Ecotoxicological effects of fluvial eroded bitumen sediments from the Alberta oil sands to model aquatic species.

To fully understand the ecological and cumulative effects of mining activities on the surrounding aquatic systems of the Canadian oil sands region, it is essential to understand the consequences of exposure to bitumen-containing soils/sediment from natural geomorphological processes. Both physical and chemical stress on aquatic biota can potentially result from exposure to natural bitumen, resulting from hillslope erosional processes and slumping of bankside soils into the rivers, affecting both riverbed habitat and water quality. The magnitude and duration of bitumen-containing soil's fluvial soils/erosional input into receiving watersheds depends on the interannual variability in the regional hydroclimatology and related seasonal and extreme flow events. The primary objective of this study was to evaluate the potential ecotoxicological effects associated with erosional input of riverbank bitumen soils using controlled exposures. A series of integrated, laboratory-based ecotoxicological bioassays were conducted using organisms with different ecological and functional traits (Daphnia magna (Cladocera), Physa acuta (Gastropoda), and Aliivibrio fischeri (Bacteria)). All model organisms were exposed to elutriates produced from natural bitumen from four different regional rivers: fresh bitumen from shoreline outcrops at the Steepbank River upper and lower reaches (STB-CF and STB-MF, respectively) and the lower-Ells River (EL-MF) and aged, fluvially processed/weathered bitumen from the shoreline of the Athabasca River (ATB-MF). All tested organisms responded negatively to STB-MF and EL-MF elutriates. Low toxicity was also observed in the STB-CF and ATB-MF samples. These results follow the chemical analysis of the parental material and elutriates, where higher levels of metals, polycyclic aromatic compounds and naphthenic acids were detected in the EL-MF sample. In summary, this study shows that eroded and transported bitumen-containing soils and sediments could be a natural source of contaminant exposure to aquatic biota. This fluvial pathway should be considered when assessing background toxicity and the toxicological and ecological effects of oil sands mining activities.

Toxicokinetics of silver and silver sulfide nanoparticles in Chironomus riparius under different exposure routes.

Engineered nanoparticles released into surface water may accumulate in sediments, potentially threatening benthic organisms. This study determined the toxicokinetics in Chironomus riparius of Ag from pristine silver nanoparticles (Ag NPs), a simulating aged Ag NP form (Ag2S NPs), and AgNO3 as an ionic control. Chironomid larvae were exposed to these Ag forms through water, sediment, or food. The potential transfer of Ag from larvae to adult midges was also evaluated. Results revealed higher Ag uptake by C. riparius upon exposure to Ag2S NPs, while larvae exposed to pristine Ag NPs and AgNO3 generally presented similar uptake kinetics. Uptake patterns of the different Ag forms were generally similar in the tests with water or sediment exposures, suggesting that uptake from water was the most important route of Ag uptake in both experiments. For the sediment bioaccumulation test, uptake was likely a combination of water uptake and sediment particles ingestion. Ag uptake via food exposure was only significant for Ag2S NPs. Ag transfer to the terrestrial compartment was low. In our environmentally relevant exposure scenario, chironomid larvae accumulated relatively high Ag concentrations and elimination was extremely low in some cases. These results suggest that bioaccumulation of Ag in its nanoparticulate and/or ionic form may occur in the environment, raising concerns regarding chronic exposure and trophic transfer. This is the first study determining the toxicokinetics of NPs in Chironomus, providing important information for understanding chironomid exposure to NPs and their potential interactions in the environment.

Effects of sulfidation of silver nanoparticles on the Ag uptake kinetics in Brassica rapa plants.

Land application of sewage sludge containing increasing levels of silver nanoparticles (AgNPs) raises concerns about the risk for plant exposure. This study compared the uptake kinetics and distribution of Ag in Brassica rapa seedlings grown in Lufa 2.2 natural soil spiked with 20 nm Ag2S NPs, with those from 3 to 8 nm AgNPs, 50 nm AgNPs and AgNO3 exposures (10 mg Ag/kg dry soil). A two-compartment model was used to describe the uptake kinetics of Ag in plants, distinguishing two stages: stage I with increasing Ag uptake followed by stage II with decreasing Ag uptake. The concentration of Ag in roots from Ag2S NPs was about 14 and 10 times lower than for the other AgNPs and AgNO3 exposures, respectively, at the end of stage I, with root translocation rate constants being higher for Ag2S NPs. In stage II, Ag uptake occurred only for the 50 nm AgNPs. The distribution of Ag in B. rapa exposed to pristine, ionic and sulfidized AgNPs differed at the end of exposure. This study shows that Ag uptake and distribution in plants depends on the Ag form in soil, highlighting the importance of studying the environmentally relevant chemical species in NPs risk assessment.

Mixture toxicity prediction of substances from different origin sources in Daphnia magna.

Due to several anthropogenic activities, water bodies have been heavily impacted by contaminants identified in aquatic ecosystems, including pharmaceuticals, personal care products, agricultural and industrial chemicals. Risk assessment based on chemical mixtures is still default in many monitoring studies, with decisions being based solely on a chemical-by-chemical basis. The present study aimed to improve risk assessment procedures in water bodies by focusing on mixtures of chemical substances of different origins. The goal was to analyze potential interactions occurring at different complexity levels (binary and quaternary mixtures) using standardised toxicity assays. Mixture toxicity effects were assessed using Daphnia magna as the model organism and the compounds sodium fluoride, boric acid, ammonium hydroxide and acetaminophen as general representatives of contaminants in the aquatic ecosystem. The results revealed interactions between the compounds, mainly showing antagonism but also dose level and dose ratio-dependent deviations. Overall antagonism was the dominant deviation pattern, particularly at low doses, though synergism was also detected at higher doses or specific ratios. Synergism at low doses was found for the binary mixture of ammonium hydroxide and acetaminophen, two common pollutants, which denotes an enhanced risk to aquatic ecosystems. Independent Action provided more accurate predictions for the quaternary mixture, whereas Concentration Addition overestimated the toxicity of the mixture. Regarding the environmental risk assessment of water bodies, the interaction between chemicals in a mixture should not be neglected. The complexity of the mixture interactions found in the present study highlights the importance of complementing chemical screenings of water bodies with mixture toxicity data, particularly when considering chemicals of multiple origins whose joint action remains unknown.

Toxicokinetics of silver nanoparticles in the mealworm Tenebrio molitor exposed via soil or food.

Silver nanoparticles (AgNPs) may reach the soil compartment via sewage sludge or nanoagrochemical applications. Understanding how NPs interact with biological systems is crucial for an accurate hazard assessment. Therefore, this study aimed at determining the Ag toxicokinetics in the mealworm Tenebrio molitor, exposed via Lufa 2.2 soil or via food to different Ag forms (uncoated 50 nm AgNPs, paraffin coated 3-8 nm and PVP-stabilised 60 nm, Ag2S NPs 20 nm, and ionic Ag). Mealworms were exposed for 21 days followed by a 21-day elimination phase (clean soil/food). A one-compartment kinetics model with inert fraction (simulating a storage compartment, where detoxified forms are located) was used to describe Ag accumulation. Fully understanding the uptake route in mealworms is difficult. For that reason several approaches were used, showing that food, soil and pore water all are valid uptake routes, but with different importance. Silver taken up from soil pore water or from soil showed to be related to Ag dissolution in soil pore water. In general, the uptake and elimination rate constants were similar for 3-8 nm and 60 nm AgNPs and for AgNO3, but significantly different for the uncoated 50 nm AgNPs. Upon food exposure, uptake rate constants were similar for 50 nm AgNPs and AgNO3, while those for 60 nm and 3-8 nm AgNPs and for Ag2S NPs also grouped together. NP exposure in soil appeared more difficult to characterize, with different patterns obtained for the different NPs. But it was evident that upon soil or food exposure, particle characteristics highly affected Ag bioavailability and bioaccumulation. Although Ag2S NPs were taken up, their elimination was faster than for other Ag forms, showing the lowest inert fraction. The significantly different elimination rate constants suggest that the mechanism of elimination may not be the same for different AgNPs either.

Site-specific hazard evaluation for improved groundwater risk assessment.

Groundwater represents one of the most important natural water resources worldwide. Contamination is a key driver in sustaining water quality to populations and the environment. Therefore, it is crucial to look at contamination and potential effects. Within the WaterJPI project "We-Need - WatEr NEEDs, Availability, Quality and Sustainability", the Cremona and the Bologna Aquifers (Italy) were chosen as case studies since both aquifers represent two major Italian water resources of the Emilia-Romagna region. Aiming for a site-specific groundwater hazard assessment, the groundwaters from the Cremona and Bologna aquifers were simulated by preparing synthetic waters, CSW and BSW, respectively. Boron (as boric acid), fluoride (as sodium fluoride), and ammonium (as ammonium hydroxide), detected in the aquifers, were used to assess potential negative impacts on groundwater systems using aquatic organisms. Acute toxicity tests with Daphnia magna and Fish Embryo Toxicity Tests (FET) with Danio rerio were performed in the CSW and BSW synthetic waters and respective culture media, and toxicity was assessed for each organism. Boron, fluoride and ammonium had no ecological hazard effects at the concentrations detected in the groundwaters. Besides, a crucial result from this study regards the use of different media when addressing toxicity assessment. In this case, it was observed that toxicity was media and organism dependent. Therefore, adapting testing protocols for higher relevance should be considered for site-specific hazard assessment.

Combined toxicity of graphite-diamond nanoparticles and thiabendazole to Daphnia magna.

Carbon-based nanomaterials exhibit unique properties that make them suitable for a wide variety of industrial and biomedical applications. In this work, we studied the acute toxicity of graphite-diamond nanoparticles (GDN) combined with the fungicide thiabendazole (TBZ) to the immobilization of the cladoceran Daphnia magna in the presence and absence of the micro green algae Raphidocelis subcapitata, supplied as food source. The toxicity of GDN to D. magna decreased in the presence of R. subcapitata, while that of TBZ increased, the latter suggesting a carrier effect to TBZ. GDN-TBZ mixtures were fitted to the most common conceptual models applied to mixture toxicity: Concentration Addition (CA), Independent Action (IA) and Combination Index (CI). For GDN-TBZ mixtures in the absence of food the best fit was obtained with dose ratio deviation from CA model, while in the presence of food, dose level deviation from CA gave a better fit. The binary mixtures of GDN and TBZ showed synergistic toxic interactions at low concentrations, which could be attributed to the increased bioavailability of TBZ adsorbed on GDN. For higher concentrations of GDN, the binary mixtures turned antagonistic due to particle agglomeration. Our study provides evidence that deviations from additivity are dose dependent and relevant for the risk assessment of mixtures of nanoparticles with other chemical pollutants.

An ecotoxicological analysis of the sediment quality in a European Atlantic harbor emphasizes the current limitations of the Water Framework Directive.

The "PortoNovo" project was developed to standardize the methodologies for water quality management in the port areas of coastal Atlantic regions to improve the Water Frame Directive (WFD) for these specific water bodies. Under this scope, water and sediment samples were collected from five sites within the Port of Aveiro, Portugal. According to the physical and chemical parameters that were analyzed (i.e., metals, total organic carbon, polychlorinated biphenyls and polycyclic aromatic hydrocarbons), the sediments were not considered at risk based on European sediment quality laws. However, the bioassays that were performed on the sediment samples (Microtox®) and the standardized acute toxicity test using the marine rotifer, Brachionus plicatilis, on sediment elutriates revealed higher toxicity levels. The use of bioassays to assess sediment quality clearly complements more conservative approaches and highlights current gaps within the WFD. The approach presented here can be easily transferred to other port areas for more reliable water quality management.

Richness and composition of sediment bacterial assemblages in an Atlantic port environment.

In the present study, we assessed the bacterial richness and composition of sediment samples collected in and around the port of Aveiro, on the Atlantic coast of mainland Portugal. Sediment samples were collected in five locations: two within the port harbor, two in port areas along a channel adjacent to the harbor and one in a relatively undisturbed reference location. These areas were characterized as under high, medium and no port activity, respectively. In-depth, barcoded-pyrosequencing analysis indicated that port activity affects the composition and abundance of bacterial communities colonizing surface sediments. Sampling sites under the influence of port activities (channel and harbor) were associated with higher relative abundances of Desulfobacterales and a marked decline in the abundance of Flavobacteriia. In addition, there was a pronounced prevalence of operational taxonomic units (OTUs) in the port area that were closely related to hydrocarbon-degrading bacteria (Desulfococcus spp.), antifouling paint (bacterium strain WH6-7) and copper rich sediments (bacterium strain CanalPD16A). Here we provide evidence that specific phylotypes detected have the potential to be used as biomarkers and should be evaluated in future studies as proxies for sediment disturbance associated with port activity.