Precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans in Arctic and Antarctic marine sediments: Environmental concern in the face of climate change.

Polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/F) and their precursors - pentachlorophenol (PCP) and triclosan (TCS), constitute a group of persistent, highly toxic multimedia pollutants, being easily transported via atmosphere over long distances, thus particularly threatening to the polar areas. The global fate of PCDD/Fs is temperature-dependent, and their transfer and immobilization at the Poles are described by the grasshopper effect and the cold trap phenomenon. The aim of this interdisciplinary study was to perform a preliminary assessment of the present state of pollution of Arctic and Antarctic marine sediments by PCP and TCS along with determination of PCDD/Fs contamination by immunoassay. Sediments from 20 stations were collected during two polar expeditions (2013-2016). The study area covered Hornsund Fjord and the southwest coast of Wedel-Jarlsberg Land (Arctic) - Skodde Bay, Nottingham Bay, Isbjørnhamna Bay and Admiralty Bay (Antarctica) - Suszczewski Cove, Halfmoon Cove and Herve Cove. The studied contaminants were quantified in 60% of the collected sediments, with almost half exceeding the environmentally safe levels according European regulations and worldwide literature. The determined levels of PCP, TCS and PCDD/F in Arctic and Antarctic sediments were to be comparable to those reported in the southern Baltic Sea located in the intense industrialized mid-latitudes. Maximum concentrations were observed in the vicinity of retreating, marine terminating glaciers. This observation confirms reemission of POPs into the global cycle with respect to the worldwide ocean warming. The results of this study should gain attention of the international and regional environmental agencies as well as the main chlorine production decision makers.

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.

Toxicity assessment of sediments associated with the wreck of s/s Stuttgart in the Gulf of Gdansk (Poland).

The paper presents the results of toxicity determinations carried out on sediment samples collected in the vicinity of the wreck of the German s/s Stuttgart (the southern part of the Gulf of Gdansk, off the Polish coast) in relation to the determination of polycyclic aromatic hydrocarbons (PAHs). The toxicity of surface and core sediment samples was assessed using two biotest organisms-the bioluminescent bacteria Vibrio fischeri and the ostracod Heterocypris incongruens. PAH levels in these samples were determined by GC-MS. The surface sediments collected at W2 (ca. 34 m north of the shipwreck) and W4 (ca. 415 m north-east of the wreck) as well as the core sediments collected at WR3 (ca. 400 m north-east of the wreck) were the most heavily polluted with substances toxic to the biotest organisms. The chronic and acute toxicities in the case of most of the surface sediment samples studied are correlated. This may suggest that not only hydrophobic chemicals (like PAHs from fuel residues) but also more polar chemicals (resulting from the conversion of aromatic hydrocarbons) are responsible for the toxicity levels found. There is a clear dependence between the levels of chronic toxicity and PAH concentrations in the core sediment samples. In addition, a simultaneous decrease in the PAH content and chronic toxicity was noted in all the core sediment samples at depths below 80 cm.

Organotin compounds in surface sediments from seaports on the Gulf of Gdansk (southern Baltic coast).

Sediment samples were collected in two Polish ports of international significance--the Port of Gdansk and the Port of Gdynia (Gulf of Gdansk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdansk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.

The content of butyl- and phenyltin derivatives in the sediment from the Port of Gdansk.

Harbor sediments containing large deposits of organotin compounds constitute a potential threat to the marine environment. Samples of harbor sediments were collected twice in the years 2003 and 2005 from the following locations: Ziólkowskiego, Siarkowe, Wislane, Weglowe, Chemików and Paliw Plynnych Quays. The cores of 25cm length sliced into 2- and 5-cm segments were analyzed. After drying and homogenization, samples were split into two granulometric fractions, i.e. <2.00 and <0.063mm. The dominant fraction in whole sediment, i.e. fraction grain diameter <2.00mm, was sand (grain diameter 2.00-0.063mm). However, the highest concentrations of butyltin (BT) and phenyltin (PT) compounds were found in the fine sediment fraction. The mean values of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) in the analyzed samples in the <2.00mm fraction were 2144.9, 434.7 and 148.1ngSng(-1)d.w., respectively, while the corresponding mean values in the <0.063mm fraction were 6556.4, 1593.7 and 450.0ngSng(-1)d.w. The mean concentrations of monophenyltin (MPhT) have been estimated at 29.0 and 49.9ngSng(-1)d.w. for the <2.00 and <0.063mm fraction sizes, respectively. The estimated content levels of diphenyltin (DPhT) and triphenyltin (TPhT) were in most cases below the detection limit of the applied method. The sediment cores collected from the locations characterized by high industrialization and intense exploitation (Wislane, Weglowe Quays) contained the highest concentrations of BT and PT.