Fast Determination of Arsenic Species and Total Arsenic in Urine by HPLC-ICP-MS: Concentration Ranges for Unexposed German Inhabitants and Clinical Case Studies

Heitland, Peter; Köster, Helmut D.

doi:10.1093/jat/32.4.308

Cited by 46 publications

(27 citation statements)

References 38 publications

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“…A commonly used biomarker of arsenic exposure has been the measurement of total urinary arsenic, as most arsenic compounds present in food items are excreted in urine with a half time generally of a few days (Vahter, 1994;Vahter, 2002;Hughes, 2006). However, because seafood can contain high concentrations of organic arsenic compounds, in particular arsenobetaine, consumption of even small amounts of such food, or food items containing fish products, may markedly increase the total urinary arsenic concentrations, thereby leading to an overestimation of the exposure to inorganic arsenic (Heitland and Koster, 2008;Caldwell et al, 2009;Sirot et al, 2009). Only in the case of very low total arsenic concentrations in urine, can it be assumed that the exposure to inorganic arsenic must also be low.…”

Section: Biomarkers Of Exposurementioning

confidence: 99%

Scientific Opinion on Arsenic in Food

2009

EFSA Journal

879

220

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The EFSA Panel on Contaminants in the Food Chain (CONTAM Panel) assessed the risks to human health related to the presence of arsenic in food. More than 100,000 occurrence data on arsenic in food were considered with approximately 98 % reported as total arsenic. Making a number of assumptions for the contribution of inorganic arsenic to total arsenic, the inorganic arsenic exposure from food and water across 19 European countries, using lower bound and upper bound concentrations, has been estimated to range from 0.13 to 0.56 µg/kg bodyweight (b.w.) per day for average consumers, and from 0.37 to 1.22 µg/kg b.w. per day for 95 th percentile consumers. Dietary exposure to inorganic arsenic for children under three years of age is in general estimated to be from 2 to 3-fold that of adults. The CONTAM Panel concluded that the provisional tolerable weekly intake (PTWI) of 15 µg/kg b.w. established by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) is no longer appropriate as data had shown that inorganic arsenic causes cancer of the lung and urinary bladder in addition to skin, and that a range of adverse effects had been reported at exposures lower than those reviewed by the JECFA. The CONTAM Panel modelled the dose-response data from key for providing consumption information and calculating exposure, the partners of the EFSA project on the "Individual food consumption data and exposure" coordinated by Ghent University (Department of Public Health, University Hospital, Ghent University, Belgium), and RIKILT (Institute of Food Safety, Wageningen, The Netherlands) for the accessibility of the exposure assessment tools. 4 Table of contents shows now the fourth level of subheadings. 5 An error in the interpretation of the total number of the population in the study of Rahman et al. (2006a) was discovered (Table 41). The BMDL was recalculated and as a consequence it was not considered a potential reference point. The text in the opinion, Table 43 and Appendix were revised accordingly. In addition, the header of the "total number of cases" was replaced by "total number of individuals" in Tables 40-42 and the erroneous units were corrected to µg/L in the text below SUMMARYArsenic is a metalloid that occurs in different inorganic and organic forms, which are found in the environment both from natural occurrence and from anthropogenic activity. The inorganic forms of arsenic are more toxic as compared to the organic arsenic but so far most of the occurrence data in food collected in the framework of official food control are still reported as total arsenic without differentiating the various arsenic species. The need for speciation data is evident because several investigations have shown that especially in seafood most of the arsenic is present in organic forms that are less toxic. Consequently, a risk assessment not taking into account the different species but considering total arsenic as being present exclusively as inorganic arsenic would lead to a considerable overestimation of the health risk rel...

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Section: Biomarkers Of Exposurementioning

confidence: 99%

Scientific Opinion on Arsenic in Food

2009

EFSA Journal

879

220

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“…Dans ces conditions l'emploi d'une colonne anionique permet de séparer dans l'ordre pKa, As III , DMA V MMA V et As V . C'est ce type de colonne que nous avons utilisée et qui est majoritairement citée dans la bibliographie concernant la spé-ciation de cet élément [13][14][15]. L'arsenocholine se trouvant sous forme de cation est éluée dans le front de solvant.…”

Section: Discussionunclassified

“…Avec une chromatographie liquide de paire d'ions il est possible de ré-duire considérablement la durée de l'analyse, la séparation des espèces est réalisée en 3 minutes et semble bien adaptée à des dosages en série [18]. Après séparation chromatographique, les dérivés arséniés sont analysés par spectromé-trie d'absorption atomique [19][20][21] ou par ICP-MS [13][14][15][16][17][18]. La génération d'hydrures a également été utilisée avec succès pour séparer As III , As V , MMA V et DMA V , le dosage de l'arsenic étant effectué par ICP-MS [22].…”

Section: Discussionunclassified

Validation du dosage des espèces de l'arsenic urinaire par HPLC-ICP-MS

et al. 2009

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Résumé -La récupération des ajouts dans une urine de contrôle chargée avec 100 µg/L de chaque espèce est comprise entre 100,3 % (MMA) et 102,8 % (DMA). Pour les deux formes d'arsenic les plus toxiques, As III et As V , la répétabilité analytique et la fidélité intermédiaire sont inférieures à 10 %. En l'absence d'urines contenant des concentrations certifiées des 5 dérivés considérés, la somme de concentrations des 5 formes d'arsenic quantifiées a été calculée dans deux urines du commerce titrées en arsenic total. Pour les deux concentrations d'arsenic total (153 µg/L et 109 µg/L), la somme des concentrations mesurées des 5 espèces d'arsenic est respectivement de 154,6 µg/L et de 114,6 µg/L (n = 5). Conclusion : Nous avons appliqué cette méthode avec succès à des échantillons urinaires et à des poudres suspectes, elle permet de déterminer avec précision les différentes formes d'arsenic et leur concentration. Mots clés : HPLC-ICP-MS, arsenic, spéciationAbstract -Objective: Determination of arsenic species and total arsenic in urine by liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS) are presented. Methods: The ICP-MS measurements were performed using a Thermo Elemental X7CCT series coupled to a Finnigan Spectro P1000XR HPLC. An anion exchange Hamilton PRP-X100 column and a gradient elution using ammonium carbonate, allowed the chromatographic separation of the main five arsenic species within 13.5 min: arsenobetaine (AB), arsenite (As III ), dimethylarseniate (DMA V ), monomethylarseniate (MMA V ), arseniate (As V ). Results: Aqueous or urinary calibration produced similar results. The method was linear up to 2000 µg/L total arsenic (i.e. 20 000 µg/L total arsenic for a ten fold urine dilution). Linear regression was higher than 0.998 for the 5 arsenic species. With ten fold urine dilution, the limits of quantitation were: AB = 1.0 µg/L − As III = 1.7 µg/L − DMA V = 3.5 µg/L − MMA = 3.4 µg/L − As V = 1.7 µg/L. Standard addition in control urine charged with 100 µg/L of the species produced recoveries in the range 100.3% (MMA) and 102.8% (DMA). For As III and As V , the most toxic forms of arsenic, the intra-assay and inter-assay variation coefficient were below 10%. Due to the absence of certified reference material containing the 5 species, two commercial samples have been measured. The sum of the five species were 154.6 µg/L (n = 5), and 114.6 µg/L (n = 5), for 153 µg/L

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“…In this case, no further speciation of As compounds is required. When the total As concentration is high, speciation of the As compounds in urine becomes necessary, which was demonstrated in different cases by application of HPLC combined with ICP-MS [111][112][113][114].…”

Section: Multielemental Determinationsmentioning

confidence: 99%