Can Bottom Sediments Be a Prospective Fertilizing Material? A Chemical Composition Analysis for Potential Reuse in Agriculture.

Every year, huge amounts of bottom sediments are extracted worldwide, which need to be disposed. The recycling of bottom sediments for soil fertilization is in line with the long-promoted circular economy policy and enables the use of micro and macronutrients accumulated in sediments for soil fertilization. When considering potential agricultural reuse of the dredge sediments, the first necessary step should be to analyze whether the heavy metal content meets the obligatory criteria. Then, the contents of valuable elements required for plant growth and their ratios should be assessed. In this study, the content of nitrogen, organic carbon, phosphorus, and potassium was tested and iron, sulfur, calcium, and magnesium were also analyzed along vertical profiles of sediments extracted from four urban retention tanks in Gdansk (Poland). The sediments were indicated to have a low content of nutrients (Ntot 0.01-0.52%, Corg 0.1-8.4%, P2O5 0.00-0.65%, K 0.0-1.0%), while being quite rich in Fe and S (0.2-3.3%, 0.0-2.5%, respectively). The C/N ratio changed in the range of 17.4-28.4, which proved good nitrogen availability for plants. The mean values of the Fe/P ratio were above 2.0, which confirms that phosphorus in the sediments would be available to the plants in the form of iron phosphate. To summarize, the bottom sediments from municipal retention reservoirs are not a perfect material for soil fertilization, but they are a free waste material which, when enriched with little cost, can be a good fertilizer. Future research should focus on cultivation experiments with the use of sediments enriched with N, P, Corg.

Acute aquatic toxicity of arsenic-based chemical warfare agents to Daphnia magna.

Sea dumping of chemical warfare (CW) took place worldwide during the 20th century. Submerged CW included metal bombs and casings that have been exposed for 50-100 years of corrosion and are now known to be leaking. Therefore, the arsenic-based chemical warfare agents (CWAs), pose a potential threat to the marine ecosystems. The aim of this research was to support a need for real-data measurements for accurate risk assessments and categorization of threats originating from submerged CWAs. This has been achieved by providing a broad insight into arsenic-based CWAs acute toxicity in aquatic ecosystems. Standard tests were performed to provide a solid foundation for acute aquatic toxicity threshold estimations of CWA: Lewisite, Adamsite, Clark I, phenyldichloroarsine (PDCA), CWA-related compounds: TPA, arsenic trichloride and four arsenic-based CWA degradation products. Despite their low solubility, during the 48 h exposure, all CWA caused highly negative effects on Daphnia magna. PDCA was very toxic with 48 h D. magna LC50 at 0.36 µg × L-1 and Lewisite with EC50 at 3.2 µg × L-1. Concentrations at which no immobilization effects were observed were slightly above the analytical Limits of Detection (LOD) and Quantification (LOQ). More water-soluble CWA degradation products showed no effects at concentrations up to 100 mg × L-1.

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.

Exposure status of sea-dumped chemical warfare agents in the Baltic Sea.

About 50 000 tons of chemical weapons (CW) were dumped to the Baltic Sea after the Second World War. Munitions are located in the deep areas of the Baltic Sea, and there they act as a point source of contamination to the ecosystem. Corroded munitions release chemical warfare agents (CWAs) to nearby water and sediments. In this study we investigated known dumpsites (Bornholm, Gotland and Gdansk Deep) and dispersed chemical munitions, to evaluate the extent of contamination of nearby sediments, as well as to assess the degradation process of released CWA. It was found that CWA-related phenylarsenic chemicals (Clark I, Clark II and Adamsite) and sulfur mustard are released to the sediments and undergo environmental degradation to chemicals, of which some remain toxic. The extent of pollution of released CWAs and their corresponding degradation products reaches more than 250 m from the CW objects, and seem to follow a power curve decrease of concentration from the source. Bornholm Deep is characterised with the highest concentration of CWAs in sediments, but occasional concentration peaks are also observed in the Gdansk Deep and close to dispersed munitions. Detailed investigation of spreading pattern show that the range of pollution depends on bottom currents and topography.

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.

Impact of intense rains and flooding on mercury riverine input to the coastal zone.

The aim of the present research was to determine the impact of intense rains and flooding on mercury riverine input to the coastal zone. This study focused on four small rivers (Reda, Zagórska Struga, Plutnica, Gizdepka), typical of the Southern Baltic region, with no significant mercury sources. Samples were collected for 16months during average flow conditions and during selected meteorological events: floods, downpours, thaws and droughts. Results showed decreased retention of mercury during intense rainfalls, thus demonstrating mercury elution from the catchment. Floods and melting snow also have a tremendous impact on the outflow of mercury from the catchment. Development of urban infrastructure and farmlands increases the outflow of mercury from the catchment too, making such areas a significant source of mercury in the river. On the other hand, areas with natural character, predominated by forests, stimulate retention of mercury that reaches them through dry and wet atmospheric deposition.

Deep sea habitats in the chemical warfare dumping areas of the Baltic Sea.

The Baltic Sea is a severely disturbed marine ecosystem that has previously been used as a dumping ground for Chemical Warfare Agents (CW). The presence of unexploded underwater ordnance is an additional risk factor for offshore activities and an environmental risk for the natural resources of the sea. In this paper, the focus is on descriptions of the marine habitat based on the observations arising from studies linked to the CHEMSEA, MODUM and DAIMON projects. Investigated areas of Bornholm, Gotland and Gdansk Deeps are similarly affected by the Baltic Sea eutrophication, however, at depths greater than 70m several differences in local hydrological regimes and pore-water heavy metal concentrations between those basins were observed. During the lifespan of presented studies, we were able to observe the effects of Major Baltic Inflow, that started in December 2014, on local biota and their habitats, especially in the Bornholm Deep area. Reappearance of several meiofauna taxa and one macrofauna specimen was observed approximately one year after this phenomenon, however it's ecological effects already disappeared in March 2017. According to our findings and to the EUNIS Habitat Classification, the three reviewed areas should be characterized as Deep Sea Muddy Sands, while the presence of suspicious bomb-like objects both beneath and on top of the sediments confirms their CW dumpsite status.

Mercury in the eggs of aquatic birds from the Gulf of Gdansk and Wloclawek Dam (Poland).

The aim of this paper was to assess the influence of diet on the concentrations of total mercury (HgTOT) in the eggs of aquatic birds. Trophic level was determined using stable isotopes (δ(15)N, δ(13)C). Analysis was carried out on eggs (laid in 2010-2012) belonging to two species of terns nesting at the River Vistula outlet on the Gulf of Gdansk and on herring gulls nesting both in Gdynia harbour and on the Vistula dam in Wloclawek. The results show that seafood diet causes the highest load of mercury, that which is transferred into terns eggs. The amounts of accumulated mercury obtained were found to be different in the particular egg components with Hgalbumen > Hgyolk > Hgmembrane > Hgshell. In the herring gull eggs, three stages of embryo development with varying levels of mercury were determined. It was observed that mercury received from the albumen and yolk was most effectively removed when developing embryo into down.

The impact of land use and season on the riverine transport of mercury into the marine coastal zone.

In Mediterranean seas and coastal zones, rivers can be the main source of mercury (Hg). Catchment management therefore affects the load of Hg reaching the sea with surface runoff. The major freshwater inflows to the Baltic Sea consist of large rivers. However, their systems are complex and identification of factors affecting the outflow of Hg from its catchments is difficult. For this reason, a study into the impact of watershed land use and season on mercury biogeochemistry and transport in rivers was performed along two small rivers which may be considered typical of the southern Baltic region. Neither of these rivers are currently impacted by industrial effluents, thus allowing assessment of the influence of catchment terrain and season on Hg geochemistry. The study was performed between June 2008 and May 2009 at 13 sampling points situated at different terrain types within the catchments (forest, wetland, agriculture and urban). Hg analyses were conducted by CVAFS. Arable land erosion was found to be an important source of Hg to the aquatic system, similar to urban areas. Furthermore, inflows of untreated storm water discharge resulted in a fivefold increase of Hg concentration in the rivers. The highest Hg concentration in the urban runoff was observed with the greatest amount of precipitation during summer. Moderate rainfalls enhance the inflow of bioavailable dissolved mercury into water bodies. Despite the lack of industrial effluents entering the rivers directly, the sub-catchments with anthropogenic land use were important sources of Hg in the rivers. This was caused by elution of metal, deposited in soils over the past decades, into the rivers. The obtained results are especially important in the light of recent environmental conscience regulations, enforcing the decrease of pollution by Baltic countries.