]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Condit... more ]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Fast characterization of coated materials requires direct solid analytical techniques able to pro... more Fast characterization of coated materials requires direct solid analytical techniques able to provide high sensitivity and high depth resolution. Well-established techniques, such as Glow Discharge Optical Emission Spectroscopies (GD-OES), show...
Journal of the Marine Biological Association of the United Kingdom
The objective of this study was to identify potential recruitment sources of Prochilodus lineatus... more The objective of this study was to identify potential recruitment sources of Prochilodus lineatus from freshwater areas (Paraná and Uruguay rivers) to estuarine population of the Río de la Plata Estuary (La Plata Basin, South America), considering young (age-1) and adult (age-7) fish. LA-ICP-MS chemical analysis of the otolith core (nine element:Ca ratios) of an unknown mixed sample from Río de la Plata Estuary (2011 and 2017) was compared with a young-of-year baseline data set (same cohort) and classified into freshwater nurseries (Paraná or Uruguay river) by using maximum classification-likelihood models (MLE and MCL) and quadratic discriminant analysis (QDA). Considering the three models used, the Uruguay River was the most important contributor for both young and adult populations. The young population (2011) was highly mixed with contributions between 31.7 to 68.3%, while the degree of mixing was found to decrease in 2017 (adult fish) from 97.1 to 100% contributions. The three ...
The application of a new methodology for direct solid analysis of fluorine by LIBS is evaluated. ... more The application of a new methodology for direct solid analysis of fluorine by LIBS is evaluated. This approach, based on the nebulization of a Ca solution over a fluorine-containing sample, allows the F quantification using the emission of the CaF molecular bands.
The needle-Flowing Atmospheric Pressure Afterglow (n-FAPA) is a miniaturized plasma device with A... more The needle-Flowing Atmospheric Pressure Afterglow (n-FAPA) is a miniaturized plasma device with Ambient Desorption/Ionization capabilities. It is generated in flowing He using two concentric electrodes: a stainless steel capillary tube (outer electrode), and a hypodermic needle with a bevel-cut edge (inner electrode).
2007 IEEE Industry Applications Annual Meeting, 2007
The goal of this paper is to study how the vapour pressure and the electrical characteristics of ... more The goal of this paper is to study how the vapour pressure and the electrical characteristics of a high pressure sodium (HPS) lamp are affected by acoustic resonances to determine if some of those parameters can be used as acoustic resonances detector.
The capabilities of radiofrequency pulsed glow discharge time of flight mass spectrometry (rf-pul... more The capabilities of radiofrequency pulsed glow discharge time of flight mass spectrometry (rf-pulsed-GD-TOFMS) for the analysis of thin film composite membranes have been investigated in this work.
The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionizat... more The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionization of the material provided by laser ablation (LA) have been compared to conventional laser induced breakdown spectroscopy (LIBS). In LA-GD both sources can be independently adjusted to optimize the sampling process and then its subsequent excitation. This could involve a number of analytical performance advantages, such as reduced matrix dependence, greater precision and sensitivity than those encountered in LIBS. For such purpose, an ablation chamber design including two electrodes to generate the GD discharge has been built and assayed. A comparison between LIBS and LA-GD-OES has been carried out, both, under reduced argon and helium atmospheres. Different sets of samples (conducting reference materials, glass and fluorine pellets) have been used to evaluate the novel coupled technique. The LA-GD coupled system has shown to provide lower detection limits. In addition, best linear correlations between intensities and concentrations and lower matrix effects have also been found using the coupled system. Moreover, special advantages of the LA-GD-OES have also been demonstrated for the analysis of fluorine.
Conference Record of the 2004 IEEE Industry Applications Conference, 2004. 39th IAS Annual Meeting., 2004
A spectroscopic study on the behavior of a high-pressure- sodium lamp is performed in this work. ... more A spectroscopic study on the behavior of a high-pressure- sodium lamp is performed in this work. The lamp works at 50 Hz and high frequencies. The study includes the analysis of the detected spectra from 400 to 700 nm, the determination of the lamp stabilization time, the Na vapour pressure and the electronic excitation temperatures.
The goal of this paper is to study how the vapour pressure and the electrical characteristics of ... more The goal of this paper is to study how the vapour pressure and the electrical characteristics of a high pressure sodium (HPS) lamp are affected by acoustic resonances to determine if some of those parameters can be used as acoustic resonances detector.
Spectrochimica Acta Part B: Atomic Spectroscopy, 2014
Abstract Laser Ablation and Glow Discharge (LAGD) plasmas have been coupled and optical emission ... more Abstract Laser Ablation and Glow Discharge (LAGD) plasmas have been coupled and optical emission measurements have been performed in order to study the spatial and temporal distribution of LA and GD species and hence to get further insights into the interaction between them. The relative delay between the laser event and the emission measurement along the GD pulse has been found as a crucial parameter. In addition, no post excitation of the ablated material has been observed when laser ablation takes place during GD prepeak or plateau. In contrast, emission enhancements (e.g. Al I lines at ~ 877 nm presented an enhancement of up to 4 times in the LAGD plasma) were obtained during the afterglow or late plateau, when firing the laser at delays close (
2010 Abstracts IEEE International Conference on Plasma Science, 2010
ABSTRACT Summary form only given. Radiofrequency Glow Discharges (rf-GD) are commonly used as pla... more ABSTRACT Summary form only given. Radiofrequency Glow Discharges (rf-GD) are commonly used as plasma sources in combination with optical emission spectroscopy (OES) or mass spectrometry (MS) due to their ability to produce temporally and spatially separated atomization and excitation/ionization processes. Rf-GD spectroscopy is a fast and reliable analytical technique, which allows bulk and depth profile analysis, of conducting and non-conducting solid samples. In addition, the time resolved signal acquisition of pulsed- rf-GD has been shown to be of particularly interest for analytical applications.
Hollow-cathode (HC) radiofrequency glow-discharge (rf-GD) optical-emission spectrometry (OES) has... more Hollow-cathode (HC) radiofrequency glow-discharge (rf-GD) optical-emission spectrometry (OES) has been used as detector for the determination of inorganic mercury by cold-vapour (CV) generation in a flow-injection (FI) system. Both NaBH 4 and SnCl 2 were evaluated as reducing reagents for production of mercury CV. The conditions governing the discharge (pressure, He flow rate, and delivered power) and Hg CV generation (NaBH 4 or SnCl 2 concentration and reagent flow rate) were optimized using both reducing agents. The analytical performance characteristics of FI-CV-rf-GD-OES for mercury detection were evaluated at the 253.6 nm emission mercury line. Detection limits (DL) of 0.2 ng mL-1 using SnCl 2 and 1.8 ng mL-1 using NaBH 4 were obtained (100 µL sample injections were used). When the optimized experimental conditions using SnCl 2 had been determined, the analytical potential of this CV-rf-GD-OES method was investigated as on-line detector for high-performance liquid chromatographic (HPLC) speciation of mercury (Hg(II) and methylmercury). The HPLC-CV-rf-GD-OES detection limits for 100 µL sample injections were found to be 1.2 and 1.8 ng mL-1 (as mercury) of inorganic mercury and methylmercury, respectively. The reproducibility observed was below ±8% for both species. Finally, the HPLC-CV-rf-GD-OES system developed was successfully applied to the determination of methylmercury (speciation) in two certified reference materials, Dorm-2 and Dolt-2.
The effect of hydrogen (0.5%, 1% and 10% v/v) added to the argon plasma gas on the emission spect... more The effect of hydrogen (0.5%, 1% and 10% v/v) added to the argon plasma gas on the emission spectra of selected atomic lines for copper, zinc and nickel has been studied by radiofrequency glow discharge optical emission spectrometry (rf-GD-OES). Conductive homogeneous samples containing different concentrations of the elements under study in different matrices have been investigated. Results show different trends of the emission intensity lines with increasing hydrogen concentration in the rf-GD, depending on the line characteristics. In most cases, the emission yields of the lines under study did not change or increased when hydrogen was added to the discharge (no decreases were observed). The emission yields of certain lines showed much higher increases than other lines of the same element (for example, lines 213.86 nm of Zn and 231.10 nm of Ni). Our experiments indicate that such notorious increases could be related with the possible decrease of the self-absorption when hydrogen is added to the discharge. Overall, the results obtained for the emission yield changes of certain lines of a given element in different matrices (with different analyte content) showed that while for resonance emission lines very notorious increases are observed, the values for non-resonance lines do not change significantly (specially if the matrices employed are similar).
A simple and small-sized direct current glow discharge (dc-GD) ion source has been designed and c... more A simple and small-sized direct current glow discharge (dc-GD) ion source has been designed and constructed for direct analysis of solid samples. The glow discharge (about 100 mm 3 of internal volume) was coupled to a commercial on-axis time-of-flight mass ...
]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Condit... more ]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Fast characterization of coated materials requires direct solid analytical techniques able to pro... more Fast characterization of coated materials requires direct solid analytical techniques able to provide high sensitivity and high depth resolution. Well-established techniques, such as Glow Discharge Optical Emission Spectroscopies (GD-OES), show...
Journal of the Marine Biological Association of the United Kingdom
The objective of this study was to identify potential recruitment sources of Prochilodus lineatus... more The objective of this study was to identify potential recruitment sources of Prochilodus lineatus from freshwater areas (Paraná and Uruguay rivers) to estuarine population of the Río de la Plata Estuary (La Plata Basin, South America), considering young (age-1) and adult (age-7) fish. LA-ICP-MS chemical analysis of the otolith core (nine element:Ca ratios) of an unknown mixed sample from Río de la Plata Estuary (2011 and 2017) was compared with a young-of-year baseline data set (same cohort) and classified into freshwater nurseries (Paraná or Uruguay river) by using maximum classification-likelihood models (MLE and MCL) and quadratic discriminant analysis (QDA). Considering the three models used, the Uruguay River was the most important contributor for both young and adult populations. The young population (2011) was highly mixed with contributions between 31.7 to 68.3%, while the degree of mixing was found to decrease in 2017 (adult fish) from 97.1 to 100% contributions. The three ...
The application of a new methodology for direct solid analysis of fluorine by LIBS is evaluated. ... more The application of a new methodology for direct solid analysis of fluorine by LIBS is evaluated. This approach, based on the nebulization of a Ca solution over a fluorine-containing sample, allows the F quantification using the emission of the CaF molecular bands.
The needle-Flowing Atmospheric Pressure Afterglow (n-FAPA) is a miniaturized plasma device with A... more The needle-Flowing Atmospheric Pressure Afterglow (n-FAPA) is a miniaturized plasma device with Ambient Desorption/Ionization capabilities. It is generated in flowing He using two concentric electrodes: a stainless steel capillary tube (outer electrode), and a hypodermic needle with a bevel-cut edge (inner electrode).
2007 IEEE Industry Applications Annual Meeting, 2007
The goal of this paper is to study how the vapour pressure and the electrical characteristics of ... more The goal of this paper is to study how the vapour pressure and the electrical characteristics of a high pressure sodium (HPS) lamp are affected by acoustic resonances to determine if some of those parameters can be used as acoustic resonances detector.
The capabilities of radiofrequency pulsed glow discharge time of flight mass spectrometry (rf-pul... more The capabilities of radiofrequency pulsed glow discharge time of flight mass spectrometry (rf-pulsed-GD-TOFMS) for the analysis of thin film composite membranes have been investigated in this work.
The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionizat... more The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionization of the material provided by laser ablation (LA) have been compared to conventional laser induced breakdown spectroscopy (LIBS). In LA-GD both sources can be independently adjusted to optimize the sampling process and then its subsequent excitation. This could involve a number of analytical performance advantages, such as reduced matrix dependence, greater precision and sensitivity than those encountered in LIBS. For such purpose, an ablation chamber design including two electrodes to generate the GD discharge has been built and assayed. A comparison between LIBS and LA-GD-OES has been carried out, both, under reduced argon and helium atmospheres. Different sets of samples (conducting reference materials, glass and fluorine pellets) have been used to evaluate the novel coupled technique. The LA-GD coupled system has shown to provide lower detection limits. In addition, best linear correlations between intensities and concentrations and lower matrix effects have also been found using the coupled system. Moreover, special advantages of the LA-GD-OES have also been demonstrated for the analysis of fluorine.
Conference Record of the 2004 IEEE Industry Applications Conference, 2004. 39th IAS Annual Meeting., 2004
A spectroscopic study on the behavior of a high-pressure- sodium lamp is performed in this work. ... more A spectroscopic study on the behavior of a high-pressure- sodium lamp is performed in this work. The lamp works at 50 Hz and high frequencies. The study includes the analysis of the detected spectra from 400 to 700 nm, the determination of the lamp stabilization time, the Na vapour pressure and the electronic excitation temperatures.
The goal of this paper is to study how the vapour pressure and the electrical characteristics of ... more The goal of this paper is to study how the vapour pressure and the electrical characteristics of a high pressure sodium (HPS) lamp are affected by acoustic resonances to determine if some of those parameters can be used as acoustic resonances detector.
Spectrochimica Acta Part B: Atomic Spectroscopy, 2014
Abstract Laser Ablation and Glow Discharge (LAGD) plasmas have been coupled and optical emission ... more Abstract Laser Ablation and Glow Discharge (LAGD) plasmas have been coupled and optical emission measurements have been performed in order to study the spatial and temporal distribution of LA and GD species and hence to get further insights into the interaction between them. The relative delay between the laser event and the emission measurement along the GD pulse has been found as a crucial parameter. In addition, no post excitation of the ablated material has been observed when laser ablation takes place during GD prepeak or plateau. In contrast, emission enhancements (e.g. Al I lines at ~ 877 nm presented an enhancement of up to 4 times in the LAGD plasma) were obtained during the afterglow or late plateau, when firing the laser at delays close (
2010 Abstracts IEEE International Conference on Plasma Science, 2010
ABSTRACT Summary form only given. Radiofrequency Glow Discharges (rf-GD) are commonly used as pla... more ABSTRACT Summary form only given. Radiofrequency Glow Discharges (rf-GD) are commonly used as plasma sources in combination with optical emission spectroscopy (OES) or mass spectrometry (MS) due to their ability to produce temporally and spatially separated atomization and excitation/ionization processes. Rf-GD spectroscopy is a fast and reliable analytical technique, which allows bulk and depth profile analysis, of conducting and non-conducting solid samples. In addition, the time resolved signal acquisition of pulsed- rf-GD has been shown to be of particularly interest for analytical applications.
Hollow-cathode (HC) radiofrequency glow-discharge (rf-GD) optical-emission spectrometry (OES) has... more Hollow-cathode (HC) radiofrequency glow-discharge (rf-GD) optical-emission spectrometry (OES) has been used as detector for the determination of inorganic mercury by cold-vapour (CV) generation in a flow-injection (FI) system. Both NaBH 4 and SnCl 2 were evaluated as reducing reagents for production of mercury CV. The conditions governing the discharge (pressure, He flow rate, and delivered power) and Hg CV generation (NaBH 4 or SnCl 2 concentration and reagent flow rate) were optimized using both reducing agents. The analytical performance characteristics of FI-CV-rf-GD-OES for mercury detection were evaluated at the 253.6 nm emission mercury line. Detection limits (DL) of 0.2 ng mL-1 using SnCl 2 and 1.8 ng mL-1 using NaBH 4 were obtained (100 µL sample injections were used). When the optimized experimental conditions using SnCl 2 had been determined, the analytical potential of this CV-rf-GD-OES method was investigated as on-line detector for high-performance liquid chromatographic (HPLC) speciation of mercury (Hg(II) and methylmercury). The HPLC-CV-rf-GD-OES detection limits for 100 µL sample injections were found to be 1.2 and 1.8 ng mL-1 (as mercury) of inorganic mercury and methylmercury, respectively. The reproducibility observed was below ±8% for both species. Finally, the HPLC-CV-rf-GD-OES system developed was successfully applied to the determination of methylmercury (speciation) in two certified reference materials, Dorm-2 and Dolt-2.
The effect of hydrogen (0.5%, 1% and 10% v/v) added to the argon plasma gas on the emission spect... more The effect of hydrogen (0.5%, 1% and 10% v/v) added to the argon plasma gas on the emission spectra of selected atomic lines for copper, zinc and nickel has been studied by radiofrequency glow discharge optical emission spectrometry (rf-GD-OES). Conductive homogeneous samples containing different concentrations of the elements under study in different matrices have been investigated. Results show different trends of the emission intensity lines with increasing hydrogen concentration in the rf-GD, depending on the line characteristics. In most cases, the emission yields of the lines under study did not change or increased when hydrogen was added to the discharge (no decreases were observed). The emission yields of certain lines showed much higher increases than other lines of the same element (for example, lines 213.86 nm of Zn and 231.10 nm of Ni). Our experiments indicate that such notorious increases could be related with the possible decrease of the self-absorption when hydrogen is added to the discharge. Overall, the results obtained for the emission yield changes of certain lines of a given element in different matrices (with different analyte content) showed that while for resonance emission lines very notorious increases are observed, the values for non-resonance lines do not change significantly (specially if the matrices employed are similar).
A simple and small-sized direct current glow discharge (dc-GD) ion source has been designed and c... more A simple and small-sized direct current glow discharge (dc-GD) ion source has been designed and constructed for direct analysis of solid samples. The glow discharge (about 100 mm 3 of internal volume) was coupled to a commercial on-axis time-of-flight mass ...
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