Interface-Driven Strain in Heavy Ion-Irradiated Zr/Nb Nanoscale Metallic Multilayers: Validation of Distortion Modeling via Local Strain Mapping.

Nanolayered metallic alloys are promising materials for nuclear applications thanks to their resistance to radiation damage. Here, we investigate the effect of ion (C, Si, and Cu) irradiation at room temperature with different fluences into sputtered Zr/Nb metallic multilayer films with periods 27 nm (thin) and 96 nm (thick). After irradiation, while a high strain in the entire thin nanoscale metallic multilayer (NMM) is observed, a quite small strain in the entire thick NMM is established. This difference is further analyzed by a semianalytical model, and the reasons behind it are revealed, which are also validated by local strain mapping. Both methods show that within a thick layer, two opposite distortions occur, making the overall strain small, whereas in a thin layer, all the atomic planes are affected by the interface and are subjected to only a single type of distortion (Nb─tension and Zr─compression). In both thin and thick NMMs, with increasing damage, the strain around the interface increases, resulting in a release of the elastic energy at the interface (decrease in the lattice mismatch), and the radiation-induced transition of the Zr/Nb interfaces from incoherent to partially coherent occurs. Density functional theory simulations decipher that the inequality of point defect diffusion flux from the inner to the interface-affected region is responsible for the presence of opposite distortions within a layer. Technologically, based on this work, we estimated that Zr/Nb55 with thicknesses around Zr = 24 nm and Nb = 31 nm is the most promising multilayer system with the high radiation damage resistance and minimum swelling for nuclear applications.

Characterization of the role of phosphogypsum foam in the transport of metals and radionuclides in the Southern Mediterranean Sea.

The Gabes Gulf had received huge quantities of phosphogypsum discharged from fertilizer plants. Dumping phosphogypsum in coastal waters leads to the formation of foam layers which can float on the surface and be passively transported to distant areas. This is the first attempt at geochemical and mineralogical characterization of these industrial foams in order to understand their role in the dynamic and behavior of contaminants in marine environment. Chemically, phosphogypsum foams (PGFs) are heavily loaded with radiochemical contaminants. Their mineralogical composition showed a prevalence of synthetic gypsum followed by other secondary minerals including halite, quartz, dolomite, sphalerite-Cd and fluorapatite. PGFs are rich in organic matter (OM), precursor of their formation. Once released in gypseous water, the OM in solution undergoes agglomeration, cementing and flotation steps leading to the formation of floating foams. The foams' OM was found to control the mobility of industrial contaminants contributing then to the marine environment pollution. Consequently, PGFs are the main accumulating, transporting and dispersion agent of phosphogypsum radiochemical contaminants. Thus, PGFs removal has the potential to reduce enormously the dynamics of contaminants transferred from the fertilizer plants to the aquatic environment, reducing thus their impacts on the marine environment and health status in Gabes.

Characterization of phosphate rock and phosphogypsum from Gabes phosphate fertilizer factories (SE Tunisia): high mining potential and implications for environmental protection.

Since the establishment of the coastal industrial complex in Gabes city (Gulf of Gabes, SE Tunisia), hundred million tons of untreated phosphogypsum have been discharged in the open sea causing serious environmental problems. To better understand the dynamic and behavior of phosphate/phosphogypsum contaminants from raw ores to marine environment, a chemical, organic, mineralogical, and morphological characterization of phosphate rock and phosphogypsum was conducted using several sophisticated techniques. The chemical analysis showed that phosphate and phosphogypsum contain high loads of trace elements and that the transfer factors of pollutants varied from 5.83% (U) to 140% (Hg). Estimated annual flows of phosphogypsum contaminants into the marine environment ranged between 0.05 (Re) and 87,249.60 (F) tons. The phosphate rock was found to be formed by carbonate fluorapatite, calcite, dolomite, natural gypsum, quartz, calcite-Mg, apatite, pyrite, fluorite, and sphalerite-Cd and phosphogypsum by synthetic gypsum and sphalerite-Cd. The phosphate was found to be richer in organic compounds compared to phosphogypsum. Based on this work, the Tunisian phosphogypsum has a high mining potential and encourages the development of an economically beneficial and environmentally friendly phosphogypsum-treating industry.

Seawater quality assessment and identification of pollution sources along the central coastal area of Gabes Gulf (SE Tunisia): Evidence of industrial impact and implications for marine environment protection.

Temperature, pH and trace elements (F, P, Cr, Cu, Zn, Cd, and Pb) contents were determined in 16 stations as well as in 2 industrial and 2 domestic discharge sources, in the central coastal area of the Gulf of Gabes. Compared to the northern and southern areas of the study area, the highest contents of contaminants were reached in the central area which hosts the coastal industrial complex. The seawater in this central area was also found to be acid and of higher temperature. Based on the Water Pollution Index results, an increasing degradation gradient of the seawater quality was revealed from northern and/or southern stations to central ones, categorized as 'strongly to seriously affected'. Phosphogypsum wastes dumped by the Tunisian Chemical Group (GCT) seem to have continuously degraded the seawater quality in the study area. A rapid intervention is needed to stop the effects on the marine environment.

Metal bioaccumulation in two edible cephalopods in the Gulf of Gabes, South-Eastern Tunisia: environmental and human health risk assessment.

Samples of Octopus vulgaris and Sepia officinalis were collected from four areas in the Gulf of Gabes, south-eastern Tunisia, and their edible tissues (mantle and arms) were analyzed for cadmium, copper, mercury, and zinc. While the concentrations of metals showed significant differences between the sampling sites, no differences were revealed between the tissues of the two species. The spatial distribution of metals analyzed showed similar pattern for both tissues of the two species, with the highest concentrations found in the central area of Gabes Gulf, and the lowest in the northern and/or southern areas. From a human health risk point of view, the highest values of estimated daily intake, target hazard quotient, and hazard index were found in the central area of Gabes Gulf. Although the results of these indices were, in general, not alarming, the health risks posed by the consumption of cephalopods on local consumers cannot be excluded.

Biomonitoring of coastal pollution in the Gulf of Gabes (SE, Tunisia): use of Posidonia oceanica seagrass as a bioindicator and its mat as an archive of coastal metallic contamination.

Within the framework of a study on the extent and history of marine pollution in the central area of Gabes Gulf, the concentrations of four trace metals (Cd, Cu, Pb, and Zn) were assessed in three different tissues of the seagrass species, Posidonia oceanica (leaves, rhizomes, and roots), in the mat of P. oceanica meadows at different depths from the sea floor (- 30 to - 150 cm) and in sediments. The results showed that P. oceanica leaves accumulate more Cd, Cu, and Zn, whereas Pb was found to be more concentrated in roots. The analysis of P. oceanica mat highlighted a clear decreasing gradient of trace metal concentrations from lower (- 30 cm) to higher (- 150 cm) depths. Considering that P. oceanica mat continuously rises above the initial level, with a rate of 1 m per century (~1 cm year-1; Molinier and Picard Ann Inst Océanogr Fr 27:157-234, 1952), the latter observation suggested that the pollution level in Gabes Gulf increased continuously during the last few decades. The results of the P. oceanica mapping in the study area showed a continuous regression of its meadows as well as its local disappearance from various areas in the central part of Gabes Gulf. The current status of P. oceanica is most likely due to the cumulative effects of the discharges from the coastal industrial complex of Gabes-Ghannouche represented mainly by the phosphogypsum discharges. This study confirms the usefulness of P. oceanica not only as a bioindicator of the "health status" of coastal ecosystems but also as a record register tracing back the history and temporal evolution of coastal contamination level.