Zostera noltei response to transplantation into historically Hg-contaminated sediments (A mesocosm experiment): Growth, bioaccumulation and photosynthetic performance.

The present study aimed to evaluate the effectiveness of seagrass recolonization as a nature-based solution for the recovery of a coastal area historically contaminated by mercury (Laranjo Bay, Ria de Aveiro, Portugal). A mesocosm approach was employed to assess the resistance of Zostera noltei to transplantation into contaminated sediments collected in-situ (0.5-20 mg kg-1 Hg). At each sampling time (15, 30, 60, 120 and 210 days), the resistance of transplanted Z. noltei was evaluated through growth parameters (biomass and coverage area), photosynthetic performance and elemental composition. Although some significant differences (p ≤ 0.05) were observed between treatments, essentially associated with the elemental composition of plant tissues, the most relevant variations were associated with seasonality. Overall, plants were found to not be affected by sediment contamination, under the tested concentrations, suggesting that recolonization with Z. noltei can be an effective restoration strategy for historically contaminated coastal areas.

Mercury pollution in Ria de Aveiro (Portugal): a review of the system assessment.

The Ria de Aveiro (Portugal) is a coast al lagoon adjacent to the Atlantic Ocean and it has an inner bay (Laranjo bay) that received a highly contaminated effluent discharged by a mercury cell chlor-alkali plant from the 1950s until 1994. The aim of this study is to review in a holistic way several research studies that have been carried out in the Ria de Aveiro, in order to evaluate the remobilization of the mercury accumulated within the system and the recovery of the lagoon. The spatial distribution of the total mercury in the surrounding terrestrial environment has also been considered. Results indicate that the main mercury contamination problems in the Ria de Aveiro are confined to the Laranjo bay. Mercury export to the coastal waters and its impact on the nearshore compartments (water column, sediment and biota) are low. No direct effects of the mercury from nearby industrial activities were detected in Aveiro's urban soils, although historical mercury contamination is still affecting soil quality in the immediate vicinity of the chlor-alkali plant, located in Estarreja. Moreover, macrophyte harvesting for human direct or indirect use and the consumption of mussels, crabs and the sea bass from the Laranjo bay may constitute a health risk. Further studies focusing on developing skills for the restoration of the ecosystem are presently underway.

Advances on assessing nanotoxicity in marine fish - the pros and cons of combining an ex vivo approach and histopathological analysis in gills.

The need to overcome logistic and ethical limitations of in vivo nanotoxicity evaluation in marine organisms is essential, mostly when dealing with fish. It is well established that medium/solvent conditions affect dispersion and agglomeration of nanoparticles (NPs), which represents a constraint towards a solid and realistic toxicity appraisal. In this way the pros and cons of an ex vivo approach, using a simplified exposure medium (seawater) and addressing gills histopathology, were explored. The nanotoxic potential of environmentally realistic concentrations of titanium dioxide NPs (TiO2 NPs) was also assessed, disclosing the morpho-functional effects on the gills and the possible uptake/elimination processes. Excised gills of the Senegalese sole (Solea senegalensis) were directly exposed in artificial seawater to 20 and 200 µg L-1 TiO2 NPs, for 2 h and 4 h. Semi-quantitative and quantitative histological analyses were applied. The normal morphology of the gill's epithelia was only slightly altered in the control, reflecting protective mechanisms against the artificiality of the experimental conditions, which, together with the absence of differences in the global histopathological index (Ih), corroborated that the gill's morpho-functional features were not compromised, thereby validating the proposed ex vivo approach. TiO2 NPs induced moderate severity and dissemination of histopathological lesions. After 2 h, a series of compensatory mechanisms occurred in NP treatments, implying an efficient response of the innate defense system (increasing number of goblet cells) and effective osmoregulatory ability (chloride cells proliferation). After 4 h, gills revealed signs of recovery (normalization of the number of chloride and goblet cells; similar Ih), highlighting the tissue viability and effective elimination and/or neutralization of NPs. The uptake of the TiO2 NPs seemed to be favored by the higher particle sizes. Overall, the proposed approach emerged as a high-throughput, reliable, accurate and ethically commendable methodology for nanotoxicity assessment in marine fish.

Influence of bioturbation by Hediste diversicolor on mercury fluxes from estuarine sediments: a mesocosms laboratory experiment.

Mercury, with its reactive forms being the most deleterious for the trophic chains, has been identified as a major pollutant in a few confined bodies of the coastal zone. Due to feeding, burrowing, and bioirrigation activities, infauna are known to play a crucial role in the biogeochemical processes of contaminants. The main goal of the present study is to evaluate the effects of Hediste diversicolor bioturbation on mercury fluxes from estuarine sediments in a mesocosms laboratory experiment. Additionally, an attempt was made to establish a relationship between the amount of remobilised mercury to the water column and the degree of contamination of the sediments using a mercury contamination gradient. The present experiment demonstrated that the bioturbation activity caused by the gallery-diffuser H. diversicolor did not influence the remobilisation of mercury (in dissolved reactive forms) from the sediment to the water column. The concentration of dissolved reactive mercury in the water column also did not reflect the degree of contamination in the sediments. The results obtained were in accordance with the sediment characteristics of the Mondego Estuary and Ria de Aveiro (Portugal), since they are very rich in organic matter content, iron/manganese total and hydrous oxides. These physicochemical characteristics of the sediments may partially justify the retention of mercury by these systems, even when they are subjected to bioturbation. In conclusion, sediments with high organic matter content and a high concentration of iron/manganese hydrous oxides allowed for efficient retention of mercury, and the bioturbation process did not seem to affect the system. Another conclusion from this study is that the remobilisation of mercury by bioturbation to the water column is not a fast process, requiring more than 24h. This study constitutes an important work in the area of the effects of bioturbation on mercury remobilisation. Considering the toxicity of mercury for the biota, it is essential to evaluate the real magnitude of mercury processes occurring in estuarine systems in order to obtain essential information on metal behaviour.

The effect of the association of NIR laser therapy BMPs, and guided bone regeneration on tibial fractures treated with wire osteosynthesis: Raman spectroscopy study.

Bone fractures are lesions of different etiology; may be associated or not to bone losses; and have different options for treatment, such as the use of biomaterials, guided bone regeneration, techniques considered effective on improving bone repair. Laser therapy has also been shown to improve bone healing on several models. The association of these three techniques has been well documented by our group using different models. This study aimed to assess, through Raman spectroscopy, the incorporation of calcium hydroxyapatite (CHA approximately 958 cm(-1)) on the repair of complete tibial fractures in rabbits treated with wire osteosynthesis (WO); treated or not with laser therapy; and associated or not with the use of BMPs and/or Guided Bone Regeneration. Complete tibial fractures were created in 12 animals that were divided into four groups: WO; WO+BMPs; WO+laser therapy; and WO+BMPs+laser therapy. Irradiation started immediately after surgery; was repeated at every other day during 2 weeks; and was carried out with lambda 790 nm laser light (4 J/cm(2) per point, 40 mW, phi approximately 0.5 cm(2), 16J per session). Animal death occurred after 30 days. Raman spectroscopy was performed at both the surface and the depth of the fracture site. Statistical analysis showed significant difference on the concentrations of CHA between surface and depth. The analysis in each of the areas showed at the depth of the fracture significant differences between all treatment groups (p<0.0001). Significant differences were also seen between WO+BMPs+laser therapy and WO (p<0.001) and WO+laser therapy (p<0.001). At the surface, significant difference was seen only between the treatment groups and the non-fractured subjects (p=0.0001). However, no significant difference was seen between the treatment groups (p=0.14). It is concluded that the use of NIR laser therapy associated to BMPs and GBR was effective in improving bone healing on the fractured bones as a result of the increasing deposition of CHA measured by Raman spectroscopy.

Seasonal fluctuations of tissue mercury contents in the European shore crab Carcinus maenas from low and high contamination areas (Ria de Aveiro, Portugal).

The main objective was to study the seasonal variation of mercury concentrations in different tissues (muscle, hepatopancreas and gills) of Carcinus maenas from low and high Hg contaminated areas, a valuable resource in temperate estuaries and a possible pathway for human uptake. Individuals of two size classes (around 35 and 55 mm cephalothorax wide) were captured monthly between March 1999 and May 2000 in two areas of Ria de Aveiro: in the main navigation channel that connects the lagoon to the sea, and in the inner lagoon area heavily contaminated by mercury (maximum Hg in sediments of 5.4 microg g(-1)). Pronounced decreases in salinity and temperature and reduced food availability in winter seemed to be the responsible for the decline of the crab condition index (0.75-0.45) in larger individuals. Muscle and hepatopancreas exhibited higher mercury concentrations than gills, with concentrations in the contaminated site ranging from 0.03 to 0.63 microg g(-1) and 0.02 to 0.34 microg g(-1), respectively. Linear regressions between muscle and hepatopancreas (r=0.94, p<0.001) and muscle and gills (r=0.97, p<0.001) suggested a rapid redistribution of mercury inside the organism. During winter, a rapid elimination of mercury was found in the three analysed tissues followed by uptake. Larger crabs presented elimination rates from 18 to 34 ng g(-1) per week, while the smaller crabs showed lower elimination rates (10-24 ng g(-1) per week). The uptake was similar in both size classes (11-15 ng g(-1) and 8.1-15 ng g(-1) per week, respectively for large and small crabs). Our results suggest that C. maenas harvested in the contaminated areas must be considered with caution, since Hg concentrations were found to exceed the threshold concentration allowed for human consumption (0.5 microg g(-1)).

Core-shell magnetite-silica dithiocarbamate-derivatised particles achieve the Water Framework Directive quality criteria for mercury in surface waters.

The sorption capacity of nanoporous titanosilicate Engelhard titanosilicate number 4 (ETS-4) and silica-coated magnetite particles derivatised with dithiocarbamate groups towards Hg(II) was evaluated and compared in spiked ultra-pure and spiked surface-river water, for different batch factors. In the former, and using a batch factor of 100 m(3)/kg and an initial Hg(II) concentrations matching the maximum allowed concentration in an effluent discharge, both materials achieve Hg(II) uptake efficiencies in excess of 99 % and a residual metal concentration lower than the guideline value for drinking water quality. For the surface-river water and the same initial concentration, the Hg(II) uptake efficiency of magnetite particles is outstanding, achieving the quality criteria established by the Water Framework Directive (concerning Hg concentration in surface waters) using a batch factor of 50 m(3)/kg, while the efficiency of ETS-4 is significantly inferior. The dissimilar sorbents' Hg(II) removal efficiency is attributed to different uptake mechanisms. This study also highlights the importance of assessing the effective capacity of the sorbents under realistic conditions in order to achieve trustable results.

Removal of mercury (II) by dithiocarbamate surface functionalized magnetite particles: application to synthetic and natural spiked waters.

In order to take advantage of the high affinity between mercury and sulphur, magnetite (Fe(3)O(4)) particles functionalized with dithiocarbamate groups (CS(2)(-)), were synthesized to be used as a new type of sorbent to remove Hg (II) from synthetic and natural spiked waters. The effectiveness of this type of sorbent was studied, and its potential as cleanup agent for contaminated waters was assessed. Batch stirred tank experiments were carried out by contacting a volume of solution with known amounts of functionalized Fe(3)O(4) particles, in order to study the effect of sorbent dose, salinity, and the kinetics and the equilibrium of this unit operation. A complete Hg (II) removal (ca. 99.8%) was attained with 6 mg/L of magnetic particles for an initial metal concentration of 50 µg/L. It was confirmed that highly complex matrices, such as seawater (ca. 99%) and river water (ca. 97%), do not affect the removal capacity of the functionalized magnetic particles. Concerning isotherms, no significant differences were observed between two- and three-parameter models (P = 0.05%); however, Sips isotherm provided the lowest values of SS and S(x/y), predicting a maximum sorption capacity of 206 mg/g, in the range of experimental conditions under study. The solid loadings measured in this essay surmount the majority of the values found in literature for other type of sorbents.

Mercury partition in the interface between a contaminated lagoon and the ocean: the role of particulate load and composition.

After having estimated the patterns of flow to the ocean and found some seasonal and tidal differences, mainly with regard to the relative importance of dissolved and particulate fractions, mercury partitioning at the interface between a contaminated lagoon and the Atlantic Ocean was investigated during four tidal cycles in contrasting season and tidal regimes. Mercury was found to be located predominantely in the particulate fraction throughout the year, contributing to its retention within the system. Seasonal conditions, variations in marine and fluvial signals and processes affecting bed sediment resuspension influenced the character and concentration of suspended particulate matter in the water column. Variation in the nature, levels and partitioning of organic carbon in the particulate fraction affected levels of particulate mercury as well as mercury partitioning. These results highlight the dominant role of suspended particulate matter in the distribution of anthropogenic mercury and reinforce the importance of competitive behavior related to organic carbon in mercury scavenging.