Publications

@article{C4JA00176A,

title = {High-resolution continuum source graphite furnace atomic absorption spectrometry for direct analysis of solid samples and complex materials: a tutorial review},

author = {Martín Resano and Maite Aramendía and Miguel A. Belarra},

url = {http://dx.doi.org/10.1039/C4JA00176A},

doi = {10.1039/C4JA00176A},

year  = {2014},

date = {2014-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {29},

issue = {12},

pages = {2229-2250},

publisher = {The Royal Society of Chemistry},

abstract = {The purpose of this review is to examine the literature devoted to direct sample analysis using high-resolution continuum source atomic absorption spectrometry in a tutorial way, in an attempt to provide guidelines on the most critical issues to consider when developing a new method. This review discusses in detail the advantages and limitations of this technique, highlighting its benefits in comparison with classic line source atomic absorption spectrometry instrumentation in the context of direct analysis of solid samples, slurries and complex liquid samples, trying to establish in which situations the use of this technique can be particularly beneficial. Some of the aspects that are addressed comprise: (i) the improved potential to detect and correct for spectral interferences; (ii) the different options to adjust the sensitivity to the analyte content; (iii) strategies to minimize matrix effects and calibrate with aqueous standard solutions; (iv) possibilities to carry out multi-element analysis.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{pmid25012579,

title = {Birth Prevalence of Fatty Acid β-Oxidation Disorders in Iberia},

author = {Hugo Rocha and Daisy Castiñeiras and Carmen Delgado and José Egea and Raquel Yahyaoui and Yolanda González and Manuel Conde and Inmaculada González and Inmaculada Rueda and Luis Rello and Laura Vilarinho and José Cocho},

doi = {10.1007/8904_2014_324},

issn = {2192-8304},

year  = {2014},

date = {2014-01-01},

journal = {JIMD Rep},

volume = {16},

pages = {89--94},

abstract = {Mitochondrial fatty acid β-oxidation disorders (FAOD) are main targets for newborn screening (NBS) programs, which are excellent data sources for accurate estimations of disease birth prevalence. Epidemiological data is of key importance for the understanding of the natural history of the disorders as well as to define more effective public health strategies. In order to estimate FAOD birth prevalence in Iberia, the authors collected data from six NBS programs from Portugal and Spain, encompassing the screening of more than 1.6 million newborns by tandem mass spectrometry (MS/MS), and compared it with available data from other populations. The participating NBS programs are responsible for the screening of about 46% of all Iberian newborns. Data reveals that Iberia has one of the highest FAOD prevalence in Europe (1:7,914) and that Portugal has the highest birth prevalence of FAOD reported so far (1:6,351), strongly influenced by the high prevalence of medium-chain acyl-CoA dehydrogenase deficiency (MCADD; 1:8,380), one of the highest ever reported. This is justified by the fact that more than 90% of Portuguese MCADD patients are of Gypsy origin, a community characterized by a high degree of consanguinity. From the comparative analysis of various populations with comparable data other differences emerge, which points to the existence of significant variations in FAOD prevalences among different populations, but without any clear European variation pattern. Considering that FAOD are one of the justifications for MS/MS NBS, the now estimated birth prevalences stress the need to screen all Iberian newborns for this group of inherited metabolic disorders. },

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{pmid23546894,

title = {Cross-sectional relationship between chronic stress and mineral concentrations in hair of elementary school girls},

author = {Barbara Vanaelst and Nathalie Michels and Inge Huybrechts and Els Clays and Maria R Flórez and Lieve Balcaen and Martin Resano and Maite Aramendia and Frank Vanhaecke and Noellie Rivet and Jean-Sebastien Raul and Anne Lanfer and Stefaan De Henauw},

doi = {10.1007/s12011-013-9647-2},

issn = {1559-0720},

year  = {2013},

date = {2013-06-01},

journal = {Biol Trace Elem Res},

volume = {153},

number = {1-3},

pages = {41--49},

abstract = {Chronic stress exposure is associated with diverse negative health outcomes. It has been hypothesised that stress may also negatively affect the body's mineral status. This study investigates the association between chronic stress and long-term mineral concentrations of calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), phosphorus (P) and zinc (Zn) in scalp hair among elementary school girls. Complete information on child-reported stress estimates (Coddington Life Events Scale (CLES)), hair cortisone and hair mineral concentrations, and predefined confounders in the stress-mineral relationship (i.e. age, body mass index, physical activity, diet, hair colour and parental education) was provided cross-sectionally for 140 girls (5-10 years old). The relationship between childhood stress measures (predictor) and hair minerals (outcome) was studied using linear regression analysis, adjusted for the abovementioned confounders. Hair cortisone concentrations were inversely associated with hair mineral concentrations of Ca, Mg, Zn and the Ca/P ratio. Children at risk by life events (CLES) presented an elevated Ca/Mg ratio. These findings were persistent after adjustment for confounders. This study demonstrated an independent association between chronic stress measures and hair mineral levels in young girls, indicating the importance of physiological stress-mineral pathways independently from individual or behavioural factors. Findings need to be confirmed in a more heterogeneous population and on longitudinal basis. The precise mechanisms by which stress alters hair mineral levels should be further elucidated.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{pmid23622690,

title = {CSF biomarker variability in the Alzheimer's Association quality control program},

author = {Niklas Mattsson and Ulf Andreasson and Staffan Persson and Maria C Carrillo and Steven Collins and Sonia Chalbot and Neal Cutler and Diane Dufour-Rainfray and Anne M Fagan and Niels H H Heegaard and Ging-Yuek Robin Hsiung and Bradley Hyman and Khalid Iqbal and Stephan A Kaeser and D Richard Lachno and Alberto Lleó and Piotr Lewczuk and José L Molinuevo and Piero Parchi and Axel Regeniter and Robert A Rissman and Hanna Rosenmann and Giuseppe Sancesario and Johannes Schröder and Leslie M Shaw and Charlotte E Teunissen and John Q Trojanowski and Hugo Vanderstichele and Manu Vandijck and Marcel M Verbeek and Henrik Zetterberg and Kaj Blennow and },

doi = {10.1016/j.jalz.2013.01.010},

issn = {1552-5279},

year  = {2013},

date = {2013-05-01},

journal = {Alzheimers Dement},

volume = {9},

number = {3},

pages = {251--261},

abstract = {BACKGROUND: The cerebrospinal fluid (CSF) biomarkers amyloid beta 1-42, total tau, and phosphorylated tau are used increasingly for Alzheimer's disease (AD) research and patient management. However, there are large variations in biomarker measurements among and within laboratories.



METHODS: Data from the first nine rounds of the Alzheimer's Association quality control program was used to define the extent and sources of analytical variability. In each round, three CSF samples prepared at the Clinical Neurochemistry Laboratory (Mölndal, Sweden) were analyzed by single-analyte enzyme-linked immunosorbent assay (ELISA), a multiplexing xMAP assay, or an immunoassay with electrochemoluminescence detection.



RESULTS: A total of 84 laboratories participated. Coefficients of variation (CVs) between laboratories were around 20% to 30%; within-run CVs, less than 5% to 10%; and longitudinal within-laboratory CVs, 5% to 19%. Interestingly, longitudinal within-laboratory CV differed between biomarkers at individual laboratories, suggesting that a component of it was assay dependent. Variability between kit lots and between laboratories both had a major influence on amyloid beta 1-42 measurements, but for total tau and phosphorylated tau, between-kit lot effects were much less than between-laboratory effects. Despite the measurement variability, the between-laboratory consistency in classification of samples (using prehoc-derived cutoffs for AD) was high (>90% in 15 of 18 samples for ELISA and in 12 of 18 samples for xMAP).



CONCLUSIONS: The overall variability remains too high to allow assignment of universal biomarker cutoff values for a specific intended use. Each laboratory must ensure longitudinal stability in its measurements and use internally qualified cutoff levels. Further standardization of laboratory procedures and improvement of kit performance will likely increase the usefulness of CSF AD biomarkers for researchers and clinicians.},

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pubstate = {published},

tppubtype = {article}

}

@article{pmid23254772,

title = {Hair minerals and metabolic health in Belgian elementary school girls},

author = {Barbara Vanaelst and Inge Huybrechts and Nathalie Michels and Maria R Flórez and Maite Aramendía and Lieve Balcaen and Martin Resano and Frank Vanhaecke and Karin Bammann and Silvia Bel-Serrat and Stefaan De Henauw},

doi = {10.1007/s12011-012-9573-8},

issn = {1559-0720},

year  = {2013},

date = {2013-03-01},

journal = {Biol Trace Elem Res},

volume = {151},

number = {3},

pages = {335--343},

abstract = {Literature has repeatedly shown a relationship between hair minerals and metabolic health, although studies in children are currently lacking. This study aims to investigate hair levels of calcium (Ca), copper (Cu), magnesium (Mg), iron (Fe), phosphorus (P), and zinc (Zn) and their association with (1) overweight/obesity and (2) metabolic health in Flemish elementary school girls between 5 and 10 years old. Two hundred eighteen girls participated in this study as part of the baseline ChiBS project. Children were subjected to physical examinations, blood and hair sampling. Hair minerals were quantitatively determined via inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion. Body mass index (BMI) and body fat percentage (BF%) were studied as anthropometric parameters, and a metabolic score (including systolic and diastolic blood pressure, insulin resistance and non-high-density lipoprotein (non-HDL) cholesterol as parameters) was calculated, with higher scores indicating a more unhealthy metabolic profile. Hair Ca, Ca/Mg, and Ca/P positively correlated with the anthropometric parameters. An inverse correlation was observed between Ca, Mg, and Ca/P in hair and the metabolic score. Inverse correlations were also observed for individual metabolic parameters (i.e., diastolic blood pressure, homeostasis model assessment for insulin resistance, non-HDL cholesterol). In particular, girls with a total number of three or more metabolic parameters above the age-specific 75th percentile showed significantly reduced hair Ca, Mg, and Ca/P concentrations. This study showed reduced hair mineral concentrations in young girls with a more unhealthy metabolic profile. Positive associations were observed between some minerals and BMI and BF%.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{pmid23180083,

title = {Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology},

author = {Eleonora Balliana and Maite Aramendía and Martin Resano and Carlo Barbante and Frank Vanhaecke},

doi = {10.1007/s00216-012-6542-1},

issn = {1618-2650},

year  = {2013},

date = {2013-03-01},

journal = {Anal Bioanal Chem},

volume = {405},

number = {9},

pages = {2973--2986},

abstract = {Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{FLOREZ201332,

title = {Direct determination of bromine in plastic materials by means of solid sampling high-resolution continuum source graphite furnace molecular absorption spectrometry},

author = {M. R. Flórez and M. Resano},

url = {https://www.sciencedirect.com/science/article/pii/S058485471300222X},

doi = {https://doi.org/10.1016/j.sab.2013.07.013},

issn = {0584-8547},

year  = {2013},

date = {2013-01-01},

journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},

volume = {88},

pages = {32-39},

abstract = {This work investigates the potential of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers, which could be interesting in view of the current regulations restricting the use of organobrominated compounds. The method developed is based on the addition of Ca (300μg) and Pd (30μg) to favor the formation of CaBr, which is monitored at the main molecular “lines” (rotational spectra) found in the vicinity of 625.315nm. It was found that accurate results could be obtained for all the samples investigated (polyethylene, polypropylene and acrylonitrile butadiene styrene certified reference materials) using any of the lines studied and constructing the calibration curve with aqueous standards. Furthermore, the combined use of the main four CaBr lines available in the spectral area simultaneously monitored permits to easily expand the linear range up to 2000ng, provides a limit of detection of 1.8ng (1.8μgg−1 for a mass of 1mg) and further improves precision to values between 3–7% RSD. Overall, the method proposed seems suited for the fast and simple control of these types of samples (approximately 10min for sample are required), circumventing the traditional problems associated with sample digestion (e.g., losses of volatile compounds), and providing sufficient sensitivity to easily comply with regulations.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{RELLO201311,

title = {A dried urine spot test to simultaneously monitor Mo and Ti levels using solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry},

author = {L. Rello and A. C. Lapeña and M. Aramendía and M. A. Belarra and M. Resano},

url = {https://www.sciencedirect.com/science/article/pii/S0584854712003734},

doi = {https://doi.org/10.1016/j.sab.2012.12.001},

issn = {0584-8547},

year  = {2013},

date = {2013-01-01},

journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},

volume = {81},

pages = {11-19},

abstract = {Home-based collection protocols for clinical specimens are actively pursued as a means of improving life quality of patients that require frequent controls, such as patients with metallic prosthesis, for whom monitoring the evolution of Mo and Ti in biological fluids may play a decisive role to detect prosthesis mal-functioning. The collection of biological fluids on clinical filter papers provides a simple way to implement these protocols. This work explores the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the simultaneous and direct determination of Mo and Ti in urine, after its deposition onto clinical filter paper, giving rise to a dried urine spot. The approach used for depositing the sample was found crucial to develop a quantitative method, since the filter paper acts as a chromatographic support and produces a differential distribution of the target analytes. Furthermore, the high spreading of urine onto a filter paper results in a small amount of urine per surface unit, and thus, ultimately, in lack of sensitivity. In order to circumvent these problems, the use of an alternative approach based on the use of pre-cut 17×19mm filter paper pieces onto which larger amounts of sample (500μL) can be retained by single deposition was proposed and evaluated. In this way, an approximately 12-fold increase in sensitivity and a more homogeneous distribution of the target analytes were obtained, permitting the development of a quantification strategy based on the use of matrix-matched urine samples of known analyte concentrations, which were subjected to the same procedure as the samples. Accuracy of this method, which provides LODs of 1.5μgL−1 for Mo and 6.5μgL−1 for Ti, was demonstrated after analysis of urine reference materials. Overall, the performance of the method developed is promising, being likely suitable for determination of other analytes in dried urine spots.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{C3JA50087J,

title = {Isotope ratio mapping by means of laser ablation-single collector-ICP-mass spectrometry: Zn tracer studies in thin sections of Daphnia magna},

author = {María R. Flórez and Maite Aramendía and Martín Resano and Ana C. Lapeña and Lieve Balcaen and Frank Vanhaecke},

url = {http://dx.doi.org/10.1039/C3JA50087J},

doi = {10.1039/C3JA50087J},

year  = {2013},

date = {2013-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {28},

issue = {7},

pages = {1005-1015},

publisher = {The Royal Society of Chemistry},

abstract = {In this paper, the possibilities of LA-single collector-ICP-mass spectrometry for obtaining isotope ratio images of thin sections of Daphnia magna specimens exposed to isotopically enriched Zn tracers were evaluated. Zn was selected considering its importance in ecotoxicological studies. All aspects of the analytical methodology deployed were carefully studied and optimized for obtaining the best isotope ratio precision and accuracy. The development of this methodological approach consisted of: (i) evaluation of the performance of two different medium mass resolution exit slits, a conventional one providing a mass resolution of m/Δm ≈ 4000 and triangular shaped peaks, and another (wider) one, offering a lower mass resolution (m/Δm ≈ 2000), but providing enhanced ion transmission and flat-topped peaks; (ii) the use of a wet plasma for improving plasma robustness; (iii) thorough optimization of the ablation conditions (such as laser spot size, repetition rate, scan speed and laser fluence) and data acquisition parameters (such as scan mode, the number of nuclides monitored, mass window, the number of samples per peak and dwell times); and (iv) adequate data treatment including the use of the moving average of 5 individual values. With the methodology developed, isotope ratio images with 30 micrometer spatial resolution scale were obtained for exposed and unexposed Daphnia magna individuals. The typical overall uncertainty of the measurements was approximately 5% RSD for the 66Zn/64Zn and 68Zn/64Zn ratios, which can be considered as satisfactory taking into account that the amount of Zn present per 30 μm × 30 μm pixel only reached a few picograms in the most favourable cases (giving rise to 10 000–20 000 counts per s for 64Zn). These results open the possibility for tracer studies with stable isotopes to be carried out using single collector instrumentation, a much more widespread analytical technique than multi-collector ICP-MS.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{RESANO201385,

title = {High-resolution continuum source atomic absorption spectrometry for the simultaneous or sequential monitoring of multiple lines. A critical review of current possibilities},

author = {M. Resano and M. R. Flórez and E. García-Ruiz},

url = {https://www.sciencedirect.com/science/article/pii/S0584854713001596},

doi = {https://doi.org/10.1016/j.sab.2013.06.004},

issn = {0584-8547},

year  = {2013},

date = {2013-01-01},

journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},

volume = {88},

pages = {85-97},

abstract = {This work examines the capabilities and limitations of commercially available high-resolution continuum source atomic absorption spectrometry instrumentation for multi-line monitoring, discussing in detail the possible strategies to develop multi-element methodologies that are truly simultaneous, or else sequential, but from the same sample aliquot. Moreover, the simultaneous monitoring of various atomic or molecular lines may bring other important analytical advantages, such as: i) expansion of the linear range by monitoring multiplets; ii) improvements in the limit of detection and in precision by summing the signals from different lines of the same element or molecule; iii) simple correction for matrix-effects by selecting a suitable internal standard; or iv) accurate mathematical correction of spectral overlaps by simultaneous monitoring of free lines of the interfering molecule or element. This work discusses how authors have made use of these strategies to develop analytical methodologies that permit the straightforward analysis of complex samples.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{C2AY26456K,

title = {Potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry to monitor the Ag body burden in individual Daphnia magna specimens exposed to Ag nanoparticles},

author = {Martín Resano and Ana C. Lapeña and Miguel A. Belarra},

url = {http://dx.doi.org/10.1039/C2AY26456K},

doi = {10.1039/C2AY26456K},

year  = {2013},

date = {2013-01-01},

journal = {Anal. Methods},

volume = {5},

issue = {5},

pages = {1130-1139},

publisher = {The Royal Society of Chemistry},

abstract = {This work evaluates the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) for the direct determination of the Ag body burden in individual specimens of Daphnia magna (a small aquatic invertebrate of approx. 2 mm length typically used in ecotoxicological studies) exposed to different Ag species, and particularly to Ag nanoparticles (NPs). It is shown that this technique offers unique features for this type of application, permitting the direct analysis of these organisms in a very straightforward way (only approx. 2–3 min are required for the analysis of every individual) and constructing the calibration curve with aqueous standards. Moreover, appropriate selection of the detector pixels used for signal quantification makes it feasible to achieve a very broad linear range for any set of experimental conditions, contrary to what occurs for traditional line source-GFAAS. This feature is particularly important for this application, as every Daphnia magna specimen can be measured only once and its Ag content is not known in advance. In this case, the use of central and/or side pixels permits achieving a working range between 3 pg and 1 μg for the 328.068 nm Ag line, thus allowing analysis of all the samples of interest with the same experimental settings.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{C3JA30377B,

title = {Simultaneous determination of Co, Fe, Ni and Pb in carbon nanotubes by means of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry},

author = {Martín Resano and Eduardo Bolea-Fernández and Engracia Mozas and María R. Flórez and Patricia Grinberg and Ralph E. Sturgeon},

url = {http://dx.doi.org/10.1039/C3JA30377B},

doi = {10.1039/C3JA30377B},

year  = {2013},

date = {2013-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {28},

issue = {5},

pages = {657-665},

publisher = {The Royal Society of Chemistry},

abstract = {This work explores the possibilities of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct analysis of carbon nanotubes. In particular, the simultaneous determination of Co, Fe, Ni and Pb is intended, as these elements are typically found in these samples as impurities. The results demonstrate that it is possible to find spectral (monitoring of the region between 283.168 and 283.481 nm), furnace (2500 °C for atomization; use of 100 ng Pd as a chemical modifier) and detector (use of side pixels to expand the linear range) conditions that permit the development of a fast and straightforward method for the simultaneous determination of the target elements at the levels at which they are typically found (mg g−1 for Co, Fe and Ni; μg g−1 for Pb) in carbon nanotubes. Limits of detection of 23 pg (Pb), 6 ng (Fe), 65 ng (Ni) and 86 ng (Co) were obtained, which are suitable for this type of sample. In this way, it was feasible to carry out the analysis of the samples investigated (one candidate reference material and three commercially available samples) and achieve accurate results when constructing the calibration curve with aqueous standards. Precision values for 5 solid sample replicates varied between 7 and 15% RSD in most cases. Overall, the proposed method shows important benefits for the cost-effective analysis of such complex samples in routine labs.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{C2JA30262D,

title = {Direct determination of Cu isotope ratios in dried urine spots by means of fs-LA-MC-ICPMS. Potential to diagnose Wilson's disease},

author = {Martín Resano and Maite Aramendía and Luis Rello and Mª Luisa Calvo and Sylvain Bérail and Christophe Pécheyran},

url = {http://dx.doi.org/10.1039/C2JA30262D},

doi = {10.1039/C2JA30262D},

year  = {2013},

date = {2013-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {28},

issue = {1},

pages = {98-106},

publisher = {The Royal Society of Chemistry},

abstract = {This work investigates the potential of a 257 nm femtosecond (fs) laser ablation (LA) device operating at a high repetition rate (10 000 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 diameter). The sampling capabilities offered by the fs LA system, permitting ablation of 150 μm thick coronas in the rim area of the filter, together with the use of admixed Ni as an internal standard, the proper optimization of the MC-ICPMS conditions (e.g., use of pseudo high-resolution mode to avoid interferences) and the use of a data processing approach particularly suitable for short transient signals (linear regression fit) enabled analysis of real urine samples with precision values around 500 ppm (RSD) for urinary Cu contents of a few hundred μg L−1. The methodology developed could prove to be useful for implementing screening protocols to detect Wilson's disease (WD), a well-known disorder related to Cu metabolism. In fact, the use of this analytical methodology permitted us to observe significant differences between (i) untreated WD patients and (ii) WD patients that are under treatment and control samples. This work represents the first time that determination of 65Cu/63Cu ratios has been used in the context of WD research, and serves as a proof of principle, suggesting that Cu isotope analysis could help in developing earlier and more reliable means to diagnose WD.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{C2JA30265A,

title = {Accurate determination of S in organic matrices using isotope dilution ICP-MS/MS},

author = {Lieve Balcaen and Glenn Woods and Martín Resano and Frank Vanhaecke},

url = {http://dx.doi.org/10.1039/C2JA30265A},

doi = {10.1039/C2JA30265A},

year  = {2013},

date = {2013-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {28},

issue = {1},

pages = {33-39},

publisher = {The Royal Society of Chemistry},

abstract = {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 of a recently developed ‘triple quadrupole’ ICP-MS instrument, operated in MS/MS mode. The added value of the MS/MS approach for this application has been clearly visualised by varying the width of the bandpass of the first quadrupole analyzer from “fully open” (standard mode) down to single mass width (MS/MS mode). As a proof-of-concept, a biodiesel reference material has been analysed for its S content with the proposed method, using isotope dilution for calibration, and the results obtained were in excellent agreement with the certified value (within experimental uncertainty).},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{C3JA30349G,

title = {Isotopic analysis of Cu in serum samples for diagnosis of Wilson's disease: a pilot study},

author = {Maite Aramendía and Luis Rello and Martín Resano and Frank Vanhaecke},

url = {http://dx.doi.org/10.1039/C3JA30349G},

doi = {10.1039/C3JA30349G},

year  = {2013},

date = {2013-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {28},

issue = {5},

pages = {675-681},

publisher = {The Royal Society of Chemistry},

abstract = {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 disease can be still arrested, has been attempted in the past. These attempts, however, have been unsuccessful, as healthy new-borns often show low Cu levels in serum due to liver immaturity. In this work, the potential use of isotopic analysis of Cu in serum samples as an alternative diagnostic parameter for Wilson's disease has been investigated. For this purpose, the Cu isotopic composition of a set of serum samples from different groups showing either low (i.e. WD patients, patients who had undergone bariatric surgery, infants) or normal (supposedly healthy adults) Cu concentration levels was determined by means of multi-collector ICP-mass spectrometry (MC-ICP-MS), after chromatographic isolation of Cu. For this purpose, AG-MP-1 strong anion exchange resin was relied upon, enabling quantitative recovery of Cu in pure form from the serum samples. MC-ICP-MS measuring conditions were optimized to avoid the influence of spectral overlap, and Ni was admixed as an internal standard for correction of instrumental mass discrimination. The use of this optimized method provided δ65Cu for the serum samples with a typical analytical uncertainty of ±0.20‰ (k = 2). Our results show that, for the population considered in this study, combination of Cu concentration values and Cu isotopic information allows classification of WD patients, infants and controls into different groups, while the use of concentration values only is not sufficient for this purpose. Although further studies with a larger number of samples are needed, results are encouraging as far as the use of Cu isotopic analysis for early diagnosis of Wilson's disease is concerned.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{pmid22907558,

title = {Mineral concentrations in hair of Belgian elementary school girls: reference values and relationship with food consumption frequencies},

author = {Barbara Vanaelst and Inge Huybrechts and Nathalie Michels and Krishna Vyncke and Isabelle Sioen and Tineke De Vriendt and Maria R Flórez and Maite Aramendía and Lieve Balcaen and Martin Resano and Frank Vanhaecke and Stefaan De Henauw},

doi = {10.1007/s12011-012-9495-5},

issn = {1559-0720},

year  = {2012},

date = {2012-12-01},

journal = {Biol Trace Elem Res},

volume = {150},

number = {1-3},

pages = {56--67},

abstract = {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 consumption frequencies) and hair mineral concentrations in 218 Belgian elementary school girls by reduced rank regression (RRR). Hair minerals were quantitatively determined via inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion of 6-cm long vertex posterior hair samples. The Children's Eating Habits Questionnaire-Food Frequency Questionnaire was used to obtain information on food consumption frequency of 43 food items in the month preceding hair collection. The established reference ranges were in line with data for other childhood or adolescent populations. The retained RRR factors explained 40, 50, 45, 46, 44 and 48 % of the variation of Ca, Cu, Fe, Mg, P and Zn concentrations in hair, respectively. Although this study demonstrated that a large proportion of hair mineral variation may be influenced by food consumption frequencies in elementary school girls, a number of food groups known to be rich sources of minerals did not show a relation with certain hair minerals. Future research should focus on mechanisms and processes involved in mineral incorporation and accumulation in scalp hair, in order to fully understand the importance and influence of diet on hair minerals.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{pmid22935036,

title = {Direct trace-elemental analysis of urine samples by laser ablation-inductively coupled plasma mass spectrometry after sample deposition on clinical filter papers},

author = {Maite Aramendía and Luis Rello and Frank Vanhaecke and Martín Resano},

doi = {10.1021/ac3018839},

issn = {1520-6882},

year  = {2012},

date = {2012-10-01},

journal = {Anal Chem},

volume = {84},

number = {20},

pages = {8682--8690},

abstract = {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, several problems arise, such as lack of sensitivity or different distribution of the analytes on the filter paper, rendering obtaining reliable quantitative results quite difficult. In this paper, a novel approach for urine collection is proposed, which circumvents many of these problems. This methodology consists on the use of precut filter paper discs where large amounts of sample can be retained upon a single deposition. This provides higher amounts of the target analytes and, thus, sufficient sensitivity, and allows addition of an adequate internal standard at the clinical lab prior to analysis, therefore making it suitable for a strategy based on unsupervised sample collection and ulterior analysis at referral centers. On the basis of this sampling methodology, an analytical method was developed for the direct determination of several elements in urine (Be, Bi, Cd, Co, Cu, Ni, Sb, Sn, Tl, Pb, and V) at the low μg L(-1) level by means of LA-ICPMS. The method developed provides good results in terms of accuracy and LODs (≤1 μg L(-1) for most of the analytes tested), with a precision in the range of 15%, fit-for-purpose for clinical control analysis.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{RESANO201224,

title = {Direct analysis of silica by means of solid sampling graphite furnace atomic absorption spectrometry},

author = {M. Resano and E. Mozas and C. Crespo and J. Pérez and E. García-Ruiz and M. A. Belarra},

url = {https://www.sciencedirect.com/science/article/pii/S0584854712000572},

doi = {https://doi.org/10.1016/j.sab.2012.03.005},

issn = {0584-8547},

year  = {2012},

date = {2012-01-01},

journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},

volume = {71-72},

pages = {24-30},

abstract = {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 optimization of the working conditions, paying particular attention to the atomization temperature and the use of proper modifiers (graphite powder, HNO3 or Pd), it is possible to develop suitable procedures that rely on the use of aqueous standard solutions to construct the calibration curves for all the elements investigated. The proposed method shows important benefits for the cost-effective analysis of such difficult samples in routine labs, permitting fast screening of those elements that are very rarely present in this type of sample, but also accurate quantification of those often found, while offering low limits of detection (always below 0.1mgg−1) that comply well with legal requirements, and precision levels that are fit for the purpose (approx. 6–9% R.S.D.).},

note = {COLLOQUIUM SPECTROSCOPICUM INTERNATIONALE XXXVII (CSI XXXVII)},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{EVENS201280,

title = {The use of liposomes to differentiate between the effects of nickel accumulation and altered food quality in Daphnia magna exposed to dietary nickel},

author = {Roel Evens and Karel A. C. De Schamphelaere and Lieve Balcaen and Yingying Wang and Karen De Roy and Martin Resano and M. Flórez and Nico Boon and Frank Vanhaecke and Colin R. Janssen},

url = {https://www.sciencedirect.com/science/article/pii/S0166445X1100333X},

doi = {https://doi.org/10.1016/j.aquatox.2011.11.017},

issn = {0166-445X},

year  = {2012},

date = {2012-01-01},

journal = {Aquatic Toxicology},

volume = {109},

pages = {80-89},

abstract = {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 dietary metal exposure and also complicates the analysis of the mechanisms of dietary metal toxicity in filter-feeding freshwater invertebrates like Daphnia magna. This problem has been partly circumvented by the production of liposomes, since these vectors are invulnerable to metal-induced food quality shifts and as such can be applied to study the mechanisms of dietary metal toxicity without the confounding effect of nutritional quality shifts. The aim of current study was to evaluate if there is relevance for dietary Ni toxicity under natural exposures, i.e., when D. magna is exposed to dietary Ni via living algae, and secondly, to quantify how nutritional quality shifts contribute to the toxic effects that are observed when algae are used as contaminated food vectors. For this aim, liposomes were prepared by the hydration of phosphatidylcholine in media containing 0 (control), 10, 50, 100 and 500mgNi/L. The liposome particles were then mixed with uncontaminated green algae in a 1/10 ratio (on a dry wt basis) to make up diets with constant nutrient quality and varying Ni contents (i.e., 1.2μgNi/gdry wt in the control and 18.7, 140.3, 165.0 and 501.6μgNi/gdry wt in the Ni-contaminated diet, respectively). A second food type was prepared on the basis of a 1/10 mixture (on a dry weight basis) of control liposomes and Ni-contaminated algae, representing a diet that differed in Ni content (i.e., 1.2, 26.8, 84.7, 262.3 and 742.7μgNi/gdry wt) and concentrations of essential nutrients (in terms of P and omega 3 poly-unsaturated fatty acids like eicosapentaenoic acid and α-linolenic acid). Both diets were then simultaneously fed to D. magna during a 21-day chronic bioassay, using reproduction, growth, survival, ingestion rate and Ni bioaccumulation as endpoints. Ni delivered by liposomes caused a significant inhibition of reproduction and growth when the metal accumulated to minimum levels of 11.9 and 20.0μgNi/gdry wt after 7 and 14 days, respectively. Using algae as Ni vector, similar effects of dietary Ni exposure occurred when algae had been pre-exposed to concentrations of at least 133μg/L of bioavailable Ni (i.e., Ni2+), which is similar to the reproductive EC50 of waterborne Ni exposure for D. magna (115μgNi2+/L). While this may have some consequences for predicting chronic Ni toxicity in this range of Ni concentrations with the biotic ligand model – which could be further improved by including the dietary toxicity pathway in this model, the occurrence of such high concentrations in the field is very rare. Hence, there seems to be very little environmental relevance for dietary Ni toxicity to D. magna. Finally, besides the direct effects of Ni there was no evidence that nutritional quality shifts could have affected daphnids’ growth, but it is very likely that the impairment of reproduction at toxic exposure levels of Ni was also partly the result of reduced fatty acid levels.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{C2JA10322B,

title = {Direct determination of sulfur in solid samples by means of high-resolution continuum source graphite furnace molecular absorption spectrometry using palladium nanoparticles as chemical modifier},

author = {Martín Resano and María R. Flórez},

url = {http://dx.doi.org/10.1039/C2JA10322B},

doi = {10.1039/C2JA10322B},

year  = {2012},

date = {2012-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {27},

issue = {3},

pages = {401-412},

publisher = {The Royal Society of Chemistry},

abstract = {This work investigates the potential benefits of using Pd nanoparticles, 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) Pd nanoparticles are evenly distributed over the platform surface, offering a larger surface for interaction with the analyte during the drying and pyrolysis steps. In this way, a more efficient stabilization of sulfur species can be achieved. Furthermore, a similar analytical response is obtained regardless of the chemical form in which sulfur species are originally found, thus making it easier to develop quantitative analytical methods for this analyte. When using these modifiers, and under optimized working conditions, it is possible to use this technique for direct analysis of different types of solid samples (biological, petroleum coke, polyethylene and steel CRMs), thus circumventing the traditional drawbacks associated with sample digestion when sulfur determination is aimed at. Accurate results are obtained using only the central CS line found at 257.958 nm, with precision values in the 5–10% RSD range (14 ng characteristic mass; 9 ng limit of detection). Moreover, the combined use of the main six CS lines available in the spectral area simultaneously monitored by the detector permits to further improve precision to 3–5% RSD, while decreasing the limit of detection down to 3 ng (the characteristic mass is also 3 ng), which represents a relative limit of detection of approx. 1 μg g−1, as calculated for the sample with the lowest sulfur content. In all cases, straightforward calibration with aqueous standards was proved to be feasible, and the sample throughput is of 3–4 samples per hour (5 replicates per sample).},

keywords = {},

pubstate = {published},

tppubtype = {article}

}