Persistent organic pollutants (POPs) pose a risk in aquatic environments. In sediment, this risk is frequently evaluated using total or organic carbon-normalized concentrations. However, complex physicochemical sediment characteristics affect POP bioavailability in sediment, making its prediction a challenging task. This task can be addressed using chemical activity, which describes a compound's environmentally effective concentration and can generally be approximated by the degree of saturation for each POP in its matrix. We present a proof of concept to load artificial sediments with POPs to reach a target chemical activity. This approach is envisioned to make laboratory ecotoxicological bioassays more reproducible and reduce the impact of sediment characteristics on the risk assessment. The approach uses a constantly replenished, saturated, aqueous POP solution to equilibrate the organic carbon fraction (e.g., peat) of an artificial sediment, which can be further adjusted to target chemical activities by mixing with clean peat. We demonstrate the applicability of this approach using four polycyclic aromatic hydrocarbons (acenaphthene, fluorene, phenanthrene, and fluoranthene). Within 5 to 17 weeks, the peat slurry reached a chemical equilibrium with the saturated loading solution. We used two different peat batches (subsamples from the same source) to evaluate the approach. Variations in loading kinetics and eventual equilibrium concentrations were evident between the batches, which highlights the impact of even minor disparities in organic carbon properties within two samples of peat originating from the same source. This finding underlines the importance of moving away from sediment risk assessments based on total concentrations. The value of the chemical activity-based loading approach lies in its ability to anticipate similar environmental impacts, even with varying contaminant concentrations. 

Artificial sweeteners are widely used in food and pharmaceuticals, but their stability and persistence raise concerns about their impact on aquatic life. Although standard toxicity tests do not reveal lethal effects, recent studies suggest a potential neurotoxic mode of action. Using environmentally relevant concentrations, we assessed the effects of sucralose and acesulfame, common sugar substitutes, on Daphnia magna focusing on biochemical (acetylcholinesterase activity; AChE), physiological (heart rate), and behavioural (swimming) endpoints. We found dose-dependent increases in AChE and inhibitory effects on heart rate and behaviour for both substances. Moreover, acesulfame induced a biphasic response in AChE activity, inhibiting it at lower concentrations and stimulating at higher ones. For all endpoints, the EC₅₀ values were lower for acesulfame than for sucralose. Additionally, the relationship between acetylcholinesterase and heart rate differed depending on the substance, suggesting possible differences in the mode of action between sucralose and acesulfame. All observed EC₅₀ values were at μg/l levels, i.e., within the levels reported for wastewater, with adverse effects observed at as low as 0.1 μg acesulfame /l. Our findings emphasise the need to re-evaluate risk assessment thresholds for artificial sweeteners and provide evidence for the neurotoxic effects of artificial sweeteners in the environment, informing international regulatory standards.

To ensure sustainable use of antifouling paints, the European Union have developed a new environmental risk assessment tool, which a product must pass prior to its placement on the market. In this new tool, environmental concentrations are predicted based on estimated release rates of biocides to the aquatic environment and risk characterization ratios are calculated in regional spreadsheets. There are currently two methods in use to predict release rates of biocides; a calculation method and a laboratory method. These methods have been believed to overestimate environmental release of biocides and therefore fixed correction factors to reduce the release rate can be applied. An alternative method, known as the XRF method, has recently been developed and used to derive field release rates from antifouling paints. The aim of this study was to review the new environmental risk assessment tool and assess how the choice of release rate method and application of correction factors impact the approval of antifouling paint products. Eight coatings were environmentally risk assessed for usage in four European marine regions; Baltic, Baltic Transition, Atlantic and Mediterranean; by applying release rates of copper and zinc determined with the different methods. The results showed none of the coatings to pass the environmental risk assessment in the Baltic, Baltic Transition and the Mediterranean if field release rates were used. In contrast, most of the coatings passed if the correction factors were applied on the release rates obtained with the calculation or laboratory method. The results demonstrate the importance of release rate method choice on the outcome of antifouling product approval in EU. To reduce the impact of antifouling paints on the marine environment it is recommended that no correction factors should be allowed in the environmental risk assessment or preferably that site-specific field release rates are used. If the regulation in the European Union (and elsewhere) continues to allow correction factors, the pressure of biocides to the environment from leisure boating will result in degradation of marine ecosystems.

Antifouling paints are biocidal products applied to ship and boat hulls in order to prevent the growth and settlement of marine organisms, i.e. fouling. The release of biocides from the surface of the paint film act to repel or poison potential settling organisms. Currently, the most commonly used biocide in antifouling paints is cuprous oxide. In the EU, antifouling products are regulated under the Biocidal Products Regulation (BPR), which states that the recommended dose should be the minimum necessary to achieve the desired effect. For antifouling products, the dose is measured as the release rate of biocide(s) from coating. In this study, the release rates of copper and zinc from eight different coatings for leisure boats were determined through static exposure of coated panels in four different harbors located in Swedish waters along a salinity gradient ranging from 0 to 27 PSU. The results showed the release rate of copper to increase with increasing salinity. Paints with a higher content of cuprous oxide were also found to release larger amounts of copper. The coatings' ability to prevent biofouling was also evaluated and no significant difference in efficacy between the eight tested products was observed at the brackish and marine sites. Hence, the products with high release rates of copper were equally efficient as those with 4 - 6 times lower releases. These findings suggest that current antifouling paints on the market are leaching copper in excess of the effective dose in brackish and marine waters. Additionally, the results from the freshwater site showed no benefit in applying a copper-containing paint for the purpose of fouling prevention. This indicates that the use of biocidal paints in freshwater bodies potentially results in an unnecessary release of copper. By reducing the release rates of copper from antifouling paints in marine waters and restricting the use of biocidal paints in freshwater, the load of copper to the environment could be substantially reduced.

The seasonal variations of dissolved and bioavailable copper (Cu) and zinc (Zn) were studied in two recreational marinas in Sweden and Finland. The time series from the two marinas were characterized by rising concentrations during the spring boat launching, elevated concentrations all through the peak boating season, and decreasing concentrations in autumn when boats were retrieved for winter storage. This pattern shows a clear link between Cu and Zn concentrations and boating activity, with antifouling paints as the principal source. The leaching from antifouling paints was also found to significantly alter the speciation of dissolved Cu and Zn in marina waters, with an increase of the proportion of metals that may be considered bioavailable. This change in speciation, which occurred without any change in dissolved organic carbon (DOC), further increases the environmental risk posed by antifouling paints. In the Swedish marina, dissolved Cu and Zn exceed both Environmental Quality Standards (EQS) and Predicted No Effect Concentrations (PNEC), indicating that the current Swedish risk assessment (RA) of antifouling paints is failing to adequately protect the marine environment. An evaluation of the RA performance showed the underlying cause to be an underestimation of the predicted environmental concentration (PEC) by factors of 2 and 5 for Cu and Zn, respectively. For both metals, the use of inaccurate release rates for the PEC derivation was found to be either mainly (Cu) or partly (Zn) responsible for the underestimation. For Zn, the largest source of error seems to be the use of an inappropriate partitioning coefficient (K-D) in the model. To ensure that the use of antifouling coatings does not adversely impact the sensitive Baltic Sea, it is thus recommended that the K-D value for Zn is revised and that representative release rates are used in the RA procedure.

Over two million leisure boats use the coastal areas of the Baltic Sea for recreational purposes. The majority of these boats are painted with toxic antifouling paints that release biocides into the coastal ecosystems and negatively impact non-targeted species. Regulations concerning the use of antifouling paints differ dramatically between countries bordering the Baltic Sea and most of them lack the support of biological data. In the present study, we collected data on biofouling in 17 marinas along the Baltic Sea coast during three consecutive boating seasons (May-October 2014, 2015 and 2016). In this context, we compared different monitoring strategies and developed a fouling index (FI) to characterise marinas according to the recorded biofouling abundance and type (defined according to the hardness and strength of attachment to the substrate). Lower FI values, i.e. softer and/ or less abundant biofouling, were consistently observed in marinas in the northern Baltic Sea. The decrease in FI from the south-western to the northern Baltic Sea was partially explained by the concomitant decrease in salinity. Nevertheless, most of the observed changes in biofouling seemed to be determined by local factors and interannual variability, which emphasizes the necessity for systematic monitoring of biofouling by end-users and/or authorities for the effective implementation of non-toxic antifouling alternatives in marinas. Based on the obtained results, we discuss how monitoring programs and other related measures can be used to support adaptive management strategies towards more sustainable antifouling practices in the Baltic Sea.

In the present study a recently developed benthic flow-through chamber was used to assess the sediment-to-water flux of polycyclic aromatic hydrocarbons (PAHs) at 4 sites on the Swedish Baltic Sea coast. The flow-through chamber allows for assessment of the potential effect of bioturbation on the sediment-to-water flux of hydrophobic organic contaminants. The sediments at the 4 investigated sites have both varying contamination degree and densities of bioturbating organisms. The flux of individual PAHs measured with the flow-through chamber ranged between 21 and 510, 11 and 370, 3 and 9700, and 62 and 2300 ng m(-2) d(-1) for the 4 sites. To assess the potential effect of bioturbation on the sediment-to-water flux, 3 flow-through and closed chambers were deployed in parallel at each site. The activity of benthic organisms is attenuated or halted because of depletion of oxygen in closed benthic chambers. Therefore, the discrepancy in flux measured with the 2 different chamber designs was used as an indication of a possible effect of bioturbation. A potential effect of bioturbation on the sediment-to-water flux by a factor of 3 to 55 was observed at sites with a high density of bioturbating organisms (e.g., Marenzelleria spp., Monoporeia affinis, and Macoma balthica of approximately 860-1200 individuals m(-2)) but not at the site with much lower organism density (<200 individuals m(-2)). One site had a high organism density and a low potential effect of bioturbation, which we hypothesize to be caused by the dominance of oligochaetes/polychaetes at this site because worms (Marenzelleria spp.) reach deeper into the sediment than native crustaceans and mollusks.

Anthropogenic pressures, such as contaminant exposure, may affect stable isotope ratios in biota. These changes are driven by alterations in the nutrient allocation and metabolic pathways induced by specific stressors. In a controlled microcosm study with the amphipod Gammarus spp., we studied effects of the beta-blocker propranolol on stable isotope signatures (delta N-15 and delta C-13), elemental composition (%C and %N), and growth (protein content and body size) as well as biomarkers of oxidative status (antioxidant capacity, ORAC; lipid peroxidation, TBARS) and neurological activity (acetylcholinesterase, AChE). Based on the known effects of propranolol exposure on cellular functions, i.e., its mode of action (MOA), we expected to observe a lower scope for growth, accompanied by a decrease in protein deposition, oxidative processes and AChE inhibition, with a resulting increase in the isotopic signatures. The observed responses in growth, biochemical and elemental variables supported most of these predictions. In particular, an increase in %N was observed in the propranolol exposures, whereas both protein allocation and body size declined. Moreover, both ORAC and TBARS levels decreased with increasing propranolol concentration, with the decrease being more pronounced for TBARS, which indicates the prevalence of the antioxidative processes. These changes resulted in a significant increase of the delta N-15 and delta C-13 values in the propranolol-exposed animals compared to the control. These findings suggest that MOA of beta-blockers may be used to predict sublethal effects in non-target species, including inhibited AChE activity, improved oxidative balance, and elevated stable isotope ratios. The latter also indicates that metabolism-driven responses to environmental contaminants can alter stable isotope signatures, which should be taken into account when interpreting trophic interactions in the food webs.

The release of harmful metals from antifouling paints to water bodies is a well-known problem. In this study, we measured both the amount of biofouling growth on leisure boats during one season as well as the concentration of metals accumulated by the biofouling matrix. Furthermore, the efficiency of antifouling paints and mechanical boat cleaning as well as the effect of hull colour on biofouling were evaluated. Unlike paint residues, biofouling waste has never been regarded as a source of metal contamination and has previously been neglected in the scientific literature. Our results revealed that the biofouling waste contained very high concentrations of metals, up to 28,000 mg copper/kg dw and 171,000 mg zinc/kg dw, which exceeds the guidance values for least sensitive land use in Sweden by factors of 140 and 340, respectively. This observation is important because the contaminated biofouling waste is commonly disposed of in boatyard soils at the end of each season, thus increasing the levels of metal pollution. Moreover, there was no significant difference in the amount of biofouling if the boats were coated with copper or zinc containing paints or no paint at all, indicating that biocide paints might not be necessary in low-salinity areas such as the Stockholm archipelago. For boats that were not painted at all during the season, those washed on boat washers (mechanically) had on average half of the amount of biofouling compared to boats that were not cleaned mechanically. The results of the study indicate the importance of proper management of biofouling waste as well as the use of more environmentally friendly removal methods for biofouling such as boat washers.

Contaminated sediment can release hydrophobic organic contaminants (HOCs) and thereby act as a secondary source of primarily legacy hazardous substances to the water column. There is therefore a need for assessments of the release of HOCs from contaminated sediment for prioritization of management actions. In situ assessment of HOC sediment-to-water flux is currently done with (closed) benthic flux chambers, which have a sampling time exceeding one month. During this time, the water inside the chamber is depleted of oxygen and the effect of bioturbation on the sediment-to-water release of HOCs is largely ignored. Here we present a novel benthic flux chamber, which measures sediment-to-water flux of legacy HOCs within days, and includes the effect of bioturbation since ambient oxygen levels inside the chamber are maintained by continuous pumping of water through the chamber. This chamber design allows for sediment-to-water flux measurements under more natural conditions. The chamber design was tested in a contaminated Baltic Sea bay. Measured fluxes were 62–2300 ng m⁻² d⁻¹ for individual polycyclic aromatic hydrocarbons (PAHs), and 5.5–150 ng m⁻² d⁻¹ for polychlorinated biphenyls (PCBs). These fluxes were 3–23 times (PAHs) and 12–74 times (PCBs) higher than fluxes measured with closed benthic chambers deployed in parallel at the same location. We hypothesize that the observed difference in HOC flux between the two chamber designs are partly an effect of bioturbation. This hypothesized effect of bioturbation was in accordance with literature data from experimental studies.