Factors controlling methylmercury concentration in soils of Northern Poland.

Soil acts as storage for many toxic substances, including mercury and its compounds. However, in addition to its storage function, soil can also be a source of many substances to the aquatic environment. Methylmercury (MeHg) is one of the most toxic form of mercury (Hg) present in the environment. Some studies consider Poland to be one of the major emitters of Hg into both the atmosphere and the Baltic Sea. The purpose of the study was to identify factors affecting the formation and retention of MeHg in the soil as well as it remobilization to the river. Fifteen soil core samples with a length of 200 cm were collected during the fall/winter of 2021-2022. The factors responsible for the inflow and formation of MeHg were precipitation, distance from the riverbank, soil moisture and age of organic matter. MeHg can be transported to topsoil with precipitation. An increase in MeHg concentration was also observed in moist soils located in the vicinity of riverbank. MeHg concentration was lower in soils with degraded organic matter than with fresh organic matter.

The impact of global climate changes on trace and rare earth elements mobilization in emerging periglacial terrains: Insights from western shore of Admiralty Bay (King George Island, Antarctic).

In the rapidly changing climate, the biogeochemical behaviours of trace elements and Rare Earth Elements (REEs) in emerging periglacial environments assumes profound importance. This study provides pivotal insights into this dynamic by investigating the Antarctic's response to global climate change. The bedrock of King George Island is rich in REEs, with the presence of trace metals (TEs), with the highest concentrations of metals found in ornithogenic soil (∑REE 84.01-85.53 mg∙kg-1 dry weight). REEs in the studied soil, found mainly in igneous rocks, as is indicated by the positive correlation of these elements with sodium and calcium. The TEs released as a result of weathering are leached by water flowing down local watercourses to Admiralty Bay, as indicated by the decreasing results of ∑REE = 11.59 µg∙dm-3 in watercourse water, ∑REE = 1.62 µg∙dm-3 in watercourse pools and ∑REE = 0.66 µg∙dm-3 in the water of Admiralty Bay at the outlet of the watercourse. Water originating from the melting of snow on the glacier also carried REEs (∑REE = 0.14 µg∙dm-3), a fact which suggest the further influx of these elements from atmospheric deposition. The Prasiola crispa turned out to be the most susceptible to the accumulation of REEs (∑ 80.73 ± 5.05 µg g-1) and TEs, with the exception of chromium and zinc, whose concentrations were found to be at their highest in Deschampsia antarctica. In Usnea antarctica, Xanthoria candelaria, and Ceratodon purpureus and Politrichastrum alpinum, a dominant role in the accumulation of REEs was played by HREEs. The determined enrichment factor (EF) indicates that the soil cover is a source of REEs (EFAlgae for ∑REE = 5.07; EFLichen for ∑REE = 6.65; EFBryophyta for ∑REE = 5.04; EFVascular for ∑REE = 4.38), while Ni, As and Pb accumulated in plants may originate from other sources than the soil.

Distribution of 137Cs in the marine environment from King George Island (Southern Shetlands, maritime Antarctica).

The article presents data on the activity of the radionuclide 137Cs in seawater, sediment, macroalgae, and zoobenthos from different locations in Admiralty Bay, King George Island, maritime Antarctica. The activity of 137Cs in the macrophytobenthos remained relatively stable across species, oscillating at the level of 1 Bq kg-1dw. However, a few individuals exhibited higher activity, particularly at stations closer to the glacier front. This result could have been caused by specific conditions resulting from melting glaciers and meltwater inflow and mixing with oceanic water. The activities of 137Cs in zoobenthic were in the range from 0.12 Bq kg-1dw (Asteroidea) to 24.2 Bq kg-1dw (Porifera) and the total doses in marine species were several orders of magnitude lower than reference levels. Stable isotopes of δ13C and δ15N suggest that the main factor influencing 137Cs activity may be the source of carbon (marine vs. terrestrial/glacial), rather than feeding strategy or trophic niches.

Assessing the present levels of 137Cs in the remote ecosystem of Bjornoya (South Svalbard).

The remoteness and small size of Bjornoya (S Svalbard) make the island one of the most unreachable places in the Arctic. Limited accessibility contributes to still-existing knowledge gap on isotope accumulation in compartments of its ecosystem. Therefore, in this study we aimed to investigate the current concentration of 137Cs in the terrestrial samples of vascular plants, cryptogams, and soil collected on Bjornoya in 2021. The measured average activity of 137Cs in bryophytes was 56.5 Bq kg-1, lichens 27.6 Bq kg-1, vascular plants 7.26 Bq kg-1, and soil 9.63 Bq kg-1. In the case of bryophytes, 137Cs activity was negatively correlated with δ15N. Our results suggest that bird guano was the main source of nitrogen and 137Cs for vascular plants. For bryophytes, significantly lower values of δ15N than in vascular plants suggests that this group is more sensitive to atmospheric N intake, with fallout being the main source of 137Cs.

Mercury and methylmercury in birds and marine mammals inhabiting the coastal zone of the two King George Island's bays: Admiralty and King George Bay (maritime Antarctic).

The Antarctic is particularly sensitive to mercury (Hg) pollution and even low levels of Hg may cause significant damage in this fragile environment. The aim of this study was to investigate routes of mercury and methylmercury (MeHg) elimination by animals inhabiting the maritime Antarctic. The results showed that organisms at the highest trophic level (elephant seal) have the highest concentrations of THg and MeHg in both excrement and fur samples. Interspecies differences in mercury levels were observed in materials sourced from penguins of the genus Pysgocelis.13C and 15N values confirmed differences in the diets and foraging areas, which may affect Hg concentration in the tissues we analyzed. Time variations in THg and MeHg concentrations were observed in the excrement of the penguin species, which may be due to periods of fasting and intense feeding closely related to egg laying and moulting stages.

Distribution of 90Sr and 137Cs in biotic and abiotic elements of the coastal zone of the King George Island (South Shetland Archipelago, Antarctic Peninsula).

For many years Antarctic ecosystems have been considered pristine, however recent studies, including our results, contradict this assumption. Our comprehensive study on the activity of anthropogenic radioisotopes (137Cs and 90Sr) in the most common species of green algae, bryophytes, lichens, and vascular plants, as well as soil and guano samples collected over a large area on King George Island (South Shetland Archipelago) in the austral summer 2018/2019 clearly indicate the importance of large-scale transport in shaping the level of pollution in areas very distant from potential sources of contamination. Additionally, radioisotope pollution can be measured even after a very long period (>60 years) since their occurrence. The mean activity of 137Cs measured in lichens, bryophytes, vascular plants, green algae, soil, and guano was, respectively: 3.72 Bq kg-1dw, 3.70 Bq kg-1dw, 2.62 Bq kg-1dw, 2.26 Bq kg-1dw, 4.07 Bq kg-1dw and 2.08 Bq kg-1dw. For 90Sr mean activity in lichens, bryophytes, vascular plants, green algae, and soil was, respectively: 1.99 Bq kg-1dw, 3.05 Bq kg-1dw, 2.42 Bq kg-1dw, 1.08 Bq kg-1dw, and 6.43 Bq kg-1dw. Increased activities of 90Sr and 137Cs were observed in species collected in the area influenced by glacier melt and penguin guano.

Mercury fractionation - Problems in method application.

Mercury (Hg) is a global pollutant with a negative effect on human and ecosystem health. Mercury is toxic in all forms. The toxicity, however, varies depending on the form of mercury, determining its physical and chemical properties. Therefore, knowledge on the chemical speciation of mercury is key for the understanding of its transport and transformations in the environment. Analysis of mercury speciation, however, is time-consuming and involves high risk of contamination. The mercury thermodesorption method offers many new possibilities. The main advantages of this method are identifying which groups of compounds are being transformed in the atmosphere, sediment and soil, suspended matter and plankton, and in organisms from different trophic levels. A great advantage of the method is also its application in mercury analyzers, where it is possible to control the heating and cooling temperatures of. The standardisation of fractionation nomenclature for all matrices (both biotic and abiotic) will be helpful in application of this mercury fractionation method too. It has also disadvantages, mostly in the technical preparation of the analyzer. The analyzer must be prepared for fractionation: setting the ventilator and adjusting the PID parameters so that the pre-set heating (t1) and combustion (t2) times reach the set value in the method program. Also, any modification of the heater forces a re-optimisation of the method with mercury standards, as certified reference materials for Hg fractionation in environmental matrices are not available. The HgF2 fraction cannot be used as the methylmercury concentration, which is undoubtedly the biggest drawback of this method.

Mercury in the Polish part of the Baltic Sea: A response to decreased atmospheric deposition and changing environment.

Our review of the literature showed that since the beginning of the socio-economic transformation in Poland in the 1990s, the downward trend in Hg emissions and its deposition in the southern Baltic Sea was followed by a simultaneous decrease in Hg levels in water and marine plants and animals. Hg concentrations in the biota lowered to values that pose no or low risk to wildlife and seafood consumers. However, in the first decade of the current century, a divergence between these two trends became apparent and Hg concentrations in fish, herring and cod, began to rise. Therefore, increasing emission-independent anthropogenic pressures, which affect Hg uptake and trophodynamics, remobilization of land-based and marine legacy Hg deposits, as well as the structure of the food web, can undermine the chances of reducing both the Hg pool in the marine environment and human Hg exposure from fish.

Mercury concentration and speciation in benthic organisms from Isfjorden, Svalbard.

Polar regions are an important part of the global mercury cycle and interesting study sites due to different possible mercury sources. The full understanding of mercury transformations in the Arctic is difficult because this region is the systems in transition -where the effects of the global climate change are the most prominent. Benthic organisms can be valuable bioindicators of heavy metal contamination. In July 2018, selected benthic organisms: macroalgae, brittle stars, sea urchins, gastropods, and starfish were collected in Isfjorden, Spitsbergen. Two of the sampling stations were located inside the fjord system and one at the entrance to the fjord. The results showed that the starfish were the most contaminated with mercury. Total mercury concentrations in these organisms were at least 10 times higher than in other organisms. However, they effectively deal with mercury by transporting it to hard tissue. The dominant form of mercury was the labile form.

Status and trends of mercury pollution of the atmosphere and terrestrial ecosystems in Poland.

The goal of this paper is to assess the current status and trends of total mercury (THg) contamination of the atmosphere and terrestrial ecosystems in Poland. The study shows that the reduced domestic and worldwide atmospheric emission of Hg resulted in decreased THg level in the terrestrial biotope and biosphere. Considering that Poland is one of the main Hg emitters in Europe, the THg concentrations in its abiotic environment are still elevated. However, the THg level in terrestrial organisms is relatively low, which is because a large proportion of Hg deposited on land is accumulated in organic-rich soils. Regarding the THg concentration, consumption of wildlife and livestock from Poland is safe for humans. Nevertheless, the authors indicate the need for effective environmental monitoring, based on selected bioindicators, which is crucial considering the slowing reduction of Hg emission combined with the consequences of the changing climate.

Alimentary exposure and elimination routes of rare earth elements (REE) in marine mammals from the Baltic Sea and Antarctic coast.

Marine mammals found at the top of the trophic pyramid are excellent bioindicators of pollutants in the marine environment, the concentrations of which increase along with the trophic level of the organism. As these animals are usually protected species, their contamination has to be assessed non-invasively by analysing excrement and epidermal structures such as fur or claws. The present study involved testing the excrement and fur of the grey seal (Halichoerus grypus) from the Southern Baltic coast and the Southern elephant seal (Mirounga leonine) from Admiralty Bay, along with fish muscle (food) and the lithological background of both areas, for the presence of rare earth elements (REE). The soil on the Baltic coast is characterized by the predomination of light rare earth elements (LREE): yttrium, lanthanum and cerium (∑REE = 7.86 mg·kg-1 dw). In the soil and bedrock of Admiralty Bay all REEs were found except for terbium, thulium and lutetium (∑REE = 96.1 mg·kg-1 dw). The REE levels found in the muscles of Baltic herring (∑REE = 0.057 mg·kg-1 ww) were lower than those in the muscles of marbled rockcod (∑REE = 0.540 mg·kg-1 ww). The situation was analogous in the mammals, with the REE concentrations in grey seal fur (∑REE = 0.489 mg·kg-1 dw) and excrement (∑REE = 0.676 mg·kg-1 dw) being lower than those found in the fur (∑REE = 10.1 mg·kg-1 dw) and excrement (∑REE = 83.6 mg·kg-1 dw) of the elephant seal. The LREE/HREE partition coefficients in the grey seal excrement (3.37) and its fur (4.00), but also in the faeces of the elephant seal (2.63) and its fur (2.65), indicate that in each species the process of elimination from the body occurs in similar proportions.

Meteorological phenomenon as a key factor controlling variability of labile particulate mercury in rivers and its inflow into coastal zone of the sea.

Mercury (Hg) is recognized as a global pollutant, which can be transported to the sea by suspended particulate matter (SPM) via rivers constituting the main source of mercury in the southern Baltic sea. The aim of the present study was to characterize the mercury fractions in suspended particulate matter, as well as the transformations of Hg during its riverine transportation into the sea. The thermo-desorption method was used to determine the labile and stable mercury fractions in SPM of rivers (Reda, Zagórska Struga, Gizdepka, Plutnica) within the Baltic Sea basin. In this paper six "periods" were designated (heating, non-heating, drought, rains, downpour/flood and thaws), during which the river suspended particulate matter was enriched with various fractions of mercury. Meteorological and hydrological phenomena such as downpours and thaws intensified surface runoff, causing an increase in the share of Hgabs and Hgads1 mercury fractions in suspended particulate matter. Whereas, droughts contributed to the formation of HgS in a large river and to an inflow of adsorbed Hg in smaller rivers decrease of air temperature leads to increase of fossil fuel combustion and then increases the share of adsorbed Hg (mainly bound with halides) in riverine particulate matter. In the non-heating season, the main fraction was the mercury absorbed inside organic matter.

Fur and faeces - Routes of mercury elimination in the Baltic grey seal (Halichoerus grypus grypus).

This study focused on evaluating the elimination of Hg by Baltic grey seals (Halichoerus grypus grypus) via faeces and pelage. In addition, we investigated the potential for ecosystem contamination via these routes. Faeces and fur were collected in 2014-2017 from captive adult grey seals and their pups. The concentrations of total mercury (THg) and methylmercury (MeHg) were measured in the samples. The amount of mercury eliminated in a labile form (the sum of the bioavailable Hg(II) and methylmercury) was also determined. An adult seal removed about 46% of mercury supplied with food via the faeces, of which only 17% was MeHg. Considering that mercury is mainly supplied to the body as MeHg, it can be assumed that mercury excreted along with faeces has undergone transformation inside the animal body. Despite the much higher THg and MeHg concentrations measured in fur, the incorporation of mercury into newly formed fur is a less effective method of Hg elimination removing just 4% of mercury entering the body via the alimentary route. The presence of mercury in lanugo is evidence of maternal transfer. First droppings of the pups were characterised by the highest content of MeHg and a low THg concentration. Then, despite the limited supply of mercury with food, and the rapid growth of the pup, the concentration of THg increased, suggesting that mercury started to be transformed into less toxic forms. It was estimated that faeces and fur expelled by seals could deliver about 800 g of mercury to the Baltic Sea. For both faeces and fur, most of the mercury (>95% for excrements and >85% for fur) was expelled in a labile form that can be quickly recycled.

Mobility of mercury in soil and its transport into the sea.

Mercury (Hg) is deposited temporarily in soil and can be remobilised into rivers and seas. Given that rivers are a significant part of the mercury budget in the southern Baltic region (inland sea located in northern Europe) and meteorological changes (e.g. intense rain, drought) are observed more frequently, it is important to recognize the factors affecting the cycling of bioavailable Hg forms. The aim of this study was to identify the processes influencing the changes of labile and stabile mercury proportion in soil and the potential impact on the outflow of labile Hg into fluvial systems. For this purpose, soil samples, river sediments, and river water were collected from the Reda River (southern Baltic Sea catchment area) during the 2015 hydrologic year. The material was analysed for total and particulate mercury content and Hg forms, by a thermo-desorption method. The analysis showed that due to changes of meteorological and hydrological conditions Hg can enter rivers and then be introduced into the marine environment in various forms. On the one hand due to high precipitation events washing out of labile (i.e. bond with halogenides, MeHg, HgSO4), Hg forms into the river can be enhanced which affects increasing of availability of the most dangerous Hg form in the water systems. On the other hand the same event can cause the limitation of bioavailable mercury forms by a conversion of labile Hg into the most stable one (HgSO4 ➔ HgS) under anaerobic conditions.

Temporal changes in the content of labile and stabile mercury forms in soil and their inflow to the southern Baltic Sea.

Rivers represent the main source of mercury (Hg) in the Southern Baltic. Nevertheless, the concentration and proportion of individual Hg forms in rivers depend on the management of the river basin, as well as on the intensity of meteorological phenomena. Hence the aim of the present study was to determine the influence of drought and rains/intense rains on the content of labile and stable Hg forms in the soil of river catchments with various types of land management, and on the inflow of bioavailable mercury to the coastal zone of the sea. Soil and sediment samples were taken from two rivers flowing into Puck Bay (Southern Baltic): the Reda and Gizdepka. In order to determine Hg concentration and the proportions of its particular forms in the collected material, the thermo-desorption method was used. Five periods were identified during which the soil was enriched with various Hg forms. The obtained results showed that in periods of intensive development of vegetation, the soil becomes enriched with absorbed mercury (Hgabs). On the other hand, as a result of Hg emissions during the heating of buildings, mercury associated with halides (Hgads1) is deposited on land, as was primarily recorded in catchments where individual household furnaces were found. Both mild and intense rainfalls intensified the surface run-off, which contributed to soil erosion, causing the transport of both Hgabs and Hgads1 to the river bed. However, the soil was more enriched with labile mercury in anthropogenic catchments, as they are only slightly overgrown with vegetation, the presence of which limits soil erosion. During periods of snow melting, there was intensive leaching and transportation of Hgads1, which had been deposited on the land surface during the intensive combustion of fossil fuels. In each of the designated periods, stable mercury sulphide was formed in the soil. However, the highest proportion of HgS was found during a period of drought, when organic matter decomposed and there was inflow of sulphur compounds from farms. Taking into consideration the anomalous study periods, the largest load of mercury introduced along with the bed sediment of the Gizdepka into the sea was recorded during downpour/flood. Nevertheless, the most bioavailable Hg-enriched load was introduced during snow melting period.

Impact of hydrotechnical works on outflow of mercury from the riparian zone to a river and input to the sea.

The aim of this research was to assess the impact of hydrotechnical works within the riverbed and riparian zone on the mobility of mercury in soil and its outflow to the river and the sea. Deepening and reconstruction of the riverbed or the cutting of reeds, influenced the fate of mercury in the river system. However, only activitis that disturbed the riperian zone increased mobilization of Hg in soils. Hg transformations in these places were controled by inflow of fresh organic matter in soil and sediments as well as by oxidation-reduction potential. In areas where reducing conditions occurred, mercury released from the soil was incorporated into the sediment. However, in areas where oxidizing conditions prevailed in the sediment, mercury flowing out of the soil occurred mainly in dissolved form and most of it was transported downstream from where it could reach the sea.

Changes in total mercury, methylmercury, and selenium blood levels during different life history stages of the Baltic grey seal (Halichoerus grypus grypus).

Using the blood of grey seal pups, the blood and milk of female grey seals inhabiting the Hel Marine Station of Gdansk University's Institute of Oceanography (HMS), we monitored the transfer of total mercury (THg), methylmercury (MeHg), and selenium (Se) with blood during foetal life and nursing. Changes in the concentration of mercury and selenium were characterised in the pups' blood during their first three months of life when they transition from suckling, to a post-weaning fast, to eating fish. In the blood of pregnant females, there was a significant decrease in THg and MeHg concentrations throughout the gestation, indicating the transfer of these toxins through the placenta into the foetus. At no other stage of the pup's development was there such a high level of THg and MeHg as on the day of birth, despite the incorporation of mercury into the lanugo during foetal growth. This suggests that the maternal transfer of mercury during gestation may be the time of greatest mercury exposure for a young seal pup. The consumption of milk caused a rapid increase in weight and a lowering of the mercury level in the blood in the subsequent days of the pups' life. The postweaning fast was the period of the lowest mercury concentration. The switch to a diet consisting of fish caused a systematic increase in the concentration of mercury in the blood of the pups. Milk was the significant source of selenium for pups and the selenium concentration in females' blood was reduced during lactation. The nursing period seemed to have the greatest impact on the mercury and selenium blood levels in examined seals. Natural development of the grey seal pup created an opportunity to decrease the levels of toxic substances obtained through the maternal transfer during foetal growth.

137Cs and 40K in gray seals Halichoerus grypus in the southern Baltic Sea.

This study presents levels of 137Cs and 40K concentrations in the placentas of seals gathered in the period 2007-2015. The mean activity of 137Cs and 40K was 5.49 Bq kg-1w.w. and 136.6 Bq kg-1 ww respectively. Statistically significant correlation was observed between the 137Cs activities in placenta and in herring-the staple food for seals. The concentrations of 137Cs and 40K were also determined in other tissues (muscle, liver, lung, and brain) of wild seals. The concentrations of 137Cs were from 2.59 Bq-1 ww (lungs) to 24.3 Bq kg-1 ww (muscles). The transfer factor values for 137Cs (seal tissue/fish) ranged from 0.89 to 2.42 in the case of the placentas and from 1.35 to 8.17 in the case of the muscle. For adults seal, the effective dose from 137Cs was 2.98 nGy h-1. The mean external radiation dose to pup was 0.77 nGy h-1 from 137Cs and 6.69 nGy h-1 from 40K.

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.

The effect of land use in the catchment and meteorological conditions on the riverine transport of dissolved organic carbon into the Puck Lagoon (southern Baltic).

Dissolved organic carbon (DOC) concentration and fluxes from four rivers draining the catchment of the Puck Lagoon in southern Baltic are presented. Water samples from rivers and coastal zone close to the rivers' mouth were collected from April 2015 to March 2017. DOC was measured using high temperature catalytic oxidation with an NDIR detection. DOC concentration in rivers as well as area specific load discharged to the lagoon reflected variations of land use along their course. Area specific load of DOC discharged by rivers with high proportion of forests, meadows, and pastures in the catchment was significantly higher as compared to rivers with catchment dominated by arable land. However, the main controlling factor of the total discharged loads of DOC was the water flow. The highest loads were observed during the downpour. That was due to the larger volumes of water transported with rivers and the higher concentration of DOC resulting from increased leaching from the catchment area. The obtained results are especially important in the light of climate change in the southern Baltic region. According to the forecasts, we can expect increased precipitation and flooding and consequently increased leaching from the catchment and transport of DOC to the sea via rivers.