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We collected a sediment core from the 6th (6J) Triglav Lake, a remote mountain lake in NW Slovenia, and analysed it for 25 elements, using k0-instrumental neutron activation analysis (k0-INAA). For Hg, we used cold vapour atomic absorption spectrometry (CVAAS). Data were analysed using Principal Component Analysis (PCA). PCA indicated several distinct groups of elements and sediment core samples. Ca distribution was entirely different from all other sediment components. Ba, Br, Hg, Sb and Zn were associated with organic matter (OM), with Hg showing the strongest affinity to OM. As, Cr, Fe and U formed a group of redox-sensitive elements. Two events that occurred ca. 1915 and in the 1940s/1950s, were identified in the core. They were associated with increased inputs of allochthonous material into the lake, and significantly affected the stratigraphic distributions of all elements. Some trace elements, such as As, Hg and Zn, are probably effectively retained in the catchment, whereas Cr tends to be readily exported from the catchment. Atmospheric deposition affected not only elements of anthropogenic origin (As, Ba, Br, Hg, Sb, Zn and Cr) that started to increase after the 1970s, but also those of terrestrial origin (Ca, Fe, Na). Introduction of fish into the lake in 1991 and the subsequent increase in primary production, affected the distribution of Ca and elements that are redox-sensitive and/or associated with OM (As, Ba, Fe, Sb, U, Zn). Fe minerals in uppermost 6J sediments have a strong influence on the distribution of several trace elements. As and Zn closely tracked Fe, whereas Sb was likely released after oxidation. Climate change could also have enhanced inputs of elements from the catchment, but such changes were likely overwhelmed by the effects of increased eutrophication. [ABSTRACT FROM AUTHOR]

Mercury and its speciation were studied in surface and deep waters of the Adriatic Sea. Several mercury species (i.e. DGM – dissolved gaseous Hg, RHg – reactive Hg, THg – total Hg, MeHg – monomethyl Hg and DMeHg – dimethylmercury) together with other water parameters were measured in coastal and open sea deep water profiles. THg concentrations in the water column, as well as in sediments and pore waters, were the highest in the northern, most polluted part of the Adriatic Sea as the consequence of Hg mining in Idrija and the heavy industry of northern Italy. Certain profiles in the South Adriatic Pit exhibit an increase of DGM just over the bottom due to its diffusion from sediment as a consequence of microbial and/or tectonic activity. Furthermore, a Hg mass balance for the Adriatic Sea was calculated based on measurements and literature data. [ABSTRACT FROM AUTHOR]

Mercury tracers are powerful tools that can be used to study mercury transformations in environmental systems, particularly mercury methylation, demethylation and reduction in sediments and water. However, mercury transformation studies using tracers can be subject to error, especially when used to assess methylation potential. The organic mercury extracted can be as low as 0.01% of the endogenous labeled mercury, and artefacts and contamination present during methylmercury (MeHg) extraction processes can cause interference. Solvent extraction methods based on the use of either KBr/H2SO4 or HCl were evaluated in freshwater sediments using 197Hg radiotracer. Values obtained for the 197Hg tracer in the organic phase were up to 25-fold higher when HCl was used, which is due to the coextraction of 197Hg2+ into the organic phase during MeHg extraction. Evaluations of the production of MeHg gave similar results with both MeHg extraction procedures, but due to the higher Hg2+ contamination of the controls, the uncertainty in the determination was higher when HCl was used. The Hg2+ contamination of controls in the HCl extraction method showed a nonlinear correlation with the humic acid content of sediment pore water. Therefore, use of the KBr/H2SO4 method is recommended, since it is free from these interferences. 197Hg radiotracer ( T 1/2 = 2.673 d) has a production rate that is about 50 times higher than that of 203Hg ( T 1/2 = 46.595 d), the most frequently used mercury radiotracer. Hence it is possible to obtain a similar level of performance to 203Hg when it is used it in short-term experiments and produced by the irradiation of 196Hg with thermal neutrons, using mercury targets with the natural isotopic composition. However, if the 0.15% natural abundance of the 196Hg isotope is increased, the specific activity of the 197Hg tracer can be significantly improved. In the present work, 197Hg tracer was produced from mercury 51.58% enriched in the 196Hg isotope, and a 340-fold increase in specific activity with respect to natural mercury targets was obtained. When this high specific activity tracer is employed, mercury methylation and reduction experiments with minimum mercury additions are feasible. Tracer recovery in methylation experiments (associated with Me197Hg production from 197Hg2+ spike, but also with Hg2+ contamination and Me197Hg artefacts) with marine sediments was about 0.005% g−1 WS (WS: wet sediment) after 20 h incubation with mercury additions of 0.05 ng g−1 WS, which is far below natural mercury levels. In this case, the amount of Hg2+ reduced to Hg0 (expressed as the percent 197Hg0 recovered with respect to the 197Hg2+ added) varied from 0.13 to 1.6% g−1 WS. Me197Hg production from 197Hg2+ spike after 20 h of incubation of freshwater sediment ranged from 0.02 to 0.13% g−1 WS with mercury additions of 2.5 ng g−1 WS, which is also far below natural levels. 197Hg0 recoveries were low, 0.0058 ± 0.0013% g−1 WS, but showed good reproducibility in five replicates. Me197Hg production from 197Hg2+ spiked in freshwater samples ranged from 0.1 to 0.3% over a period of three days with mercury additions of 10 ng L−1. A detection limit of 0.05% for Me197Hg production from 197Hg2+ spike was obtained in seawater in a 25 h incubation experiment with mercury additions of 12 ng L−1. [ABSTRACT FROM AUTHOR]

Potential uses of dredged sediments have raised questions about leaching of contaminants from such material once transported to other locations and exposed to other environments. In order to estimate leachable, i.e. available fractions of chemical elements in such materials, a number of analytical protocols were proposed, of which none is internationally accepted as a standard procedure. As a consequence, comparability of the results obtained by different protocols in various laboratories is difficult to demonstrate. In the present study some commonly used protocols including a leaching test with (i) seawater, following the modified German Standard Method (DIN), (ii) a single extraction with 25% acetic acid, following the method proposed by the United Nations Environment Programme (UNEP), and (iii) a three-step sequential extraction, following both the original and the modified protocols of the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference - BCR), were performed for assessing the availability of lead, zinc, nickel and copper leachable from dredged marine sediments. A comparison of the results obtained by the different protocols indicated that the single extraction with acetic acid is a reliable simplified technique and allows more rapid evaluations of dredged areas of coastal lagoons in the Northern Adriatic. This procedure provides information on the potentially bioavailable portion of metals. [ABSTRACT FROM AUTHOR]

An inter-laboratory study was conducted to compare results from different analytical methods for monomethylmercury (MeHg) concentrations in 17 soil and sediment samples. The samples were collected from mercury-contaminated areas, including Minamata Bay and Kagoshima Bay in Japan, the Idrija mercury mine in Slovenia, and an artisanal small-scale gold mining area in Indonesia. The Hg in these samples comes from several different sources: industrial waste from an acetaldehyde production facility, volcanic activity, Hg mining activity, and artisanal and small-scale gold mining activity (ASGM). MeHg concentrations in all the samples were measured in four separate laboratories, using three different determination methods: Kagoshima University (Japan), using high-performance liquid chromatography–chemiluminescence detection (HPLC-CL); National Institute for Minamata Disease (Japan), using gas chromatography–electron capture detection; and Metropolitan Council Environmental Services (USA) and Jozef Stefan Institute (Slovenia), both using alkylation-gas chromatography–atomic fluorescence spectrometry detection. The methods gave comparable MeHg results for most of the samples tested, but for some samples, the results exhibited significant variability depending on the method used. The HPLC-CL method performed poorly when applied to samples with elevated sulfur concentrations, producing MeHg concentrations that were much lower than those from the other methods. Additional analytical work demonstrated the elimination of this sulfur interference when the method was modified to bind sulfur prior to the analytical step by using Hg 2+ as a masking agent. These results demonstrate the value of laboratory intercomparison exercises in contributing to the improvement of analytical methods. [ABSTRACT FROM AUTHOR]

Abstract: The existence of mining tailings in Idrija (Slovenia) and their subsequent transportation via the Isonzo River has been the primary source of mercury (Hg) in the northern Adriatic Sea for almost 500 years, making the Gulf of Trieste and the adjacent Marano and Grado Lagoon two of the most contaminated marine areas in the world. A further, more recent, contribution of Hg has been added by the operation of a chlor-alkali plant (CAP) located in the drainage basin flowing into the Lagoon. On the basis of previous research, as well as new data obtained from the “MIRACLE” project (Mercury Interdisciplinary Research for Appropriate Clam farming in a Lagoon Environment), the spatial distribution of Hg and its relationships with methylmercury (MeHg), organic matter and several geochemical parameters in surface sediments were investigated. The predominant and long-term impacts of the cinnabar-rich Isonzo River particulate matter in the Lagoon surface sediments are evident and confirmed by a decreasing concentration gradient from east (>11μgg−1) to west (0.7μgg−1). Hg originated from the CAP is only significant in the central sector of the Lagoon. Hg is primarily associated with fine-grained sediments (<16μm), as a consequence of transport and dispersion from the fluvial source through littoral and tidal currents. However, speciation analyses highlighted the presence of Hg sulphides in the coarse sandy fraction of sediments from the eastern area, as expected given the origin of the sedimentary material. Unlike Hg, the distribution of MeHg (0.47–7.85ngg−1) does not show a clear trend. MeHg constitutes, on average, 0.08% of total Hg and percentages are comparable to those obtained in similar lagoon environments. Higher MeHg concentrations in low to intermediate Hg-contaminated sediments indicate that the metal availability is not a limiting factor for MeHg occurrence, thus suggesting a major role played by environmental conditions and/or speciation. The reasonably good correlation between MeHg normalized to humic acid (HA) content and humic δ 13C indicates that MeHg is preferentially associated with autochthonous δ 13C-enriched HAs in lagoon surface sediments, suggesting that the structure of “marine” HAs, less refractory and less aromatic, could favor MeHg binding and/or production. In the context of the potential hazard of Hg and MeHg accumulation in reared clams, the choice of a site for the extension of farming activities inside the Marano and Grado Lagoon is dependent on several factors and cannot be decided solely on the basis of the total Hg content in the sediment. [Copyright &y& Elsevier]

Abstract: Marano and Grado lagoons are polluted by mercury from the Isonzo River and a chlor-alkali plant, yet despite this contamination, clam cultivation is one of the main activities in the region. Four stations (MA, MB, MC and GD) were chosen for clam seeding and surficial sediments were monitored in autumn, winter and summer to determine the Hg detoxifying role of bacteria. Biotransformation of Hg species in surficial sediments of Marano and Grado lagoons was investigated while taking into consideration the speciation of organic matter in the biochemical classes of PRT (proteins), CHO (carbohydrates) and LIP (lipids), water-washed cations and anions, bacterial biomass, Hg-resistant bacteria, some specific microbial activities such as sulfate reduction rates, Hg methylation rates, Hg-demethylation rates, and enzymatic ionic Hg reduction. MeHg in sediments was well correlated with PRT content, whereas total Hg in sediments correlated with numbers of Hg-resistant bacteria. Correlations of the latter with Hg-demethylation rates in autumn and winter suggested a direct role Hg-resistant bacteria in Hg detoxification by producing elemental Hg (Hg0) from ionic Hg and probably also from MeHg. MeHg-demethylation rates were ∼10 times higher than Hg methylation rates, were highest in summer and correlated with high sulfate reduction rates indicating that MeHg was probably degraded in summer by sulfate-reducing bacteria via an oxidative pathway. During the summer period, aerobic heterotrophic Hg-resistant bacteria decreased to <2% compared to 53% in winter. Four Hg-resistant bacterial strains were isolated, two Gram-positive (Staphylococcus and Bacillus) and two Gram-negative (Stenotrophomonas and Pseudomonas). Two were able to produce Hg0, but just one contained a merA gene; while other two strains did not produce Hg0 even though they were able to grow at 5μgml of HgCl2. Lagoon sediments support a strong sulfur cycle in summer that controls Hg methylation and demethylation. However, during winter, Hg-resistant bacteria that are capable of degrading MeHg via the mer-catalyzed reductive pathway increase in importance. [Copyright &y& Elsevier]

Abstract: A closed chlor-alkali plant (CAP) discharged Hg for decades into the Aussa River, which flows into Marano Lagoon, resulting in the large-scale pollution of the lagoon. In order to get information on the role of bacteria as mercury detoxifying agents, analyses of anions in the superficial part (0–1 cm) of sediments were conducted at four stations in the Aussa River. In addition, measurements of biopolymeric carbon (BPC) as a sum of the carbon equivalent of proteins (PRT), lipids (LIP), and carbohydrates (CHO) were performed to correlate with bacterial biomass such as the number of aerobic heterotrophic cultivable bacteria and their percentage of Hg-resistant bacteria. All these parameters were used to assess the bioavailable Hg fraction in sediments and the potential detoxification activity of bacteria. In addition, fifteen isolates were characterized by a combination of molecular techniques, which permitted their assignment into six different genera. Four out of fifteen were Gram negative with two strains of Stenotrophomonas maltophilia, one Enterobacter sp., and one strain of Brevibacterium frigoritolerans. The remaining strains (11) were Gram positive belonging to the genera Bacillus and Staphylococcus. We found merA genes in only a few isolates. Mercury volatilization from added HgCl2 and the presence of plasmids with the merA gene were also used to confirm Hg reductase activity. We found the highest number of aerobic heterotrophic Hg-resistant bacteria (one order magnitude higher) and the highest number of Hg-resistant species (11 species out of 15) at the confluence of the River Aussa and Banduzzi''s channel, which transport Hg from the CAP, suggesting that Hg is strongly detoxified [reduced to Hg(0)] at this location. [Copyright &y& Elsevier]

Abstract: Mercury (Hg) transformation activities and sulfate (SO4 2 −) reduction were studied in sediments of the Marano and Grado Lagoons in the Northern Adriatic Sea region as part of the “MIRACLE” project. The lagoons, which are sites of clam (Tapes philippinarum) farming, have been receiving excess Hg from the Isonzo River for centuries. Marano Lagoon is also contaminated from a chlor-alkali plant. Radiotracer methods were used to measure mercury methylation (230Hg, 197Hg), methylmercury (MeHg) demethylation (14C-MeHg) and SO4 2 − reduction (35S) in sediment cores collected in autumn, winter and summer. Mercury methylation rate constants ranged from near zero to 0.054 day−1, generally decreased with depth, and were highest in summer. Demethylation rate constants were much higher than methylation reaching values of ∼0.6 day−1 in summer. Demethylation occurred via the oxidative pathway, except in winter when the reductive pathway increased in importance in surficial sediments. Sulfate reduction was also most active in summer (up to 1600nmolmL−1 day−1) and depth profiles reflected seasonally changing redox conditions near the surface. Methylation and demethylation rate constants correlated positively with SO4 2 − reduction and pore-water Hg concentrations, and inversely with Hg sediment–water partition coefficients indicating the importance of SO4 2 − reduction and Hg dissolution on Hg cycling. Hg transformation rates were calculated using rate constants and concentrations of Hg species. In laboratory experiments, methylation was inhibited by amendments of the SO4 2 −-reduction inhibitor molybdate and by nitrate. Lagoon sediments displayed a dynamic seasonal cycle in which Hg dissolution in spring/summer stimulated Hg methylation, which was followed by a net loss of MeHg in autumn from demethylation. Sulfate-reducing bacteria (SRB) tended to be responsible for methylation of Hg and the oxidative demethylation of MeHg. However, during winter in surficial sediments, iron-reducing bacteria seemed to contribute to methylation and Hg-resistant bacteria increased in importance in the reductive demethylation of MeHg. The high rates of MeHg demethylation in lagoon sediments may diminish the accumulation of MeHg. [Copyright &y& Elsevier]

Abstract: As part of the “MIRACLE” project, the biogeochemical cycling of mercury (Hg) at the sediment–water interface was studied in the field in the Marano and Grado Lagoon (Northern Adriatic Sea). Seasonal investigations were conducted at selected experimental sites, where Manila Clams (Tapes philippinarum) were previously seeded. Measurements were performed seasonally during three campaigns, using two benthic chambers, one transparent and one dark, to evaluate the effect of light on Hg cycling. Total dissolved Hg (THg), methylmercury (MeHg), and dissolved gaseous Hg (DGM) species were considered. Diurnal benthic fluxes were found to significantly exceed the diffusive fluxes at all stations. The assessment of the annual recycling of Hg species from sediments to the water column showed that up to 99% of MeHg is recycled annually to the water column, while Hg recycling ranges from 30 to 60%. MeHg poses the higher risk for potential bioaccumulation in clams, but it is partially mitigated by Hg reduction, which seems to be an important process leading to evasion losses of Hg from these environments. Estimated benthic fluxes suggest that Hg recycling at the sediment–water interface is more active in the Grado sector. Hence, based on the estimated release of MeHg from sediments, it is suggested that the western sector seems to be more suitable for clam farming and the extension of rearing activities. [Copyright &y& Elsevier]

The Ramsar site Pialassa Baiona is an intertidal brackish lagoon lying 5 km north of the city of Ravenna and covering a surface area of about 1100 ha. From 1958 to 1976 Pialassa Baiona was heavily impacted by industrial pollution; mercury, polycyclic aromatic hydrocarbons, polymers were among the most important pollutants which nowadays contaminate the sedimentary compartment. Following earlier investigations on total mercury (THg) distribution and bioavailability, this study is focused on mercury speciation in sediments and clams. Methylmercury (MMHg) concentrations were determined in surface sediments (0–5 cm) in different seasons, and compared to THg. Selected sediments were subjected to a sequential extraction procedure to study solid state THg distribution. Operationally, three fractions of inorganic mercury were defined: mobile mercury (Hgm), humic acid complexed mercury (Hgha), and sulphide-bound mercury (Hgs). THg and MMHg concentrations in sediments ranged in the 0.2–250 μg g−1 and 0.13–45 ng g−1 d.w. intervals, respectively. MMHg/THg ratios were higher in summer as well as in sites where the THg burden was lower; the highest MMHg/THg values were observed in Chiaro del Pontazzo, an area subjected to a drastic reduction of salinity.THg and MMHg concentrations were also determined in tissues of clams (Tapes philippinarum) collected in the lagoon. MMHg in clams felt in the 180–470 ng g−1 interval and accounts for 72–95% of tissue THg. [Copyright &y& Elsevier]