Bioaccumulation of inorganic and organic mercury in the cuttlefish Sepia officinalis: Influence of ocean acidification and food type.

The bioaccumulation of mercury (Hg) in marine organisms through various pathways has not yet been fully explored, particularly in cephalopods. This study utilises radiotracer techniques using the isotope 203Hg to investigate the toxicokinetics and the organotropism of waterborne inorganic Hg (iHg) and dietary inorganic and organic Hg (methylHg, MeHg) in juvenile common cuttlefish Sepia officinalis. The effect of two contrasting CO2 partial pressures in seawater (400 and 1600 µatm, equivalent to pH 8.08 and 7.54, respectively) and two types of prey (fish and shrimp) were tested as potential driving factors of Hg bioaccumulation. After 14 days of waterborne exposure, juvenile cuttlefish showed a stable concentration factor of 709 ± 54 and 893 ± 117 at pH 8.08 and 7.54, respectively. The accumulated dissolved i203Hg was depurated relatively rapidly with a radiotracer biological half-life (Tb1/2) of 44 ± 12 and 55 ± 16 days at pH 8.08 and 7.54, respectively. During the whole exposure period, approximately half of the i203Hg was found in the gills, but i203Hg also increased in the digestive gland. When fed with 203Hg-radiolabelled prey, cuttlefish assimilated almost all the Hg provided (>95%) independently of the prey type. Nevertheless, the prey type played a major role on the depuration kinetics with Hg Tb1/2 approaching infinity in fish fed cuttlefish vs. 25 days in shrimp fed cuttlefish. Such a difference is explained by the different proportion of Hg species in the prey, with fish prey containing more than 80% of MeHg vs. only 30% in shrimp. Four days after ingestion of radiolabelled food, iHg was primarily found in the digestive organs while MeHg was transferred towards the muscular tissues. No significant effect of pH/pCO2 variation was observed during both the waterborne and dietary exposures on the bioaccumulation kinetics and tissue distribution of i203Hg and Me203Hg. Dietary exposure is the predominant pathway of Hg bioaccumulation in juvenile cuttlefish.

Rapid determination of femtomolar methylmercury in seawater using automated GC-AFS method: Optimisation of the extraction step and method validation.

Among ionic mercury species methyl mercury (MMHg) is the most toxic form present in the environment, which is known to be bio-accumulative neurotoxin in the aquatic food chain and could provide the major route of exposure for humans to mercury through consumption of marine food products. The availability of reliable analytical methods for evaluating spatial and temporal contamination trends of MMHg in the ocean is an important prerequisite for marine monitoring. Sound strategies for marine monitoring call also for measurement systems capable of producing comparable analytical results with demonstrated quality. A sensitive analytical procedure for environmental monitoring of MMHg content in seawater, based on specific extraction and Gas Chromatography Atomic Fluorescence Spectrometry validated according to the requirements of international guidelines and standards, ISO 17025 and Eurachem guidelines, is presented in this study. The entire measurement process was described by mathematical equations and all factors influencing the results were systematically investigated. Selectivity, working range, linearity, recovery (94 ± 4%), repeatability (3.3%-4.5%), intermediate precision (2.9%), limits of detection (0.0004 ng kg-1as Hg) were systematically assessed. The relative expanded uncertainties obtained were in the range from 16% to 25%, (k = 2). Modelling of the entire measurement process related obtained values for MMHg in seawater to the International System of units (Kg). The potential of this analytical procedure was tested and additionally validated via inter laboratory comparison exercise organised under the Geotraces programme. Obtained results were in excellent agreement with the assigned values. The proposed analytical procedure from the sample preparation to the measurement step combined with the high efficiency of the new generation of the automated MMHg analyzers is fit for purpose for routine monitoring studies on the dissolved MMHg in the costal and open ocean seawaters.

Comparative study on Hg bioaccumulation and biotransformation in Mediterranean and Atlantic sponge species.

In this work we present an assessment of mercury (Hg) and methyl mercury (MeHg) bioaccumulation in different species of marine sponges collected off the Northwestern Mediterranean and Northeastern Atlantic coasts. Overall the results showed significant accumulation of Hg in sponges, with the Mediterranean sponge Chondrilla nucula exhibiting the highest total Hg content (up to 0.5 mg kg-1) and bio-concentration factor (BCF) up to 23. A significant inter-species variability of Hg bioaccumulation was observed among species collected at the same site. The sponges, collected in marine environment contaminated with Hg show consistently higher Hg accumulation, meaning that the bioaccumulation is proportional to the Hg availability in the surrounding environment. Different extraction protocols were tested for MeHg analysis and, generally, a low MeHg ratio in Hg species (4% and 17% average for Mediterranean and Irish sponges respectively) was detected suggesting a possible demethylation process and therefore a promising role of sponges for Hg bioremediation Additionally, the Hg isotopic composition in these organisms was determined and it showed that MDF (mass dependent fractionation) is the main process in sponges, with the absence of significant MIF. This result suggests a dominant role of associated microbial population in the methylation and/or demethylation processes.

Trace elements contamination assessment in marine sediments from different regions of the Caribbean Sea.

Trace elements (TEs), rare earth elements (REEs), and methylmercury (MeHg) concentrations as well as mercury (Hg) and lead (Pb) isotope compositions in sediment samples collected from strategic locations along the Caribbean Sea were determined. The analyzed sediment samples were collected at different core depths from localities in Colombia, Cuba, Haiti, and the Dominican Republic. The evaluation of pollution assessment indices i.e. enrichment factors and geoaccumulation index revealed significant enrichment of several priority substances, such as Pb, Cd and Hg, in most of the sampling sites. Hg was found in extremely high concentrations (up to 22 ± 3 mg kg-1) in bottom samples of Colombian core, which led the authors to further investigate this area with respect to the source for Hg contamination. The analysis of Hg isotope ratios in Colombian sediments and the Pb isotope ratios in all studied cores, helped in the identification of likely pollution sources and represents a critically important record of anthropogenic influence in the region. Finally, the REEs patterns determined in all samples, also provide a needed baseline for these contaminants in the Caribbean region.

Determination of methylmercury in marine biota samples with advanced mercury analyzer: method validation.

In this paper, we present a simple, fast and cost-effective method for determination of methyl mercury (MeHg) in marine samples. All important parameters influencing the sample preparation process were investigated and optimized. Full validation of the method was performed in accordance to the ISO-17025 (ISO/IEC, 2005) and Eurachem guidelines. Blanks, selectivity, working range (0.09-3.0ng), recovery (92-108%), intermediate precision (1.7-4.5%), traceability, limit of detection (0.009ng), limit of quantification (0.045ng) and expanded uncertainty (15%, k=2) were assessed. Estimation of the uncertainty contribution of each parameter and the demonstration of traceability of measurement results was provided as well. Furthermore, the selectivity of the method was studied by analyzing the same sample extracts by advanced mercury analyzer (AMA) and gas chromatography-atomic fluorescence spectrometry (GC-AFS). Additional validation of the proposed procedure was effectuated by participation in the IAEA-461 worldwide inter-laboratory comparison exercises.

Cadmium bioaccumulation and retention kinetics in the Chilean blue mussel Mytilus chilensis: seawater and food exposure pathways.

The Chilean blue mussel (Mytilus chilensis, Hupe 1854) represents the most important bivalve exploited along the Chilean coast and is a major food source for the Chilean population. Unfortunately, local fish and shellfish farming face severe problems as a result of bioaccumulation of toxic trace metals into shellfishes. Blue mussels collected along the Chilean coasts contain levels of Cd above the regulatory limits for human consumption. In this study, we examined the bioaccumulation, depuration and organ distribution of Cd in the M. chilensis, from 109Cd-labelled bulk seawater and from feeding with 109Cd-labelled algae. The uptake of 109Cd via seawater displayed a simple exponential kinetic model suggesting that cadmium activity tends to reach an equilibrium value of 1.838+/-0.175 ng g(-1) (mean+/-asymptotic standard error, p < 0.001) after 78+/-9 days. The depuration rate for 109Cd accumulated via seawater was slow, with only 21% of the total 109Cd accumulated in the whole mussel being eliminated after 52 days. Total elimination of Cd in mussels was adequately described by a double component kinetic model, in which the biological half-life for the long-lived component represents more than 6 months. In contrast, depuration after radiolabelled food uptake was fast, reaching only 20% of retention in 10 days. This knowledge of the long half-life of cadmium accumulated via seawater as well as the non-negligible level of cadmium accumulated into the shells is relevant to the management of Cd levels in this species and the refinement of detoxification processes in order to comply with authorized Cd levels.

Hair mercury levels in relation to fish consumption in a community of the Moroccan Mediterranean coast.

Coastal populations with high seafood consumption in the Mediterranean have a significant exposure to dietary methylmercury, and areas where environmental mercury pollution is an issue due to industrial activities are of special concern. The study was undertaken with the aim of assessing methylmercury exposure through fish consumption in a community of north Morocco and characterizing the relevant health risk. Concentrations of total mercury were determined in human hair, a biomarker of methylmercury exposure, and in locally consumed fish by cold vapour atomic absorption spectrophotometry. Based on consumption frequencies reported by the 108 subjects included in the study the weekly intake of methylmercury was estimated and biomarker data were evaluated in relation to the estimated intake and the sociodemographic characteristics of the population. Multiple regression analysis was employed for the interpretation of hair mercury data in relation to fish consumption frequency, gender and the age of individuals. Mercury concentrations in hair ranged from 0.22 to 9.56 microg g(-1) (geometric mean = 1.79 microg g(-1)) and were closely related to fish intake. Fisherman and their families consumed fish three to five times per week and were the most exposed population subgroup. A high proportion of women of child-bearing age (50%) had relatively high levels of mercury in their hair (3.08-7.88 microg g(-1)).

Arsenic in sediments from the southeastern Baltic Sea.

Arsenic occurs as a persistent constituent in many of the chemical weapons dumped into the Baltic Sea; it can be used as an indicator of leakage and dispersal of released munitions to the marine environment. Total arsenic was analysed in sediment samples taken from the Lithuanian economic zone in the Baltic Sea, which included samples from the chemical munitions dumpsite in the Gotland Basin and national monitoring stations in the southeastern Baltic Sea. Arsenic concentrations in sediments ranged from 1.1 to 19.0 mg kg(-1), with an average of 3.4 mg kg(-1). Although there was evidence of slightly elevated arsenic content in sediments near the weapons dumpsite, arsenic concentrations were nevertheless quite low relative to other investigations in the Baltic and North Seas.

Distribution of heavy metals in marine bivalves, fish and coastal sediments in the Gulf and Gulf of Oman.

An assessment of marine contamination due to heavy metals was made in the Gulf and Gulf of Oman based on marine biota (fish and various bivalves) and coastal sediment collected in Bahrain, Oman, Qatar, and the United Arab Emirates (UAE) during 2000-2001. Sediment metal loadings were generally not remarkable, although hot spots were noted in Bahrain (Cu, Hg, Pb, Zn) and on the east coast of the UAE (As, Co, Cr, Ni). Concentrations of As and Hg were typically low in sediments and the total Hg levels in top predator fish commonly consumed in the region were < 0.5 microg g(-1) and posed no threat to public health. Very high Cd concentrations (up to 195 microg g(-1)) in the liver of some fish from southern Oman may result from food-chain bioaccumulation of elevated Cd levels brought into the productive surface waters by upwelling in the region. Very high As concentrations (up to 156 microg g(-1)) were measured in certain bivalve species from the region. Although not certain, the As is probably derived from natural origins rather than anthropogenic contamination.

Characterisation of trace elements and methylmercury in an estuarine sediment reference material, IAEA-405.

An estuarine sediment sample, IAEA-405, was recently characterised for trace elements and methylmercury (MeHg) for ultimate use as a marine reference material. The reference values were calculated using data sets from 120 laboratories that participated in a world-wide intercomparison exercise. The data evaluation is highlighted, and includes comparisons of different analytical methods, as well as the distribution of data. Overall laboratory performance for this exercise was encouraging: 86 laboratories (72%) reported data with <25% outliers. There was sufficient acceptable data to establish recommended values for 17 elements and information values for a further 15 elements. In addition, a recommended value was established for methylmercury. The estuarine sediment sample, IAEA-405, can be used as a reference material for quality control in the determination of trace elements and methylmercury in moderately polluted sediments.

An assessment of metal contamination in coastal sediments of the Caspian Sea.

An assessment of marine pollution due to metals was made in the Caspian Sea based on coastal sediment collected in Azerbaijan, Iran, Kazakhstan, Russia and Turkmenistan. Despite the high carbonate content, the distribution of most metals was largely controlled by terrigenous inputs. Several metals (As, Cr, Ni) exhibited concentrations that exceed sediment quality guidelines. Such metals have a high natural background but anthropogenic activities, notably mining, may further enhance concentrations. This would explain hot spots for Cu and Zn in Azerbaijan and Iran, and Cr at the mouth of the Ural River in Kazakhstan. Contamination by Hg was observed to the south of Baku Bay, Azerbaijan. Some anomalously high concentrations of Ba in the central Caspian are probably from offshore drilling operations, but the elevated U concentrations (up to 11.1 microg g(-1)) may be natural in origin. Several metals (Ag, Cd, Pb) have relatively low levels that pose no environmental concerns.