Ultrasound-promoted cold vapor generation in the presence of formic acid for determination of mercury by atomic absorption spectrometry

A new cold vapor technique within the context of green chemistry is described for determination of mercury in liquid samples following high-intensity ultrasonication. Volatile Hg evolved in a sonoreactor without the use of a chemical reducing agent is carried to a quartz cell kept at room temperature for measurement of the atomic absorption. The mechanism involved lies in the reduction of Hg(II) to Hg(0) by reducing gases formed upon sonication and subsequent volatilization of Hg(0) due to the degassing effect caused by the cavitation phenomenon. Addition of a low molecular weight organic acid such as formic acid favors the process, but vapor generation also occurs from Hg solutions in ultrapure water. The detection limit of Hg was 0.1 microg/L, and the repeatability, expressed as relative standard deviation, was 4.4% (peak height). Addition of small amounts of oxidizing substances such as the permanganate or dichromate anions completely suppressed the formation of Hg(0), which confirms the above mechanism. Effect of other factors such as ultrasound irradiation time, ultrasound amplitude, and the presence of concomitants are also investigated. Some complexing anions such as chloride favored the stabilization of Hg(II) in solution, hence causing an interference effect on the ultrasound-assisted reduction/volatilization process.     

Fast determination of arsenic,selenium, nickel and vanadium in fish and shellfish by electrothermal atomic absorption spectrometry following ultrasound-assisted extraction

Ultrasound-assisted extraction of As, Se, Ni and V from fish and shellfish has been applied as a fast and reliable sample pre-treatment method for accurate determination of the four elements by electrothermal atomic absorption spectrometry with Zeeman (As, Se) or Deuterium (Ni, V) background correction. A multivariate optimization approach has been employed for establishing the effect of variables influencing the extraction process. Under suitable conditions, quantitative extractions occurred from a 10 mass sample (particle size <100 μm) suspended in 1.5 mL of acidic extractant (0.5 or 3% v/v HNO₃) and subjected to high intensity ultrasound (50% amplitude; 3 min). The method was successfully validated against the following certified reference materials: NRCC-DORM-2 dogfish muscle, NRCC-DOLT-2 dogfish liver, NRCC-TORT-2 lobster hepatopancreas, NIST-SRM 1566b oyster tissue and BCR 627 tuna fish. The following seafood samples were analyzed: hake (Merluccius merluccius), sole (Solea solea), clam (Venerupis rhomboides), prawn (Panaeus kerathurus), cuttlefish (Sepia officinalis), shrimp (Palaemon elegans), razor shell (Ensis ensis), cockle (Cardium edule), Mussel (Mytilus galloprovincialis), edible crab (Cancer pagurus), meagrin (Lepidorhombus whiffiagonis). The concentration ranges (μg/g, dry weight) for the elements determined were as follows: As (12.6–190), Se (0.73–2.34), Ni (2.94–46) and V (0.82–5.14). The detection limits (LODs), defined as 3s/m (s being the standard deviation of 10 blank and m the slope of the calibration graph), in dry tissue were 0.6, 0.3, 0.2 and 0.4 μg/g for As, Se, Ni and V, respectively. Between-batch precision was expressed as relative standard deviation from three separate extractions was in the range 3–10%.     

Photofermentation of tequila vinasses by Rhodopseudomonas pseudopalustris to produce hydrogen

Hydrogen production by photofermentation of tequila vinasses (VT) was studied using Rhodopseudomonas pseudopalustris DSM 123. To the best of our knowledge this is the first report on hydrogen production by photofermentation on VT. Hydrogen production was doubled on VT (260 m$props_value{literPattern}/L) as compared to a synthetic medium. Storing VT changed its chemical composition; however, in photofermentations of a sixty-day old stock, growth and hydrogen production were similar to fresh VT. The periodic displacement of hydrogen with nitrogen resulted in a three-fold increase in both hydrogen and growth of R. pseudopalustris (860 mL H₂/L and 4.5 g/L respectively) as compared to non-displaced headspace. Hydrogen almost doubled at a light intensity of 270 W/m² (2249 mL H₂) as compared to 68 W/m². In dark-light cycles, biomass and hydrogen production were highest with continuous illumination. The potential of VT to produce hydrogen in high amounts using R. pseudopalustris has been demonstrated.     

Quantum dots confined in an organic drop as luminescent probes for detection of selenium by microfluorospectrometry after hydridation: study of the quenching mechanism and analytical performance

Following a preliminary work (Costas-Mora, I.; Romero, V.; Pena-Pereira, F.; Lavilla, I.; Bendicho, C. Anal. Chem.2011, 83, 2388-2393), a quenching mechanism has been established for the selective detection of Se (as selenium hydride) by microfluorospectrometry using CdSe quantum dots (QDs) as luminescent probes stabilized with hexadecylamine and confined in an organic droplet. For this purpose, luminescence, luminescence lifetime, UV-vis absorption, total reflection X-ray fluorescence, transmission electron microscopy, and atomic force microscopy measurements were performed. The presence of stabilizing agents of QDs in the droplet was found to cause a critical effect on both extraction efficiency of selenium hydride in the drop and luminescence quenching. A self-quenching mechanism due to the aggregation of QDs is suggested. Aggregation is thought to occur as a result of the binding between selenide trapped into the organic drop as selenium hydride and Cd(2+) present in the surface of QDs, which in turn, may cause the loss of stabilizing hexadecylamine groups. After full optimization of main variables influencing the luminescent response, the analytical performance was established. A detection limit as low as 0.08 μg L(-1) Se(IV) and a repeatability expressed as relative standard deviation of 4.6% were obtained. The method was validated against CRM NWTM-27.2 lake water, and a recovery study was performed with synthetic seawater. The use of CdSe as luminescent probes in an organic drop may constitute an extremely selective, sensitive, and miniaturized assay for in situ detection of Se(IV) in water.