, prematurity, type of feeding and inflammatory conditions. However, in the case described in this paper was a low serum Cu concentration the first clue for diagnosing Menkes disease. It is so demonstrated the usefulness of Cu determination within neurometabolic or psychomotor retardation protocols for newborn and infant populations.
González-Tarancón, Ricardo; Calvo-Ruata, Luisa; Aramendía, Maite; Ortega, Carmen; García-González, Elena; Rello, Luis
Serum copper concentrations in hospitalized newborns Journal Article
En: Journal of Trace Elements in Medicine and Biology, vol. 39, pp. 1-5, 2017, ISSN: 0946-672X.
@article{GONZALEZTARANCON20171,
title = {Serum copper concentrations in hospitalized newborns},
author = {Ricardo González-Tarancón and Luisa Calvo-Ruata and Maite Aramendía and Carmen Ortega and Elena García-González and Luis Rello},
url = {https://www.sciencedirect.com/science/article/pii/S0946672X16301171},
doi = {https://doi.org/10.1016/j.jtemb.2016.06.010},
issn = {0946-672X},
year = {2017},
date = {2017-01-01},
journal = {Journal of Trace Elements in Medicine and Biology},
volume = {39},
pages = {1-5},
abstract = {Background
Low serum Cu and ceruloplasmin (Cp) concentrations in newborns can be the first indication of a severe Cu deficient intake or, alternatively, of genetic diseases affecting Cu metabolism. However, Cu and Cp concentrations can also be influenced by other variables that render their quantitative results difficult to interpret. Therefore, it is necessary to identify these variables and stratify Cu and Cp concentrations according to these altering factors.
Methods
Serum Cu and Cp concentrations for 564 hospitalized newborns (0–12days of life) are stratified according to their age, prematurity (birth weight or gestational age), type of feeding and inflammatory state (assessed by the serum high sensitivity C-reactive protein (hs-CRP) level) to identify potential correlations.
Results
Serum Cu and Cp concentrations are influenced by all four variables analyzed, although inflammation is the most significant: the greater the hs-CRP concentration, the greater the serum Cu and Cp concentrations. Prematurity is also an important factor and preterm infants often show very low Cu and Cp concentrations. Age of life and type of feeding have in turn a more modest effect on these magnitudes, being slightly greater at 3–5days of age in breastfed newborns.
Conclusions
Inflammation and prematurity are the main variables affecting serum Cu and Cp concentrations in newborns. Therefore, hs-CRP should always be assayed in parallel to Cu status. When there is an inflammatory state proper interpretation of these concentrations can be challenging.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Background
Low serum Cu and ceruloplasmin (Cp) concentrations in newborns can be the first indication of a severe Cu deficient intake or, alternatively, of genetic diseases affecting Cu metabolism. However, Cu and Cp concentrations can also be influenced by other variables that render their quantitative results difficult to interpret. Therefore, it is necessary to identify these variables and stratify Cu and Cp concentrations according to these altering factors.
Methods
Serum Cu and Cp concentrations for 564 hospitalized newborns (0–12days of life) are stratified according to their age, prematurity (birth weight or gestational age), type of feeding and inflammatory state (assessed by the serum high sensitivity C-reactive protein (hs-CRP) level) to identify potential correlations.
Results
Serum Cu and Cp concentrations are influenced by all four variables analyzed, although inflammation is the most significant: the greater the hs-CRP concentration, the greater the serum Cu and Cp concentrations. Prematurity is also an important factor and preterm infants often show very low Cu and Cp concentrations. Age of life and type of feeding have in turn a more modest effect on these magnitudes, being slightly greater at 3–5days of age in breastfed newborns.
Conclusions
Inflammation and prematurity are the main variables affecting serum Cu and Cp concentrations in newborns. Therefore, hs-CRP should always be assayed in parallel to Cu status. When there is an inflammatory state proper interpretation of these concentrations can be challenging.
Low serum Cu and ceruloplasmin (Cp) concentrations in newborns can be the first indication of a severe Cu deficient intake or, alternatively, of genetic diseases affecting Cu metabolism. However, Cu and Cp concentrations can also be influenced by other variables that render their quantitative results difficult to interpret. Therefore, it is necessary to identify these variables and stratify Cu and Cp concentrations according to these altering factors.
Methods
Serum Cu and Cp concentrations for 564 hospitalized newborns (0–12days of life) are stratified according to their age, prematurity (birth weight or gestational age), type of feeding and inflammatory state (assessed by the serum high sensitivity C-reactive protein (hs-CRP) level) to identify potential correlations.
Results
Serum Cu and Cp concentrations are influenced by all four variables analyzed, although inflammation is the most significant: the greater the hs-CRP concentration, the greater the serum Cu and Cp concentrations. Prematurity is also an important factor and preterm infants often show very low Cu and Cp concentrations. Age of life and type of feeding have in turn a more modest effect on these magnitudes, being slightly greater at 3–5days of age in breastfed newborns.
Conclusions
Inflammation and prematurity are the main variables affecting serum Cu and Cp concentrations in newborns. Therefore, hs-CRP should always be assayed in parallel to Cu status. When there is an inflammatory state proper interpretation of these concentrations can be challenging.
2016
Journal Articles
García-González, Elena; González-Tarancón, Ricardo; Aramendía, Maite; Rello, Luis
En: Clin Chem Lab Med, vol. 54, no. 8, pp. 1329–1335, 2016, ISSN: 1437-4331.
@article{pmid26677886,
title = {Analytical interference by monoclonal immunoglobulins on the direct bilirubin AU Beckman Coulter assay: the benefit of unsuspected diagnosis from spurious results},
author = {Elena García-González and Ricardo González-Tarancón and Maite Aramendía and Luis Rello},
doi = {10.1515/cclm-2015-0608},
issn = {1437-4331},
year = {2016},
date = {2016-08-01},
journal = {Clin Chem Lab Med},
volume = {54},
number = {8},
pages = {1329--1335},
abstract = {BACKGROUND: Monoclonal (M) components can interfere with the direct bilirubin (D-Bil) assay on the AU Beckman Coulter instrumentation and produce spurious results, such as D-Bil values greater than total bilirubin (T-Bil) or very low/negative D-Bil values. If properly detected, this interference may uncover undiagnosed patients with monoclonal gammopathy (MG).
METHODS: We investigated the interference rate on the D-Bil AU assay in serum samples known to contain M proteins along with their isotype and described the protocol set up in our laboratory to help with the diagnosis of MG based on D-Bil spurious results as first indication.
RESULTS: During a period of 4 years, 15.4% (345 of 2235) of serum samples containing M immunoglobulins produced erroneous D-Bil results, although no clear relationship between the magnitude or isotype of the M component and interference could be found. In total 22 new patients were diagnosed with MG based on the analytical artefact with the D-Bil as first indication.
CONCLUSIONS: The D-Bil interference from MG on the Beckman AU analysers needs to be made known to laboratories in order to prevent clinical confusion and/or additional workup to explain the origin of anomalous results. Although this information may not add to the management of existing patients with serum paraproteins, it can benefit patients that have not been diagnosed with MG by triggering follow up testing to determine if M components are present.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
BACKGROUND: Monoclonal (M) components can interfere with the direct bilirubin (D-Bil) assay on the AU Beckman Coulter instrumentation and produce spurious results, such as D-Bil values greater than total bilirubin (T-Bil) or very low/negative D-Bil values. If properly detected, this interference may uncover undiagnosed patients with monoclonal gammopathy (MG).
METHODS: We investigated the interference rate on the D-Bil AU assay in serum samples known to contain M proteins along with their isotype and described the protocol set up in our laboratory to help with the diagnosis of MG based on D-Bil spurious results as first indication.
RESULTS: During a period of 4 years, 15.4% (345 of 2235) of serum samples containing M immunoglobulins produced erroneous D-Bil results, although no clear relationship between the magnitude or isotype of the M component and interference could be found. In total 22 new patients were diagnosed with MG based on the analytical artefact with the D-Bil as first indication.
CONCLUSIONS: The D-Bil interference from MG on the Beckman AU analysers needs to be made known to laboratories in order to prevent clinical confusion and/or additional workup to explain the origin of anomalous results. Although this information may not add to the management of existing patients with serum paraproteins, it can benefit patients that have not been diagnosed with MG by triggering follow up testing to determine if M components are present.
METHODS: We investigated the interference rate on the D-Bil AU assay in serum samples known to contain M proteins along with their isotype and described the protocol set up in our laboratory to help with the diagnosis of MG based on D-Bil spurious results as first indication.
RESULTS: During a period of 4 years, 15.4% (345 of 2235) of serum samples containing M immunoglobulins produced erroneous D-Bil results, although no clear relationship between the magnitude or isotype of the M component and interference could be found. In total 22 new patients were diagnosed with MG based on the analytical artefact with the D-Bil as first indication.
CONCLUSIONS: The D-Bil interference from MG on the Beckman AU analysers needs to be made known to laboratories in order to prevent clinical confusion and/or additional workup to explain the origin of anomalous results. Although this information may not add to the management of existing patients with serum paraproteins, it can benefit patients that have not been diagnosed with MG by triggering follow up testing to determine if M components are present.
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.
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.
Bolea-Fernandez, Eduardo; Balcaen, Lieve; Resano, Martín; Vanhaecke, Frank
Tandem ICP-mass spectrometry for Sr isotopic analysis without prior Rb/Sr separation Journal Article
En: J. Anal. At. Spectrom., vol. 31, iss. 1, pp. 303-310, 2016.
@article{C5JA00157A,
title = {Tandem ICP-mass spectrometry for Sr isotopic analysis without prior Rb/Sr separation},
author = {Eduardo Bolea-Fernandez and Lieve Balcaen and Martín Resano and Frank Vanhaecke},
url = {http://dx.doi.org/10.1039/C5JA00157A},
doi = {10.1039/C5JA00157A},
year = {2016},
date = {2016-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {31},
issue = {1},
pages = {303-310},
publisher = {The Royal Society of Chemistry},
abstract = {The use of a mixture of 10% of CH3F and 90% of He as a reaction gas in tandem ICP-mass spectrometry (ICP-MS/MS) enables the accurate determination of the 87Sr/86Sr isotope ratio in geological materials, provided that mass discrimination is corrected for by using a combination of internal (Russell law, assuming a constant 88Sr/86Sr isotope ratio) and external correction (using the isotopic reference material NIST SRM 987 SrCO3) in a sample-standard bracketing approach. No prior Rb/Sr separation is required as the isobaric overlap at a mass-to-charge ratio of 87 is avoided by monitoring SrF+ reaction product ions instead of Sr+ ions. Rb shows no reactivity towards CH3F. The double mass selection (MS/MS mode) prevents both spectral overlap from atomic ions at the mass-to-charge ratios of SrF+ reaction product ions and a measurable effect from the matrix on the 87Sr/86Sr result. This aspect is critical, as it enables accurate results to be obtained without the need for using a matrix-matched standard to correct for mass discrimination, in contrast to previous work with a quadrupole ICP-MS instrument with a CH3F/Ne-pressurized cell, in which the use of a matrix-matched standard was compulsory. The precision attainable – 0.05% RSD external precision – suffices for making the newly developed method useful in a variety of applications.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The use of a mixture of 10% of CH3F and 90% of He as a reaction gas in tandem ICP-mass spectrometry (ICP-MS/MS) enables the accurate determination of the 87Sr/86Sr isotope ratio in geological materials, provided that mass discrimination is corrected for by using a combination of internal (Russell law, assuming a constant 88Sr/86Sr isotope ratio) and external correction (using the isotopic reference material NIST SRM 987 SrCO3) in a sample-standard bracketing approach. No prior Rb/Sr separation is required as the isobaric overlap at a mass-to-charge ratio of 87 is avoided by monitoring SrF+ reaction product ions instead of Sr+ ions. Rb shows no reactivity towards CH3F. The double mass selection (MS/MS mode) prevents both spectral overlap from atomic ions at the mass-to-charge ratios of SrF+ reaction product ions and a measurable effect from the matrix on the 87Sr/86Sr result. This aspect is critical, as it enables accurate results to be obtained without the need for using a matrix-matched standard to correct for mass discrimination, in contrast to previous work with a quadrupole ICP-MS instrument with a CH3F/Ne-pressurized cell, in which the use of a matrix-matched standard was compulsory. The precision attainable – 0.05% RSD external precision – suffices for making the newly developed method useful in a variety of applications.
García-González, Elena; Aramendía, Maite; Álvarez-Ballano, Diego; Trincado, Pablo; Rello, Luis
Serum sample containing endogenous antibodies interfering with multiple hormone immunoassays. Laboratory strategies to detect interference Journal Article
En: Practical Laboratory Medicine, vol. 4, pp. 1-10, 2016, ISSN: 2352-5517.
@article{GARCIAGONZALEZ20161,
title = {Serum sample containing endogenous antibodies interfering with multiple hormone immunoassays. Laboratory strategies to detect interference},
author = {Elena García-González and Maite Aramendía and Diego Álvarez-Ballano and Pablo Trincado and Luis Rello},
url = {https://www.sciencedirect.com/science/article/pii/S2352551715300020},
doi = {https://doi.org/10.1016/j.plabm.2015.11.001},
issn = {2352-5517},
year = {2016},
date = {2016-01-01},
journal = {Practical Laboratory Medicine},
volume = {4},
pages = {1-10},
abstract = {Objectives
Endogenous antibodies (EA) may interfere with immunoassays, causing erroneous results for hormone analyses. As (in most cases) this interference arises from the assay format and most immunoassays, even from different manufacturers, are constructed in a similar way, it is possible for a single type of EA to interfere with different immunoassays. Here we describe the case of a patient whose serum sample contains EA that interfere several hormones tests. We also discuss the strategies deployed to detect interference.
Subjects and methods
Over a period of four years, a 30-year-old man was subjected to a plethora of laboratory and imaging diagnostic procedures as a consequence of elevated hormone results, mainly of pituitary origin, which did not correlate with the overall clinical picture.
Results
Once analytical interference was suspected, the best laboratory approaches to investigate it were sample reanalysis on an alternative platform and sample incubation with antibody blocking tubes. Construction of an in-house ‘nonsense’ sandwich assay was also a valuable strategy to confirm interference. In contrast, serial sample dilutions were of no value in our case, while polyethylene glycol (PEG) precipitation gave inconclusive results, probably due to the use of inappropriate PEG concentrations for several of the tests assayed.
Conclusions
Clinicians and laboratorians must be aware of the drawbacks of immunometric assays, and alert to the possibility of EA interference when results do not fit the clinical pattern.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Objectives
Endogenous antibodies (EA) may interfere with immunoassays, causing erroneous results for hormone analyses. As (in most cases) this interference arises from the assay format and most immunoassays, even from different manufacturers, are constructed in a similar way, it is possible for a single type of EA to interfere with different immunoassays. Here we describe the case of a patient whose serum sample contains EA that interfere several hormones tests. We also discuss the strategies deployed to detect interference.
Subjects and methods
Over a period of four years, a 30-year-old man was subjected to a plethora of laboratory and imaging diagnostic procedures as a consequence of elevated hormone results, mainly of pituitary origin, which did not correlate with the overall clinical picture.
Results
Once analytical interference was suspected, the best laboratory approaches to investigate it were sample reanalysis on an alternative platform and sample incubation with antibody blocking tubes. Construction of an in-house ‘nonsense’ sandwich assay was also a valuable strategy to confirm interference. In contrast, serial sample dilutions were of no value in our case, while polyethylene glycol (PEG) precipitation gave inconclusive results, probably due to the use of inappropriate PEG concentrations for several of the tests assayed.
Conclusions
Clinicians and laboratorians must be aware of the drawbacks of immunometric assays, and alert to the possibility of EA interference when results do not fit the clinical pattern.
Endogenous antibodies (EA) may interfere with immunoassays, causing erroneous results for hormone analyses. As (in most cases) this interference arises from the assay format and most immunoassays, even from different manufacturers, are constructed in a similar way, it is possible for a single type of EA to interfere with different immunoassays. Here we describe the case of a patient whose serum sample contains EA that interfere several hormones tests. We also discuss the strategies deployed to detect interference.
Subjects and methods
Over a period of four years, a 30-year-old man was subjected to a plethora of laboratory and imaging diagnostic procedures as a consequence of elevated hormone results, mainly of pituitary origin, which did not correlate with the overall clinical picture.
Results
Once analytical interference was suspected, the best laboratory approaches to investigate it were sample reanalysis on an alternative platform and sample incubation with antibody blocking tubes. Construction of an in-house ‘nonsense’ sandwich assay was also a valuable strategy to confirm interference. In contrast, serial sample dilutions were of no value in our case, while polyethylene glycol (PEG) precipitation gave inconclusive results, probably due to the use of inappropriate PEG concentrations for several of the tests assayed.
Conclusions
Clinicians and laboratorians must be aware of the drawbacks of immunometric assays, and alert to the possibility of EA interference when results do not fit the clinical pattern.
2015
Journal Articles
Balcaen, Lieve; Bolea-Fernandez, Eduardo; Resano, Martín; Vanhaecke, Frank
En: Analytica Chimica Acta, vol. 894, pp. 7-19, 2015, ISSN: 0003-2670.
@article{BALCAEN20157,
title = {Inductively coupled plasma – Tandem mass spectrometry (ICP-MS/MS): A powerful and universal tool for the interference-free determination of (ultra)trace elements – A tutorial review},
author = {Lieve Balcaen and Eduardo Bolea-Fernandez and Martín Resano and Frank Vanhaecke},
url = {https://www.sciencedirect.com/science/article/pii/S000326701501065X},
doi = {https://doi.org/10.1016/j.aca.2015.08.053},
issn = {0003-2670},
year = {2015},
date = {2015-01-01},
journal = {Analytica Chimica Acta},
volume = {894},
pages = {7-19},
abstract = {This paper is intended as a tutorial review on the use of inductively coupled plasma – tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H2, O2 and NH3, also the use of promising alternative gases, such as CH3F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This paper is intended as a tutorial review on the use of inductively coupled plasma – tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H2, O2 and NH3, also the use of promising alternative gases, such as CH3F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis.
Rello, Luis; Aramendía, Maite; Belarra, Miguel A; Resano, Martín
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.
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 Journal Article
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
Journal Articles
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
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.