Mercury species, selenium, metallothioneins and glutathione in two dolphins from the southeastern Brazilian coast: Mercury detoxification and physiological differences in diving capacity.

In the present study, the concentration of trace elements, total mercury (Hg) and selenium (Se) and mercury forms (MeHg, Hginorg and HgSe) in the vulnerable coastal dolphins Pontoporia blainvillei and Sotalia guianensis were appraised and compared, using metallothioneins (MT) and glutathione (GSH) as biomarkers for trace element exposure. The trace element concentrations varied between muscle and liver tissues, with liver of all dolphin specimens showing higher Hg and Se concentrations than those found in muscle. Hg, MeHg and Hginorg molar concentrations showed a clear increase with Se molar concentrations in the liver of both dolphins, and Se concentrations were higher than those of Hg on a molar basis. Se plays a relevant role in the detoxification of MeHg in the hepatic tissue of both dolphins, forming Hg-Se amorphous crystals in liver. In contrast, MT were involved in the detoxification process of Hginorg in liver. GSH levels in P. blainvillei and S. guianensis muscle tissue suggest that these dolphins have different diving capacities. Muscle Hg concentrations were associated to this tripeptide, which protects dolphin cells against Hg stress.

Trace-elements, methylmercury and metallothionein levels in Magellanic penguin (Spheniscus magellanicus) found stranded on the Southern Brazilian coast.

Magellanic penguins have been reported as good biomonitors for several types of pollutants, including trace-elements. In this context, selenium (Se), total mercury, methylmercury, inorganic mercury (Hg(inorg)), cadmium (Cd) and lead (Pb), as well as metallothionein (MT) levels, were evaluated in the feathers, liver and kidney of juvenile Magellanic penguins found stranded along the coast of Southern Brazil. The highest concentrations of all trace-elements and methylmercury were found in internal organs. Concentrations of Cd and Se in feathers were extremely low in comparison with their concentrations in soft tissues. The results showed that both Se and MT are involved in the detoxification of trace-elements (Cd, Pb and Hg(inorg)) since statistically significant relationships were found in liver. Conversely, hepatic Se was shown to be the only detoxifying agent for methylmercury.

Differences in methylmercury and inorganic mercury biomagnification in a tropical marine food web.

Methylmercury (MeHg), inorganic mercury (Hginorg) and their biomagnification factors (BMF) were evaluated along a non-degraded Brazilian bay food web. Highly significant differences (p < 0.0001) were found between MeHg and Hginorg concentrations among all organisms (microplankton, shrimp, fish and dolphin). MeHg increased with increasing trophic position while Hginorg did not present the same pattern. BMF values for MeHg were higher than 1 for all trophic interactions from source to consumer, indicating that MeHg was transferred more efficiently and biomagnified over the entire web. Only one BMF exceeding one was observed for Hginorg (27) between microplankton and their consumer, planktivorous fish. BMF values for Hginorg were significantly different than those found for MeHg (20) at the base of the food web.

Mercury and selenium biomagnification in a Brazilian coastal food web using nitrogen stable isotope analysis: a case study in an area under the influence of the Paraiba do Sul River plume.

Mercury (Hg), selenium (Se) and nitrogen (δ(15)N) stable isotope were assessed in a tropical food web of Rio de Janeiro's north coast. Isotopic data on muscle suggest a difference related to this parameter along the food web; where top-predators (cetacean and voracious fish) displayed heavier δ(15)N over the entire food web. Both top-predators presented similar δ(15)N values. Cetacean displayed higher Hg and lower Se than voracious fish. Five trophic positions (TP) were found in relation to primary consumer as baseline, ranging from 2.0 to 4.0. Positive relationships were found between trace-element and δ(15)N. The slope of regression equations (0.11 for Se and 0.21 for Hg) and food web magnification factors (2.4 for Se and 5.4 for Hg) showed that Hg presented higher rate of increase over the food web. Simultaneous measurements of trace-elements and ecological tracers emphasize the importance of TP into the trophic structure and distribution of Hg and Se throughout the food web.

Selenium and mercury in widely consumed seafood from South Atlantic Ocean.

The growing ingestion of predatory fish by humans has increased their exposure to toxic chemicals. Mercury (Hg) is an exogenous and harmful trace-element that accumulates in all marine organisms. Selenium (Se) is nutritionally important as a micronutrient, but is potentially harmful at intakes above 1mg per day. Se:Hg molar ratios in excess of 1:1 are thought to counteract the adverse effects of Hg, protecting against Hg toxicity. Evaluation of the health risk posed by Hg exposure from seafood consumption requires concurrent consideration of Se content in the same individuals. This study evaluated the Se and Hg concentrations in the edible tissues of 652 individual samples of commonly consumed varieties of carnivorous and planktivorous fish, squid, mussel, shrimp and crab collected from south-eastern Brazil. The Se:Hg molar ratios showed significant variation among and within tropical seafood. All organisms presented Se concentration in muscle of less than 2.0µgg(-1), the maximum allowed selenium concentrations. Only seven individuals of a carnivorous fish species presented Hg in muscle above the maximum permissible limit of 0.5µgg(-1) established by WHO and Brazilian legislation for human consumption of most aquatic species. These same individuals also showed Se:Hg molar ratio of less than 1:1. Se:Hg molar ratios were found to decline with increasing fish length, potentially reducing Se-dependent protection. As a result of their rich Se, low Hg contents and Se:Hg molar ratios exceeding 1:1, nearly all species included in this study provide benefits for human consumption. Two popular seafoods in the region, the carnivorous fish Centropomus undecimalis (common snook) and Micropogonias furnieri (Atlantic croaker), had the most favorable Se:Hg molar ratio values of 33 and 21, respectively. Among the invertebrates, Xiphopenaeus kroyeri (seabob shrimp) and Loligo sanpaulensis (squid) had the most favorable Se:Hg molar ratio values, higher than 20. A selenium health benefit value based on the absolute amounts and relative proportions of Se and Hg in seafood was proposed as a more comprehensive seafood safety criterion.

Ecological and biological determinants of methylmercury accumulation in tropical coastal fish.

This research investigated whether environmental conditions, biological fish characteristics and anthropogenic impacts influenced mercury (Hg) assimilation into the muscle tissue of two fish species from two Brazilian bays, Ilha Grande Bay and Guanabara Bay. Fish and superficial water were collected in different periods. Hg was determined by CV-AAS. Methylmercury (MeHg) was identified and quantified by ECD-GC. Chlorophyll a concentrations in the water column indicated that Ilha Grande Bay and Guanabara Bay were oligotrophic and eutrophic, respectively. Hg in fish ranged from 2.10 to 870.17 µg kg(-1) dry wt. in Ilha Grande Bay and 40.90 to 809.24 µg kg(-1) dry wt. in Guanabara Bay. Slight differences were found between the length-normalized Hg concentrations and its percent of Hg in a voracious predator from the bays. In Guanabara Bay, where the presence of a chlor-alkali plant causes Hg input, the iliophagous fish species showed the highest length-normalized Hg concentrations and the voracious predator the lowest. Iliophagous fish is consumed by voracious predator and, consequently, acts as their MeHg food supply. Iliophagous fish from Ilha Grande Bay presented a higher percent of MeHg (80.0 %) than specimens from Guanabara Bay (54.5 %). This fact suggests that more MeHg was transferred from iliophagous fish to voracious predator in Ilha Grande Bay. At Guanabara Bay, the bioproduction is greater than that at Ilha Grande Bay, presenting the highest biomass in it ecosystem, which may subsequently dilute Hg and reduce its availability to the biota; i.e., influencing in Hg and MeHg availability throughout the food chain. Consequently, more MeHg is available in the aquatic environment of Ilha Grande Bay.

Mercury and selenium in a top-predator fish, Trichiurus lepturus (Linnaeus, 1758), from the tropical Brazilian Coast, Rio de Janeiro.

Muscular mercury and selenium were assessed in a voracious fish from three Brazilian coastal areas with different environmental conditions. Mercury was higher in specimens from Ilha Grande Bay (0.35 ± 0.17 µg g(-1)) than in cutlassfish from Guanabara Bay (0.30 ± 0.15 µg g(-1)) and Buzios coast (0.13 ± 0.08 µg g(-1)), respectively. No difference was found regarding selenium among these areas. Mercury was positively correlated with fish length and size intervals (sub-adult, small and large adult), suggesting that larger and older fish bioaccumulated more mercury. A large excess of molar selenium in relation to mercury was observed.

Inorganic and methylmercury: do they transfer along a tropical coastal food web?

Methylmercury (MeHg) and inorganic mercury (Hg(inorg)) were evaluated in the water of a Brazilian estuary, with two size classes of plankton and seven fish species of different feeding habits. Water partition coefficients (PCs) in microplankton were fourfold higher for MeHg than for Hg(inorg); and water PCs in mesoplankton were 26 times higher for MeHg than Hg(inorg). Difference between microplankton and mesoplankton MeHg bioaccumulation factor (BAF) was higher (0.60 log units) than Hg(inorg) BAF (0.24 log units), indicating that trophic transfer of MeHg between planktonic organisms is more efficient than Hg(inorg) transference. MeHg concentrations, proportion of mercury as MeHg and its biotransference factors (BTFs) in the microplankton, mesoplankton and fish increased with increasing trophic level while biotic concentrations of Hg(inorg) and proportion of mercury as Hg(inorg) decreased thus indicating that MeHg was indeed the biomagnified species of mercury. MeHg reflected the vertical trophic guilds distribution, due to the fact that the top predator fish presented the highest concentration (0.77 µg g(-1)d.w.), followed by the less voracious species (0.43 µg g(-1)d.w.); while planktivorous fish presented the lowest concentrations (0.044 µg g(-1)d.w.). Hg(inorg) did not present the same behavior. Results suggest that feeding habits and trophic guild are important parameters, influencing biotransference and biomagnification processes.

Seasonal differences in mercury accumulation in Trichiurus lepturus (Cutlassfish) in relation to length and weight in a Northeast Brazilian estuary.

BACKGROUND, AIM, AND SCOPE: At tropical latitudes, and especially on the semi-arid coasts of the Brazilian Northeast, the rainfall regime governs the water quality of estuaries due to the pronounced difference between the rainy and dry seasons. These changes may be responsible for seasonal changes in bioavailability of mercury (Hg) and other pollutants to the estuarine and coastal biota. Mercury bioaccumulates along estuarine-marine food chains usually result in higher concentrations in tissues of top predators and posing a risk to both marine mammals and humans alike. The Goiana River Estuary (7.5 degrees S) is a typical estuary of the semi-arid tropical regions and supports traditional communities with fisheries (mollusks, fish, and crustacean). It is also responsible for an important part of the biological production of the adjacent coastal waters. MATERIALS AND METHODS: Trichiurus lepturus (Actinopterygii: Perciformes) is a pscivorous marine straggler. Fish from this species (n = 104) were captured in a trapping barrier used by the local traditional population and using an otter trawl net along the main channel of the low estuary during two dry seasons (D1 = November, December 2005, January 2006; D2 = November, December 2006, January 2007) and the end of a rainy season (R = August, September, October 2006). Fish muscle samples were preserved cold and then freeze-dried prior to analysis of its total mercury (Hg-T) contents. Total mercury was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. RESULTS: The studied individuals (n = 104) were sub-adult (30-70 cm, 71 ind.) and adult fish (>70 cm, 33 ind.). Weight (W) (204.1 +/- 97.9 g, total biomass = 21,229.7 g) and total length (TL) (63.1 +/- 10.1 cm, range 29.5-89.0 cm) presented a significant (p < 0.05) correlation. Two-way ANOVA (n = 81) showed that TL and W had significant differences (p < 0.05) among seasons, being higher in D1 than in D2 and R, respectively. Moreover, season vs. month interaction were detected for the variables length and weight. For the variable weight was detected significant difference for the factor month (p < 0.05). It suggests that the fish enter the estuary at the end of the rainy season and increase in length and weight during the time they spend in the estuary. Fish from this estuary are shown to be fit for human consumption (125.3 +/- 61.9 microgHg-T kg(-1) w.wt.; n = 104). Fish mercury contents increased with size and weight. Correlations between TL and Hg-T (r = 0.37286) and between W and Hg-T (r = 0.38212) were significant (p < 0.05). Dryer months showed higher mercury concentrations in fish (D1 773.4 +/- 207.5 microgHg-T kg(-1) d.wt., n = 27; D2 370.1 +/- 78.8 microgHg-T kg(-1) d.wt., n = 27; R 331.2 +/- 138.5 microgHg-T kg(-1) d.wt., n = 27). The variable mercury concentration showed differences in relation to the factor season (p < 0.05), where fish captured during the first dry season showed the highest concentration of mercury. The correlation between Hg-T and rainfall (Rf) showed a negative correlation (r = -0.56; p < 0.05). DISCUSSION: The main likely source of mercury to this estuary is diffuse continental run off, including urban and industrial effluents. Since concentration of mercury in fish tissue is negatively correlated to rainfall, but positively correlated with fish length and weight, it suggests that fish growth in this estuary results in mercury uptake and concentration on the fish tissue. In the dry season of 2005-2006, when rainfall remained below the historic average, fish bioaccumulated significantly more mercury than in the dry season 2006-2007, when rainfall was within the predictable historic average. It is suggested that less rainfall, and consequently less particulate matter and less primary production in the estuary, make mercury more available to the higher levels of the estuarine food chain. In the case of higher rainfall, when river flow increases and water quality in the estuary is reduced, mercury probably is quickly exported associated to the particulate matter to the adjacent coastal waters where it then disperses. This species is a potential routine bioindicator for mercury contamination of the biota, but so far was used only with a limited number of individuals and contexts. CONCLUSIONS: Fish from the Goiana River estuary can still be safely consumed by the local population. However, any further contamination of this resource might lead to total mercury levels above the recommended limits for pregnant women and small children. The proposed heavy dependency of total mercury levels in fish on water quality indicates that land use and water quality standards must be more closely watched in order to guarantee that best possible practices are in place to prevent bioaccumulation of mercury and its transfer along the food chain. Human interventions and climatic events which affect river water flow are also playing a role in the mercury cycle at tropical semi-arid estuaries. RECOMMENDATIONS AND PERSPECTIVES: T. lepturus is largely consumed by coastal populations of tropical and sub-tropical countries all over the world. It is also consumed by a number of marine mammals over which we have a strong conservation interest. This species is also a link among different ecosystems along the estuarine ecocline. Therefore, knowledge of its degree of contamination might contribute to public health issues as well as marine conservation actions. Studies on mercury and other contaminants using this species as bioindicator (cosmopolitan, readily available) could help elucidating mechanisms through which pollutants are being transferred not only through the food chain, but also from estuarine-coastal-open waters. In addition, using the same species in marine pollution studies, especially as part of a mosaic of species, allows for wide range comparisons of marine food chain contamination.

The relationships between mercury and selenium in plankton and fish from a tropical food web.

BACKGROUND, AIM, AND SCOPE: Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70-290 microm) and mesoplankton (>or=290 microm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. MATERIALS AND METHODS: Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. RESULTS AND DISCUSSION: Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 microg g(-1) dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g(-1)) than in Micropogonias furnieri (2.9 and 15.3 nmol g(-1)), Bagre spp (1.3 and 3.4 nmol g(-1)) and Mugil liza (0.3 and 5.1 nmol g(-1)), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. CONCLUSIONS: Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. RECOMMENDATIONS AND PERSPECTIVES: There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.

Total mercury, organic mercury and selenium in liver and kidney of a South American coastal dolphin.

Selenium and total and organic mercury were determined in the liver and kidney of franciscana dolphin (Pontoporia blainvillei) incidentally caught in fishing nets along two Brazilian coastal areas (southeast and south). Regional differences in the concentrations of these contaminants were observed in P. blainvillei. Liver showed the highest organic and total mercury. In general, samples of individuals collected at the southern of Brazil had the highest concentrations of selenium and total and organic mercury. No significant gender differences were observed. Growth stage influenced the accumulation of these contaminants in both organs, and hepatic concentrations increased with the body length, according to the sampling area. Molar mercury and selenium concentrations in liver were significantly correlated, with a Se:Hg ratio close to 4. The among-site differences we found may be related to differences in preferred prey, bioavailability in the marine environment, environmental conditions, or these individuals may belong to distinct populations.

Ecological and biological determinants of trace elements accumulation in liver and kidney of Pontoporia blainvillei.

The present work tested whether ecological and biological variables have an influence on the assimilation of trace elements by the tissues of a cetacean from the Western South Atlantic Ocean. No significant differences were observed in the concentrations for both sexes. As individuals from the two sampling areas belong to distinct genetic and morphological populations, animals of similar body length were older on the southeastern than on the southern coast. The liver showed the highest concentrations of mercury, whereas the highest levels of cadmium were found in the kidney. Hepatic mercury, cadmium and selenium in individuals from the south coast were about four times as high as those from the southeast coast. However, arsenic in the liver and kidney were similar in both coastal areas. Hepatic mercury, cadmium and selenium concentrations increased with body length in individuals from the southeastern coast, although no significant correlations (P>0.05) were observed between body length from either area and the renal and hepatic As concentrations. A significant positive linear relationship was observed between molar concentrations of Hg and Se in the liver of all individuals from both areas (r2=0.93; P<0.001), presenting Se:Hg ratios close to 4. Differences found among the concentrations of Hg, Cd and Se in dolphins from both areas were probably due to the preferred prey, bioavailability of elements in each marine environment, and environment variables (water temperature, net primary production). As a consequence, concentrations of trace elements in the tissues of this species can be considered to be a result of the surrounding environment.