Speciation analysis of Sn(II) and Sn(IV) using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a substrate to selectively retain Sn(II) and Sn(IV) has been investigated. Several factors affecting the retention of the analytes by yeast, such as pH, amount of biomass, temperature and time of contact were evaluated. Based on this study, a method for determination of Sn(II) and Sn(IV) combining inductively coupled plasma optical emission spectrometry (ICP OES) and solid phase extraction using Saccharomyces cerevisiae is proposed. The procedure consists of the selective retention of Sn(IV) by yeast at pH = 2.0 while Sn(II) remains in solution. Determination of tin in the solid phase was easily carried out by submitting a slurry of the yeast (0.5 g/40 mL) directly to ICP OES. The precision of the extraction procedure was characterized by an RSD lower than 4%. The detection limits of tin (3 sigma) in the solid phase and the liquid phase were 1.1 and 0.7 mu g L-1, respectively. The proposed approach was evaluated for determination of Sn(II) and Sn(IV) in spiked river water and real samples of industrial waste water (untreated and treated). For all samples, recoveries of spiked Sn(II) and Sn(IV) were between 85 and 112%.

On-line preconcentration and speciation analysis of Cr(III) and Cr(VI) using baker's yeast cells immobilised on controlled pore glass

A study was undertaken to evaluate Saccharonzyces cerevisiae as a substrate for the biosorption of Cr(III) and Cr(VI) aiming to the selective determination of these species in aqueous solutions. The yeast cells were covalently immobilised on controlled pore glass (CPG), packed in a minicolumn and incorporated in an on-line flow injection system. The effect of chemical and physical variables affecting the biosorption process was tested in order to select the optimal analytical conditions for the Cr retention by S. cerevisiae. Cr(III) was retained by the immobilised cells and Cr(VI) were retained by CPG. The speciation was possible by selective and sequential elution of Cr(III) with 0.05 mol L-1 HCl and 2.0 mol L-1 HNO3 for Cr(VI). The influence of some concomitant ions up to 20 mg L-1 was also tested. Quantitative determinations of Cr were carried out by means of inductively coupled plasma optical emission spectrometry (ICP OES). Preconcentration factors of 12 were achieved for Cr(III) and 5 for Cr(VI) when 1.7 mL of sample were processed reaching detection limits of 0.45 for Cr(III) and 1.5 mu g L-1 for Cr(VI). The speciation of inorganic Cr in different kinds of natural waters was performed following the proposed method. Spiked water samples were also analysed and the recoveries were in all cases between 81 and 103%. (c) 2005 Elsevier B.V. All rights reserved.

On-line redox speciation analysis of antimony using L-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Speciation analysis of inorganic arsenic in river water by Amberlite IRA 910 resin immobilized in a polyacrylamide gel as a selective binding agent for As(v) in diffusive gradient thin film technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Speciation analysis of Arsenic in fish and rice samples using liquid chromatography-inductively coupled plasma mass spectrometry

Chemical speciation in foodstuffs is of uttermost importance since it is nowadays recognized that both toxicity and bioavailability of an element depend on the chemical form in which the element is present. Regarding arsenic, inorganic species are classified as carcinogenic while organic arsenic, such as arsenobetaine (AsB) or arsenocholine (AsC), is considered less toxic or even non-toxic. Coupling a High Performance Liquid Chromatographer (HPLC) with an Inductively Coupled Plasma Mass Spectrometer (ICP-MS) combines the power of separation of the first with the selectivity and sensitivity of the second. The present work aims at developing a method, using HPLC-ICP-MS technique, to identify and quantify the chemical species of arsenic present in two food matrices, rice and fish. Two extraction methods, ultrasound and microwave, and different settings were studied. The best method was chosen based on recovery percentages. To ensure that no interconversion of species was occurring, individual spikes of each species of arsenic were made in both matrices and recovery rates were calculated. To guaranty accurate results reference material BCR-627 TUNA FISH, containing certified values for AsB and DMA, was analyzed. Chromatographic separation was achieved using an anion exchange column, HAMILTON-PRP X-100, which allowed to separate the four arsenic species for which standards were available (AsB, dimethylarsenic (DMA), arsenite (AsIII), arsenate (AsV). The mobile phase was chosen based on scientific literature and adjusted to laboratory conditions. Different gradients were studied. As a result we verified that the arsenic species present in both matrices were not the same. While in fish 90% of the arsenic present was in the form of arsenobetaine, in rice 80% of arsenic was present as DMA and 20% as inorganic arsenic.

Sequential Injection Analysis (SIA) for Arsenic Speciation by Capillary Electrophoresis Hyphenated to Inductively Coupled Plasma Sector Field Mass Spectrometry (CE-ICP-SFMS)

Sequential injection analysis (SIA) is proposed for managing microvolumes of sample and arsenic species solutions for speciation analysis by capillary electrophoresis focusing on the reduction of hazardous waste residues. An electronically controlled hydrodynamic injector was projected to introduce microvolumes of solutions prepared by SIA into the CE capillary with precision better than 2%. The determination of arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine was performed from 50 mu L volumes of lyophilized urine and extract of shrimp with the system hyphenated to inductively coupled plasma mass spectrometry (CE-ICP-SFMS).

Scanned stripping chronopotentiometry at bismuth film rotating disc electrodes: a method for quantitative dynamic metal speciation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Speciation of metals in agricultural lime and contaminated soil

Die Verwendung von Metallen zur Entwicklung der heutigen fortschrittlichen technologischenrnGesellschaft lässt auf eine lange Geschichte zurück blicken. Im Zuge des letzten Jahrhundertsrnwurde realisiert, dass die chemischen und radioaktiven Eigenschaften von Metallen einernernsthafte Bedrohung für die Menschheit darstellen können. In der modernen Geochemie ist esrnallgemein akzeptiert, dass die spezifischen physikochemische Formen entscheidender sind, alsrndas Verhalten der gesamten Konzentration der Spurenmetalle in der Umwelt. Die Definition derrnArtbildung kann grob als die Identifizierung und Quantifizierung der verschiedenen Formen oderrnPhasen für ein Element zugeordnet werden. Die chemische Extraktion ist eine gemeinsamernSpeziierungstechnik bei der die Fraktionierung des Gesamtmetallgehaltes zur Analyse der Quellernanthropogener Metallkontamination und zur Vorhersage der Bioverfügbarkeit von verschiedenenrnMetallformen dient. Die Philosophie der partiellen und sequenziellen Extraktionsmethodernbesteht darin, dass insbesondere das Extraktionsmittel phasenspezifisch unter chemischemrnAngriff unterschiedlicher Mischungsformen steht. Die Speziation von Metall ist wichtig bei derrnBestimmung der Toxizität, Mobilität, Bioverfügbarkeit des Metalls und damit ihr Schicksal inrnder Umwelt und biologischem System. Die Artenbildungsanalyse kann für das Verständnis derrnAuswirkung auf die menschliche Gesundheit und bei ökologischen Risiken durch diernQuantifizierung von Metallspezies bei einem Untersuchungs-standort angewendet werden undrnanschließend können Sanierungsstrategien für den Standort umgesetzt werden. Mit Hilfe derrnSpezifizierung wurden Arsen und Kupfer in landwirtschaftlichem Kalkdünger und Thallium inrnkontaminierten Böden untersucht und in den folgenden Abschnitten im Einzelnen dargestellt.

Iodine speciation at time series station DYFAMED

Iodine speciation analysis was carried out upon seawater samples collected in July 1993 at the DYFAMED station (43 °25?N, 7 °52?E) located in the northwestern Mediterranean Sea. Dissolved iodate and iodide were directly determined by differential pulse polarography and cathodic stripping square wave voltammetry, respectively, and organically bound iodine was estimated by wet-chemical oxidation with sodium hypochlorite. Iodate is the predominant species ranging from 416 nM in surface waters to 480 nM in bottom waters. Iodide is present in significant concentrations up to 60 nM in surface waters, undetectable between 500 and 1000 m depth and present in very low but measurable concentrations (about 6 nM) in deep waters. The vertical profile of total free iodine demonstrates observable removal from surface waters, slight enrichment at about 200 m depth and constant there below. Up to 40 nM of organically bound iodine has been estimated between 20 to 30 m. Factorial analysis of different iodine species with biologically relevant parameters provided strong evidence for iodine biophilic features.

Arsenic speciation in edible alga samples by microwave-assisted extraction and high performance liquid chromatography coupled to atomic fluorescence spectrometry

Twelve commercially available edible marine algae from France, Japan and Spain and the certified reference material (CRM) NIES No. 9 Sargassum fulvellum were analyzed for total arsenic and arsenic species. Total arsenic concentrations were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) after microwave digestion and ranged from 23 to 126 μg g−1. Arsenic species in alga samples were extracted with deionized water by microwave-assisted extraction and showed extraction efficiencies from 49 to 98%, in terms of total arsenic. The presence of eleven arsenic species was studied by high performance liquid chromatography–ultraviolet photo-oxidation–hydride generation atomic–fluorescence spectrometry (HPLC–(UV)–HG–AFS) developed methods, using both anion and cation exchange chromatography. Glycerol and phosphate sugars were found in all alga samples analyzed, at concentrations between 0.11 and 22 μg g−1, whereas sulfonate and sulfate sugars were only detected in three of them (0.6-7.2 μg g−1). Regarding arsenic toxic species, low concentration levels of dimethylarsinic acid (DMA) (<0.9 μg g−1) and generally high arsenate (As(V)) concentrations (up to 77 μg g−1) were found in most of the algae studied. The results obtained are of interest to highlight the need to perform speciation analysis and to introduce appropriate legislation to limit toxic arsenic species content in these food products.

Direct Solid-Phase Optical Measurements in Flow Systems: A Review

Measurements based on absorption, reflectance, or luminescence of molecular species or complex ions can be carried out directly on a solid support simultaneously to the retention of the analyte. The use of this strategy in flow-based systems is advantageous in view of the reproducible handling of solutions in retention and elution steps of the analyte. This approach can be exploited to increase sensitivity, minimize reagent consumption as well as waste generation, improve selectivity or for simultaneous determination based on selective retention or differences in sorption rates of the analytes. This review focuses on the main characteristics of direct solid-phase measurements in flow systems, including the discussion of advantages and limitations and practical guidelines to the successful implementation of this approach. Selected applications in diverse fields, such as pharmaceutical, food, and environmental analysis are discussed.

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.

Migration of antimony from polyethylene terephthalate used in mineral water bottles.

The influence of storage time and temperature on Sb migration from PET bottles into mineral water was studied in short-term tests lasting up to 15 days and long-term studies lasting up to 220 days. Samples purchased were stored in three different coloured bottles: clear (CL), light blue (LB) and dark blue (DB). Sb migration was assayed by HG-AFS for total determination and HPLC-ICP-MS for speciation analysis. Migration studies showed that waters stored at 4 and 20 oC were not subject to Sb migration. At 40 oC there was a significant increase in Sb concentration, although the maximum limit established by the European Union (5.0 ug/L) was not exceeded, whereas at 60 oC samples were subject to considerable Sb migration after 30 days of storage. In this case, the maximum limit established by the European Union was exceeded and both Sb (V) and Sb (III) were detected.

A importância da análise de especiação do chumbo em plasma para a avaliação dos riscos à saúde

Lead absorption is influenced by the species that are formed and the physicochemical characteristics of lead, among others. Lead plasma concentration is < 5% of total blood lead and represents the biologically active fraction able to cross the cell membranes. Health risks mainly depend on a specific metal and its species. Speciation analysis is the analytical activity of identifying and determining different metal species. Chromatographic methods are very useful in the identification of species and the techniques most used to determine metals in biological fluids are ICP OES/MS and AAS. Lead speciation analysis in blood plasma is fundamental for understanding and evaluating the interaction mechanisms between that analyte and its biological targets.