In vivo bioconcentration of a metal mixture by Danio rerio eleutheroembryos.

Exposure to heavy metals has represented one of the most serious health risks of environmental pollution over the last 50 years. Most of the bioconcentration studies that have been carried out to date explored only individual contaminants, unlike the real situations that occur in the environment. In this work, zebrafish eleutheroembryos were exposed to a mixture of CH3Hg(II), iAs(III), Ag(I) and Cd(II), and new BCFs were calculated and compared with those calculated from single metal exposures. In both cases, experimental conditions meet the OECD Test 305 conditions established for aquatic systems. In addition, spatial imaging obtained by laser ablation coupled to inductively plasma mass spectrometry (LA-ICP/MS), has been directly performed in these samples providing complementary information. The new BCF's have revealed some differences compared to single metal exposures when eleutheroembryos were exposed to the metal mixture, especially for iAs(III) and Cd(II). LA-ICP/MS images are in good agreement with the BFC's found, representing an interesting approach to get spatial distribution of metals that reinforces the toxicokinetic information.

Photocatalytic air purifiers for indoor air: European standard and pilot room experiments.

At the European level (CEN/TC386), some efforts are currently devoted to new standards for comparing the efficiency of commercial photocatalytic material/devices in various application fields. Concerning prototype or commercial indoor photocatalytic air purifiers designed for volatile organic compounds (VOC) abatement, the methodology is based on a laboratory airtight chamber. The photocatalytic function is demonstrated by the mineralization of a mixture of five VOCs. Experimental data were obtained for four selected commercial devices and three commercial materials: drop of VOC concentration, but also identification of secondary species (with special attention to formaldehyde), mineralization rates, and Clean Air Delivery Rate (CADR). With two efficient air purifiers, these laboratory experiments were compared to the results in two experimental rooms (35-40 m3) where air pollution was introduced through wooden floor and furniture. The systems' ageing was also studied. The safety of the commercial products was also assessed by the determination of nanoparticle release. Standardized tests are useful to rank photocatalytic air purifiers and passive materials and to discard inefficient ones. A good correlation between the standard experiments and the experimental room experiments was found, even if in the latter case, the concentration of lower weight VOCs drops less quickly than that of heavier VOCs.

Spatial and temporal variations in otolith chemistry and relationships with water chemistry: a useful tool to distinguish Atlantic salmon Salmo salar parr from different natal streams.

Otolith elemental (Sr:Ca, Ba:Ca, Mn:Ca, Mg:Ca and Rb:Ca) and isotopic (87Sr:86Sr) profiles from several annual cohorts of juvenile Atlantic salmon Salmo salar were related to the physico-chemical characteristics (chemical signatures, flow rate, temperature and conductivity) of their natal rivers over an annual hydrological cycle. Only Sr:Ca, Ba:Ca and 87Sr:86Sr in otoliths were determined by their respective ratios in the ambient water. Sr:Ca ratios in stream waters fluctuated strongly on a seasonal basis, but these fluctuations, mainly driven by water flow regimes, were not recorded in the otoliths. Otolith Sr:Ca ratios remained constant during freshwater residency at a given site and were exclusively related to water Sr:Ca ratios during low flow periods. While interannual differences in otolith elemental composition among rivers were observed, this variability was minor compared to geographic variability and did not limit classification of juveniles to their natal stream. Success in discriminating fish from different sites was greatest using Sr isotopes as it remained relatively constant across years at a given location.

Accumulation of Mn, Co, Zn, Rb, Cd, Sn, Ba, Sr, and Pb in the otoliths and tissues of eel (Anguilla anguilla) following long-term exposure in an estuarine environment.

Aiming at increasing the resolution of otolith tracers, we investigated the possibility to use Mn, Co, Zn, Rb, Cd, Sn, Ba, Sr, and Pb otolith composition to retrieve the movements of eels (Anguilla anguilla) in the lower Gironde watershed. Caging experiments were designed to validate the site specific otolith signatures. Individually identified eels were reared in cages in three locations along the estuarine and river gradient. Three trials were set up for successive periods of 3 months and 6 months. Water Mn, Co, Zn, Rb, Cd, Sn, Ba, Sr, and Pb concentrations were monitored. The eel otolith composition corresponding to the experimental period was measured with an ICPMS coupled with a femtosecond laser. Liver Cd, Zn and Pb concentrations were measured. For each caging experiments, we tested the influence of individual weight gain, caging site and trial on elemental otolith concentrations. Mn, Co, Zn, Rb, Cd, Sn, Ba, Sr, and Pb were detected in eel otolith above the detection limits. Otolith Sr and Ba concentrations significantly discriminated the caging sites for one trial. Individual weight gain did not have a significant influence on otolith elemental concentrations. Co, Rb, Cd, Sn, Zn, Sr and Ba otolith concentrations were significantly influenced by the trials. Water elemental composition was only partly reflected by otolith elemental composition. The results showed that otolith composition had a more integrative value than water composition. Complex elemental seasonal variations and individual eel incorporation potential complicated the interpretation of otolith composition. Liver and otolith Cd and Zn concentrations did not show a statistically significant correlation.

Femtosecond laser ablation ICP-MS measurement of otolith Sr:Ca and Ba:Ca composition reveal differential use of freshwater habitats for three amphidromous Sicyopterus (Teleostei: Gobioidei: Sicydiinae) species.

The use of freshwater habitats was examined in three amphidromous goby species of the genus Sicyopterus using otolith microchemistry. Two species were endemic to either New Caledonia or Vanuatu whilst the other was widely distributed. Depositional patterns of strontium (Sr) and barium (Ba) in the otolith of adults were analysed with femtosecond laser ablation inductively coupled plasma mass spectrometry (ICP-MS). The Sr:Ca and Ba:Ca results uncovered three different adult behaviours within the freshwater habitat. Some fishes stayed in elevated locations (square profile); others undertook back-and-forth migrations between higher and lower reaches (up-and-down profile), and finally, others stayed in the lower reaches (constant profile). The consequences of these movements to larval survival or competition for food and territory are discussed. This work brings new knowledge on amphidromous behaviour, and it highlights the necessity of multi-elemental analysis to study amphidromy in freshwater systems.

Bioinspired material based on femtosecond laser machining of cast sheet micromolding as a pattern transfer process.

We present herein a simple, fast, and easy-to-use process to replicate poly(methyl methacrylate) (PMMA) plates generating surface effects. First, a femtosecond laser has been used to fabricate, with sufficient accuracy, a periodic pattern on a glass plate at the microscale. This glass plate, used as a master, can be structured on a large distance with a good control of its roughness. Then, the polymer plates were obtained by bulk polymerization without any solvents with a good replication from the cast sheet process, which has been industrially performed for years. Thus, the modification of this process, environmentally friendly, lets us foresee new applications for commodity polymers by introducing visual iridescent properties and hydrophobicity exaltation.

Simultaneous use of strontium:calcium and barium:calcium ratios in otoliths as markers of habitat: application to the European eel (Anguilla anguilla) in the Adour basin, South West France.

Sr:Ca and Ba:Ca ratios in water from the Adour estuary show a clear relationship with the salinity of the surrounding water for salinities <20, while ratios are almost constant above this level of salinity. A positive relationship was observed for the Sr:Ca ratio, whereas it was inverse for the Ba:Ca ratio. These two elemental ratios were measured in the otoliths of the European eels (Anguilla anguilla L.) using femtosecond laser ablation linked to an ICP-MS (fs-LA-ICP-MS). There was a direct relationship between the elemental ratios recorded in eel otoliths and those found in water from fresh and marine areas, suggesting that Sr:Ca and Ba:Ca ratios in eel otoliths can be used as markers of habitat in this estuary. Continuous profiling allowed the determination of three behaviour patterns in terms of habitat: freshwater, estuary and migratory individuals. Finally, the above results support the simultaneous use of both ratios for a better understanding of the migratory contingents and also as a relevant method to avoid a misidentification of environmental migratory history due to the presence of vaterite crystal in the otolith matrix.

High-frequency archives of manganese inputs to coastal waters (Bay of Seine, France) resolved by the LA-ICP-MS analysis of calcitic growth layers along scallop shells (Pecten maximus).

During their growth, bivalves are recognized to archive minor and trace elements within their shells which may reflect environmental conditions at the sediment-water interface (SWI). Shells from juvenile Great Scallops (Pecten maximus (L.)), which develop a daily calcite growth layer, were collected in the Bay of Seine (France) and examined by matrix-matched LaserAblation ICP-MS analysis for Mn concentrations along their growth period, from April to October (year 2004). The backdated Mn concentration profiles were compared with environmental variables (e.g., temperature, salinity, chlorophyll a, oxygen, etc.) measured continuously at monitoring stations in riverine, estuarine, and coastal waters. The objective was first to perform microanalyses of Mn composition along the shell reflecting episodic enrichment or depletion in such environment, and second, to depict Mn cycling and inputs at the SWI according to the measured profiles. Basically, Mn concentration profiles mostly depend on established estuarine and coastal biogeochemical processes that lead to an increase of dissolved Mn concentration available for shell uptake. Potential particulate Mn fluxes from the Seine River, that control both particulate and dissolved Mn input to the bay, are strongly correlated with shell Mn concentrations from April to July (?r = 0.95, n = 8, p < 0.05). In late summer, riverine inputs can not only provide an explanation for the shell Mn enrichments which suggest additional sources of Mn. During this period, two other processes also contribute to the release of dissolved Mn in coastal waters and the increase of shell Mn content: (1) successive redox oscillations within the high turbidity zone of the macrotidal Seine estuary and (2) postbloom reductive conditions developed at the SWI of the Seine Bay under periodic seasonal eutrophication. This study demonstrates that incremental Mn concentrations profiles in scallop shells are a relevant natural archive to evaluate the processes governing Mn inputs into coastal environments at a daily scale.

Matrix-matched quantitative analysis of trace-elements in calcium carbonate shells by laser-ablation ICP-MS: application to the determination of daily scale profiles in scallop shell (Pecten maximus).

A micro-scale method has been developed for analysis of trace-element concentration profiles in the calcium carbonate shell of the Great Scallop (Pecten maximus). UV laser ablation at 266-nm coupled with ICP-MS detection was used to analyse daily calcite striae of shell samples to obtain high temporal resolution of trace element incorporation. Analysis of scallop shells was carefully examined to determine the quality of calcium carbonate ablation and calibration. An accurate external calibration method based on matrix matching was developed. Twelve sodium-free enriched calcium carbonate standards containing up to twenty-four elements were prepared, by co-precipitation with aqueous ammonia and NH(4)HCO(3), and subsequently back-calibrated in the laboratory. These CaCO(3) standards were found to be homogenous and their use enabled sensitive quantitative analysis (detection limits of a few ng g(-1)) over a wide range of concentrations (0.1 to 500 microg g(-1)). Use of these CaCO(3) standards was also evaluated by analysis of three calcium-rich certified reference materials. Because calibration was consistent with the certified results, this analytical method is a sensitive tool for analysis of environmental calcium carbonate matrices. Repeated analysis of scallop shell samples collected simultaneously at the same location showed that the trace elements are homogeneously distributed along a stria. The reliability of such in-situ records of biogenic calcium carbonate (scallop shells) is apparent from the inter-individual and inter-annual reproducibility of the trace element profiles.

Precise isotope-ratio measurements of lead species by capillary gas chromatography hyphenated to hexapole Multicollector ICP-MS.

The precision and accuracy of lead isotope-ratio determination on a short transient signal has been assessed by coupling capillary gas chromatography to the Isoprobe (Micromass, UK), a single-focusing inductively coupled plasma mass spectrometer with multicollector detection. A T-piece connecting the GC transfer line to the torch enabled continuous aspiration of thallium solution for mass-bias correction. The volatile lead species PbEt4 was derivatized from NIST isotopic certified lead standard SRM 981 and different amounts of PbEt4 dissolved in iso-octane were injected into the GC. Chromatograms were recorded in multicollection mode by use of Faraday cups; seven isotopes (204Pb, 206Pb, 207Pb, 208Pb,

Simultaneous Determination of Volatile Metal (Pb, Hg, Sn, In, Ga) and Nonmetal Species (Se, P, As) in Different Atmospheres by Cryofocusing and Detection by ICPMS.

A sensitive method for multielemental speciation analysis of volatile metal and metalloid compounds in air has been developed. The analytes are sampled simultaneously in the field by cryofocusing on a small glass wool-packed column at -175 °C. Detection is performed in the laboratory by low-temperature GC hyphenated with ICPMS. Oxygen addition in the carrier gas was used to reduce interferences originating from the presence of volatile carbon-containing species in the samples. Plasma stability during analysis was monitored continuously by internal standardization (Xe). This system provides routine absolute detection limits of 0.06-0.07 pg (as Pb) for tetraalkyllead species (Me(4)Pb, Et(4)Pb), 0.2 pg (as Sn) for tetraalkyltin species (Me(4)Sn, Et(4)Sn), 0.8 pg (as Hg) for mercury species (Hg(0), Me(2)Hg, Et(2)Hg), and 2.5 pg (as Se) for selenium species (Me(2)Se). This instrumentation makes it possible to collect small air sample volumes and has been successfully applied to the determination of volatile metal and metalloid species in the atmosphere in urban and rural locations. Qualitative application in the semiconductor industry is also reported with regard to the detection of arsenic (ASH(3), tert-butylarsine), phosphorus (PH(3), tert-butylphosphine), alkylindium, and gallium species.