Bird guano and the faeces of marine mammals appear to be a significant yet undisclosed biotransporter of Endocrine Disrupting Compounds in the marine environment. The authors determined the concentration of bisphenol A (BPA), 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) removed from birds and seals in their droppings into the coastal zone of the Gulf of Gdansk (Southern Baltic Sea).The research was carried out on samples of bird guano collected during the breeding season and after in 2016 at nesting sites, as well as on faecal samples from grey seals (Halichoerus grypus grypus) living in the Seal Centre of the Marine Station in Hel between 2014 and 2018. Measurements were carried out using high performance chromatography with fluorescence detector. Results have shown that the presence of seabird habitats and grey seal colonies in the coastal zone of the Gulf of Gdansk can have an impact on the pollution of the seashore (beach sand, bottom sediment and surface seawater) with phenol derivatives. The concentrations of BPA, 4-t-OP and 4-NP ranged from 0.1 to 32.97 ng∙g⁻¹dw in sediment and beach sand, and from 0.23 to over 800 ng dm⁻³ in seawater. In the cases of bisphenol A and 4-tert-octylphenol safe concentration levels in the waters were exceeded. Bisphenol A concentrations were almost always found to be the highest. This was also noted in bird guano and seal faeces, although it was found to be much higher in the seal faeces - average 10149.79 ng g⁻¹ dw, than in bird guano. An experiment conducted to assess BPA, 4-t-OP, 4-NP leaching from bird guano and seal faeces into seawater, also confirmed the importance of animal excrement in the circulation of these compounds in the marine ecosystem. The highest % of leaching related to BPA was noted at 20 °C and reached 84%. The lowest % of leaching was for 4-nonylphenol (44%).

The release of copper (Cu) and zinc (Zn) from vessels and leisure crafts coated with antifouling paints can pose a threat to water quality in semi-enclosed areas such as harbors and marinas as well as to coastal archipelagos. However, no reliable, practical and low-cost method exists to measure the direct release of metals from antifouling paints. Therefore, the paint industry and regulatory authorities are obliged to use release rate measurements derived from either mathematical models or from laboratory studies. To bridge this gap, we have developed a novel method using a handheld X-Ray Fluorescence spectrometer (XRF) to determine the cumulative release of Cu and Zn from antifouling paints. The results showed a strong linear relationship between XRF Kα net intensities and metal concentrations, as determined by ICP-MS. The release of Cu and Zn were determined for coated panels exposed in harbors located in the Baltic Sea and in Kattegat. The field study showed salinity to have a strong impact on the release of Cu, i.e. the release increased with salinity. Contrary, the effect of salinity on Zn was not as evident. As exemplified in this work, the XRF method also makes it possible to identify the governing parameters to the release of Cu and Zn, e.g. salinity and type of paint formulation. Thus, the XRF method can be used to measure environmentally relevant releases of metallic compounds to design more efficient and optimized antifouling coatings.

Despite their ban on small vessels in 1989 in the EU, organotin compounds (OTCs) are still being released into the environment due to their presence in historic paint layers on leisure boats. 23 paint samples scraped from recreational boats from three countries around the Baltic Sea were analyzed for total tin (Sn) and OTCs. Two antifouling paint products were also subjected to the same analyses. A new method for the detection of Sn in paint flake samples was developed and found to yield more accurate results compared to four different acid digestion methods. A new method was also developed for the extraction of OTCs from ground paint flakes. This endeavor revealed that existing methods for organotin analysis of sediment may not have full recoveries of OTCs if paint flakes are present in the sample. The hull paint samples had Sn concentrations ranging from 25 to 18,000 mg/kg paint and results showed that tributyltin (TBT) was detected in all samples with concentrations as high as 4.7 g (as Sn)/kg paint. TBT was however not always the major OTC. Triphenyltin (TPhT) was abundant in many samples, especially in those originating from Finland. Several other compounds such as monobutyltin (MBT), dibutyltin (DBT), tetrabutyltin (TeBT), monophenyltin (MPhT) and diphenyltin (DPhT) were also detected. These could be the result of degradation occurring on the hull or of impurities in the paint products as they were also identified in the two analyzed paint products. A linear correlation (r2 = 0.934) was found between the total tin content and the sum of all detected OTCs. The detection of tin can therefore be used to indicate the presence of OTCs on leisure boats.

Leachates of anti-fouling paints for use on ships and leisure boats are examined for their ecotoxicological potential. Paint leachates were produced in both 7‰ artificial (ASW) and natural seawater (NSW) and tested on three organisms, the bacterium Vibrio fischeri, the macroalga Ceramium tenuicorne, and the crustacean Nitocra spinipes. Generally, leaching in ASW produced a more toxic leachate and was up to 12 times more toxic to the organisms than was the corresponding NSW leachate. The toxicity could be explained by elevated concentrations of Cu and Zn in the ASW leachates. Of the NSW leachates, those from the ship paints were more toxic than those from leisure boat paints. The most toxic paint was the biocide-free leisure boat paint Micron Eco. This implies that substances other than added active agents (biocides) were responsible for the observed toxicity, which would not have been discovered without the use of biological tests. Leachate from a biocide-free anti-fouling paint for leisure boat use was more toxic than leachates from ship paints.

Decades of intensive discharge from industrial activities into coastal systems has resulted in the accumulation of a variety of persistent organic pollutants (POPs) in marine waters and sediments, having detrimental impacts on aquatic ecosystems and the resident biota. POPs are among the most hazardous chemicals originating from industrial activities due to their biotoxicity and resistance to environmental degradation. Bacterial communities are known to break down many of these aromatic compounds, and different members of naturally occurring bacterial consortia have been described to work in syntrophic association to thrive in heavily contaminated waters and sediments, making them potential candidates as bioindicators of environmental pollution. In this study environmental, sampling was combined with chemical analysis of pollutants and high-resolution sequencing of bacterial communities using Next Generation Sequencing molecular biology tools. The aim of the present study was to describe the bacterial communities from marine sediments containing high loads of POPs and to identify relevant members of the resident microbial communities that may act as bioindicators of contamination. Marine sediments were collected from a coastal bay area of the Baltic Sea historically influenced by intense industrial activity, including metal smelting, oil processing, and pulp and paper production. Different types of POPs were detected at high concentrations. Fiberbank sediments, resulting from historic paper industry activity, were found to harbour a clearly distinct bacterial community including a number of bacterial taxa capable of cellulolytic and dechlorination activities. Our findings indicate that specific members of the bacterial communities thrive under increasing levels of POPs in marine sediments, and that the abundances of certain taxa correlate with specific POPs (or groups), which could potentially be employed in monitoring, status assessment and environmental management purposes.

Edible cod liver products including cod liver oil and canned cod liver, sampled over the last five decades from the North Atlantic region, including the Baltic Sea were analysed for a set of persistent and toxicologically significant polychlorinated naphthalene (PCN) congeners with some of the highest relative potencies (dioxin-like toxicity) among PCNs. The targeted congeners showed a near-universality of occurrence in all samples apart from the most recent sample of cod liver oil which was assumed to be highly purified, as cod livers from the same period and location showed appreciable amounts of PCNs. The majority of dominant congeners in legacy technical PCN mixtures were absent or occurred in low concentrations, raising the possibility that congeners arising from combustion related sources may be acquiring a greater significance following the decline and elimination of PCN production. The apparent appreciation in the relative amounts of PCN#70 in the last three to four decades may provide support for this view. The PCN contribution to dioxin-like toxic equivalence (TEQ) that was estimated for these samples (range 1.2–15.9 pg TEQ g⁻¹) was significant in comparison to the EU regulated value of 1.75 pg TEQ g⁻¹ for dioxins in fish oils. Most of the TEQ was associated with PCNs 66/67, 64/68, 69 and 73. Although metabolic processes are likely to influence this distribution, the profile is a little different to that observed in the tissues of higher order animals where PCNs #66/67 and #73 may contribute approximately 90% to the summed TEQ.

Levels of neurotoxic methylmercury (MeHg) in phytoplankton are strongly associated to water MeHg concentrations. Because uptake by phytoplankton is the first and largest step of bioaccumulation in aquatic food webs many studies have investigated factors controlling seasonal changes in water MeHg concentrations. However organic matter (OM), widely accepted as an important driver of MeHg production and uptake by phytoplankton, is known for strong interannual variability in concentrations and composition within systems. In this study, we explore the role of OM on spatial and interannual variability of MeHg in a subarctic coastal sea, the northern Baltic Sea. Using MeHg (2014: 80 ± 25 fM; 2015: <LOD fM; 2016: 21 ± 9 fM) and OM measurements during late summer/early fall, we find that dissolved organic carbon (DOC) and humic matter content explain 60% of MeHg variability. We find that while labile DOC increases MeHg levels in the water, humic content reduces it. We propose that the positive association between MeHg and labile DOC shows that labile DOC is a proxy for OM remineralization rate in nearshore and offshore waters. This is consistent with other studies finding that in situ MeHg production in the water column occurs during OM remineralization. The negative association between water humic content and MeHg concentration is most likely due to humic matter decreasing inorganic mercury (HgII) bioavailability to methylating microbes. With these relationships, we develop a statistical model and use it to calculate MeHg concentrations in late summer nearshore and offshore waters between 2006 and 2016 using measured values for water DOC and humic matter content. We find that MeHg concentrations can vary by up to an order of magnitude between years, highlighting the importance of considering interannual variability in water column MeHg concentrations when interpreting both short and long term MeHg trends in biota.

Polyurethane foam (PUF) disk passive samplers were deployed at one inland and two island locations in the Bothnian Bay region of the northern Baltic Sea. Uptake was linear over 81–147 d and a temperature range of −2.6 to 14.2 °C for organochlorine pesticides (OCPs) and current-use pesticides (CUPs) having log KOA ≥9 at ambient temperatures. Partial saturation of the PUF disks occurred for the more volatile OCPs hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB), and for bromoanisoles (BAs), which are products of bromophenols released by natural and anthropogenic sources. Correction for nonlinear uptake of these was made using experimentally measured PUF-air partition coefficients. Passive-derived air concentrations of pesticides were uniform over the bay and agreed within a factor of 2 or better with levels determined by active (pumped) sampling at one of the island stations. Levels of OCPs were similar to those reported at background sites in the European and Canadian Arctic and at monitoring stations in the central Baltic and southern Scandinavia, indicating long-range transport. The insecticide chlorpyrifos was 10 times lower at bay stations than in the Canadian Arctic. Insight to sources and processes was gained by examining compound profiles. Fractions Falpha = α-HCH/(α-HCH + γ-HCH) and FTC = trans-chlordane/(trans-chlordane + cis-chlordane) at bay stations were higher than in the Norwegian and Finnish Arctic and similar to those at the southern monitoring stations. Volatilization of chlordanes from Baltic seawater may also modify FTC. Higher FTriBA = 2,4,6-TriBA/(2,4,6-TriBA + 2,4-DiBA) distinguished local volatilization from the Baltic Sea versus lower FTriBA found at the inland site and reported in air on the Norwegian coast, suggesting westerly transport from the Atlantic across Norway and Sweden.

Endocrine disrupting compounds (EDCs) like bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP) are introduced to the trophic webs through among others phytoplankton. This paper describes BPA, OP and NP concentrations in phytoplankton in the Gulf of Gdansk (Southern Baltic Sea) in the years 2011–2012. The assays of BPA, OP and NP in samples were performed using HPLC with fluorescence detection. The concentrations of BPA, the most commonly used of the three compounds, were over ten times higher than OP and NP concentrations. The concentrations of the studied EDCs in phytoplankton from the Gulf of Gdansk depended on anthropogenic factors and on phytoplankton properties (species composition, biomass, volume). An increase in phytoplankton biomass did not always result in an increase of BPA, OP and NP concentrations. However, the load of the studied EDCs accumulated in phytoplankton biomass increase with a rise of biomass. An increase in BPA, OP and NP concentrations was effected by biomass growth and the proportions ofciliates, dinoflagellates, diatoms and green algae. A strong positive correlation between OP and NP concentrations and negative correlation between BPA concentrations and biomass of organisms with cells measuring <1000 μm3 in volume results from the differing properties of these compounds.

Hexabromocyclododecane (HBCDD) is an additive brominated flame retardant and a recognized PBT chemical. However, little is known about its effects on coastal species, and even less on ecosystem effects. We investigated the dose–response effects of HBCDD over 8 months in 1000 L experimental mesocosms assembled from coastal Baltic Sea ecosystem components. HBCDD was added via spiked plankton material and a range of structural and functional endpoints were measured during the experiment. Increasing HBCDD concentration decreased the biomass of large Macoma balthica, resulting in a decreased recirculation of nutrients to the water. Changes in plankton communities were also observed, either due to direct toxic HBCDD effects or indirect via changes in benthic-pelagic coupling of nutrients. Such complex ecosystem responses can only be quantified and understood by using realistic experimental set-ups, and including knowledge of system-specific ecological interactions. This is the first study of HBCDD effects on ecosystem level.