Martin Resano

University of Zaragoza | UNIZAR · Department of Analytical Chemistry

This work explores the possibilities of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct analysis of carbon nanotubes. In particular, the simultaneous determination of Co, Fe, Ni and Pb is intended, as these elements are typically found in these samples as impurities. The results demonst...

This work investigates the potential of a 257 nm femtosecond (fs) laser ablation (LA) device operating at a high repetition rate (10000 Hz) coupled to a multicollector (MC)-ICPMS to develop a method for the direct determination of Cu ratios in dried urine spots, prepared by deposition of urine (300 μL) onto precut clinical filter paper discs (16 mm...

The aim of this work is to review and compare the present possibilities of electrothermal atomic absorption spectrometry (ETAAS), electrothermal vaporization-inductively coupled plasma-optical emission spectrometry (ETV-ICP-OES) and electrothermal vaporization-inductively coupled plasma-mass spectrometry (ETV-ICP-MS) for analysis of solid samples,...

The determination of platinum group metals in solid samples at ultratrace levels is demanded in many situations. This complicated analytical task traditionally requires a complex, time-consuming analytical procedure if sample digestion is intended.This article discusses recent advances in several analytical techniques (spark-optical emission spectr...

In this work, several red-colored paintings of post-Paleolithic schematic style found in 10 different shelters in the vicinity of the Vero River (Huesca) were sampled and subjected to analysis by means of scanning electron microscopy-energy-dispersive X-ray spectrometry (SEM-EDX), Raman spectroscopy, and laser ablation-inductively coupled plasma ma...

After 40 years of development, inductively coupled plasma-mass spectrometry (ICP-MS) can hardly be considered as a novel technique anymore. ICP-MS has become the reference when it comes to multi-element bulk analysis at (ultra)trace levels, as well as to isotope ratio determination for metal(loid)s. However, over the last decade, this technique has...

This paper presents a novel approach, based on the standard addition method, for overcoming the matrix effects that often hamper the accurate characterization of nanoparticles (NPs) in complex samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). In this approach, calibration of the particle size is performed by two...

High-resolution continuous source graphite furnace molecular absorption spectrometry (HR CS GFMAS) can provide isotopic information under certain conditions, thus broadening its field of application. However, up to date, only elements...

Information about Cu fractionation and Cu isotopic composition can be paramount when investigating Wilson’s disease (WD). This information can provide a better understanding of the metabolism of Cu. Most important,...

Este trabajo plantea la aplicación de HR-CS-GF-MAS para el análisis isotópico de estroncio como una aproximación al estudio de las posibilidades de la técnica en el análisis de elementos con múltiples isótopos estables. Para ello, se formará la molécula de SrF y se aplicarán correcciones para obtener señales isotópicas individuales.

Technological developments have brought significant upgrades to classic analytical techniques, such as the evolution of atomic absorption spectrometry (AAS) to high-resolution continuum source (HR CS) AAS. The possibility to obtain...

A new method for Cu isotopic analysis was developed using a commercially available electrothermal vaporization (ETV) device coupled to multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS). The method demonstrated potential for the isotopic analysis of microsamples (e.g., 5 μL) in a biological context. For example, Cu isotopic ana...

The performance of state-of-the-art high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) instrumentation and four novel devices to produce dried blood spots of perfectly defined volumes is evaluated with the aim of developing a simple, direct method for the determination of Cu in blood samples. In all cases...

Recommendations are given concerning the terminology of concepts and methods used in spectroscopy in analytical chemistry, covering nuclear magnetic resonance spectroscopy, atomic spectroscopy, and vibrational spectroscopy.

The use of an internal standard to correct for potential matrix effects and instrument instability is common practice in ICP-MS. However, with the introduction of a new generation of ICP-MS...

Cu isotopic analysis -can provide valuable hindsight when investigating Wilson’s disease (WD), but one of the problems related with this type of study is that usually low sample volumes are...

Toxicological studies concerning nanomaterials in complex biological matrices usually require a carefully designed workflow that involves handling, transportation and preparation of a large number of samples without affecting the nanoparticle...

This manuscript explores the advantages of using multi-signal calibration approaches for the determination of non-metals via high-resolution continuum source graphite furnace molecular absorption spectrometry (HR CS GFMAS), targeting Br as an example. Besides multi-energy calibration (MEC), a novel approach deriving from it, multi-energy ratios (ME...

This study describes the determination of phosphorus by the molecular absorption of phosphorus monoxide (PO) at 213.647 nm using high-resolution continuum source graphite furnace molecular absorption spectrometry with direct solid sample analysis (HR CS SS-GFMAS). Furthermore, the paper shows how the observation of the background signal provided by...

Since the development of atomic spectrometry, trace element and isotopic analysis has been mainly based on the monitoring of atomic spectra and monoionic species. However, according to the literature and considering the current instrumental developments, it seems that some of the remaining challenges in this field can be mitigated via the measureme...

Use of dried matrix spots, such as dried blood spots -DBS- and dried urine spots -DUS-, is becoming more popular in clinical analyses, beyond their traditional use for sampling newborns. Currently, there are new types of microsampling devices that have been designed to collect a low and known volume of biological fluids, regardless of the hematocri...

This study investigates the possibility of obtaining Ca isotopic information by monitoring the absorption spectrum of a diatomic molecule generated in a graphite furnace using a high-resolution continuum source spectrometer (HR CS GFMAS). The method proposed enables calcium isotopic analysis using CaF as the target species. The difference in wavele...

This study reports a simple and efficient method for the simultaneous determination of Cd, Mn, Pb, and Sb at trace levels in gasoline samples by discrete sample introduction in inductively coupled plasma mass spectrometry (ICP-MS), employing the extraction induced by microemulsion breaking as a sample preparation method. In this work, a microemulsi...

In this work, the effects of using collision/reaction cell (CRC) technology in quadrupole-based ICP-MS (ICP-QMS) instrumentation operated in single-particle (SP) mode have been assessed. The influence of (i) various CRC gases, (ii) gas flow rates, (iii) nanoparticle (NP) sizes and (iv) NP types was evaluated using Ag, Au and Pt NPs with both a trad...

The aim of the present work is the development of a simple, sensitive and sustainable EDXRF method for the determination of trace amounts of sulfur in biodiesel samples. In this method, the deposition of several microliters of sample onto an organic thin layer and the analysis of the resulting adsorbed biodiesel spot by benchtop EDXRF is proposed....

After more than a decade since its commercial introduction, high-resolution continuum source atomic/molecular absorption spectrometry maybe facing a mid-life crisis. Certainly, it is no longer a novel technique full of unknown potential, so it would be already time to establish the fields for which it is most suitable. This is, however, not so simp...

En estudios anteriores, mediante la aplicación de una rampa de atomización lenta (150ºC s-1), ha sido posible la caracterización del tamaño medio de nanopartículas de oro (AuNPs) mediante espectroscopia de absorción atómica de fuente contínua de alta resolución con atomización electrotérmica (HR CS GFAAS) sin utilización de modificantes de matriz o...

Este trabajo usa la Espectrometría de Absorción Atómica con Horno de Grafito (HR CS GFAAS) para cuantificación de mercurio (Hg) en muestras certificadas (CRM) de orina y sangre, usando nanopartículas de oro (AuNPs) como modificante químico. Los porcentajes de recuperación obtenidos de muestras de CRM concuerdan con los valores de referencia (86 al...

This article examines the increasing importance of dried matrix spots (DMS), such as dried blood spots, dried urine spots, etc., in biomedical research, the challenges associated with their analysis when quantitative elemental information is aimed at, as well as the benefits deriving from the further usage of these types of samples. The article bri...

Home-based collection protocols for clinical specimens are actively pursued as a means of improving life quality of patients. In this sense, dried blood spots (DBS) are proposed as a non-invasive and even self-administered alternative to sampling whole venous blood. This contribution explores the potential of energy dispersive X-ray fluorescence sp...

The determination of Hg in biological fluids, such as blood and urine, is important considering its known toxicity towards human health. This kind of analysis typically requires the use of expensive instrumentation and/or sample pretreatment, which can be a problem for implementation in laboratories in low and middle-income countries. In this work,...

The increase in the use of SiO2 nanoparticles (NPs) is raising concern about their environmental and health effects, thus necessitating the development of novel methods allowing for their straightforward detection and characterization. Single Particle ICP- mass spectrometry (SP-ICP-MS) is able to provide information on the size of NPs, their partic...

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 applicatio...

A total consumption low sample introduction system has been applied for the first time to the multielemental analysis of non-diluted cerebrospinal fluids (CSF) by means of inductively coupled plasma mass spectrometry (ICP-MS). A 2.5 µL sample volume has been injected into an air carrier stream in agreement with the air-segmented injection principle...

An analytical method was developed for Ca determination in ultrapure water, concentrated acids and hydrogen peroxide by ICP-MS, using CH3F as reaction gas in the dynamic reaction cell (DRC) and isotopic dilution (ID) as strategy of calibration for improve the accuracy and allow interference- free Ca determination.

Debido a la matriz compleja de las muestras orgánicas oleosas, los procedimientos tradicionales para la determinación directa de metales empleando técnicas espectroscópicas se vuelven prácticamente inviables, siendo necesaria la introducción de una etapa de preparación de esas muestras. La preparación de muestras con alto contenido de materia orgán...

This work uses the tandem ICP-MS (ICPMS/MS) for obtaining interference-freeconditions to characterize SiO2 nanoparticles ranging between 80 and 400nm. These NPs have been detected and accurately characterized. For SiO2 NPs >100 nm, it was possible to provide accurateresults in a straightforward way, as theirsignal distributions are well resolved fr...

Mediante la aplicación de una rampa de atomización lenta (150ºC s-1), ha sido posible la caracterización del tamaño medio de nanopartículas de oro (AuNPs) mediante espectroscopia de absorción atómica de fuente contínua de alta resolución con atomización electrotérmica (HR CS GFAAS) sin utilización de modificantes de matriz o etapas previas. El pará...

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 d...

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 400 µg Ca as molecule-forming reagent and of 20 µg Pd as ch...

This paper reports on an evaluation of the suitability of a novel sample collection approach, volumetric absorptive micro-sampling (VAMS), in the context of the determination of ultra-trace concentrations of prosthesis-related metals (Al, Ti, V, Co, Cr, Ni, Sr and Zr) in whole blood. In a first phase, a simple dilute-and-shoot approach (100-fold di...

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...

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 b...

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 absorp...

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...

The combination of laser ablation and tandem ICP-mass spectrometry (LA-ICP-MS/MS) allows for successful Sr isotopic analysis of solid samples with high Rb/Sr ratios. Isobaric overlap at a mass-to-charge ratio of 87 (87Sr–87Rb) is overcome via chemical resolution. By using CH3F/He (10% CH3F in He), in an octopole collision-reaction cell, Sr+ ions ar...

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. The development of the screening model is ba...

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. Th...

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)...

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 (30000 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...

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 calibr...

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 pr...

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 purpose of this review is to examine the literature devoted to direct sample analysis using high-resolution continuum source atomic absorption spectrometry in a tutorial way, in an attempt to provide guidelines on the most critical issues to consider when developing a new method. The review discusses in detail the advantages and limitations of...

Ti is frequently used in implants and prostheses and it has been shown before that the presence of these in the human body can lead to elevated Ti concentrations in body fluids such as serum and urine. As identification of the exact mechanisms responsible for this increase in Ti concentrations, and the risks associated with it, are not fully unders...

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...

This work examines the capabilities and limitations of commercially available high-resolution continuum source atomic absorption spectrometry instrumentation for multi-line monitoring, discussing in detail the possible strategies to develop multi-element methodologies that are truly simultaneous, or else sequential, but from the same sample aliquot...

This work investigates the potential of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers, which could be interesting in view of the current regulations restricting the use of organobrominated compounds. The method developed is based on the addition of Ca (300 μg)...

In this paper, the possibilities of LA-single collector-ICP-mass spectrometry for obtaining isotope ratio images of thin sections of Daphnia magna specimens exposed to isotopically enriched Zn tracers were evaluated. Zn was selected considering its importance in ecotoxicological studies. All aspects of the analytical methodology deployed were caref...

Wilson's disease (WD) is a genetic disorder affecting Cu metabolism, which can lead to severe physiological and neurological symptoms, and even death if untreated. Based on the fact that WD patients show low Cu levels in serum, implementation of screening programs for diagnosis of this condition at the moment of birth, when progression of the disea...

Chronic stress exposure is associated with diverse negative health outcomes. It has been hypothesised that stress may also negatively affect the body's mineral status. This study investigates the association between chronic stress and long-term mineral concentrations of calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), phosphorus (P) and zinc (...

Home-based collection protocols for clinical specimens are actively pursued as a means of improving life quality of patients that require frequent controls, such as patients with metallic prosthesis, for whom monitoring the evolution of Mo and Ti in biological fluids may play a decisive role to detect prosthesis mal-functioning. The collection of b...

This work evaluates the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) for the direct determination of the Ag body burden in individual specimens of Daphnia magna (a small aquatic invertebrate of approx. 2 mm length typically used in ecotoxicological studies) exposed to dif...

Literature has repeatedly shown a relationship between hair minerals and metabolic health, although studies in children are currently lacking. This study aims to investigate hair levels of calcium (Ca), copper (Cu), magnesium (Mg), iron (Fe), phosphorus (P), and zinc (Zn) and their association with (1) overweight/obesity and (2) metabolic health in...

Accurate determination of low levels of S in organic matrices by means of isotope dilution ICP-single quadrupole MS (e.g., for quantification of S components in reverse phase HPLC-ICP-MS experiments) is often not feasible. This work describes an accurate, sensitive and fast analytical method for the determination of S in organic matrices by means o...

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of “non-traditional” isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via op...

Collection of biological fluids on clinical filter papers shows important advantages from a logistic point of view, although analysis of these specimens is far from straightforward. Concerning urine analysis, and particularly when direct trace elemental analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) is aimed at,...

Although evidence suggests that hair elements may reflect dietary habits and/or mineral intake, this topic remains controversial. This study therefore presents age-specific reference values for hair concentrations of Ca, Cu, Fe, Na, Mg, P and Zn using the LMS method of Cole, and investigates the relationship between dietary habits (i.e. food consum...

IntroductionForensic Applications Based on ICP-MS Isotopic AnalysisFuture OutlookAcknowledgmentsReferences

IntroductionPrinciple of LA-ICPMSKey Aspects for Developing an LA-ICPMS Method in Archaeometric Research: Multielemental ApplicationsLA-ICPMS for Isotopic Analysis of Archaeological SamplesConclusions and Future ResearchAcknowledgmentsReferences

This paper reports on the use of solid sampling-graphite furnace atomic absorption spectrometry for the direct analysis of synthetic amorphous silica. In particular, determination of hazardous elements such As, Cd, Cr, Cu, Pb and Sb is investigated, as required by regulations of the food industry.The conclusion of the work is that, after proper opt...

This work investigates the potential benefits of using Pdnanoparticles, in combination with Ru as permanent modifier, for sulfur monitoring as CS by means of high-resolution continuum source graphite furnace molecular absorption spectrometry. Upon heating, these small (approx. 20 nm diameter) Pdnanoparticles are evenly distributed over the platform...

This paper explores the potential of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) for the determination of Au, Ir, Pd, Pt, Rh and Ru in NiS buttons obtained by fire assay of platiniferous ores using a new type of ICP-MS instrument equipped with an array detector Mattauch–Herzog spectrometer. The method evaluated comprises...

A potential drawback of traditional dietary metal toxicity studies is that it is difficult to distinguish between the direct toxicity of the metal and indirect effects caused by altered concentrations of essential nutrients in the metal-contaminated diet. In previous studies it has become clear that this can hamper the study of the real impact of d...

In this work, a new methodology for direct determination of Al in whole blood samples by means of high-resolution continuum source graphite furnace molecular absorption spectrometry has been developed, based on the formation of the AlF diatomic molecule in the graphite furnace and the subsequent monitoring of its molecular absorption. The proposed...

Dietary metal toxicity studies with invertebrates such as Daphnia magna are often performed using metal-contaminated algae as a food source. A drawback of this approach is that it is difficult to distinguish between the direct toxicity of the metal and indirect effects caused by a reduced essential nutrient content in the metal-contaminated diet, d...

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The recent arrival of high-resolution continuum source atomic absorption spectrometry represents a potential revolution in this field, in particular for direct analysis of complex samples. This review tries to illustrate the main advantages of this technology, paying particular attention to the development of direct solid sampling methods. Three so...

This paper explores the potential of commercially available high-resolution continuum source graphite furnace atomic absorption spectrometry instrumentation for the simultaneous or sequential monitoring of various atomic lines, in an attempt to highlight the analytical advantages that can be derived from this strategy. In particular, it is demonstr...

In this work, the capabilities of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (GFAAS) for the direct determination of the Au content in different body compartments of mice that were previously exposed to Aunanoparticles (AuNP) capped with different compounds have been investigated. It was conclude...

This work explores the performance of laser ablation-inductively coupled plasma mass spectrometry using different types of single-collector devices (sector field and time-of-flight instrumentation) for lead isotopic analysis of bronze coins, minted in the ancient city of Bilbilis. The aim of the study was achieving sufficient discrimination power t...

Owing to the shorter time interval during which energy is delivered to the sample material, femtosecond (fs) laser ablation is preferable over nanosecond laser ablation for metallic samples. In this project, the influence of various laser parameters-beam diameter, repetition rate and laser fluence-on the ablation of Pb as a heavy metallic matrix us...