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In the early XXth century, the Gulf of Gabes in SE Tunisia used to host the most extended Posidonia oceanica seagrass beds in the Mediterranean basin and was a highly productive hotspot of benthic species. Since the 70's,500 million t of wet toxic phosphogypsum discharges from a fertilizer industrial complex have led to the gradual loss of ∼90 % of its initial surface. This drastic shrinkage is accompanied by significant value losses originated from the direct and indirect-use services of which the most important ones are small scale fisheries and carbon storage function. Using market valuations of a number of services we estimate economic losses at 105 million € in 2014 (∼915€/ha), i.e., around 115 % of the added value of the gabesian fertilizer factories for the same year. Value losses should increase in the near future in relation with the COP26 agreements which boosted the open carbon credit market. Without actions to reduce negative production externalities caused by the fertilizer industry in the Gulf of Gabes it would not be possible to recover Posidonia ecosystems in this region leading to further economic, ecologic, and cultural losses.

Mismanaged plastic waste interacts with secondary environmental pollutants, potentially aggravating their impact on ecosystems and human health. Here we characterized the natural and artificial radionuclides in polyethylene terephthalate (PET) bottles collected from the industrial littoral discharge of a phosphate fertilizer plant. The activity concentrations in littered bottles ranged from 0.47 (

This work is a first contribution to the knowledge of natural radionuclides (226Ra, 238U, 40K, and 232Th) activities in phosphate rock (NORM), phosphogypsum, and phosphogypsum foam (TENORM) from the coastal fertilizer plants of Gabes (Southeastern Tunisia) and the assessment of their radiation hazards on human health and the surrounding environment. In the three studied materials, activities were found to be in the range of 35.4 (40K)–375.1 (226Ra), 10.0 (40K)–220.2 (226Ra), and 79.2 (232Th)–1168.6 Bq kg−1 (226Ra), respectively. Considering the studied radionuclides and materials, the corresponding decreasing activity orders were found to be 226Ra > 238U > 40K > 232Th and PGF > PR > PG, respectively. All human health hazard indices exceeded the worldwide recommended safety limits, which show that the workers in Gabes phosphate fertilizer plants as well as the neighboring human community may potentially be exposed to significant radiation, which may cause several diseases and malformations. It is therefore recommended to avoid and/or reduce the potential fertilizer industry radioactive impact in the area.

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.

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.

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.

This is the first study on the behavior and industrial fluxes of rare earth elements (REE) in the coastal fertilizer plants of Gabes (south-eastern Tunisia), the economic losses related to their wastes, and their environmental and human health hazards. The concentrations of 16 REE were assessed in phosphate rock (PR), phosphogypsum (PG) and phosphogypsum foam (PGF) samples, collected from Gabes plants. REE concentrations ranged from 0.23 (for Sc in PG) to 309.33 mg kg−1 (for Ce in PGF). Ce was the most abundant in the three matrices, with concentrations ranging between 80.40 (in PG) and 309.33 mg kg−1 (in PGF). PGF was the most enriched with REE (1075.32 mg kg−1). The annual flow of REE from the fertilizer factories to the marine environment may reach 1523.67 t. The economic losses related to the discharge of phosphogypsum REE in the Gulf of Gabes (GG) was estimated at ~58 million US$ y−1. The potential hazards of discharged REE on the local environment and human health were also evaluated and discussed. These findings show the need for the development of a new industry exploiting REE from phosphogypsum wastes (short term) and phosphate ores (long term) which should lead to reduce its high environmental and human health footprint and to potential economic gains.

Although several studies previously assessed the contents of trace metals in the sediments of the heavily human-impacted lagoon of Bizerte (northern Tunisia), multi-analytical approaches have not been, so far, used to assess the ecological risks in this water body. This study attempts to provide a comprehensive ecological risk assessment related to the enrichment of the lagoon sediments with seven metals (As, Cd, Cr, Cu, Hg, Pb, and Zn). Significant spatial variations were found in the metal concentrations in sediments, in relation to the degree of coastal human activities and hydrodynamics. This was confirmed with the results of the three pollution indices, Cf, PLI, and Igeo. Concordant results were found with most of the indices used to assess the ecological risks (PERI, PEL, ERL, ERM, M-ERM-Q, TU), indicating higher risks in the southern part of the lagoon. These findings can help to improve the environmental management plan of the socio-economic important lagoon of Bizerte.

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 Oceanogr 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.

In early XXth century, the Gulf of Gabes (SE Tunisia) used to host the most extended Posidonia oceanica seagrass beds in the Mediterranean Sea, and a highly productive hotspot of benthic/demersal biodiversity. Sponge harvesting and seabed trawling provoked a first step of seagrass degradation. Subsequently, phosphogypsum releases from Gabes Industrial Complex, since mid-1970s, accelerated the decline of the remaining patches. A sharp reduction of coastal fisheries landings took place with the establishment of the last industrial plant units in 1985. The decrease in coastal commercial species landings was found to be directly correlated with P. oceanica decline. The trophic web system switched from a ‘benthic-dominated’ to a ‘pelagic-dominated’ system. The economic loss related to coastal fisheries was estimated at ~60 million € in 2014 and the 1990–2014 cumulated loss exceeded 750 million €. This first economic valuation of the only direct-use consumptive value of the coastal fishing service provided by P. oceanica in Gabes Gulf is a first step towards the assessment of the environmental cost of the negative externalities caused by the local phosphate industry. It may be used as a preliminary decision-making aid to consider alternative industrial solutions.

In the present study, the concentrations of 6 trace metals (Hg, Cd, Cu, Pb, Cr and Zn) were assessed in the surface sediments of the central coastal area of Gabes Gulf to determine their contamination status, source, spatial distribution and ecological risks. The ranking of metal contents was found to be Zn>Cd>Cr>Pb>Cu>Hg. Correlation analysis indicated that Cd and Zn derived mainly from the Tunisian Chemical Group phosphogypsum. The other pollutants may originate from other industrial wastes. Metallic contamination was detected in the south of chemical complex, especially in the inter-harbor zone, where the ecological risk of surface sediments is the highest, implying potential negative impacts of industrial pollutants. The spatial distribution of pollutants seems to be due to the effect of harbor installations and coastal currents. The metallic pollution status of surface sediments of Gabes Gulf is obvious, very worrying and requires rapid intervention.

The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO4 solutions to measure the distribution coefficients (Kd) of Eu as a trace element (

The microscopic reversibility of the sorption of Sm and Yb onto kaolinite and smectite is investigated by introducing an isotopic disequilibrium between the clay and the solution. The experiments are performed at 25°C, in 0.025 or 0.5 M NaClO4 and from pH 4 up to pH 7. The isotopic exchange is monitored as a function of time over a duration of 355 hours. The first stage of the experiment consists of equilibrating the clays with a natural or spiked lanthanide solution. The second stage consists of interchanging the solutions between twin phials (same clay, pH and ionic strength, but with different lanthanide isotopic compositions). The isotopic composition and concentration of aqueous lanthanides are analysed by ICP-MS. The results are as follows: (1) the lanthanide isotopic composition of the solution is rapidly modified and stabilised within 24 h; (2) the isotopic exchange between the solid and the solution is not always complete; (3) the degree of microscopic reversibility (isotopic exchange) decreases with increasing pH. These results are explained by the fact that exchange is easier for lanthanides linked to the surface as outer-sphere complexes (physical sorption), which predominate at low pH, than for atoms sorbed as inner-sphere complexes (chemical sorption) which predominate at high pH. The contrasted kinetics observed for the different kind of sites provide additional constraints for the modeling of migration processes in natural systems.

Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3–9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO 3 or NaClO 4 ) under atmospheric conditions or N 2 flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO 2 , but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient ( K D ) above pH 5.5. At 0.025 M, the measured K D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K D . This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.

The stability of aqueous complexes formed by gadolinium (Gd 3+ ) and ytterbium (Yb 3+ ) aqueous species with the acetate ion (AcO − ) was investigated at 25°C, 40°C, 60°C and 80°C, and saturated vapor pressure, using potentiometric measurements. In the large range of [AcO] T /[REE] T molal ratio investigated (1 to 120), the results are interpreted in terms of the formation of two complexes, REEAcO 2- and REE(AcO) 2 - (where REE denotes Gd or Yb). The corresponding association constants β 11 and β 12 that we proposed are successfully used to predict high Gd(OH) 3 (cr) solubilities measured in acetate containing solutions in this study. The data show an increasing stability of the REE–acetate complexes with increasing temperature. The regression of the obtained association constant values using either a linear equation or a simplified formulation of the revised HKF thermodynamic model allows the retrieval of thermodynamic properties for the aqueous complexes. Combining these results with those obtained with lanthanum in a previous study [Deberdt, S., Castet, S., Dandurand, J.-L., Harrichoury, J.-C., Louiset, I., 1998. Experimental study of La(OH) 3 and Gd(OH) 3 solubilities (25 to 150°C), and La–acetate complexing (25 to 80°C). Chem. Geol. 151, 349–372.] demonstrates that the stability of the REE–AcO − complexes increases from La to Gd, then decreases to Yb.

The solubilities of pure synthetic La and Gd hydroxides were measured in aqueous solutions over a wide range of pH (5–9.5) and temperature (40–150°C). The regression of these data is used to determine the first dissociation constant (KS0*) of the minerals as a function of temperature. The logarithm of these constants is found to be linearly related to the reciprocal temperature, which allows their reliable extrapolation to 25°C. In the range of temperature and pH investigated, only the REE3+ ion (where REE denotes La or Gd) is present in solution, indicating that the first hydrolysis constants proposed by Baes and Mesmer (1976), which are generally admitted, are overestimated. The complexation of La with acetate ion (AcO−) was studied by both solubility and potentiometric measurements. Potentiometric titrations are interpreted in terms of the formation of two complexes: LaAcO2+ and La(AcO)2+, and are used to generate the corresponding stability constants in the temperature range 25–80°C. These data allow accurate description of the La(OH)3 solubility increase, evidenced in acetate-bearing solutions.

The stoichiometry and stability constants of Na-aluminate (NaAl(OH) 4 0 ) ion pair were determined from both boehmite solubility and potentiometric measurements. Boehmite solubility was measured at temperatures from 125 to 350 °C at pressures corresponding to equilibrium between liquid and vapor ( P SAT ) in the system Na-NH 4 -Cl-OH. Potentiometric measurements were performed at temperatures from 75 to 200 °C in Na-Al-Cl-OH solutions, using a Na-selective glass electrode. NaAl(OH) 4 0 stability constants derived independently from these two methods are in excellent agreement and increase markedly with increasing temperature from 0.8 at 25 °C to 209 at 350 °C. Experimental results obtained in this study were combined with corresponding data reported by Castet et al. (1993) for boehmite solubility to generate, within the framework of the revised HKF model, the standard partial molal properties and equations of state parameters for Al(OH) 4 − , Al(OH) 3 0 , and NaAl(OH) 4 0 . The solubilities of gibbsite, boehmite, and corundum calculated in Na-rich solutions using the thermodynamic data for Al aqueous species generated in this study are in close agreement with their experimental counterparts. Thermodynamic calculations carried out at temperatures up to 800 °C and pressures up to 5 kbar indicate that the formation of NaAl(OH) 4 0 ion pairs can markedly increase the solubility of Al-bearing minerals and thus, Al mobility, both in sedimentary basin and metamorphic fluids at pHs > 4.

The solubilities of bayerite and boehmite were measured as a function of pH and acetate concentration at temperatures from 60 to 2OO"C, to determine the stoichiometries and stability constants of aluminum-acetate complexes. Analysis of these solubility data indicate that the three aluminum- acetate complexes, AlAcO *+ Al(OH)AcO+, and Al(Ac0); are significant. The logarithm ofthe stability constants of these complexei are found to be linearly related to the reciprocal of temperature over the range 60-200°C. The slopes of these relationships yield association enthalpies of -75 kJ/mol. Ther- modynamic calculations indicate that acetate can markedly enhance the solubility of Al-bearing minerals in sedimentary basin fluids over the temperature range from 100 to 2OO"C, at pH < 5, but have little effect in solutions having higher pHs.

A critical review of the literature concerning the solubility of aluminium hydroxides and oxyhydroxides has revealed some problems concerning the measurements in alkaline solutions; in addition, it has led us to regard the solubility measurements of gibbsite in acid solutions as being very questionable. As a result of this review, solubility measurements have been made in weakly concentrated alkaline solutions (which allow for easy thermodynamic modelling) for: - synthetic bayerite: dissolution and precipitation between 21 and 65°C; - synthetic gibbsite: dissolution between 21 and 70°C; - synthetic boehmite: dissolution and precipitation between 70 and 300°C; - natural diaspore: dissolution between 130 and 300°C. Our measurements permit the determination of the solubility products of these minerals with good accuracy and allow for the calculation of their thermodynamic properties as well as of the Gibbs free energy of formation of the aluminate ion, Al(OH) 4 #75 . The following values are proposed for the Gibbs free energy of formation at 298.15 K: Al(OH) 4 #75 : -1305.42 kJ/mol; gibbsite: -154.889 kJ/mol; bayerite: -1149.80 kJ/mol; boehmite: -917.82 kJ/mol; diaspore: -924.59 kJ/mol. Therefore, we can propose that the order of increasing stability of the aluminium hydroxides and oxyhydroxides at 25°C is: diaspore > boehmite ∼ gibbsite > bayerite

Equations are presented for the calculation of the equilibrium constant and standard state thermodynamic properties at high temperatures and pressures of reactions involving both aqueous species and minerals, given a knowledge of the equilibrium constant and the standard enthalpy and heat capacity of the reactions at reference conditions. The equations are based on a model variation of the heat capacity of reaction which uses reference state values and solvent properties only, notably the temperature derivative of the coefficient of thermal expansion of water.

The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs + , Ni 2+ and 14 lanthanides (Ln 3+ ) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution. The results show a weak but measurable influence of the temperature on the elements sorption. Kd’s for Ni 2+ and Ln 3+ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol −1 and 39 ± 15 kJ.mol −1 for Ni 2+ and Eu 3+ , respectively. On the other hand, the temperature effect on Cs + sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs + on the montmorillonite is −19 ± 5 kJ.mol −1 . Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature. The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry.