Mercury and stable carbon and nitrogen isotopes in the natal Fur of two Antarctic pinniped species.

Southern elephant seal (SES) and Antarctic fur seal (AFS) are short Southern Ocean food web top predators and are spatial and temporal trend bioindicators of Antarctic Hg bioavailability. Hg, stable isotope composition (δ13C and δ15N) and trophic position (TP) regarding sex were determined using lanugo samples from Antarctic pinnipeds pups (SES n = 35 and AFS n = 11). Hg concentrations in over 50% of the SES pups (mean 5.9 ± 3.1 mg kg-1 dry wt.) are compatible with those found to cause neurologic damage to polar bears in the Arctic. No significant differences regarding sexes for SES or AFS are found based on mean Hg concentrations normalized by body weight. δ15N values and TPs are similar among both species, indicating that gestating SES and AFS mothers feed at the same trophic level. Significantly different δ13C values were found, indicating distinct feeding grounds for mothers belonging to both species when pup lanugo is formed in utero; while SES females like to feed in Antarctic waters, AFS females remain in sub-Antarctic waters. The differences in Hg and δ13C observed for both species reflect not only contrasting feeding habits and anthropogenic Hg inputs, but also maternal foraging strategies.

Total and subcellular Ti distribution and detoxification processes in Pontoporia blainvillei and Steno bredanensis dolphins from Southeastern Brazil.

Titanium (Ti), used in many dailyuse products, such as shampoos and sunscreen filters, in the form of TiO2 nanoparticles (NPs), may elicit adverse marine biota effects. Marine mammal Ti data is scarce, and subcellular distribution and detoxification information is non-existent. Ti concentrations and metalloprotein detoxification in Pontoporia blainvillei and Steno bredanensis dolphins from Southeastern Brazil were assessed. Metallothionein (MT) concentrations were determined spectrophotometrically, total and subcellular Ti, by ICP-MS and detoxification, by HPLC-ICP-MS. Ti detoxification occurred through MT complexation. Statistical Ti-MT associations were observed in S. bredanensis liver, indicating TiO2 NPs contamination, as Ti binds to MT only as NPs. MT-Ti correlations were observed for both the coastal (P. blainvillei) and offshore (S. bredanensis) dolphins, evidencing oceanic TiO2 diffusion. Ti detoxification through binding to reduced glutathione occurred in both species. Thermostable subcellular fractions are a valuable tool for cetacean Ti detoxification assessments and should be applied to conservation efforts.

Mercury, selenium and stable isotopes in four small cetaceans from the Southeastern Brazilian coast: Influence of feeding strategy.

Dolphins are good bioindicators of the contamination status of marine ecosystems, since their dietary and habitat plasticity in both coastal and offshore ecotypes provide information on the trace elements levels originated from natural and anthropogenic sources. In this context, this study aimed to investigate provides mercury (Hg), selenium (Se) levels, trophic ecology and feeding environments of four small cetaceans (Tursiops truncatus, Steno bredanensis, Sotalia guianensis and Pontoporia blainvillei) inhabiting the central-northern coast of Rio de Janeiro State, southeastern Brazil. For the latter, δ15N and δ13C stable isotopes were used as indicators in this regard. Stable isotope values indicate that the four studied species have distinctive foraging habitats, coastal and least coastal, and occupy different trophic positions. The significant relationship found between muscle Hg and δ15N suggests that individual foraging preference remains relatively constant for the studied dolphin species over extended periods. The individual prey size and species are probably responsible for the differences found in Hg and Se concentrations in muscle tissue among all dolphin species. The vulnerable small coastal cetacean, P. blainvillei, which feeds on small teleost fish and squid, presented the lowest muscular Hg concentrations (less than 3.5 µg g-1 dry wt.). Meanwhile, S. bredanensis is more likely to uptake large amounts of trace elements among the four dolphin species, due to its feeding habits mainly being large offshore fish that accumulate high amounts of trace elements in organs and tissues. Differences found between Hg concentrations in fetus-mother pairs were much higher in S. guianensis than in P. blainvillei, suggesting that maternal contribution of Hg via placenta was more significant for the former.

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.

Isotopic profile and mercury concentration in fish of the lower portion of the rio Paraíba do Sul watershed, southeastern Brazil

The aim of this study was to evaluate the isotopic profile and mercury (Hg) concentrations in fish (carnivores, omnivores and detritivores) in the lower portion of the rio Paraíba do Sul watershed, southeastern Brazil. Carbon (δ13C) isotopic analyses revealed that pelagic and benthonic sources are part of the feeding of the fish from the different guilds (-14.0 to -24.8 ‰). The benthic sources are usually enriched in δ13C (-16.9‰, from watershed runoff) compared to pelagic sources because the phytoplankton, important primary producer that supports several pelagic chains, has δ13C signature lighter (-23.9‰). The nitrogen (δ15N) isotopic signatures indicated that most guilds were at the same trophic position (10.0 to 15.5 ‰), except for pelagic omnivorous fish, which had a lower trophic position. Niche overlap was observed among pelagic and demersal carnivorous fish, demersal omnivorous fish, and demersal detritivorous fish. The lower isotopic niche breadth of pelagic carnivorous fish reveals the specialized resource use by this guild. Hg concentrations (ng g-1 dry weight) differed significantly between demersal carnivorous fish (185.3 dry weight; 27.8 wet weight) and demersal omnivorous fish (277.9 dry weight; 41.7 wet weight) and between pelagic omnivorous fish (197.2 dry weight; 29.6 wet weight) and demersal omnivorous fish due to (1) differences in food sources: guilds that fed on bottom resources were more affected by contamination because the sediment is an important Hg accumulator in the study area, and (2) because of its trophic positions. Considering that the fish consumed prey of similar trophic positions, the guilds did not show a well-defined food hierarchy. Therefore, in this study, there was no clear relationship between Hg and δ15N.

O objetivo deste estudo foi avaliar o perfil isotópico e as concentrações de mercúrio (Hg) em peixes (carnívoros, onívoros e detritívoros) na bacia inferior do rio Paraíba do Sul, sudeste do Brasil. As análises isotópicas de carbono (δ13C) revelaram participação de fontes pelágica e bentônica na alimentação dos peixes das diferentes guildas (-14,0 a -24,8 ‰). As fontes bentônicas são usualmente mais enriquecidas em δ13C (-16,9‰, derivado do escoamento superficial da bacia de drenagem) comparadas às fontes pelágicas pois, o fitoplâncton, importante produtor primário que suporta inúmeras cadeias pelágicas, tem assinatura de δ13C mais leve (-23,9‰). As assinaturas isotópicas de nitrogênio (δ15N) indicaram que a maioria das guildas estava no mesmo nível trófico (10,0 a 15,5 ‰), exceto os peixes onívoros pelágicos cuja posição trófica foi inferior. Observou-se sobreposição de nicho entre peixes carnívoros pelágicos e demersais, onívoros demersais, e detritívoros demersais. A menor amplitude de nicho isotópico dos peixes carnívoros pelágicos revela o uso de recursos especializados por esta guilda. A concentração de Hg (ng g-1 peso seco) diferiu significativamente entre peixes carnívoros demersais (185,3 peso seco; 27,8 peso úmido) e onívoros demersais (277,9 peso seco; 41,7 peso úmido), e entre peixes onívoros pelágicos (197,2 peso seco; 29,6 peso úmido) e onívoros demersais devido a (1) diferenças nas fontes alimentares: guildas que utilizaram recursos de fundo foram mais afetadas pela contaminação pois o sedimento é um importante acumulador de Hg na área de estudo, e (2) por causa das suas posições tróficas. Tendo em vista que os peixes consumiram presas com níveis tróficos semelhantes, as guildas não apresentaram uma hierarquia alimentar definida. Desse modo, no presente estudo não se verificou uma relação clara entre Hg e δ15N.

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.

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.