Mercury speciation analysis in human hair by species-specific isotope-dilution using GC–ICP–MS

We optimized a mercury (Hg) speciation extraction method for human hair in combination with species-specific isotope-dilution analysis by gas chromatography–inductively coupled plasma–mass spectrometry (GC–ICP–MS). The method was validated on human hair reference material RM (IAEA-086), which is recommended for analysis of monomethylmercury (MMHg) and inorganic mercury (IHg). Three reagents, hydrochloric acid (HCl), nitric acid (HNO₃), and tetramethylammonium hydroxide (TMAH), and three extraction procedures, at ambient temperature for 12 h, microwave-assisted at 75 °C for 6 min, and oven heated at 80 °C for 2 h were tested. Extraction efficiency, recovery, and potential species transformations were evaluated for each method. The most efficient procedures, with recovery of ~90 % for each species with limited demethylation (<5 %) and methylation (0 %), were HNO₃ digestion, irrespective of temperature, and microwave-assisted TMAH extraction. Acidic extraction with HCl induces significant demethylation, with production of artifacts. To correct for potential demethylation artifacts we recommend spiking with isotopically enriched standards before the extraction step.     

Sol-gel preparation of In2O3-Al2O3 supports with controlled textural and structural properties

Alumina supports with a very narrow pore size distribution were obtained with indium-doped alumina prepared by the sol-gel method. The formation of aluminum in pentahedral coordination was identified by ²⁷Al NMR-MAS-spectroscopy. A good correlation was obtained with the Al^V NMR-MAS intensity signal and the activity in isopropanol dehydration. The insertion of In³⁺ substituting some Al³⁺ in the alumina network was suggested.     

In situ ethylation of organolead,organotin and organomercury species by bromomagnesium tetraethylborate prior to GC‐ICP‐MS analysis

An analytical method for simultaneous in situ ethylation, of organolead, organotin and organomercury compounds in aqueous samples was developed using a new derivatisation agent, bromomagnesium tetraethylborate (BrMgEt₄B). The determination of lead, tin and mercury compounds was done by species‐specific isotope dilution, derivatisation and GC–inductively coupled plasma MS (GC‐ICP‐MS) or by GC‐MS. The recovery and accuracy of the derivatisation were evaluated. The effect of pH and the relative quantity of derivatisation agent were studied.     

Evaluation of acid-base properties of ammonia plasma-treated polypropylene by means of XPS

Acid-base properties of ammonia plasma-treated polypropylene (APTPP) were characterized by X-ray photoelectron spectroscopy (XPS) in conjunction with the molecular probe technique and using chloroform (TCM) as a reference Lewis acid. It is shown that TCM is retained by the basic surfaces of APTPP but not by the untreated PP. The retention of TCM is shown to be entirely due to the formation of TCM:APTPP acid-base complexes. This is supported by the C12p^3/2 binding energy (BE) and the shape of the Cl2p peak from the adsorbed TCM. ΔH^AB, the heat of TCM:APTPP acid-base interaction was found to be in the range of 3.1–4.3 kcal/mol using a published Cl2p^3/2 BE−ΔH^AB correlation. This ΔH^AB compares remarkably well with the values of 4.3–4.9 kcal/mol determined for TCM:amine complexes, and shows indeed that TCM is complexed by nitrogen containing basic groups grafted at the surface. However, the TCM/N ratio has an optimal value up to 1 second of plasma treatment and then decreases sharply, showing that less specific interaction sites are accessible at the surface for longer treatment times. This parallels previous findings about the metallization of APTPP by aluminium which was found to be optimal for treatment times lower than 1 second in our experimental conditions. This work shows that XPS can now indeed be used to quantitatively assess the acid-base properties of modified polymer surfaces.     

Preparation of photovoltaic silicon by purification of metallurgical grade silicon with a reactive plasma process

The main methods of silicon purification involve physicochemical techniques of separation. They yield an ultrapure metal, but its price is not compatible with photovoltaic central power generation. The plasma zone melting process consists in the horizontal displacement of a melted zone under an argon-hydrogen-oxygen plasma. The melt zone is characterized by a vertical gradient of concentration and temperature which drains impurities toward the upper surface of the bar. Moreover, the displacement of the zone from the head to the tail of the bar ensures a horizontal drainage of impurities toward the tail. This technique has been used with success for purification of metallurgical grade silicon; for example, iron was reduced from 3500 ppm to 0.5 ppm at a displacement rate between 20 and 40 cm/h. The final impurity level was less than 1 ppm. The mass transfer was independent of the displacement rate at 40 cm/h, but dependent on the heat transfer rate. The segregation of the metals is caused by drainage toward the tail of the bar, while the plasma vaporizes impurities since the metallic and metalloidic impurities have high vapor pressures (e.g., S, P, C, O, Mn). Acid (HF-HNO₃) is used to dissolve the impurities between each passage of the zone. Boron elimination depends directly on the plasma oxygen concentration. Classical mathematic models of zone melting are not valid for plasma melting zone processes.     

Hemoglobin as a major binding protein for methylmercury in white-sided dolphin liver

As methylmercury (MeHg) can be bioaccumulated and biomagnified in the trophic web, its toxicity for marine mammals is of major concern. Mercury speciation in marine biota has been widely studied, mainly focused on the discrimination and quantification of inorganic Hg and MeHg. Less attention has been paid to the interactions of Hg with biomolecules and the characterization of its specific binding, which play a key role in metabolic pathways controlling its uptake, transformation, and toxicity. In the studied white-sided dolphin (Lagenorhynchus acutus) liver homogenate (QC04LH4) sample, approximately 60 % of the total MeHg was found in the water soluble fraction, specifically associated with high molecular weight biomolecules. The identity of the involved proteins was investigated (after tryptic digestion of the fraction) by μRPLC with parallel detection by ICP-MS and ESI-MS/MS. Molecular mass spectrometry experiments were carried out at high resolution (100000) to ensure accurate protein identification and determination of the MeHg binding sites. Cysteine residue on the dolphin hemoglobin β chain was found to be the main MeHg binding site, suggesting that hemoglobin is a major MeHg binding protein in this marine mammal and could be a potential carrier of this MeHg from blood to liver prior to its degradation in this organ. In parallel, a significant proportion of selenium was found to be present as selenoneine and a potential role for this compound in Hg detoxification is discussed.     

Ouverture regioselective d'alcools tetrahydrofuranniques par Me3SiCl/NaI synthese de L'exo-ET DE L'endo-brevicomine

Me₃SiCl/NaI in acetone opens regioselectively tetrahydrofurfurylalcohols and hydroxy-3 tetrahydrofuran to give the corresponding iodoacetonides in good yields. An application to the synthesis of the exo-and endo-brevicomins is described.