Metal transfer budgets in a Mediterranean marine environment subjected to natural and anthropogenic inputs: case of the Mejerda River Delta (Gulf of Tunis, northern Tunisia).

Deltaic sediments are important for biogeochemical metal cycling since they are hotspots for metal inputs. In addition, they are potential sites for diagenetic processes leading to either the burial of inorganic contaminants or their release. Diffusive fluxes of certain metals (Fe, Mn, Pb, Zn, Cu and Cd) in the sediments of the Mejerda River Delta (MRD) (Gulf of Tunis, Tunisia) were quantified by modeling the available concentration profiles in the pore water. The metals' burial and sedimentation fluxes were also calculated using both the asymptotic concentrations of available metal profiles and sediment trap results. These fluxes were assembled with the exchange fluxes at the sediment-water interface in order to develop complete metal transfer budgets. The results showed that budgets of Cu and Zn are almost neutral. The sediment appears to be a good trap for iron since its average burial flux at the three studied stations is about 332.6 g m-2 year-1. Organic matter degradation, carbonate dissolution, and oxyhydroxide reduction are the main mechanisms which accelerate the release of metals associated with the suspended particle matter once they reach the pore water in the seabed.

Distribution and assessment of heavy metal toxicity in sediment cores from Bizerte Lagoon, Tunisia.

To examine the state of pollution of Bizerte Lagoon which is exposed to intense anthropogenic pressure, two sediment cores were taken at two sites, one undergoes the dual effects of both marine waters arriving from the Mediterranean Sea through the Channel, and also of freshwater from the Tinja River; the other core is located at the center of the lagoon where water depth is maximal (12 m). Heavy metal concentrations in the two cores were assessed, with calculated enrichment factors and geo-accumulation indexes. Core sediments were also studied for chemical speciation and their monosulfide contents were measured. Results from enrichment factors and geo-accumulation indexes show an accumulation of Cd, Zn, Cr, and Pb, while chemical speciation revealed a risk only from Cd and Mn. Comparison of sequential extraction values with those of acid volatile sulfides revealed that non-toxic effects may be caused by any of the studied metals in the sediment.

Foraminiferal biotopes and their distribution control in Ria de Aveiro (Portugal): a multiproxy approach.

Ria de Aveiro, which is located in the centre of Portugal (40° 38' N, 8° 45' W), is a well-mixed and complex coastal lagoon that is separated from the sea by a sandy barrier and connects with the Atlantic through an artificial inlet. Tidal currents are the main factor controlling the lagoon's hydrodynamics and, to a great extent, the sedimentary dynamic. The inner lagoonal zones receive input from several rivers and experience the pressure caused by the accumulation of organic matter and pollutants (namely, trace metals) from diverse anthropic activities. This paper is the first piece of work aiming to recognize, characterize and explain the main benthic foraminiferal biotopes in Ria de Aveiro. To provide a broad overview of this kind of setting, our results are compared to those of previous published studies conducted in similar transitional environments. The research is based on an investigation of 225 sites spread throughout this ecosystem. Utilizing a statistical approach, this study analyses the details of dead benthic foraminiferal assemblages composed of 260 taxa, the texture and composition (mineralogical and geochemical) of the sediment and physicochemical data. On the basis of the results of R-mode and Q-mode cluster analyses, several different biotopes can be defined as marsh biotope/near-marsh biotope; marginal urban/marginal urban mixing biotope; inner-outer lagoon biotope or enclosed lagoon; outer lagoon biotope, mixed sub-biotope; and outer lagoon, marine sub-biotope. These biotopes are related to foraminifera assemblages and substrate type and are influenced by local currents, water depth, chemical and physicochemical conditions, river or oceanic proximity, and anthropogenic impact, as evidenced by the mapping of the six factor loadings of the principal component analysis conducted herein. Based on a similar methodology of analysis as that applied in previous studies in the Lagoon of Venice, comparable biotypes were identified in Lagoon of Aveiro.

Microalgae colonization and trace element accumulation on the plastisphere of marine plastic debris in Monastir Bay (Eastern Tunisia).

In this study, we examined the toxicity potential of the epiplastic microalgal community that developed on low-density polyethylene (LD-PE) plastic debris found in two distinct regions of the Monastir Bay (Tunisia): the coast exposed to anthropogenic discharges and the open sea in front of the Kuriat Islands. Concentrations of potentially toxic elements (PTEs) accumulated in sediments and plastisphere were compared in order to determine their toxicity potential to biological life. The collected plastispheres were predominantly composed of cyanobacteria, chlorophytes, and diatoms. Diatoms display a relatively high diversity (25 species). At all stations, potentially harmful microalgae (PHM) were more abundant in the plastisphere than in seawater and the coastal zone seems to harbour increased number of potentially harmful cyanobacteria within the plastisphere. At the offshore station S1, the PHM community was dominated by the potentially harmful diatoms belonging to the genus Pseudo-nitzschia. Phormidium sp. was the main potentially harmful cyanobacterium identified in the plastisphere of S1. PTEs concentration in the plastisphere was higher than in sediment and ranking with very high contamination factors at all sites according to the sequence Pb > Cu > Cd > Ni > Zn. The highest accumulation of PTEs in the plastisphere was recorded near harbors and industrial zones with important human interference. This work shows that plastisphere can be a threat to vulnerable species not only because it can contain PHM but also because it can accumulate PTEs.

Assessing the status of Ichkeul Lake and its catchment through identifying potentially toxic cyanobacteria, simultaneously extracted metals and use of acid-volatile-sulfide model.

Lake Ichkeul is considered one of the most significant wetlands in the Mediterranean basin. It serves as a crucial wintering area for numerous western Palearctic birds. A notable decline in species diversity has been observed in the past decade, attributed to excessive water usage for irrigation and the effects of climate change. This study aimed to assess the status of Ichkeul Lake and its catchment through identifying potentially toxic cyanobacteria, and sediment quality. Our first striking finding was that Lyngbya majuscula the dominant potentially toxic cyanobacterium in the lake originated from the Tinja channel. Trace element concentrations in lake sediments exceeded SQG standards which is indicative of rare detrimental effects to biological life. However, the sediment in front of the Tinja channel exhibited high contamination levels of Zn and Cd. These findings call for an urgent need to ensure the ongoing management and conservation of this world heritage site.

Distribution and accumulation of metals and metalloids in planktonic food webs of the Mediterranean Sea (MERITE-HIPPOCAMPE campaign).

Particle-size classes (7 fractions from 0.8 to 2000 µm) were collected in the deep chlorophyll maximum along a Mediterranean transect including the northern coastal zone (bays of Toulon and Marseilles, France), the offshore zone (near the North Balearic Thermal Front), and the southern coastal zone (Gulf of Gabès, Tunisia). Concentrations of biotic metals and metalloids (As, Cd, Cr, Cu, Fe, Mn, Ni, Sb, V, Zn) bound to living or dead organisms and faecal pellets were assessed by phosphorus normalisation. Biotic metals and metalloids concentrations (except Cr, Mn, and V) were higher in the offshore zone than in the coastal zones. In addition, biotic Sb and V concentrations appeared to be affected by atmospheric deposition, and biotic Cr concentrations appeared to be affected by local anthropogenic inputs. Essential elements (Cd, Cu, Fe, Mn, Ni, V, Zn) were very likely controlled both by the metabolic activity of certain organisms (nanoeukaryotes, copepods) and trophic structure. In the northern coastal zone, biomagnification of essential elements was controlled by copepods activities. In the offshore zone, metals and metalloids were not biomagnified probably due to homeostasis regulatory processes in organisms. In the southern coastal zone, biomagnification of As, Cu, Cr, Sb could probably induce specific effects within the planktonic network.

Assessment of trace elements and fluoride originating from phosphogypsum in the sediment of Gulf of Gabes (southeastern Tunisia): what are the potential sources of accumulation and bioavailability?

To assess potential impacts of industrial activities on the pollution status of Gulf of Gabes, twenty sediment and water samples along with phytoplankton enumeration were achieved at different stations with specific features. Comparing trace element concentrations in sediment to applicable SQG standards, we were intrigued by an accumulation of Zn, Cr, Ni, and especially Cd, which exhibited relatively high content compared to these standards. Moreover, trace metal bioavailability was high in front of industrial discharge areas. The chemical speciation pointed out a high affinity of Pb, Zn, Cr, Mn, Ni, Co, and Fe for the residual fraction of the sediment. Bioavailability of trace elements was confirmed in surface sediment by the presence of a potential toxic fraction especially in front of industrial discharge areas. Toxicity assessment performed for the first time in the Gulf of Gabes through SEM and AVS models pointed to a high potential risk near both Ghannouch and Gabes Ports. Finally, the correlations between phytoplankton species and the labile fraction inferred potential phytoplankton bioaccumulation of Zn, Cu, and Cd both in the seawater and in the labile fraction.

Trace metals enrichment and potential ecological risk in sediments of the Sepetiba Bay (Rio de Janeiro, SE Brazil).

The Sepetiba Bay (SB; SE Brazil) has been severely affected by growing of urbanization and industrial activity. This work aims to analyze the evolution of contamination by metals of sediments in SB. The results show a marked increasing trend in the concentrations of potentially toxic elements (PTEs), which is consistent with the rapid populational and industrial growth, mostly since 1970 CE. The remobilization and redistribution of sediments by currents have contributed to the dispersion of metals from the main source of pollutants to relatively distant regions. "Moderately to strongly polluted" sediments are also recorded in some sites in deeper sedimentary layers (namely in preindustrial periods), probably due to lithologic sources of the sediments. The concentrations of PTEs in SB are relatively high when compared with those found globally and in other Brazilian water bodies. Samples of high-resolution sediment cores confirmed that potential ecological risk to the coastal system is influenced not only through human actions but also by natural causes.

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.

3D modeling of phytoplankton seasonal variation and nutrient budget in a southern Mediterranean Lagoon.

A 3D coupled physical-biogeochemical model is developed and applied to Bizerte Lagoon (Tunisia), in order to understand and quantitatively assess its hydrobiological functioning and nutrients budget. The biogeochemical module accounts for nitrogen and phosphorus and includes the water column and upper sediment layer. The simulations showed that water circulation and the seasonal patterns of nutrients, phytoplankton and dissolved oxygen were satisfactorily reproduced. Model results indicate that water circulation in the lagoon is driven mainly by tide and wind. Plankton primary production is co-limited by phosphorus and nitrogen, and is highest in the inner part of the lagoon, due to the combined effects of high water residence time and high nutrient inputs from the boundary. However, a sensitivity analysis highlights the importance of exchanges with the Mediterranean Sea in maintaining a high level of productivity. Intensive use of fertilizers in the catchment area has a significant effect on phytoplankton biomass increase.

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.

Assessing trace metal pollution through high spatial resolution of surface sediments along the Tunis Gulf coast (southwestern Mediterranean).

Tunis Gulf (northern Tunisia, Mediterranean Sea) is of great economic importance due to its abundant fish resources. Rising urbanization and industrial development in the surrounding area have resulted in an increase in untreated effluents and domestic waste discharged into the gulf via its tributary streams. Metal (Cd, Pb, Hg, Cu, Zn, Fe, and Mn) and major element (Mg, Ca, Na, and K) concentrations were measured in the grain fine fraction <63 µm by atomic absorption spectrophotometry. Results showed varying spatial distribution patterns for metals, indicating complex origins and controlling factors such as anthropogenic activities. Sediment metal concentrations are ranked as follows: Fe > Mg > Zn > Mn > Pb > Cu > Cd > Hg. Metals tend to be concentrated in proximity to source points, suggesting that the mineral enrichment elements come from sewage of coastal towns and pollution from industrial dumps and located along local rivers, lagoons, and on the gulf shore itself. This study showed that trace metal and major element concentrations in surface sediments along the Tunis Gulf shores were lower than those found in other coastal areas of the Mediterranean Sea.

Suspended particulate matter fluxes along with their associated metals, organic matter and carbonates in a coastal Mediterranean area affected by mining activities.

A study of suspended particulate matter (SPM) fluxes along with their associated metals, organic matter and carbonates, was conducted off the Mejerda River outlet in May 2011 and in March and July 2012 at depths of 10, 20 and 40 m using sediment traps. SPM fluxes are more significant near the Mejerda outlet, especially in winter, but dissipate further offshore. Normalization reveals that the Mejerda is a major source of Pb, Zn, Cd, Cu, Ni, and Co, all of which are the result of human activities. In contrast, Fe, Mn and N are of authigenic origin. The enrichment factor shows that Pb, Zn and especially Cd are the most highly polluting metals off the Mejerda outlet. This confirms the trend observed on the shores of the Mejerda prodelta and is consistent with the type of mining activities conducted in the Mejerda catchment.

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.

Assessing pollution in a Mediterranean lagoon using acid volatile sulfides and estimations of simultaneously extracted metals.

Bizerte Lagoon is a southern Mediterranean semi-enclosed lagoon with a maximum depth of 12 m. After assessing sediment quality, the authors report on the physicochemical characteristics of the lagoon's surface sediment using SEM (simultaneously extracted metals) and AVS (acid volatile sulfides) as proxies. Biogeochemical tools are used to investigate the environmental disturbance at the water-sediment interface by means of SEM and AVS to seek conclusions concerning the study area's pollution status. Results confirm accumulation of trace elements in sediment. The use of the SEM-AVS model with organic matter in sediment (ƒOC) confirms possible bioavailability of accumulated trace elements, especially Zn, in the southern part of the lagoon, with organic matter playing an important role in SEM excess correction to affirm a nontoxic total metal sediment state. Individual trace element toxicity is dependent on the bioavailable fraction of SEMMetal on sediment, as is the influence of lagoon inflow from southern water sources on element bioavailability. Appropriate management strategies are highly recommended to mitigate any potential harmful effects on health from this heavy-metal-based pollution.

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.

Environmental Quality Assessment of Bizerte Lagoon (Tunisia) Using Living Foraminifera Assemblages and a Multiproxy Approach.

This study investigated the environmental quality of the Bizerte Lagoon (Tunisia) through an integrated approach that combined environmental, biogeochemical, and living benthic foraminiferal analyses. Specifically, we analyzed the physicochemical parameters of the water and sediment. The textural, mineralogical, and geochemical characteristics of the sediment, including total organic carbon, total nitrogen, simultaneously extracted metals (SEM), acid volatile sulfides (AVS), chlorophyll a, CaCO3, and changes in bacterial populations and carbon isotopes were measured. The SEM/AVS values indicated the presence of relatively high concentrations of toxic metals in only some areas. Foraminiferal assemblages were dominated by species such as A. parkinsoniana (20-91%), Bolivina striatula (<40%), Hopkinsina atlantica (<17%), and Bolivina ordinaria (<15%) that cannot be considered typical of impacted coastal lagoons both in Mediterranean and northeast Atlantic regions. The results of this work suggest that Bizerte Lagoon is a unique setting. This lagoon is populated by typical marine species that invaded this ecosystem, attracted not only by the prevailing favorable environmental conditions but also by the abundance and quality of food. The results indicate that the metal pollution found in some areas have a negative impact on the assemblages of foraminifera. At present, however, this negative impact is not highly alarming.

Accumulation of trace metals in sediments in a Mediterranean Lagoon: Usefulness of metal sediment fractionation and elutriate toxicity assessment.

The authors investigated sediment quality in Bizerte Lagoon (Tunisia) focusing on geochemical characteristics, metal sediment fractionation and elutriate toxicity assessment. Nickel, Cu, Zn, Pb, Cr and Cd partitioning in sediments was studied; accumulation and bioavailability were elucidated using enrichment factors, sequential extractions, redox potential, acid volatile sulfide and biotest procedures in toxicity evaluation. Results revealed an accumulation for Pb and Zn, reaching 99 and 460 mg kg(-1) respectively. In addition, the acid volatile sulfide values were high in both eastern and western lagoon areas, thus affecting metal availability. Mean enrichment factor values for Pb and Zn were 4.8 and 4.9, respectively, with these elements as the main contributors to the lagoon's moderate enrichment level. Toxicity levels were influenced by accumulation of Zn in different surface sediment areas. Core sediments were investigated in areas with the highest metal concentrations; metal fractionation and biotest confirmed that Zn contributes to sediment toxicity.