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Additional file 2: Table S2. All measured parameters with number of values below the limit of quantification. Table S3. Summarising numbers on scrubber washwater concentrations, fluxes and impact on water quality for scenario low (10% scrubbers). The numbers of scenario high (20% scrubbers) are included in the manuscript (Table 1). Figure S1. All scrubber washwater metal concentrations. Figure S2. All scrubber washwater PAH concentrations.

The present study evaluated the effect of increasing oxygen concentrations in overlying surface water on the accumulation and toxicity of sediment-bound metals in the aquatic invertebrates Lumbriculus variegatus, Asellus aquaticus and Daphnia magna. A 54 days experiment using three experimental treatments (90% O2 in overlying surface water, 40% O2 and a non-polluted control) was conducted. At 6 different time points (after 0, 2, 5, 12, 32 and 54 days) acid volatile sulfides (AVS), simultaneously extracted metals (SEM) and total organic carbon (TOC) were measured in the superficial sediment layer (01 cm). At each time point, accumulated metal levels as well as the available energy stores were measured in L. variegatus and A. aquaticus and each time D. magna was exposed to surface water in a 24 h toxicity test. Additionally metallothionein-like protein (MTLP) induction was quantified in L. variegatus. Oxygen induced changes in sediment AVS resulted in faster accumulation of metals from contaminated sediments in A. aquaticus, while no differences in toxicity in this species were observed. Ag, Cr, As and Co accumulation as well as toxicity in water exposed D. magna were clearly enhanced after 54 days, caused by oxidation of metal-sulfide complexes. Due to their feeding and burrowing behaviour, metal accumulation and toxicity in L. variegatus was not influenced by geochemical characteristics. Nevertheless, a rapid induction of MTLP was observed in both the 90% O2 and the 40% O2 treatment. The present study showed that elevated oxygen concentrations in overlying surface water can directly enhance metal accumulation and toxicity in aquatic invertebrates, however this is highly dependent on the organisms ecology and most dominant metal exposure route (water vs. sediment).

In order to evaluate the effect of improved oxygen concentrations in overlying surface water on the redox status, sediment geochemistry and metal bioavailability in metal-polluted sediments a 54 days lab experiment with two different experimental treatments was conducted (90% and 40% O2). Changes in redox potential (Eh) in the sediment were monitored over time. At 6 different time points (after 0, 2, 5, 12, 32 and 54 days) and at 4 sediment depths (01, 14, 48 and 815 cm), acid volatile sulfides (AVS), simultaneously extracted metals (SEM) and total organic carbon (TOC) were measured and metal release to overlying surface water was determined. Labile metal species in both water and sediment were measured using Diffusive Gradients in Thin films (DGT). Our results showed that elevated oxygen levels in overlying surface water led to an Eh increase in the sediment of the 90% O2 treatment from 0 to ±200 mV while AVS concentrations in the upper sediment layer decreased by 70%. Following AVS oxidation metal availability in the pore water was highly elevated after 54 days. However, Cu remained strongly bound to the sediment during the whole experiment. Only a limited metal release to the overlying surface water was noticed, which was due to the fact that SEMtot concentrations in the sediment did not yet exceeded AVS levels ([SEMtot − AVS]/fOC = 0) after 54 days. Additionally, adsorption on Fe and Mn hydroxides and particulate organic carbon also slowed down any potential metal release. Our results indicated that increasing oxygen concentrations due to general water quality improvements can enhance the mobility of trace metals which may result in the leaching of sediment-bound metals to overlying surface water, even in undisturbed watercourses.