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. 

While chronic acidification of water bodies has been steadily decreasing, episodic acidification continues to affect stream biology by temporarily decreasing pH and mobilizing aluminum. These events are becoming more common as climate change renders more frequent and intense storms and flooding. Throughout Scandinavia, the effects of acidification have been mitigated by liming since the 1980s, but remediation efforts can now be reduced. While transient acidity may reduce fish populations, also other species in streams are affected. In this in-stream study, two macro-invertebrates (Gammarus pulex and Baetis rhodani), both known as salmonid prey organisms, were exposed to snowmelt in six humic brooks with a natural gradient of pH and inorganic monomeric Al (Al-i). We hypothesize that acid toxicity thresholds can be defined using lethal (mortality) and sublethal (changes in body elemental content) metrics. Periodic observations were made of mortality and whole body concentrations of base cations (BC: Ca, Mg, Na and K) and metals (Al, Fe, Zn and Mn). Mortality increased dramatically at pH < 6.0 and Al-i > 15 mu g/L for G. pulex and at pH < 5.7 and Al-i > 20 mu g/L for B. rhodani. No accumulation of Al was found. The invertebrate body Na concentration decreased when pH dropped, suggesting that osmoregulation in both species was affected. In contrast to general BC pattern, Ca concentration in G. pulex and Mg concentration in B. rhodani increased when pH decreased. Although Ali strongly correlates to pH, the Al composition of soil and bedrock also influences Al availability, potentially contributing to toxic Al; episodes. The estimated values calculated in this study can be used to improve water quality criteria and as thresholds to adjust doses of lime compared to old recommendations in ongoing liming programs. Such adjustments may be critical since both Ali and pH levels have to be balanced to mitigate damage to recovering stream ecosystems.

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.

Harbours with limited water exchange are hotspots of contaminant accumulation. Antifouling paints (AF) contribute to this accumulation by leaching biocides that may affect non-target species. In several leisure boat harbours and reference areas in the Baltic Sea, chronic exposure effects were evaluated using caging experiments with the snail Theodoxus fluviatilis. We analysed variations in ecologically relevant endpoints (mortality, growth and reproduction) in concert with variation in metallothionein-like proteins (MTLP) levels. The latter is a biomarker of exposure to metals, such as copper (Cu) and zinc (Zn), which are used in AF paints as active ingredient and stabilizer, respectively. In addition, environmental samples (water, sediment) were analysed for metal (Cu and Zn) and nutrient (total phosphorous and nitrogen) concentrations. All life-history endpoints were negatively affected by the exposure, with higher mortality, reduced growth and lower fecundity in the harbours compared to the reference sites. Metal concentrations were the key explanatory variables for all observed adverse effects, suggesting that metal-driven toxicity, which is likely to stem from AF paints, is a source of anthropogenic stress for biota in the harbours.

Contaminants are important stressors in the aquatic environment and may exert selective pressures on organisms. We hypothesized that snails originating from a metal-contaminated habitat (B) would have increased tolerance to harbour contaminants (e.g. metals from antifouling paints), compared to snails originating from a relatively clean habitat (A). We assessed tolerance to metals in terms of survival and histopathological alterations after 2, 4 and 8 weeks of in situ exposure in three Baltic Sea boat harbours and three reference sites. We also hypothesized that any potential tolerance to contaminants would be associated with differences in genetic diversity between the two snail populations (evaluated as mitochondrial cytochrome c oxidase subunit I, COI). The results show that snails from population A survived to a higher extent compared to population B, possibly indicating either a lack of adaptation to metals in snails B or impaired health condition due to contaminant pre-exposure or a higher resilience of snails A. Moreover, the genetic diversity of COI was low within each population and did not differ between populations. In general, 83% of all the types of histopathological alterations (e.g. lysis and necrosis of gonads and digestive gland or granulocytoma and phagocytosis in the storage tissue, among others) had a higher probability of occurrence among harbour-exposed snails compared to reference exposed snails, regardless of snail population origin. The only significant difference in histological effects between the two populations was in the frequency of parasite infestations and shell fouling, both being larger for population A than B. Interestingly, the rate of parasite infestations was higher for males than females from population A, whereas no sexual dichotomy was observed for population B. Our results show that exposure to harbour contaminants causes both lethal and sublethal toxicity to snails, and the association between many of the toxic responses and metals substantiates that antifouling substances contribute to the observed effects, although there is a large proportion of variation in our data that remains unexplained.

Climate change has been suggested to lead to higher temperature and increased heterotrophy in aquatic systems. The aim of this study was to test how these two factors affect metazooplankton and food web efficiency (FWE was defined as metazooplankton production divided by basal production). We tested the following hypotheses: (1) that lower metazooplankton production and lower FWE would be found in a food web based on heterotrophic production (bacteria) relative to one based on autotrophic production (phytoplankton), since the former induces a larger number of trophic levels; (2) the metazooplankton in the heterotrophic food web would contain less essential fatty acids than those from the autotrophic food web; and (3) that higher temperature would lead to increased FWE. To test these hypotheses, a mesocosm experiment was established at two different temperatures (5 and 10A degrees C) with a dominance of either autotrophic (NP) or heterotrophic basal production (CNP). Metazooplankton production increased with temperature, but was not significantly affected by differences in basal production. However, increased heterotrophy did lead to decreased fatty acid content and lower individual weight in the zooplankton. FWE increased with autotrophy and temperature in the following order: 5CNP < 10CNP < 5NP < 10NP. Our results indicate that in the climate change scenario we considered, the temperature will have a positive effect on FWE, whereas the increase in heterotrophy will have a negative effect on FWE. Furthermore, the quality and individual weight of the metazooplankton will be reduced, with possible negative effects on higher trophic levels.

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.

This investigation set out to analyze the toxicity of surface sediments in a number of natural harbors and small boat harbors on the west coast of Sweden. This was done with the growth inhibition method with Ceramium tenuicorne. Also, concentrations of copper (Cu), lead (Pb), zinc (Zn), irgarol, organotin compounds, and polycyclic aromatic hydrocarbons (PAHs) in the sediments were analyzed. The small boat harbors were heavily polluted by Cu, Zn, butyltins, and PAHs, and to a lesser extent by Pb. The Cu, Pb, Zn, and butyltins probably originated from their past and/or present use in antifouling paints, whereas the PAHs probably had multiple sources, including boat motor exhausts. The measured toxicity of the sediment was generally related to their Cu, Zn, and butyltin content, although other toxic substances than those analyzed here probably contributed to the toxicity in some of the harbors. The natural harbor sediments contained less pollutants and were less toxic than the small boat harbor sediments. Nevertheless, our data indicate that the boating pressure today may be high enough to produce toxic effects even in natural harbors in pristine areas. The strongest relationship between toxicity and the major pollutants was obtained when the sediment toxicity was expressed as gram wet weight per liter compared with gram dry weight per liter and gram total organic carbon per liter. Hence, for pollutants that can be elutriated with natural sea water, sediment toxicity expressed as gram wet weight per liter appears preferable.

During the last two decades major changes of the benthic fauna have occurred in the northern Baltic Sea, the Gulf of Bothnia. The native amphipod, Monoporeia affinis, has shown a large-scale abundance decrease, while polychaetes, Marenzelleria spp. have invaded the system. Marenzelleria co-exist with the native fauna in the southern Baltic Sea, but in the north the pelagic production might be too low to allow co-existence. Thus, M. affinis might have been out-competed by Marenzelleria in the Gulf of Bothnia. This hypothesis was tested in a competition experiment with a high and a low fresh phytoplankton food supply. When exposed to high food supply both species showed stable or increased biomass over the four week test period. In low food supply, however, M. affinis was found to have a competitive advantage. The experimental data were also related to Baltic Sea monitoring data on primary production, sedimentation and invertebrate abundances. Data from the northern Baltic Sea show that the dominance in the benthic community by M. affinis was replaced by Marenzelleria around 2001. The amphipod decrease might be explained by a marked decrease in primary production during this period. Combining monitoring and experimental data suggests that the invasion of Marenzelleria did not cause the decrease of M. affinis in the northern Baltic Sea; it rather took advantage of the density gap that had occurred. A shift may thus have been established in the Bothnian Sea benthic community.

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.

Gammarus spp. and Fucus vesiculosus from the Baltic Sea littoral community were exposed to 3 concentrations of the pharmaceuticals ibuprofen and propranolol. Both physiological and behavioural parameters were measured to examine potential effects in the organisms. For Gammarus spp., respiration, feeding rate and activity with and without predator cues were measured, and gross production to respiration ratio (GP/R) and chlorophyll fluorescence were measured for F. vesiculosus. The results showed that propranolol decreased the activity related to movement, and Gammarus spp. could not compensate for the reduced movement when subjected to predator cues. The feeding rates of Gammarus spp. exposed to propranolol were more than 2 times higher at all concentrations compared to the control. Ibuprofen did not significantly affect any of the measured parameters of Gammarus spp. The GP/R was lower in algae exposed to propranolol. The effects of propranolol on both behaviour and physiology of Gammarus spp., in combination with the stress responses in the algae, might cause unexpected indirect and cascade effects which eventually could have implications at both community and ecosystem scales.

The invasive polychaete genus, Marenzelleria and the native amphipod, Monoporeia affinis are food and habitat competitors in the Baltic Sea. Previous studies have shown that moderate densities of Marenzelleria can affect the behaviour of M. affinis. To examine the short-term interactive effects of interspecific habitat choice and environmental contaminants a series of habitat colonisation experiments were performed. The contaminants examined included harbor sediments and sediment spiked with the antifouling substances, Cu, Zn and Irgarol. Polychaetes and amphipods were exposed to contaminants in single-species and two-species experiments. In spiked-sediment experiments, M. affinis showed clear dose-dependent response. These experiments verified that behavioural response of M. affinis to different habitats is a sensitive method for testing toxicity under controlled conditions. In experiments with three different harbor sediments and reference sediment both species showed the lowest preference for the reference sediment. This sediment also had the lowest content of quality food, indicating that factors such as food quality and quantity may override the disturbing effects of contaminants in natural sediments. The presence of Marenzelleria spp. did not affect amphipod habitat choice, indicating no short-term effects, which implies that both species can co-exist provided sufficient food is available.

Physiological responses to, and recovery from, exposure to 3 concentrations of a pharmaceutical mixture (diclofenac and propranolol) were examined experimentally in Baltic Sea blue mussels Mytilus edulis trossulus collected with increasing distance to a wastewater treatment plant (WTP) outlet. Respiration, absorption efficiency and consumption were measured, and also combined into scope for growth (SFG). The response and recovery patterns varied both between exposure concentrations and sampling site within the bay. After exposure, mussels exposed to the highest concentration (2000 mu g l(-1)) in general had lower SFG, and mussels from 2 (out of 3) sites exposed to the medium concentration (200 mu g l(-1)) had higher SFG than the controls. In general, mussels from the 2 sites nearest the WTP recovered from the exposure response, while individuals collected further from the WTP outlet were more affected by the exposure and did not recover to the same extent. The response pattern of consumption was mainly affected by exposure concentration, whereas respiration was affected by all 3 factors (concentration, time of measurement, sampling site). Absorption efficiency was not affected at all. The differences in responses and recovery patterns could possibly be explained by the mussels sampled closer to the WTP having a history of higher food availability, improving their general health status, and/or a history of pre-exposure to natural disturbances, as well as to the test substances, via the WTP effluent. Pre-exposure to stressors could have both positive and negative impact on a community by increasing the resilience towards some stressors, but may also reduce the adaptability when facing other stressors.

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.

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.

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.

Environmental mixtures of chemicals consist of a countless number of compounds with unknown identity and quantity. Yet, chemical regulation is mainly built around the assessment of single chemicals. Existing frameworks for assessing the toxicity of mixtures require that both the chemical composition and quantity are known. Quantitative analyses of the chemical composition of environmental mixtures are however extremely challenging and resource-demanding. Bioassays may therefore serve as a useful approach for investigating the combined toxicity of environmental mixtures of chemicals in a cost-efficient and holistic manner. In this study, an unknown environmental mixture of bioavailable semi-hydrophobic to hydrophobic chemicals was sampled from a contaminated sediment in a coastal Baltic Sea area using silicone polydimethylsiloxane (PDMS) as an equilibrium passive sampler. The chemical mixture was transferred to a PDMS-based passive dosing system, and its applicability was demonstrated using green algae Tetraselmis suecica in a cell viability assay. The proportion of dead cells increased significantly with increasing exposure level and in a dose–response manner. At an ambient concentration, the proportion of dead cells in the population was nearly doubled compared to the control; however, the difference was non-significant due to high inter-replicate variability and a low number of replicates. The validation of the test system regarding equilibrium sampling, loading efficiency into the passive dosing polymer, stability of the mixture composition, and low algal mortality in control treatments demonstrates that combining equilibrium passive sampling and passive dosing is a promising tool for investigating the toxicity of bioavailable semi-hydrophobic and hydrophobic chemicals in complex environmental mixtures.