Zr and U determination at trace level in simulated deep groundwater by Q ICP-MS using extraction chromatography.

In the framework of trace element analysis by Q ICP-MS in a simulated deep Callovo-Oxfordian groundwater, separation procedures based on extraction chromatography were developed to eliminate the high salt contents and to concentrate Zr and U simultaneously. Theoretical and experimental speciation studies showed the importance of adjusting the medium to HNO3/HF (0.5 M/0.005 M) to guarantee the stability over time of the analytes before removal of the matrix. Two preconcentration methods based on TRU and TODGA resins were optimized for the simultaneous isolation of Zr and U prior to Q ICP-MS measurements. Using TRU resin, alkali and alkali earth metals contained in the deep groundwater were removed with 2 M HNO3 whereas Zr and U were recovered with a HNO3/NH4HC2O4 (0.02 M/0.05 M) medium. For the separation protocol based on TODGA resin, alkali and alkali earth metals were eliminated with 3 M and 11 M HNO3 while Zr and U were simultaneously stripped with a HNO3/HF (0.5 M/0.2 M) medium. The procedure optimized on TODGA resin was validated with the French AFNOR NF T90-210 standard by studying linearity, limits of quantification (LOQ) and separation yields. The LOQ was determined at 0.008 µg L(-1) for Zr and U after the separation. Both analytes were recovered quantitatively. Compared to a sample dilution implemented to reduce the matrix effects, the developed preconcentration method allowed improving the sensitivity up to a 20 fold factor for Zr and U measurements at trace level by Q ICP-MS.

Comparisons between LIBS and ICP/OES.

In the framework of the development of new techniques, the ability of laser-induced breakdown spectroscopy (LIBS) to analyse remotely complex aqueous solutions was investigated. The jet configuration with a collimated gas stream was chosen because it appeared to be the most promising method for the LIBS probe, particularly in terms of sensitivity and repeatability. For emission collection, the echelle spectrometer offers a simultaneously recorded wavelength range from the UV to the near IR and is interesting for multielemental analysis for LIBS and also for inductively coupled plasma (ICP) optical emission spectroscopy (OES). The importance of parameters influencing the quantitative results of LIBS such as multispecies analysis, sheath gas, use of an internal standard and temporal parameters for analysis is described. LIBS quantitative data have been directly compared with results from the more standard ICP/OES technique.

Mitochondrial membrane permeabilization produced by PTP, Bax and apoptosis: a 1H-NMR relaxation study.

To analyze the involvement of structured water (bound to macromolecules) in apoptosis-induced mitochondrial outer-membrane permeability, we compared the dynamics of water protons from nuclear magnetic resonance (NMR) data in apoptotic liver mitochondria with that of control mitochondria incubated in vitro with free Ca(2+) (opening of the permeability transition pore, PTP) or with Bax alpha. Our results demonstrate that water molecules in apoptotic mitochondria exhibit an accelerated translational motion of structured water common with that induced by the opening of the PTP, but limited in amplitude. On the other hand, no significant quantitative change in structured water was observed in apoptotic mitochondria, a phenomenon also observed with Bax alpha-induced permeability. We conclude that the changes observed in the different water phases differ both quantitatively and qualitatively during the opening of the PTP and the Bax alpha-induced permeability, and that the apoptotic mitochondria exhibit mixed properties between these model situations.

Contamination of a dredged material disposal site La Rochelle Bay,France.The use of the acetylcholinesterase activity of Mytilus edulis L. as a biomarker of pesticides: the need for a critical approach.

A single aspect of the toxic impact of a dredged material disposal site located near a mussel-farming zone was followed for eight months. Acetylcholinesterase activity (AChE) of Mytilus edulis was investigated as a biomarker for possible contamination by neurotoxic compounds (carbamates and/or organophosphorous pesticides). Our observations showed that the enzymatic activities (including AChE) of these harbour mussels were decreased in sites directly and indirectly influenced (according to hydrodynamic conditions) by the dumping of dredged sediments, suggesting possible contamination by pesticides. The strong correlations observed between AChE activity and growth parameters (length and weight) seems to show, however, that the enzyme activity is also indirectly controlled through growth restriction, which may imply limitation of the development of the nervous system in juveniles. The concentration of total proteins, as well as the spawning process also seem to disturb the assessment of AChE activity. These field observations clearly indicate that the use of this enzyme activity as a biomarker should proceed with caution. For example, the seasonal variability of such activity should be taken into account in a biomonitoring programme.