Arsenosugar extracted from algae: Assessment of countercurrent chromatography for isolation.

Arsenosugars are the predominant species of arsenic in most seaweed. The analysis of these compounds is hampered by the lack of calibration standards needed in their unambiguous identification and quantification. This affects the availability of reliable information on their potential toxicity, which is scarce and controversial. Knowing the potential of centrifugal partition chromatography (CPC) as a preparative separation technique applied to a number of natural compounds, the aim of this work is to investigate the feasibility of CPC in the case of isolation and purification of arsenosugars from algae extracts. Several biphasic solvents systems have been studied to evaluate the distribution of the As species. Given the physical characteristics of these compounds, the presence of strong acids, the formation of ionic pairs or the presence of salts at high ionic strength have been considered. System 1-BuOH/EtOH/sat.(NH4)2SO4/water at a volume ratio 0.2:1:1:1 originates adequate distribution constants of analytes that allows the required separation. The total arsenic content and the arsenic speciation of the eluted solutions from CPC were analyzed by ICP-MS and IC-ICP-MS, respectively. The developed CPC procedure allows us to obtain of the three arsenosugars with a purity of 98.7 % in PO4-Sug, 90.4 % in SO3-Sug and 96.1 % in SO4-Sug.

Survey of arsenic content in edible seaweeds and their health risk assessment.

Since humans are especially sensitive to arsenic exposure, predominantly through diet, a strict control of the most widely consumed seaweeds is mandatory. Total arsenic contents and arsenic species in twenty-five different seaweeds from five different origins were studied. Seaweeds selected, included Phaeophyta (brown seaweed), Chlorophyta (green seaweed) and Rhodophyta (red seaweed) genera. The highest arsenic content appears in the Phaeophyta seaweed in the range from 11 to 162 mg kg-1 dried weight. Arsenosugars were found to be the predominant species of arsenic in most seaweeds, being up to 99.7% of total arsenic in some samples. The arsenic dietary intakes for seaweeds studied were assessed and the Target Hazard Quotients (THQ) and the Target Cancer Risk (TCR) were calculated, taking into account inorganic arsenic contents (iAs). iAs species in seaweeds showed low risk of arsenic intake except for Hizikia fusiforme samples.

Assessment and validation of ICP-MS and IC-ICP-MS methods for the determination of total, extracted and speciated arsenic. Application to samples from a soil-rice system at varying the irrigation method.

Food is the major route of arsenic (As) intake for humans, and rice is the staple food for more than half of the world's population. Unfortunately, rice bioaccumulates large amounts of As from the paddy field, and the toxicity of this element in the kernel is closely linked to its chemical form. Therefore, it is of the utmost importance to have access to an integrated set of analytical methods, capable of measuring the concentration of As in its various chemical forms in soil and rice. Hence, the principal aim of this study was to assess and validate a group of inductively coupled plasma - mass spectrometry (ICP-MS) and IC-ICP-MS (IC, Ionic Chromatography) methods designed to measure the amount of the total or extracted As and its main chemical species (As(III), As(V), monomethylarsonic acid, MMA, and dimethylarsinic acid, DMA) in flours of rice grain and in soils. Great attention has been given to the assessment and the optimization of extraction methods of As species from these matrices. No appreciable interconversion among As species has been observed using an aqueous solution 1 mol dm-3 of phosphoric acid and 0.5 mol dm-3 of L (+)-ascorbic acid for the extraction from soils, and an aqueous solution 0.2% (w/v) of nitric acid for the extraction from rice flour. Validation has been successfully accomplished in terms of limit of detection, limit of quantification, linearity and accuracy. In addition to many certified reference materials, these methods have been tested on real samples of soils and rice grains of the Aleramo genotype obtained through traditional or intermittent irrigation methods. Data obtained revealed the critical role of the intermittent irrigation methods in determining the nature and the amount of the As chemical species in rice grains as well as in soils. As(V) is the only species found in soil irrigated by sprinkling, while the most toxic As(III) dominates in soil irrigated by continuous flooding. On the other hand, the most abundant species found in continuously flooded Aleramo rice grains are As(III) and - mostly - DMA, whereas As(V), less toxic than As(III), represents 60% of the total inorganic compounds measured in sprinkler-irrigated rice. Lastly, the total amount of As measured in this rice is 3.8% of that measured in rice irrigated by continuous flooding.

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.

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 335µgAskg(-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.

Assessment of extractants for the determination of thallium in an accidentally polluted soil.

Thallium is a rare and easily dispersed element with high toxicity to organisms. Relatively high levels of thallium (approximately 9.58 mg kg(-1)) had been found in aqua regia soil extract of an accidentally polluted soil from south of Spain. To assess the available and leachable portions of thallium in the polluted soil, single and sequential extraction procedures have been utilized. Further, X-ray diffraction and scanning electron microscopic studies have also been used to find out the mineral phases. The amount of thallium extracted by the extracting agents in comparison to aqua regia, as well as the different phase associations are discussed.