M. Válega

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.

Antioxidant and biotransformation responses in Liza aurata under environmental mercury exposure - Relationship with mercury accumulation and implications for public health

This study was carried out in the Laranjo basin (Ria de Aveiro, Portugal), an area impacted by mercury discharges. Liza aurata oxidative stress and biotransformation responses were assessed in the liver and related to total mercury (Hgt) concentrations. A seasonal fish survey revealed a sporadic increase in total glutathione (GSHt) and elevated muscle Hgt levels, although Hg levels did not exceed the EU regulatory limit. As a complement study, fish were caged for three days both close to the bottom and on the water surface at three locations, and displayed higher Hgt levels accompanied by increased GSHt content and catalase activity as well as EROD activity inhibition. The bottom group displayed higher hepatic Hgt and GSHt contents compared with the surface group. Globally, both wild and caged fish revealed that the liver accumulates higher Hgt concentrations than muscle and, thus, better reflects environmental contamination levels. The absence of peroxidative damage in the liver can be attributed to effective detoxification and antioxidant defense.

Accumulation, distribution and cellular partitioning of mercury in several halophytes of a contaminated salt marsh

This work evaluates the role of a plant community in mercury (Hg) stabilization and mobility in a contaminated Portuguese salt marsh. With this aim, the distribution of Hg in below and aboveground tissues, as well as the metal partitioning between cellular fractions (soluble and insoluble) in four different species (Triglochin maritima L., Juncus maritimus Lam, Sarcocornia perennis (Miller) A.J. Scott, and Halimione portulacoides (L.) Aellen) was assessed. Mercury accumulation, translocation and compartmentation between organs and cellular fractions were related to the plant species. Results showed that the degree of Hg absorption and retention was influenced both by environmental parameters and metal translocation/partitioning strategies. Different plant species presented different allocation patterns, with marked differences between monocots (T. maritima and J. maritimus) and dicots (S. perennis, H. portulacoides). Overall, the two monocots, in particular T. maritima showed higher Hg retention in the belowground organs whereas the dicots, particularly S. perennis presented a more pronounced translocation to the aboveground tissues. Considering cellular Hg partitioning, all species showed a higher Hg binding to cell walls and membranes rather than in the soluble fractions. This strategy can be related to the high degree of tolerance observed in the studied species. These results indicate that the composition of salt marsh plant communities can be very important in dictating the Hg mobility within the marsh ecosystem and in the rest of the aquatic system as well as providing important insights to future phytoremediation approaches in Hg contaminated salt marshes.

Mercury intracellular partitioning and chelation in a salt marsh plant, Halimione portulacoides (L.) Aellen: Strategies underlying tolerance in environmental exposure

In the presence of metal stress, plants can resort to a series of tolerance mechanisms. Therefore field studies should be undertaken in order to evaluate the real role of these mechanisms in stress coping. The aim of this paper was to clarify the biochemical processes behind mercury tolerance in Halimione portulacoides (L.) Aellen (Caryophyllales: Chenopodiaceae) collected in a mercury contaminated salt marsh. Different fractions of mercury were separated: buffer-soluble (mainly cytosolic) and insoluble mercury (mainly associated with membranes and cell walls). The amounts in each fraction of metal were compared and related to metal distribution within plant organs. Protein-mercury complexes were isolated and analysed for their thiol content in order to assess wether the tolerance of this salt marsh plant was associated with the induction of metal chelation by phytochelatins. Overall, the mercury tolerance strategies of the plant are likely to involve root cell wall immobilization as a major mechanism of metal resistance, rather than metal chelation in the cytosolic fraction. Nevertheless, phytochelatins were demonstrated to chelate mercury under environmental exposure.

Amphiphilic phthalocyanine-cyclodextrin conjugates for cancer photodynamic therapy.

Three phthalocyanines (Pcs) conjugated with α-, β- and γ-cyclodextrins (CDs) were prepared and their application as photosensitizer (PS) agents was assessed by photophysical, photochemical and in vitro photobiological studies. The photoactivity of Pc-α-CD and Pc-γ-CD ensures their potential as PDT drugs against UM-UC-3 human bladder cancer cells.

Mercury in salt marshes ecosystems: Halimione portulacoides as biomonitor

Mercury concentrations were quantified in Halimione portulacoides (roots, stems and leaves) as well as in sediments from eight Portuguese estuarine systems, covering seventeen salt marshes with distinct degrees of mercury contamination. The concentration of mercury in the sediments ranged from 0.03 to 17.0 microg g(-1). The results show that the accumulation of mercury differed according to the organ of the plant examined and the concentration of mercury in the sediments. Higher mercury concentrations were found in the roots (up to 12.9 microg g(-1)) followed by the leaves (up to 0.12 microg g(-1)), while the stems had the lowest concentrations (up to 0.056 microg g(-1)). A linear model explained the relation between the concentrations of mercury in the different plant organs: roots and stems (R(adj)(2)=0.75), stems and leaves (R(adj)(2)=0.85) and roots and leaves (R(adj)(2)=0.78). However, the results show that the variation of mercury concentration in the roots versus mercury concentration in the sediments was best fitted by a sigmoidal model (R(adj)(2)=0.89). Mercury accumulation in the roots can be described in three steps: at a low range of mercury concentrations in the sediments (from 0.03 up to 2 microg g(-1)), the accumulation of mercury in roots is also low reaching a maximum concentration of 1.3 microg g(-1); the highest rates of mercury accumulation in the roots occur in a second step, until the concentrations of mercury in the sediments reach approximately 4.5 microg g(-1); after reaching this maximum value, the rate of mercury accumulation in the roots slows down leading to a plateau in the concentration of mercury in the roots of about 9.4 microg g(-1), which corresponds to a mercury concentration in the sediments of about 11 microg g(-1). A linear model explained also the accumulation of mercury in leaves versus the mercury concentration in the sediments (R(adj)(2)=0.88). Differences in responses of roots and leaves are explained by the dynamics of the plant organs: old roots are mineralised in situ close to new roots, while leaves are renewed. Previous studies have already shown that H. portulacoides is a bioindicator for mercury and the results from this work sustain that H. portulacoides may also be used as a biomonitor for mercury contamination in salt marshes. Nevertheless, caution should be taken in the application of the models, concerning the life cycle of the species and the spatial variability of the systems.

Salt Marsh Halophyte Services to Metal–Metalloid Remediation: Assessment of the Processes and Underlying Mechanisms

Salt marshes are widely distributed and most productive ecosystems in the temperate zones on the globe. These areas perform vital ecological functions and are populated mainly by halophytes—plants that are able to survive and reproduce in environments with exceptionally high salt concentrations. In salt marshes, in addition to tolerating high salt concentrations, salt marsh halophytes have to cope with damages caused by multiple anthropgenic pressures including metal and metalloid pollution. Extensive studies have been performed aiming at exploring naturally occurring endemic salt marsh halophytes with extraordinary potential for metals and metalloids remediation. However, a knowledge gap is perceptible on the basics of salt marsh halophyte adaptation/tolerance to the joint action of damaging factors such as high concentration of salt and presence of metals–metalloids. In light of available literature, the current paper is critical in: (i) highlighting ecological significance of salt marsh halophytes and their use as bioindicators or biomonitors of metal–metalloid pollution; (ii) analyzing salt marsh halophyte significant contributions for metal- and metalloid-remediation processes; (iii) overviewing salt marsh halophytes–microbes interaction influence on metal-phytoremediation processes; and (iv) cross-talking important physiological/biochemical strategies adopted by salt marsh halophytes for salinity-, metal-, and metalloid-tolerance. Conclusively, the paper highlights important aspects so far less explored in the context of salt marsh halophyte services to metal–metalloid remediation and underlying mechanisms. The discussion will enable researchers and environmentalists to set further exhaustive studies aiming at efficient and sustainable management of rapidly mounting salt marshes metal–metalloid contamination issues.

The Assembling and Application of an Automated Segmented Flow Analyzer for the Determination of Dissolved Organic Carbon Based on UV‐Persulphate Oxidation

Abstract A simple and reliable methodology developed on an automated segmented flow analyzer has been implemented for the determination of organic forms of carbon in aqueous solutions. Conversion of dissolved organic matter to carbon dioxide is performed by a UV‐persulphate oxidation. After oxidation, the concentration of carbon dioxide in the sample induces a change in pH that will alter the color intensity of a phenolphthalein solution. The color intensity of the solution is measured automatically by colorimetry. Caffeine and acid ascorbic were tested in order to assess the accuracy of the analytical methodology. Reproducibility tests demonstrated a very good precision for natural waters and for organic compounds. Salinity changes showed no interferences, which suggests how appropriate this methodology is for routine analysis and how useful and convenient it is for shipboard work on ocean and estuarine research.

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.

Mercury in plants from fields surrounding a contaminated Channel of Ria de Aveiro, Portugal

Samples of plants and soil were collected in March and June 1995 at 12 sites in fields surrounding the Estarreja Channel (Ria de Aveiro), where the mercury-rich effluent of a chlor-alkali plant has been discharged since the 1950s. Mercury concentrations in soil ranged from 0.64 to 182 μ g g−1. The highest values were attributed to soil contaminated with sediments dredged from the Estarreja Channel. Plant roots contained between 0.03 and 3.2 μ g g−1 of total mercury, and there is evidence that root systems uptake mercury from the soil. The linear relationship between mercury concentrations in the roots of Holcus lanatus and in soil over a wide range of mercury concentrations suggests that mercury uptake depends on the elements concentration in the soil. The ratio root:soil concentrations for the analyzed plants varied between 0.003 and 0.199, indicating varying mercury uptake by the root systems. Levels of mercury in the aerial parts of plants showed no clear relationship with the values found in soil or in roots, presumably being influenced mostly by the atmospheric deposition of airborne particles or absorption of atmospheric mercury.