Analytical artefacts in the speciation of arsenic in clinical samples

Šlejkovec, Zdenka; Falnoga, Ingrid; Goessler, Walter; Elteren, Johannes T. van; Raml, Reingard; Podgornik, Helena; Černelč, Peter

doi:10.1016/j.aca.2007.11.031

Cited by 66 publications

(48 citation statements)

References 26 publications

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“…There have however, been several reports of their presence in urine (Mandal et al, 2001;Valenzuela et al, 2005), although the analytical quality of these data has been questioned Slejkovec et al, 2008). It is worth noting that most studies on arsenic urine metabolites have failed to detect these reduced methylated species despite specific efforts to do so (e.g.…”

Section: Metabolismmentioning

confidence: 99%

“…It is worth noting that most studies on arsenic urine metabolites have failed to detect these reduced methylated species despite specific efforts to do so (e.g. Slejkovec et al, 2008). Thio-dimethylarsinate has been shown to be a urine metabolite from Bangladeshi women (Raml et al, 2007) and the suggestion was that this species may previously have been misidentified as dimethylarsinite.…”

Section: Metabolismmentioning

confidence: 99%

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Scientific Opinion on Arsenic in Food

2009

EFSA Journal

856

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: Metabolismmentioning

confidence: 99%

Section: Metabolismmentioning

confidence: 99%

Scientific Opinion on Arsenic in Food

2009

EFSA Journal

856

220

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“…In their case the "missing" arsenic was retained 181 after lowering the pH via an injection of 100 µL of a 3 mol L -1 HCl solution. [21] Naramandura and Suzuki…”

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confidence: 99%

Arsenic speciation in bodily fluids of harbor seals (Phoca vitulina) and harbor porpoises (Phocoena phocoena)

Kuenstl

Griesel²,

Prange³

et al. 2009

Environ. Chem.

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11 12Environmental context. Marine mammals as top predators ingest a lot of arsenic from their food. In this 13 study liver samples and body fluids of marine mammals from the North and Baltic Seas were investigated 14 for arsenic speciation in order to get some information about their feeding habits. Only organic arsenic 15 compounds with low toxicity were detected in all investigated samples. Although a high quantitative 16 variability was observed, the same compounds were determined in all fluids examined. 18Abstract. The total arsenic concentrations in whole blood of harbor seals (Phoca vitulina) and in liver 19 tissues of harbor porpoises (Phocoena phocoena) were determined using TXRF (total-reflection X-ray 20 fluorescence spectrometry). The total arsenic concentration found in whole blood was lower for fish-fed ). In porpoise liver the arsenic concentrations were higher from carcases found in the North Sea (217- ). 25Furthermore the total arsenic content and arsenic species in urine, plasma, and gastric juice of seals and 26 the urine of porpoises, which were collected from animals at different areas in the North and Baltic Seas, 27were determined using ICPMS (inductively coupled plasma mass spectrometry . The arsenic is almost entirely present in inorganic forms.[1] 49Marine organisms are known to accumulate and convert inorganic arsenic to organic arsenic compounds. 50Mammals such as porpoises and seals living in the marine environment and feeding exclusively on marine 51 organisms are in an exceptional position. As top predators they could accumulate arsenic due to their 52 position in the food web. Goessler et al., reported in 1997 the arsenic concentrations and speciation in a 53 three organism marine food chain starting with a seaweed followed by two gastropods. They showed that 54 arsenic was accumulated and metabolized within this food chain.[2] These results were in contrast to those 55of Kubota et al., who found lower arsenic concentrations in marine mammals (seals and porpoises) 56 compared to those of lower tropic level marine organisms from other studies.[3] Furthermore Kubota et al. 57investigated a possible correlation between arsenic accumulation and gender, age (or body length), or 58 feeding habits in liver tissues of 16 different marine mammal species. The determined arsenic 59concentrations varied widely among species and individuals ranging from 100 to 7680 µg kg -1 dry mass. 60Marine mammals feeding on fish contained lower arsenic concentrations compared to animals feeding on 61cephalopods and crustaceans but no trend with gender or age could be seen.[3] 62Seals feed with regional and seasonal variations on fish, crustaceans, and cephalopods, [4] in contrast to 63 harbor porpoises, which feed mainly on fish and less frequently on molluscs and squids.[5] 64Arsenic contents in tissues of field-collected marine mammals, fish, and invertebrates have been reported 65 in quantities ranges from less than 1000 up to 30000 µg As kg -1 dry mass. [6][7] Total arsenic content in 66 whole blood of...

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“…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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Analytical artefacts in the speciation of arsenic in clinical samples

Cited by 66 publications

References 26 publications

Scientific Opinion on Arsenic in Food

Scientific Opinion on Arsenic in Food

Arsenic speciation in bodily fluids of harbor seals (Phoca vitulina) and harbor porpoises (Phocoena phocoena)

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

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