• Energy Research

The concentrations of C, Fe, Mn, Zn, Cu, Pb and Cd were determined monthly in decomposing roots of Halimione portulacoides, using litterbag experiments, in two salt marshes of the Tagus estuary with different levels of contamination. Although carbon concentrations varied within a narrow interval during the experiment, litter decomposed rapidly in the first month (weight loss between 0.051 and 0.065 g d(-1)). The time variation of metals was examined in terms of Me/C ratios and metal stocks. Ratios of Fe/C and Mn/C and their metal stocks increased in spring, presumably due to the precipitation of oxides in the surface of decomposing roots. Subsequent decrease of Fe/C and Mn/C ratios suggests the use of Fe and Mn oxides, as electron acceptors, in the organic matter oxidation. Zinc, Cu, Pb and Cd ratios to C were, in general, higher than at initial conditions implying that metal that leached out was slower than carbon. However, metal stocks decreased during the experiment indicating that incorporation or sorption of metals in Fe and Mn oxides did not counterbalance the amount of Zn, Pb and Cd released from decomposing litter. An exception was observed for Cu, since stock in the less contaminated marsh (Pancas) increased during the decomposition, indicating that litter was efficient on Cu binding under more oxidising conditions. These results emphasize the importance of litter decomposition and sediment characteristics on metal cycling in salt marshes.

Results of 7-days exposure to metals, using environmentally realistic conditions, evidenced the high potential of living Fucus vesiculosus to remove Pb, Hg and Cd from contaminated salt waters. For different contamination scenarios (single- and multi-contamination), ca 450 mg L-1 (dry weight), enable to reduce the concentrations of Pb in 65%, of Hg in 95% and of Cd between 25 and 76%. Overall, bioconcentration factors ranged from 600 to 2300. Elovich kinetic model described very well the bioaccumulation of Pb and Cd over time, while pseudo-second-order model adjusted better to experimental data regarding Hg. F. vesiculosus showed different affinity toward studied metals, following the sequence order: Hg > Pb > Cd. Analysis of metal content in the macroalgae after bioaccumulation, proved that all metal removed from solution was bound to the biomass. Depuration experiments reveled no significant loss of metal back to solution. Exposure to contaminants only adversely affected the organism's growth for the highest concentrations of Cd and Pb. Findings are an important contribute for the development of remediation biotechnologies for confined saline waters contaminated with trace metal contaminants, more efficient and with lower costs than the traditional treatment methods.

Depth variation (2-cm resolution) of Fe, Mn, Zn, Cr, Ni, Cu, As and Cd concentrations were determined in belowground biomass of Spartina maritima and Sarcocornia fruticosa and in sediments between roots from two marshes in Tagus (Rosário) and Guadiana (Castro Marim) estuaries in Portugal with different anthropogenic pressures. Levels of metals were also determined in aboveground plant parts. Metal concentrations in belowground material were 2-4 orders of magnitude greater than levels in aboveground plant parts providing evidence of weak upward translocation. Although both studied species showed poor extraction of Cr and Ni from sediments, S. fruticosa exhibited a large capability to remove Zn, Cu, As and Cd from contaminated sediments and stabilised them in belowground biomass. Accumulated metals showed a sub-surface concentration maximum or increase to basal roots. To evaluate whether these preferential layers of accumulation resulted from availability in sediments or controlled by plant activity, Enrichment Factors (EF=[Me](root)/[Metal](sediment)) were calculated for each sediment layer. Maximum values in Rosário plant species (Zn=9.3, Cu=18, As=20, Cd=46) exceeded those obtained in Castro Marim (Zn=1.3, Cu=4.3, As=6.1, Cd=18). Moreover, EFs varied with the depth indicating the presence of preferential layers of metal accumulation in roots of both plants, but depth zonation was not the same as in the sediments. These results suggested that levels in belowground biomass either integrated in time changes that occurred in solid sediments and pore water, or metal uptake by roots was not proportional to levels in sediments. The same sequence of metals transferred from sediment to belowground biomass for the two plants was obtained for the two marshes (Cd > As > Cu, Zn), although metals differed from mining ore to industrial/urban sources.

Different experimental conditions were tested in order to optimize the Hg(II) removal by Eucalyptus globulus bark. Response surface methodology was applied to extract information about the significance of the factors and to obtain a model describing the sorption. The results were generated through the design of experiments by applying the methodology of a three-factor and three-level Box–Behnken design. The factors tested were pH (4.0, 6.5, and 9.0), salinity (0, 15, and 30), and biosorbent dosage (0.2, 0.5, and 0.8 g dm−3) to evaluate the Hg(II) removal using realistic conditions, such as contaminated natural waters with an initial Hg(II) concentration of 50 µg dm−3. The optimum response provided by the model was 81% of the metal removal under the optimal operating conditions: a pH value of 6.0, no salinity, and a biosorbent dosage of 0.55 g dm−3. Concerning the kinetic, the pseudo-second-order equation fitted better to the experimental results with R 2 between 0.973 and 0.996. This work highlights the promising valorization of this biomass, which is an industrial byproduct and makes available information about the influence of the variables for Hg(II) removal in water treatment processes.

Abstract The photodegradation kinetics of the neonicotinoid insecticide acetamiprid (ACT) was investigated under different conditions of pH, salinity and dissolved organic matter (DOM). Photodegradation of ACT in saline and freshwaters followed pseudo-first-order kinetics. Varying pH from 5 to 9 did not significantly affect the photodegradation rate constants (kp) of ACT. Addition of chloride ions increased significantly the value of kp. In the presence of AHA, 10 mg L−1, kp was reduced to approximately 34% of that in sodium chloride solutions 35 g L−1 The observed inhibition may be a consequence of the antioxidant properties of DOM and/or the shading of DOM in the solution. In coastal waters, kp showed a tendency to increase with increasing of salinity and to decrease in the presence of DOM. This is an important outcome since coastal lagoons are important and dynamic systems that are likely to be highly influenced by global climate changes.

This review summarizes the legislation applied to pesticides and highlights the physicochemical properties of the past and recently listed PPs under Water Framework Directive (WFD). It reports important information regarding the analysis, occurrence and long-term screening of PPs in sediments of European coastal lagoons. Among the entire list of PPs, those analyzed have been the organochloride insecticides, such as lindane, hexachlorobenzene and DDT. Although flood events pointed to the possible redistribution of pesticides, which may increase under climate change conditions, few studies are available concerning PPs screening in sediments of European coastal lagoons. Data is scarce not only in terms of the number of listed PPs that have been analyzed but also in terms of their long-term screening. This lack of data on PP concentrations is probably a consequence of the fact that less importance is given to the sediments contamination/quality.

The clam Ruditapes decussatus was transplanted from a natural recruitment area of Ria Formosa to three sites, surveyed for nutrients in water and sediments. Specimens were sampled monthly for determination of Escherichia coli, condition index and gonadal index. Higher nutrient values in low tide reflect drainage, anthropogenic sources or sediment regeneration, emphasising the importance of water mixing in the entire lagoon driven by the tide. Despite the increase of effluent discharges in summer due to tourism, nutrient concentrations and E. coli in clams were lower in warmer periods. The bactericide effect of temperature and solar radiation was better defined in clams from the inlet channel site than from sites closer to urban effluents. High temperature in summer and torrential freshwater inputs to Ria Formosa may anticipate climate change scenarios for south Europe. Seasonal variation of nutrients and clam contamination may thus point to possible alterations in coastal lagoons and their ecosystem services.

Pools of Zn, Cu, Cd and Co in the leaf, stem and root tissues of Sarcocornia fruticosa, Sarcocornia perennis, Halimione portulacoides and Spartina maritima were analysed for a Tagus estuary (Portugal) salt marsh. Pools of Cu and Cd in the salt marsh were higher in spring/summer, indicating a net uptake of these metals during the growing season. Standing stocks of Zn, Cu, Cd and Co in the leaf and stem biomass of S. fruticosa, S. perennis and H. portulacoides showed a strong seasonal variation, with higher values recorded in autumn. The metal-containing leaves and stems that shed in the autumn become metal-containing detritus. The amount of this material washed out from the total marsh area (200 ha) was estimated as 68 kg of Zn, 8.2 kg of Cu, 13 kg of Co and 0.35 kg of Cd. The high tidal amplitude, a branched system of channels and semi-diurnal tidal cycle greatly favour the export of the organic detritus to adjoining marsh areas.