Mobility and bioavailability of mercury in sediments of the southern Baltic sea in relation to the chemical fractions of iron: Spatial and temporal patterns.

Marine sediments play a significant role as reservoirs for mercury (Hg), a bioaccumulative toxic pollutant that poses risks to human and ecosystem health. Iron (Fe) has been recognized as an influential factor in the complexation and bioavailability of Hg in sediments. However, limited studies have investigated the interactions between the chemical fractions of these elements in natural settings. This study aims to examine the fractions of Hg and Fe in sediments of the Baltic Sea, a region historically impacted by Hg pollution. The Hg fractions were determined using the thermodesorption technique, while sequential extraction was employed to identify the Fe fractions. The findings confirm the crucial role of Fe in the formation, as well as the horizontal and vertical distribution of labile and stable Hg in marine sediments. Factors such as the contribution of organic matter, the presence of reactive Fe, and Fe associated with sheet silicates emerged as significant drivers that positively influenced the content of the most labile Hg fractions, potentially affecting the mobility and bioavailability of Hg in the marine environment.

Distribution and bioavailability of mercury in the surface sediments of the Baltic Sea.

The study aimed to determine the level of mercury (Hg) and its labile and stable forms in the surface sediments of the Baltic Sea. The work considers the impact of current and historical sources of Hg on sediment pollution, together with the influence of different environmental parameters, including water inflows from the North Sea. Surface sediments (top 5 cm) were collected in 2016-2017 at 91 stations located in different areas of the Baltic Sea, including Belt Sea, Arkona Basin, Bornholm Basin, Gdansk Basin, West Gotland Basin, East Gotland Basin, and the Bothnian Sea. Besides, the particulate matter suspended in the surface and near-bottom water was also collected. The analysis of total Hg concentration and individual Hg forms in collected samples was carried out using a 5-step thermodesorption method. This method allows for the identification of three labile and thus biologically available, fractions of Hg, which are mercury halides, organic Hg, mercury oxide and sulphate. Two stable fractions, mercury sulphide and residual Hg, were also determined. The highest Hg concentrations, reaching 341 ng g-1, were measured in the highly industrialised Kiel Bay, which was additionally a munition dumping site during and after World War II. High Hg level, ranging from 228 to 255 ng g-1, was also recorded in the surface sediments of the Arkona Basin, which was a result of the cumulative effect of several factors, such as deposition of Hg-rich riverine matter, favourable hydrodynamic conditions and military activities in the past. The relatively elevated Hg concentrations, varying from 60 to 264 ng g-1, were found in the Gdansk Basin, a region under strong anthropopressure and dominated by soft sediments. The sum of labile Hg in sediments was high and averaged 67% (with the domination of organic Hg compounds), which means that a large part of Hg can be released to the water column. It was found that the water inflows from the North Sea intensify the remobilisation of Hg and its transformation into bioavailable labile forms. As a consequence, the load of Hg introduced into the trophic chain can increase. Despite the significant reduction of Hg emission into the Baltic in the last decades, surface sediments can be an important secondary Hg source in the marine ecosystem. This is especially dangerous in the case of the western Baltic Sea.

Presence of mercury and methylmercury in Baltic Sea sediments, collected in ammunition dumpsites.

Methylmercury (MeHg) is the most toxic and dangerous form of mercury occurring in the environment. MeHg is highly bioaccumulative in organisms and undergoes biomagnification via the food chain. In the Baltic Sea munition dumpsites, methylmercury can be formed from mercury fulminate contained in primary explosives, as environmental conditions there favour methylation. MeHg in analysed sediments ranged from 19 to 2362 pg g-1d.w., the concentration of mercury (HgTOT) ranged from 4 to 294 ng g-1 d.w., and the values of MeHg/Hg ratio ranged from 0.1 to 2.0%. The obtained results confirmed that munition dumpsites are a source of mercury. The concentration of MeHg is elevated in a wider area than immediately next to dumped munitions. Presented results suggest that physical processes responsible for sediment and near-bottom water movement are diffusing MeHg signal, making munition dumpsites rather a diffuse source of MeHg than a number of point sources associated with particular munitions.

Forms of mercury in the Baltic mussel (Mytilus trossulus): Human and ecosystem health risk assessment.

Mercury (Hg) is one of the most dangerous environmental pollutants. A significant source of this toxic element to the human body is the consumption of seafood - including the increasingly popular mussels. Mussels also play an important role in the marine ecosystem, providing a food base for fish and birds. The study aimed to determine the level of total Hg and its labile and stable forms in the Baltic mussel (Mytilus trossulus), as well as to indicate the factors that shape them. The research was conducted in the Puck Bay (Polish part of the southern Baltic Sea) in 2012-2013. The study material consisted of M. trossulus mussels, the components of their diet (suspended matter and phytoplankton), and surface sediments. Concentrations of total Hg (HgTOT) and the individual Hg forms were established using the thermodesorption method on a DMA-80 analyser (Milestone). The obtained results showed that the level of Hg concentration in M. trossulus from the Puck Bay was shaped by the individual features of specimens, related to the growth and reproductive cycle of mussels, as well as the quality of food consumed by them. The total share of labile Hg forms in M. trossulus was high, exceeding 90% of HgTOT, and the predominant form was the most dangerous organic Hg. This means that almost all of the Hg accumulated in mussels can be transferred to higher trophic levels. The obtained results showed that Baltic mussels were characterised by levels of HgTOT and organic Hg deemed to be safe for humans. A positive relationship was noted between the HgTOT concentration in a mussel's tissues and the length of its shell. Smaller sized organisms demonstrated not only by lower Hg concentrations, but also by better condition and, consequently, higher nutritional value.

Sea-dumped ammunition as a possible source of mercury to the Baltic Sea sediments.

After World War II, as a move toward Germany demilitarization, up to 385,000 t of munitions were sunk in the Baltic Sea. Munition containing various harmful substances, including chemical warfare agents (CWA) and explosives, that can affect marine biota were dumped on the seafloor. Some of those objects contained mercury, either as elemental mercury or mercury compounds (e.g., mercury fulminate, a common explosive primer), and thus could act as a specific local source of mercury in the dumping areas. Unfortunately, there is a lack of information on how dumped munitions impact the mercury concentrations in the Baltic Sea sediments. This report aims to answer the question how much sedimentary mercury in the dumping areas originates from munitions and to determine to what extent the mercury present in those areas originates from mercury fulminate. Concentrations of total sedimentary mercury- HgTOT in samples collected from conventional (Kolberger Heide) and chemical (Bornholm Deep) munitions dumping sites are characterized by high variability. However, an increase in HgTOT concentrations was observed with a decreasing distance to particular munition objects at both study sites. Moreover, mercury speciation in sediments from Kolberger Heide proves that the mercury there can be traced back directly to mercury fulminate. Results of our study confirm that munitions dumpsites are a local point sources of mercury. Due to the ecosystem constrains, varying transport modes and pathways, and both unknown and varying decomposition rates, these sea-bed mercury concentrations are hard to evaluate quantitatively. Therefore we recommend that further detailed studies should be conducted to assess sedimentary mercury provenience in munitions dumpsites more accurately.

Mercury fractionation in marine macrofauna using thermodesorption technique: Method and its application.

Mercury (Hg) is one of the most dangerous elements, and its toxicity and ability to accumulate in organisms depend on its chemical form. There are numerous methods of Hg speciation analysis, out of which the least expensive and the least time-consuming one is thermodesorption. The method has been successfully used for the analysis of abiotic samples - soils and sediments. The aim of this study was to verify whether the simplified thermodesorption method can be used in the analysis of the tissues of animal organisms from different trophic levels. Hg fractionation analyses were performed on a DMA-80 analyser (Milestone, Italy). The results presented in this paper are the first published data on Hg fractionation by thermodesorption method in animal tissues. The study showed that the 5-step thermodesorption method can be applied to various types of environmental matrices, which makes it universal. This method is of great importance in terms of estimating the Hg uptake and transfer in the trophic chain, and also enables the assessment of global Hg circulation in the environment. The presented method does not require previous digestion of samples or the use of expensive reagents. It can also be used for the preliminary selection of samples for MeHg analysis. The results obtained by this 5-step fractionation could be comparable with different research, conducted using other Hg analysers.

Coastal erosion-a "new" land-based source of labile mercury to the marine environment.

Mercury (Hg) can be introduced into the marine environment in many different ways. In the case of the Baltic Sea, rivers and atmospheric deposition are the predominant ones. However, in the face of ongoing climate change, a new potential source, coastal erosion, is starting to become more important and is currently considered to be the third largest source of Hg in the Gdansk Basin region. It is especially significant along sections of coastline where, due to the higher frequency of extreme natural phenomena such as storms, heavy rains, and floods, increased erosion processes have already been noted. Cliffs, which account for about 20% of the Polish coastline, are particularly vulnerable. The aim of the study was to estimate the annual load of labile Hg entering the Gdansk Basin as a result of coastal erosion. Samples of down-core sediments (0-65 cm) were collected in the years 2016-2017 from selected cliffs situated in the Gulf of Gdansk area. The thermodesorption method was used to distinguish between labile and stable fractions of Hg. Considering the mean total Hg concentrations in the collected sediments (9.7 ng g-1) and the mean share of labile (64%), bioavailable mercury, it was estimated that the load of labile Hg originating from coastal erosion entering the Gdansk Basin is 10.0 kg per year. The load can increase by up to 50% in the case of episodic abrasion events during heavy storms and rains.

Simple screening technique for determination of adsorbed and absorbed mercury in particulate matter in atmospheric and aquatic environment.

The threat connected to mercury results from its capacity to be transported over long distances and its ability to bioaccumulate and biomagnify in the trophic chain, making it a global problem. Humans are situated at the top of the trophic ladder, and excess mercury manifests itself mainly in the onset of neurological conditions. The toxicity of mercury, as well as its residence time, depends on the form in which it occurs. However, analysis of mercury speciation is time-consuming and poses a high risk of additional or negative contamination. Hence, the mercury thermodesorption method, and particularly its use for fractionating Hg, offers many new possibilities. Here, the thermodesorption technique was applied to the determination of mercury fraction in particulate matter using a DMA-80 direct mercury analyser (Milestone, Italy). The presented method allows direct (without prior mineralisation) determination of labile and stabile mercury fractions within a relatively short time. Heating sample in subsequent temperatures enables determination the share of mercury adsorbed on the surface (mainly associated with halogenides (Hgads1) and HgSO4/HgO/HgF2 (Hgads2), as well as absorbed within the suspended particulate organic matter (Hgabs), in a relatively short time. This fractionation is of great importance in terms of estimating the transfer of mercury to and along the trophic chain. This method determines the contribution of two stable mercury fractions:: HgS and residual Hg, strongly bound to particulate matter matrix (Hgres). The novelty of this technique is also its joint ability to determine gaseous mercury bound to airboirne particulate matter, which will enable better understand Hg cycling in the atmosphere as well as mercury fraction in dry deposition flux. This method enables assessment of global mercury circulation in environment.

Mercury in suspended matter of the Gulf of Gdansk: Origin, distribution and transport at the land-sea interface.

The coastal regions of inland seas are particularly vulnerable to Hg pollution. An important carrier of toxic Hg in the marine environment is suspended matter originating from multiple sources. The present study was conducted in the Gulf of Gdansk and its adjoining land in the years 2011-2013. The results indicated that the HgSPM (Hg bound with suspended particulate matter) concentrations varied horizontally and vertically and were dependent on the water dynamics and the composition of organic matter. Conditions favourable for the accumulation of matter and adsorption of reactive gaseous mercury led to increasing HgSPM levels, which are especially hazardous in the case of semi-enclosed areas such as estuaries. These conditions also increase the Hg loads into the trophic chain through suspension feeders. Moreover, the HgSPM concentration was significantly affected by seasonal phenomena (mainly coastal erosion) and the quantity and quality of primary production (phytoplankton blooms, mainly Mesodinium rubrum).

Coastal erosion as a source of mercury into the marine environment along the Polish Baltic shore.

The climate changes in recent years in the southern Baltic have been resulting in an increased frequency of natural extreme phenomena (i.e. storms, floods) and intensification of abrasion processes, which leads to introduction of large amounts of sedimentary deposits into the marine environment. The aim of this study was to determine the mercury load introduced to the Baltic Sea with deposits crumbling off the cliffs-parts of the coast that are the most exposed to abrasion. The studies were carried out close to five cliffs located on the Polish coast in the years 2011-2014. The results show that coastal erosion could be an important Hg source into the marine environment. This process is the third most important route, after riverine and precipitation input, by which Hg may enter the Gulf of Gdansk. In the Hg budget in the gulf, the load caused by erosion (14.3 kg a(-1)) accounted for 80 % of the wet deposition and was 50 % higher than the amount of mercury introduced with dry deposition. Although the Hg concentration in the cliff deposits was similar to the natural background, due to their large mass, this problem could be significant. In addition, the preliminary studies on the impact of coastal erosion on the Hg level in the marine ecosystem have shown that this process may be one of the Hg sources into the trophic chain.