Mohamed Amine Helali

Geochemistry of marine sediments in the Mejerda River delta, Tunisia

Abstract Superficial sediments were collected from the Mejerda River delta between October and November 2008. Samples were analysed for 15 trace and major elements (Cd, Pb, Zn, Mn, Ni, Co, Cr, Cu, Sr, Fe, Al, Ca, Mg, Na, and K). Fine fractions, carbonates, total organic carbon, minerals and acid volatile sulfide (AVS) were also analysed to explain the spatial distributions of heavy metals. There are two theories of metal spatial distribution: metals concentrated in coastal sediments (Ca, Mn, and Sr) and metals concentrated in offshore sediments (Al, Fe, Mg, Na, K, Pb, Zn, Cr, Co, Ni). Ca, Mn and Sr show similar distributions to those of carbonates, quartz and calcite; these elements show their greatest concentrations in the coastal sediments. However, Al, Fe, Pb, Zn, Cr, Co and Ni show a large concentration in offshore sediments, such as in the clay and silts (< 20μm). None of these metals has a visible affinity with the organic carbon or AVS, indicating that the carbonates and fine fraction are the essential factors which control the distribution of heavy metals in the delta. With regard to other heavy metals studied in the Mediterranean Sea, Cd, Pb and Zn constitute the main pollutants in the delta.

Organic matter quantity and quality, metals availability and foraminiferal assemblages as environmental proxy applied to the Bizerte Lagoon (Tunisia).

This study analyzes the benthic trophic state of Bizerte Lagoon (Tunisia) based on the total organic matter and the bioavailability of biopolymeric carbon including proteins (PTN), carbohydrates (CHO), lipids (LIP), chlorophyll a, as well as bacteria counts. The overall simultaneously extracted metals (SEM), and acid volatile sulfides (AVS) as well as the SEM/AVS ratio indicative of the toxicity of the sediments also were analyzed aiming to study their impact in the dimension, composition and structure of both dead and living benthic foraminiferal assemblages. In the studied sites TOC content is relatively high and the PTN/CHO values indicate that they can be considered as meso-eutrophic environments. The CHO/TOC and C/N values suggest that the OM which accumulated on the sediments surface has mainly natural origin despite the introduction of municipal and industrial effluents in the lagoon and the large bacterial pool. The living assemblages of benthic foraminifera of Bizerte Lagoon are quite different to other Mediterranean transitional systems studied until now. They are composed of typical lagoonal species but also include several marine and opportunistic species including significant numbers of bolivinids, buliminids, Nonionella/Nonionoides spp. and Cassidulina/Globocassidulina spp. These assemblages seem to benefitfrom the physicochemical parameters and the sediment stability. They may however face environmental stress in the lagoon related to the AVS production as a result of the organic matter degradation and toxicity in some areas due to the available concentrations of metals. Nonetheless statistical results evidence that the structure and dimension of assemblages are being controlled mostly by OM quantity and quality related mainly to the availability of PTN, CHO and chlorophyll a. Results of this work support the importance of considering OM quantity and quality in studies of environmental impact in coastal systems.

Trace elements in different marine sediment fractions of the Gulf of Tunis (Central Mediterranean Sea)

Abstract Over several decades, the mouth of the Mejerda River (northern Tunisia) has received large amounts of mining tailings mainly containing Pb, Zn and Ba. We have measured the concentrations of major and trace elements (Al, Ti, P, K, Mg, Na, Ca, S, Fe, Cl, V, Cr, Co, Ni, Cu, Zn, Ga, Br, Rb, Sr, Y, Zr, Nb, I, Ba and Pb) in three different fractions of 45 surficial sediments using wavelength dispersive X-ray fluorescence. The size distribution of fine particles (<2 μm, 2–20 μm, 20–63 μm) revealed that clay and silt compounds were predominant (75–95%) in the deeper estuarine region. These condensed clay phases were mainly dioctahedral smectite, illite and kaolinite. The total organic carbon (TOC) concentration varies from 0.08 to 1.37 %. The C:N ratio varies from 1 to 17 indicating that the organic matter has a mixed marine and continental origin principal component analysis was used to determine the associations of trace elements with organic and/or inorganic phases of the sediment fractions. The correlations of Fe2O3, MnO2 and P2O5 with trace elements showed that amorphous Fe and Mn were the most active scavengers of dissolved metals from the Mejerda River. Cluster analysis clearly distinguished local trace element accumulations according to grain size fractions (< 2 μm and 2–20 μm) near the Ghar el Melh Lagoon and th River.

Bioavailability and assessment of heavy metal pollution in sediment cores off the Mejerda River Delta (Gulf of Tunis): How useful is a multiproxy approach ?

Three core samples were taken from zones offshore from the Mejerda River Delta (Tunisia) and analyzed for major and trace elements to assess their relationships with organic matter, monosulfides and carbonates, as well as for pollution and bioavailability. Chemical speciation, ∑ SEM/AVS, the enrichment factor (EF) and the geo-accumulation index (I-geo) were used. Iron, cadmium, lead and zinc - the most frequently mined metals in the Mejerda catchment - were found as contaminants in the offshore areas. Estimations of trace element accumulation using the EF and the I-geo index show that lead, and to a lesser extent zinc, are the most polluting metals off the Mejerda outlet. According to their bioavailability, these metals are also the most toxic. Only cadmium is heavily present in delta sediment (EF>100) though deeply sequestrated (100% bound to the residual fraction) and thus presents no toxicity.

Trace element accumulation and elutriate toxicity in surface sediment in northern Tunisia (Tunis Gulf, southern Mediterranean)

Metal concentrations in sediments were investigated in the Gulf of Tunis, Tunisia, in relation to anthropic activities along the Mejerda River and Ghar El Melh Lagoon, with effluents discharged into the gulf. Distribution of grain size showed that the silty fraction is dominant with 53%, while sand and clay averages are 34 and 12% respectively. Zn concentration increased in the vicinity of the Mejerda River while Pb was at its highest levels at the outlet of Ghar El Mehl Lagoon. Sediment elutriate toxicity, as measured by oyster embryo bioassays, ranged from 10 to 45% abnormalities after 24h, but no relation was found between metal concentration and sediment toxicity. The AVS fraction that represents monosulfide concentrations in the sediment was higher in the central part of the gulf than in the coastal zone. The results reveal the influence of AVS, TOC and grain size on metal speciation and sediment toxicity.

Sulfide influence on metal behavior in a polluted southern Mediterranean lagoon: implications for management

The degree of pyritization and degree of trace metal pyritization (DTMP) were investigated in sediments from Ghar El Melh Lagoon (northern Tunisia) in order to study metal deposition. A sediment core and 28 samples were thus taken in summer 2008, and metals and sulfate were analyzed in pore water/pyrite. Acid-volatile sulfide and metals were simultaneously extracted from these two fractions and the role of pyrite in the metal cycling studied. To examine pyrite presence and mineralogical form in sediments, X-ray diffraction of the washed and decarbonated sediment was performed along with scanning electron microscopy. Results showed that pyrite is present in fromboidal and euhedral forms. Thermodynamic calculation highlighted the formation of metallic sulfides and the co-precipitation of metals with iron sulfides. The DTMP increases with depth, indicating that these metals are either sequestered as sulfides or that they co-precipitate with pyrite into the deep sediment.

Hydrochemical characterization and geospatial analysis of groundwater quality in Cap Bon region, northeastern Tunisia

The hydrogeochemical characteristics of shallow groundwater in the Grombalia region, northeastern Tunisia, were investigated to evaluate suitability for irrigation and other uses and to determine the main processes that control its chemical composition. A total of 21 groundwater samples were collected from existing wells in January–February 2015 and were analyzed for the major cations and anions concentrations. Conductivity, pH, T°, O2 and salinity were also measured. Interrelationships between chemical parameters were determined by using the scatter matrix method. The suitability of groundwater for irrigation and other uses was assessed by determining the sodium adsorption ratio, soluble-sodium percentage, total dissolved solids, total hardness, Kelly’s index and permeability index values of water samples. The spatial distribution of key parameters was assessed using a GIS-based spatial gridding technique. This analysis indicated that the chemical composition of groundwater in the study area is of Cl–SO4–Na–Ca mixed facies with concentrations of many chemical constituents exceeding known guideline values for irrigation. The salinity of groundwater is controlled by most dominant cation and anion (Na–Cl). A correlation analysis shows that Na+ is the dominant cation and that reverse ion exchange is a dominant process that controls the hydrogeochemical evolution of groundwater in the area. Geospatial mapping of hydrochemical parameters and indices analyzed with the USSL and Wilcox diagrams show distinctive areas of irrigation suitability. In contrast, 76.2% of samples fall in the highly doubtful to unsuitable category and indicate that the central and north-eastern parts of the study area are unsuitable for irrigation due to a high salinity and alkalinity.