J.P. Coelho

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.

Mercury contamination in the vicinity of a chlor-alkali plant and potential risks to local population.

A mercury-cell chlor-alkali plant operated in Estarreja (North-western Portugal) for 50 years causing widespread environmental contamination. Although production by this process ceased in 2002, mercury contamination from the plant remains significant. The main objective of this study was to investigate mercury impact on the nearby environment and potential risks to local population. To assess the level of contamination soil samples were collected from agricultural fields in the vicinity of the plant, extending the study by taking samples of the predominant vegetation suitable for animal and human consumption, water samples, and fish species from a nearby coastal lagoon, to gain a preliminary insight into the potential for contamination of the terrestrial and aquatic food web. To determine population exposure to mercury, hair samples were collected from local residents. Total mercury concentration in the 0-15 cm layer of soil was found to be highly variable, ranging between 0.010 and 91 mg kg(-1), although mercury contamination of soils was found to be restricted to a confined area. Lolium perenne roots contained between 0.0070 and 2.0 mg kg(-1), and there is evidence that root systems uptake mercury from the soil. Levels of mercury in the aerial parts of plants ranged between 0.018 and 0.98 mg kg(-1). It appears that plants with higher mercury concentration in soils and roots also display higher mercury concentration in leaves. Total mercury concentration in water samples ranged between 12 and 846 ng L(-1), all samples presenting concentrations below the maximum level allowable for drinking water defined in the Portuguese law (1.0 microg L(-1)). Mercury levels in fish samples were below the maximum limit defined in the Portuguese law (0.5 mg kg(-1)), ranging from 0.0040 to 0.24 mg kg(-1). Vegetables collected presented maximum mercury concentration of 0.17 mg kg(-1). In general, food is not contaminated and should not be responsible for major human exposure to the metal. Mercury determined in human hair samples (0.090-4.2 mg kg(-1); mean 1.5 mg kg(-1)) can be considered within normal limits, according to WHO guidelines suggesting that it is not affecting the local population. Despite being subject to decades of mercury emissions, nowadays this pollutant is only found in limited small areas and must not constitute a risk for human health, should these areas be restricted and monitored. Considering the present data, it appears that the population from Estarreja is currently not being affected by mercury levels that still remain in the environment.

Lipid peroxidation vs. antioxidant modulation in the bivalve Scrobicularia plana in response to environmental mercury--organ specificities and age effect.

This study aimed at the assessment of mercury burden and its association to damage vs. antioxidant protection in the bivalve Scrobicularia plana environmentally exposed to mercury. Inter-age and organ-specific approaches were applied by using different annual size classes (2+, 3+, 4+ and 5+ year old) and assessing specific organs (gills, digestive gland), respectively. Bivalves were collected from moderately and highly contaminated sites at Laranjo basin - Ria de Aveiro (Portugal), where a mercury gradient was identified, and compared with those from a reference site. Besides total and organic mercury accumulation, endpoints combining lipid peroxidation (LPO), as a damage sign, and antioxidant protection (catalase, CAT; glutathione peroxidase, GPX; glutathione S-transferase, GST, activities) were determined. The whole-body accumulation as total mercury changed according to the environmental gradient for all age classes, while in terms of organic mercury, only 5+-year-old animals showed increased accumulation with increased environmental mercury level. Mercury induced peroxidative damage, showing that antioxidative mechanisms were insufficient. The adaptive capacity to pro-oxidant challenge, expressed as antioxidant induction and lesser vulnerability to enzyme inhibition, increased with age. The specific analyses of gills and digestive gland revealed that both organs were able to mirror external levels of exposure in the accumulation of total and organic mercury. Nevertheless, gills displayed higher potential to accumulate organic forms. The organ specificity was evident for antioxidant response with a clear pattern of overall increase in gills and decrease in digestive gland. In addition, only gills displayed statistical correlations between oxidative stress responses and mercury accumulation. Besides the contribution to understand mercury toxicodynamics, specific organs approach is strongly recommended in order to avoid misinterpretations. The use of whole-body analyses can be particularly compromising when oxidative stress responses (rather than mercury accumulation) are addressed.

Development and validation of a simple thermo-desorption technique for mercury speciation in soils and sediments

An innovative technique for rapid identification and quantification of mercury (Hg) species in soils and sediments was developed using a direct mercury analyser. Speciation was performed by the continuous thermal-desorption of mercury species (temperature range 76-770 °C), in combination with atomic absorption spectrophotometry detection. Standard materials HgCl(2), Hg bound to humic acids and HgS were characterized; thermo-desorption curves of each material showed a well-resolved peak at specific temperature intervals: 125-225 °C, 100-250 °C and 225-325 °C, respectively. Certified reference materials (CRM) BCR(®) 142R, RTC(®) CRM 021, NRC(®) MESS-3 and PACS-2 were tested. Although the CRM were not certified for Hg species, the sum of Hg species obtained was compared to the certified value for total Hg; recoveries were 92%, 100%, 97%, and 95%, respectively. One sediment and three soil samples from mercury contaminated areas (total Hg concentrations 0.067-126 mg kg(-1)) were analysed as well. It was possible to compare peaks of thermo-desorption curves from the samples with those from standard materials and thereby distinguish different Hg species in solid samples. Generally, Hg was present as bound to chloride or humic substances. The precision was satisfactory, as reflected by the relative standard deviations determined for standards and certified reference materials (<11%; n=10).

The macrobenthic community along a mercury contamination in a temperate estuarine system (Ria de Aveiro, Portugal)

Mercury is a widely distributed environmental pollutant and a toxic element to all living organisms. This study represents an attempt to evaluate its correlation with the macrobenthic community structure in a temperate estuarine system, the Ria de Aveiro (Portugal). The macrobenthic community structure showed significant differences along the mercury gradient. Overall, the increase of mercury contamination was associated with reduced total abundance, lower species richness, and dominance of tolerant taxa. The polychaetes Hediste diversicolor and Alkmaria romijni, and the isopod Cyathura carinata were associated with high levels of mercury in sediment, while the bivalves Scrobicularia plana, Cerastoderma edule and Abra alba showed higher density in lesser contaminated sites. Furthermore, highly contaminated sites showed substantially lower abundances of surface-deposit feeders and herbivores, and higher abundances of subsurface-deposit feeders and omnivores. Salinity was also a significant factor affecting the community, being responsible for seasonal variations in the macrobenthic assemblages.

Mercury biomagnification in a contaminated estuary food web: effects of age and trophic position using stable isotope analyses.

The main aim of this study was to ascertain the biomagnification processes in a mercury-contaminated estuary, by clarifying the trophic web structure through stable isotope ratios. For this purpose, primary producers (seagrasses and macroalgae), invertebrates (detritivores and benthic predators) and fish were analysed for total and organic mercury and for stable carbon and nitrogen isotopic signatures. Trophic structure was accurately described by δ(15)N, while δ(13)C reflected the carbon source for each species. An increase of mercury levels was observed with trophic level, particularly for organic mercury. Results confirm mercury biomagnification to occur in this estuarine food web, especially in the organic form, both in absolute concentrations and fraction of total mercury load. Age can be considered an important variable in mercury biomagnification studies, and data adjustments to account for the different exposure periods may be necessary for a correct assessment of trophic magnification rates and ecological risk.

Pattern and pathways for mercury lifespan bioaccumulation in Carcinus maenas

Carcinus maenas is an important and exploited natural resource in temperate estuaries, being consumed by local populations and also used as fish bait. Through bioaccumulation and bioamplification processes occurring in polluted estuarine ecosystems, this species may directly or indirectly represent a major pathway for Human contamination. No information is available on the overall lifespan bioaccumulation pattern of mercury for this species, which would be an invaluable tool for assessing the risks associated with C. maenas harvest in contaminated areas. Taking that in mind, the main objectives of this work were to clarify the lifespan bioaccumulation pattern of mercury for this species. A consistent lifespan accumulation pattern was found for this species, both for total and organic mercury, and coherent differences were found between genders, suggesting different physiological responses to contamination. From our results two scenarios emerge: (a) for low mercury contamination areas where the diet is the major pathway for metal uptake, with higher levels in muscle and hepatopancreas (twice as high as in gills) and higher organic mercury fractions (as high as 80-90% in muscle), crabs bioaccumulate with age and (b) on high contaminated areas, environmental exposure is predominant, with higher levels found in gills (reaching 0.8 mg kg(-1)), lower organic fractions and no mercury increment with age. Detoxification strategies, dietary differences and species mobility may account for these two accumulation patterns.

Mercury bioaccumulation in the spotted dogfish (Scyliorhinus canicula) from the Atlantic Ocean.

The annual and life-cycle mercury bioaccumulation pattern in selected tissues of the economically relevant Elasmobranchii species Scyliorhinus canicula was studied, and the risks associated with its consumption evaluated. Preferential mercury bioaccumulation occurred in muscle tissue, and followed the order muscle>heart>liver>gills>pancreas. Total mercury in muscle tissue ranged from 0.13mgkg(-1) (wwt) in 1+year old males to 0.8mgkg(-1) (wwt) in 8+ year old mature females, with no significant differences found between genders, and no clear lifespan bioaccumulation pattern observed, except for mature females. Organic mercury in the muscle ranged from 0.05mgkg(-1) (wwt) to 0.52mgkg(-1) (wwt), corresponding to an average of 70% of total mercury content. In mature females, a significant correlation (R=0.99, P=0.01) was found between size and organic mercury fraction, suggesting reproduction as an important factor controlling organic mercury bioaccumulation in the spotted dogfish.

Immunosuppression in the infaunal bivalve Scrobicularia plana environmentally exposed to mercury and association with its accumulation

This study aimed to test the hypothesis whether mercury (Hg) activates or suppresses inappropriately the immunity of the bivalve Scrobicularia plana inhabiting a Hg contaminated area (Laranjo basin, Ria de Aveiro, Portugal). Immunity endpoints, as well as lipid peroxidation (LPO) as a sign of damage, were evaluated in parallel with total Hg burden. Bivalves from both moderately (MO) and highly (HI) contaminated sites displayed higher haemolymph Hg load and reduced plasma agglutination. Increased haemocytes density and decreased phagocytosis were observed at HI, whereas increased oxidative burst activity (OBA) was observed at MO, pointing out that the immunotoxicity is a result of Hg direct contact involving no ROS intervention. OBA observed at MO was concomitantly associated to peroxidative damage as depicted by LPO increase in haemocytes and haemolymph plasma. Thus, S. plana can be suggested as a suitable bioindicator of metal pollution in coastal areas on the basis of Hg bioaccumulation and immunotoxicity responses.

Contribution of primary producers to mercury trophic transfer in estuarine ecosystems: Possible effects of eutrophication

There is an ongoing eutrophication process in the Ria de Aveiro coastal lagoon (Portugal), with progressive replacement of rooted primary producers for macroalgae. Taking advantage of a well-defined environmental contamination gradient, we studied mercury accumulation and distribution in the aboveground and the belowground biomass of several salt marsh plants, including the seagrass species Zostera noltii and the dominant green macroalgal species Enteromorpha sp. The results of these experiments were then placed into the context of the estuarine mercury cycle and transport from the contaminated area. All salt marsh plants accumulated mercury in the root system, with Halimione portulacoides showing the highest levels, with up to 1.3 mg kg(-1) observed in the most contaminated area. Belowground/aboveground ratios were generally below 0.4, suggesting that salt marsh plants are efficient immobilizers and retainers of mercury agents. Moreover, due to their sediment accretion capacities, salt marsh plants seem to play an important role in the sequestration of mercury in estuarine sediments. Seagrasses, on the other hand, accumulated considerable amounts of mercury in the aboveground biomass with belowground/aboveground ratios reaching as high as 1.4. These results may be due to their different routes of uptake (roots and foliar uptake) which suggests that seagrass meadows can be an important agent in the export of mercury from contaminated areas, considering the high aboveground biomass replacement rates. Rooted macrophytes accumulate less mercury in their aboveground biomass than macroalgae. The change of primary producer dominance due to eutrophication can originate a 4- to 5-fold increase in primary producer associated mercury. This mercury would be available for export, making it bioavailable to estuarine food webs, which stresses the need to reverse the current eutrophic status of estuarine systems.