Inorganic arsenic determination in food: a review of analytical proposals and quality assessment over the last six years

Here we review recent developments in analytical proposals for the assessment of inorganic arsenic (iAs) content in food products. Interest in the determination of iAs in products for human consumption such as food commodities, wine, and seaweed among others is fueled by the wide recognition of its toxic effects on humans, even at low concentrations. Currently, the need for robust and reliable analytical methods is recognized by various international safety and health agencies, and by organizations in charge of establishing acceptable tolerance levels of iAs in food. This review summarizes the state of the art of analytical methods while highlighting tools for the assessment of quality assessment of the results, such as the production and evaluation of certified reference materials (CRMs) and the availability of specific proficiency testing (PT) programmes. Because the number of studies dedicated to the subject of this review has increased considerably over recent years, the sources consulted and cited here are limited to those from 2010 to the end of 2015

Occurrence of inorganic arsenic in edible Shiitake (Lentinula edodes) products

The present study reports arsenic speciation analysis in edible Shiitake (Lentinula edodes) products. The study focused on the extraction, and accurate quantification of inorganic arsenic (iAs), the most toxic form of arsenic, which was selectively separated and determined using anion exchange LC-ICPMS. A wide variety of edible Shiitake products (fresh mushrooms, food supplements, canned and dehydrated) were purchased and analysed. A cultivated Shiitake grown under controlled conditions was also analysed. The extraction method showed satisfactory extraction efficiencies (>90%) and column recoveries (>85%) for all samples. Arsenic speciation revealed that iAs was the major As compound up to 1.38 mg As per kg dm (with a mean percentage of 84% of the total arsenic) and other organoarsenicals were found as minor species. Shiitake products had high proportions of iAs and therefore should not be ignored as potential contributors to dietary iAs exposure in populations with a high intake of Shiitake products

Establishment of a method for determination of arsenic species in seafood by LC-ICP-MS

An analytical method for determination of arsenic species (inorganic arsenic (iAs), methylarsonic acid (MA), dimethylarsinic acid (DMA), arsenobetaine (AB), trimethylarsine oxide (TMAO) and arsenocholine (AC)) in Brazilian and Spanish seafood samples is reported. This study was focused on extraction and quantification of inorganic arsenic (iAs), the most toxic form. Arsenic speciation was carried out via LC with both anionic and cationic exchange with ICP-MS detection (LC-ICP-MS). The detection limits (LODs), quantification limits (LOQs), precision and accuracy for arsenic species were established. The proposed method was evaluated using eight reference materials (RMs). Arsenobetaine was the main species found in all samples. The total and iAs concentration in 22 seafood samples and RMs ranged between 0.27-35.2 and 0.02-0.71 mg As kg-1, respectively. Recoveries ranging from 100% to 106% for iAs, based on spikes, were achieved. The proposed method provides reliable iAs data for future risk assessment analysis

Assessment of arsenic bioaccessibility in raw and cooked edible mushrooms by a PBET method

The present study reports arsenic analysis in Lentinula edodes, Agaricus bisporus and Pleurotus ostreatus before and after being cooked. Furthermore, arsenic in raw and cooked mushroom was determined in the gastric and gastrointestinal bioaccessible fractions obtained after simulating human digestion by means of an in vitro physiologically based extraction test (PBET). Several certified reference materials (SRM 1568a, SRM 1570a, CRM 7503-a, BC211 and IPE-120) were analysed to evaluate the proposed methods. Total arsenic content was 1393, 181 and 335 μg As kg-1 for L. edodes, A. bisporus and P. ostreatus, respectively, and decreased by between 53% and 71% in boiled mushroom and less than 11% in griddled mushroom. High bioaccessibility was observed in raw, boiled and griddled mushroom, ranging from 74% to 89% and from 80% to 100% for gastric and gastrointestinal extracts, respectively, suggesting the need to consider the potential health risk of consumption of the mushrooms analysed

Accuracy of a method based on atomic absorption spectrometry to determine inorganic arsenic in food: outcome of the collaborative trial IMEP-41

A collaborative trial was conducted to determine the performance characteristics of an analytical method for the quantification of inorganic arsenic (iAs) in food. The method is based on (i) solubilisation of the protein matrix with concentrated hydrochloric acid to denature proteins and allow the release of all arsenic species into solution, and (ii) subsequent extraction of the inorganic arsenic present in the acid medium using chloroform followed by back-extraction to acidic medium. The final detection and quantification is done by flow injection hydride generation atomic absorption spectrometry (FI-HG-AAS). The seven test items used in this exercise were reference materials covering a broad range of matrices: mussels, cabbage, seaweed (hijiki), fish protein, rice, wheat, mushrooms, with concentrations ranging from 0.074 to 7.55 mg kg(-1). The relative standard deviation for repeatability (RSDr) ranged from 4.1 to 10.3%, while the relative standard deviation for reproducibility (RSDR) ranged from 6.1 to 22.8%. (C) 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)

Establishment and validation of analytical methods for the determination of arsenic species in foodstuffs

[spa] El interés en la determinación de arsénico inorgánico (iAs) en los alimentos se debe al amplio reconocimiento de sus efectos tóxicos en los humanos, incluso a bajas concentraciones. Varios métodos de especiación de arsénico se han publicado, sin embargo es necesario establecer su idoneidad para una serie de muestras de alimentos y /o especies de arsénico Además, existe una necesidad urgente de métodos analíticos robustos y validados y adecuados para la determinación de arsénico inorgánico en una gama de productos alimenticios. Esta necesidad se destacó por varias agencias internacionales de seguridad y salud, y por las organizaciones encargadas de establecer los niveles máximos de la iAs en los productos alimenticios. En vista de todo esto, el objetivo principal de esta tesis es desarrollar y validar metodología analítica robusta para la determinación de arsénico inorgánico, así como otras especies de arsénico en alimentos. La metodología propuesta es aplicada a arroz, alimentos a base de cereales, productos infantiles, setas, algas, peces, crustáceos y bivalvos proporcionando resultados fiables como una respuesta a la demanda de las agencias internacionales de seguridad. Las principales conclusiones derivadas del trabajo llevado a cabo en la presente tesis doctoral se resumen a continuación: • El método de especiación propuesto fue validado con éxito de acuerdo con la norma 17025 ISO/IEC: 2005, es sensible y selectivo y podría ser considerado apropiado para su finalidad, es decir, la determinación de iAs en los alimentos. Este método es sencillo para análisis de rutina para la determinación del tóxico iAs y otras especies de arsénico en varios productos alimenticios, incluso en matrices difíciles tales como las de origen marino. Además, debido a que límites máximos de iAs en arroz y productos de arroz han sido recientemente establecidos por la Unión Europea, el método podría ser útil en los laboratorios de control de los alimentos. • La ingesta diaria promedio de iAs estimada en la población adulta Catalana está por debajo de los rangos BMDL de la EFSA y JECFA, pero teniendo en cuenta relación entre la ingesta de iAs y algunos BMDL para distintos puntos finales, la posibilidad de riesgo para los grandes consumidores de arroz y productos de arroz no pueden ser excluidos[eng] Food and drinking water are the principal routes of exposure to arsenic (As) for humans. More than 50 different naturally occurring As-containing compounds have been identified. Regarding the toxicological aspects of arsenic in food, inorganic arsenic (iAs, (arsenite or As(III) and arsenate or As(V)) is considered to be the most dangerous form and is classified as a nonthreshold, class 1 human carcinogen. The organic forms are mainly considered to be non-toxic. Therefore, species-dependent differences in toxicity must be considered when establishing the maximum tolerated levels in food directives. Recently, maximum levels have been fixed for iAs in rice and rice products in EU legislation. Scientific opinions on arsenic in food were issued by the European Food Safety Authority and the FAO/WHO Joint Expert Committee on Food Additives, focusing on dietary iAs exposure. Both reported the urgent need for further data on As species, particularly iAs data, in food groups that provide a significant contribution to the dietary exposure to iAs. As a general recommendation, dietary exposure to iAs should be reduced. Furthermore, the organisations also called upon further initiatives towards development of validated methods for specific and selective determination of inorganic arsenic in various types of foodstuffs. In view of the above, the main goal of this thesis was to develop and validate robust analytical methodology for the determination of iAs as well as other arsenic species in foodstuffs. As external quality control of the validated methods, the validated methods were tested participating in feasibility studies for the preparation of Certified Reference Materials with certified arsenic species and in proficiency tests for iAs determination The proposed methodology was applied to rice and rice products, infant cereals, cereal-based food, seaweeds, mushrooms, fish, bivalves and crustaceans, providing reliable results in response to demands made by international safety agencies. Additionally, daily dietary exposure to tAs and iAs intake to assess the toxicological implications of the ingestion of the selected foodstuffs was estimated. The main conclusions derived from the work conducted in this doctoral thesis are summarized as follows: - The proposed speciation method was successfully validated according to the ISO/IEC 17025:2005 standard, is sensitive and selective and could be considered fit for purpose, i.e. iAs determination in food. This method is straightforward enough for routine analysis for the determination of toxic iAs and other arsenic species in several foodstuffs, even in challenging matrices such as those of marine origin. Furthermore, since maximum limits of iAs in rice and rice products have recently been established by the European Union, the method could be useful in food control laboratories. - Based on our results on marine foods, wide variability in arsenic species can be expected when dealing with seafood such as seaweeds, bivalves and crustaceans, highlighting the need to carry out speciation to discern the toxic from the non-toxic species. On the other hand, only toxic iAs species were found in cereal products and iAs was the major As compound found in rice products, highlighting the importance of these food groups as a possible source of iAs in rice and cereal-based diets. - All arsenic speciation data obtained in this thesis are useful for assessing the daily intake of arsenic in the Catalan population. Furthermore, these results may contribute to on-going discussions regarding establishing and implementing maximum levels in inorganic arsenic in food commodities, as recommended within the European Union. - The average estimated iAs daily intake in the adult Catalan population is below the EFSA and JECFA BMDL ranges, but given the ratio between iAs intake and some BMDL for distinct end points, the possibility of risk for high consumers of rice and rice products cannot be excluded

Direct solid sample analysis with graphite furnace atomic absorption spectrometry -A fast and reliable screening procedure for the determination of inorganic arsenic in fish and seafood

Direct solid sample analysis with graphite furnace atomic absorption spectrometry (SS-GF AAS) was investigated initially with the intention of developing a method for the determination of total As in fish and other seafood. A mixture of 0.1% Pd + 0.06% Mg + 0.06% Triton X-100 was used as the chemical modifier, added in solution over the solid samples, making possible the use of pyrolysis and atomization temperatures of 1200 °C and 2400 °C, respectively. The sample mass had to be limited to 0.25 mg, as the integrated absorbance did not increase further with increasing sample mass. Nevertheless, the recovery of As from several certified reference materials was of the order of 50% lower than the certified value. Strong molecular absorption due to the phosphorus monoxide molecule (PO) was observed with high-resolution continuum source AAS (HR CS AAS), which, however, did not cause any spectral interference. A microwave-assisted digestion with HNO3/H2O2 was also investigated to solve the problem; however, the results obtained for several certified reference materials were statistically not different from those found with direct SS-GF AAS. Accurate values were obtained using inductively coupled plasma mass spectrometry (ICPMS) to analyze the digested samples, which suggested that organic As compounds are responsible for the low recoveries. HPLC-ICP-MS was used to determine the arsenobetaine (AB) concentration. Accurate results that were not different from the certified values were obtained when the AB concentration was added to the As concentration found by SS-GF AAS for most certified reference materials (CRM) and samples, suggesting that SS-GF AAS could be used as a fast screening procedure for inorganic As determination in fish and seafood

Determination of total cadmium, lead, arsenic, mercury and inorganic arsenic in mushrooms: outcome of IMEP-116 and IMEP-39

The Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre (JRC), a Directorate General of the European Commission, operates the International Measurement Evaluation Program (IMEP). IMEP organises interlaboratory comparisons in support of European Union policies. This paper presents the results of two proficiency tests (PTs): IMEP-116 and IMEP-39, organised for the determination of total Cd, Pb, As, Hg and inorganic As (iAs) in mushrooms. Participation in IMEP-116 was restricted to National Reference Laboratories (NRLs) officially appointed by national authorities in European Union member states. IMEP-39 was open to all other laboratories wishing to participate. Thirty seven participants from 25 countries reported results in IMEP-116, and 62 laboratories from 36 countries reported for the IMEP-39 study. Both PTs were organised in support to Regulation (EC) No. 1881/2006, which sets the maximum levels for certain contaminants in food. The test item used in both PTs was a blend of mushrooms of the variety shiitake (Lentinula edodes). Five laboratories, with demonstrated measurement capability in the field, provided results to establish the assigned values (Xref). The standard uncertainties associated to the assigned values (uref) were calculated by combining the uncertainty of the characterisation (uchar) with a contribution for homogeneity (ubb) and for stability (ust), whilst uchar was calculated following ISO 13528. Laboratory results were rated with z- and zeta (ζ)-scores in accordance with ISO 13528. The standard deviation for proficiency assessment, σp, ranged from 10% to 20% depending on the analyte. The percentage of satisfactory z scores ranged from 81% (iAs) to 97% (total Cd) in IMEP-116 and from 64% (iAs) to 84% (total Hg) in IMEP-39