Paco Bustamante

Impact of galvanic anode dissolution on metallic trace element concentrations in marine waters

Submerged harbor steel structures often employ cathodic protection using galvanic anodes to guard against corrosion. A laboratory experiment, with three different cathodic protection configurations by galvanic aluminum-based anodes, was performed to evaluate the potential metal transfer from the anodic alloy dissolution into the surrounding marine water. The anode dissolution rate is proportional to the imposed current demands and induced a significant Al, In, and Zn transfer in the dissolved and particulate fractions of the corrosion product layers covering the anode surface. These layers were poorly adherent, even under low hydrodynamic conditions. Consequently, at the anode vicinity, the suspended particle matter and dissolved fraction of surrounding marine waters showed strong enrichments in Al and Zn, respectively, the values of which could potentially affect the adjacent biota. After the anode activation period, however, the metal inputs from galvanic anode dissolution are rapidly diluted by seawater renewal. At regional scale, these metal fluxes should be negligible compared to river and wastewater fluxes. These results also showed that it is difficult to assess the impact of the anode dissolution on the concentrations of metals in the natural environment, especially for metals included in trace amounts in the anode alloy (i.e., Cu, Fe, In, Mn, and Si) in the aquatic compartment.

Distribution of trace elements in the tissues of benthic and pelagic fish from the Kerguelen Islands

New information on the concentrations of Cd, Cu, Hg and Zn in the liver, kidney and muscles of eight marine benthic and pelagic sub-Antarctic fish species are presented to determine the importance of these metals in the marine systems of the Kerguelen Islands. Compared to the reported metal concentrations in other Antarctic fish species, the present results are globally within the same range of concentrations, although Cd displayed a very high interspecific variability in liver and kidney. Indeed, the highest Cd concentrations in liver, ranging from 10.0 to 52.1 microg x g(-1) dry wt. but also the lowest Cd concentrations in muscles (<0.030 microg x g(-1) dry wt.) have been displayed by the pelagic Myctophidae Gymnoscopelus piabilis. Metal concentrations differences might be related to diet and feeding habits of benthic and pelagic fish species. However, Cd and Hg concentrations in the edible muscle are lower than the French limit values (<or=0.155 microg x Cd x g(-1) dry wt. and <or=1.51 microg x Hg x g(-1) dry wt.) for these toxic metals as well as for edible and non-commercially interesting fish species. Results for Cd in fish tissues are consistent with the hypothesis of Cd-enrichment in the polar food webs typically explained by essential elements depletion. In fact, Zn concentrations in fish from the Kerguelen Islands are comparable to those of other areas but low Cu concentrations in fish livers, ranging from 0.9 to 24.7 microg x g(-1) dry wt., might indicate low availability of this essential element in these sub-Antarctic waters.

Cadmium detoxification processes in the digestive gland of cephalopods in relation to accumulated cadmium concentrations.

The high concentrations of cadmium recorded in the digestive gland of cephalopods from various temperate and subpolar waters suggest that these molluscs have developed efficient cadmium detoxification mechanisms. The subcellular distribution of cadmium in the digestive gland cells was investigated in seven cephalopod species from the Bay of Biscay (France) and the Faroe Islands. In most species, cadmium was mainly found in the cytosolic fraction of the digestive gland cells, reaching up to 86% of the total cadmium for the squid Loligo vulgaris from the Bay of Biscay. But species with the highest total level of cadmium showed a higher percentage of cadmium associated to insoluble compounds. The quantification of metallothioneins (MTs) by the polarographic method was performed in order to evaluate the involvement of these proteins in the detoxification of the high amounts of bioaccumulated cadmium. Metallothionein levels in cephalopods ranged form 742 +/- 270 to 3478 +/- 1572 microg/g wet weight. No relationship could be established between total cadmium, cytosolic cadmium and MT levels suggesting the occurrence of other Cd-binding ligands. Although these proteins have not been characterised, as cadmium in the digestive gland of cephalopods is mainly associated with soluble ligands, a high potential transfer to predators can be predicted.

Bioaccumulation of Cadmium, Copper and Zinc in some Tissues of Three Species of Marine Turtles Stranded Along the French Atlantic Coasts

Cadmium, copper and zinc have been analysed in some tissues and organs of Loggerhead, Kemps Ridley (only muscle for this species) and Leatherback turtles stranded along the Atlantic coasts of France. The pancreas analysed only in Leatherback turtles exhibited the highest metal concentrations, which is very surprising for an organ which does not play a role in the detoxification processes. The distribution of these elements in kidney, liver and muscle were quite similar to that found in marine mammals or seabirds. Nevertheless, mean cadmium concentrations in the kidney were as high as 13.3 µg g-1 wet weight in the Loggerhead turtles and 30.3 µg g-1 wet weight in the Leatherback turtles. Such high concentrations in the Leatherback turtles have never been recorded before. The main source of cadmium for marine turtles is probably the food. The Leatherback turtles are known to feed mainly on jellyfish in this area. Ten times higher cadmium concentrations have been determined in jellyfish compared to fish. This would imply a greater exposure to cadmium for Leatherback turtles, which probably need to eat great quantities of jellyfish to cover their needs.

Bioaccumulation of 12 Trace Elements in the Tissues of the Nautilus Nautilus macromphalus from New Caledonia

Soils in New Caledonia are particularly rich in metals among which Fe and Ni are intensively exploited. Due to important natural erosion in tropical latitudes and to mining activities, coastal waters are enriched in Co, Cr, Fe and Ni. In deeper waters lives a cephalopod species which is considered as a living fossil, the nautilus Nautilus macromphalus. In this study, 12 trace elements were analysed in the tissues of 4 nautilus specimens. Results showed high metal concentrations compared to data available for cephalopods from temperate waters. These concentrations were often in the same order as those encountered in bivalves or gastropods from contaminated areas. Relatively high concentrations of Ni and Cr in the haemolymph strongly suggest a high exposure of N. macromphalus to these metals. Among the tissues, the digestive gland has the highest concentrations of Cd, Co, Fe, V and Zn while for Ag, Al, As, Cr and Ni, renal and pericardial appendages exhibited the highest values. Despite this, the digestive gland contained the largest quantities of all metals with the exception of As and Mn which were mainly found in the body muscular remains. These results highlighted the major role of digestive gland and excreting organs in the metabolism of metals in these cephalopod species.

Cadmium, copper and zinc in octopuses from Kerguelen Islands, Southern Indian Ocean

Abstract Concentrations of cadmium, copper and zinc were measured in 34 octopuses over a large range of size and weight, caught in the Kerguelen shelf waters. Compared with levels normally encountered in European cephalopods, Cd concentrations in both species were very high: 30.7–47.1 and 27.3–54.4 μg/g dry weight in Graneledone sp. and Benthoctopus thielei, respectively; Cu concentrations were generally low while Zn concentrations exhibited similar levels. Distribution of Cd in tissues showed that the high levels of Cd in Kerguelen octopuses resulted from very high levels of the metal in the digestive gland (369 and 215 μg/g dry wt in Graneledone sp. and Benthoctopus thielei, respectively). The digestive gland accumulated about 90% of the total Cd in the whole animal. Due to the very high concentrations of Cd in the Kerguelen octopuses, we hypothesize that these species play an important role in the process of Cd transfer throughout the food chain to top vertebrate predators in this area.

To breed or not to breed: endocrine response to mercury contamination by an Arctic seabird

Mercury, a ubiquitous toxic element, is known to alter expression of sex steroids and to impair reproduction across vertebrates but the mechanisms underlying these effects are not clearly identified. We examined whether contamination by mercury predicts the probability to skip reproduction in black-legged kittiwakes (Rissa tridactyla) from Svalbard. We also manipulated the endocrine system to investigate the mechanism underlying this relationship. During the pre-laying period, we injected exogenous GnRH (gonadotropin-releasing hormone) to test the ability of the pituitary to release luteinizing hormone (LH, a key hormone for the release of sex steroids and hence breeding) in relation to mercury burden. Birds that skipped reproduction had significantly higher mercury concentration in blood than breeders. Endocrine profiles of these birds also varied based on breeding status (breeders versus non-breeders), mercury contamination and sex. Specifically, in skippers (birds that did not breed), baseline LH decreased with increasing mercury concentration in males, whereas it increased in females. GnRH-induced LH levels increased with increasing mercury concentration in both sexes. These results suggest that mercury contamination may disrupt GnRH input to the pituitary. Thus, high mercury concentration could affect the ability of long-lived birds to modulate their reproductive effort (skipping or breeding) according to ongoing environmental changes in the Arctic, thereby impacting population dynamics.

Demographic responses to mercury exposure in two closely related Antarctic top predators

Although toxic chemicals constitute a major threat for wildlife, their effects have been mainly assessed at the individual level and under laboratory conditions. Predicting population-level responses to pollutants in natural conditions is a major and ultimate task in ecological and ecotoxicological research. The present study aims to estimate the effect of mercury (Hg) levels on future apparent survival rates and breeding performances. We used a long-term data set (-10 years) and recently developed methodological tools on two closely related Antarctic top predators, the South Polar Skua Catharacta maccormicki from Adélie Land and the Brown Skua C. lonnbergi from the Kerguelen Archipelago. Adult survival rates and breeding probabilities were not affected by Hg levels, but breeding success in the following year decreased with increasing Hg levels. Although South Polar Skuas exhibited much lower Hg levels than Brown Skuas, they suffered from higher Hg-induced breeding failure. This species difference could be attributed to an interaction between Hg and other environmental perturbations, including climate change and a complex cocktail of pollutants. By including Hg-dependent demographic parameters in population models, we showed a weak population decline in response to increasing Hg levels. This demographic decline was more pronounced in South Polar Skuas than in Brown Skuas. Hence, Hg exposure differently affects closely related species. The wide range of environmental perturbations in Antarctic regions could exacerbate the demographic responses to Hg levels. In that respect, we urge future population modeling to take into account the coupled effects of climate change and anthropogenic pollution to estimate population projections.

Trace elements in two odontocete species (Kogia breviceps and Globicephala macrorhynchus) stranded in New Caledonia (South Pacific)

Liver, muscle and blubber tissues of two short-finned pilot whales (Globicephala macrorhynchus) and two pygmy sperm whales(Kogia breviceps) stranded on the coast of New Caledonia have been analysed for 12 trace elements (Al, Cd, Co, Cr, Cu. Fe, organic and total Hg, Mn, Ni, Se, V, and Zn). Liver was shown to be the most important accumulating organ for Cd, Cu, Fe, Hg, Se, and Zn in both species, G. macrorhynchus having the highest Cd, Hg, Se and Zn levels. In this species, concentrations of total Hg are particularly elevated, reaching up to 1452 microg g(-1) dry wt. Only a very low percentage of the total Hg was organic. In both species,the levels of Hg are directly related to Se in liver. Thus, a molar ratio of Hg:Se close to 1.0 was found for all specimens, except for the youngest K. breviceps. Our results suggest that G. macrorhynchus have a physiology promoting the accumulation of high levels of naturally occurring toxic elements. Furthermore, concentrations of Ni, Cr and Co are close to or below the detection limit in the liver and muscles of all specimens. This suggests that mining activity in New Caledonia, which typically elevates the levels of these contaminants in the marine environment, does not seem to be a significant source of contamination for these pelagic marine mammals.

Wide range of mercury contamination in chicks of southern ocean seabirds.

Using top predators as sentinels of the marine environment, Hg contamination was investigated within the large subantarctic seabird community of Kerguelen Islands, a remote area from the poorly known Southern Indian Ocean. Chicks of 21 sympatric seabirds presented a wide range of Hg concentrations, with the highest contaminated species containing ∼102 times more feather Hg than the less contaminated species. Hence, Kerguelen seabirds encompass the whole range of chick feather Hg values that were previously collected worldwide in poorly industrialized localities. Using stable isotopes, the effects of foraging habitats (reflected by δ13C) and trophic positions (reflected by δ15N) on Hg concentrations were investigated. Species-related Hg variations were highly and positively linked to feather δ15N values, thus highlighting the occurrence of efficient Hg biomagnification processes within subantarctic marine trophic webs. By contrast, Hg contamination overall correlated poorly with feeding habitats, because of the pooling of species foraging within different isotopic gradients corresponding to distinct seabird habitats (benthic, pelagic, neritic and oceanic). However, when focusing on oceanic seabirds, Hg concentration was related to feather δ13C values, with species feeding in colder waters (lower δ13C values) south of Kerguelen Islands being less prone to be contaminated than species feeding in northern warmer waters (higher δ13C values). Within the context of continuous increase in global Hg emissions, Kerguelen Islands that are located far away from anthropogenic sources can be considered as an ideal study site to monitor the temporal trend of global Hg contamination. The present work helps selecting some seabird species as sentinels of environmental pollution according to their high Hg concentrations and their contrasted foraging ecology.