Selenium in the lower Athabasca River (Alberta, Canada) is of concern due to potential inputs from the weathering of shallow bitumen deposits and emissions from nearby surface mines and upgraders. Understanding the source of this Se, however, is complicated by contributions from naturally saline groundwater and organic matter-rich tributaries. As part of a two-year multi-disciplinary study to assess natural and anthropogenic inputs, Se and its chemical speciation were determined in water samples collected along a ∼125 km transect of the Athabasca River and associated tributaries. Selenium was also determined in the muscle of Trout-perch (Percopsis omiscomaycus), a non-migratory fish species, that were sampled from selected locations. Dissolved (<0.45 μm) Se in the Athabasca River was consistently low in 2014 (0.11 ± 0.02 μg L⁻¹; n = 14) and 2015 (0.16 ± 0.02 μg L⁻¹; n = 21), with no observable increase from upstream to downstream. Selenate was the predominant inorganic form (∼60 ng L⁻¹) and selenite was below detection limits at most locations. The average concentration of Se in Trout-perch muscle was 2.2 ± 0.4 mg kg⁻¹ (n = 34), and no significant difference (p > 0.05) was observed between upstream and midstream (industrial) or downstream reaches. Tributary waters contained very low concentrations of Se (typically < 0.1 μg L⁻¹), which was most likely present in the form of dissolved organic colloids.

Neonicotinoid insecticides are environmentally persistent and highly water-soluble, and thus are prone to leaching into surface waters where they may negatively affect non-target aquatic insects. Most of the research to date has focused on imidacloprid, and few data are available regarding the effects of other neonicotinoids or their proposed replacements (butenolide insecticides). The objective of this study was to assess the toxicity of six neonicotinoids (imidacloprid, thiamethoxam, acetamiprid, clothianidin, thiacloprid, and dinotefuran) and one butenolide (flupyradifurone) to Hexagenia spp. (mayfly larvae). Acute (96-h), water-only tests were conducted, and survival and behaviour (number of surviving mayflies inhabiting artificial burrows) were assessed. Acute sublethal tests were also conducted with imidacloprid, acetamiprid, and thiacloprid, and in addition to survival and behaviour, mobility (ability to burrow into sediment) and recovery (survival and growth following 21 d in clean sediment) were measured. Sublethal effects occurred at much lower concentrations than survival: 96-h LC50s ranged from 780 μg/L (acetamiprid) to >10,000 μg/L (dinotefuran), whereas 96-h EC50s ranged from 4.0 μg/L (acetamiprid) to 630 μg/L (thiamethoxam). Flupyradifurone was intermediate in toxicity, with a 96-h LC50 of 2000 μg/L and a 96-h EC50 of 81 μg/L. Behaviour and mobility were impaired significantly and to a similar degree in sublethal exposures to 10 μg/L imidacloprid, acetamiprid, and thiacloprid, and survival and growth following the recovery period were significantly lower in mayflies exposed to 10 μg/L acetamiprid and thiacloprid, respectively. A suite of effects on mayfly swimming behaviour/ability and respiration were also observed, but not quantified, following exposures to imidacloprid, acetamiprid, and thiacloprid at 1 μg/L and higher. Imidacloprid concentrations measured in North American surface waters have been found to meet or exceed those causing toxicity to Hexagenia, indicating that environmental concentrations may adversely affect Hexagenia and similarly sensitive non-target aquatic species.

Occurrence of per- and poly-fluoroalkyl substances (PFASs) in the environment and biota has raised a great concern to public health because these compounds are persistent, bioaccumulative, and toxic. Biodegradation of polyfluoroalkyl substances, particularly long-chain fluorotelomer-based products, can lead to production of various short-chain PFASs, with 5:3 fluorotelomer carboxylic acid (referred as 5:3 FTCA hereafter) as a dominant polyfluoroalkyl metabolite. Perfluoroalkyl acids, particularly perfluorooctanoic acid (PFOA), are toxic and current removal methods are not cost-effective. This study reports the photodegradation of 5:3 FTCA and PFOA using ZnO as a photocatalyst under neutral pH and room temperature conditions. Under long UV wavelength (365 nm), both tetrapod and commercial ZnO can photodegrade 5:3 FTCA. Five removal products—perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutyric acid, 5:2 fluorotelomer carboxylic acid (5:2 FTCA), and inorganic fluoride—were identified, with PFBA and F⁻ as dominant end products. SEM and XPS high-resolution scans on the surface of the utilized ZnO showed less units of CF₂ than that in 5:3 FTCA, supporting occurrence of photodegradation of 5:3 FTCA by ZnO. Defluorination of PFOA was not observed with ZnO only, but at pH 5 and in the co-presence of Fe-citrate. PFOA defluorination increased from 0.93% after 3 days of UV light exposure to 3.9% after additional 135 h under direct sunlight exposure. To the authors’ best knowledge, this is the first report studying ZnO-catalyzed photodegradation of 5:3 FTCA, and examining the Fe co-addition for PFOA defluorination.

The effects of elevated ozone on C (carbon), N (nitrogen) and P (phosphorus) ecological stoichiometry and nutrient resorption in different organs including leaves, stems and roots were investigated in poplar clones 546 (P. deltoides cv. ‘55/56’ × P. deltoides cv. ‘Imperial’) and 107 (P. euramericana cv. ‘74/76’) with a different sensitivity to ozone. Plants were exposed to two ozone treatments, NF (non-filtered ambient air) and NF60 (NF with targeted ozone addition of 60 ppb), for 96 days in open top chambers (OTCs). Significant ozone effects on most variables of C, N and P ecological stoichiometry were found except for the C concentration and the N/P in different organs. Elevated ozone increased both N and P concentrations of individual organs while for C/N and C/P ratios a reduction was observed. On these variables, ozone had a greater effect for clone 546 than for clone 107. N concentrations of different leaf positions ranked in the order upper > middle > lower, showing that N was transferred from the lower senescent leaves to the upper ones. This was also indicative of N resorption processes, which increased under elevated ozone. N resorption of clone 546 was 4 times larger than that of clone 107 under ambient air (NF). However, elevated ozone (NF60) had no significant effect on P resorption for both poplar clones, suggesting that their growth was only limited by N, while available P in the soil was enough to sustain growth. Understanding ecological stoichiometric responses under ozone stress is crucial to predict future effects on ecological processes and biogeochemical cycles.

Understanding of the interaction of graphene with natural polysaccharides (e.g., alginate) is crucial to elucidate its environmental fate. We investigated the impact of alginate on the agglomeration and stability of ¹⁴C-labeled few-layer graphene (FLG) in varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Enhanced agglomeration occurred at high CaCl₂ concentrations (≥5 mM) due to the alginate gel networks formation in the presence of Ca²⁺. FLG enmeshed within extended alginate gel networks was observed under transmission electron microscope and atomic force microscope. However, background Na⁺ competition for binding sites with Ca²⁺ at the alginate surfaces shielded the gelation of alginate. FLG was readily dispersed by alginate under environmentally relevant ionic strength conditions (i.e., <200 mM Na⁺ and <5 mM Ca²⁺). In comparison with the bare FLG, the slow sedimentation of the alginate-stabilized FLG (158 μg/L) caused continuous exposure of this nanomaterial to freshwater snails, which ingested 1.9 times more FLG through filter-feeding within 72 h. Moreover, surface modification of FLG by alginate significantly increased the whole-body and intestinal levels of FLG, but reduced the internalization of FLG to the intestinal epithelial cells. These findings indicate that alginate will act as a stabilizing agent controlling the transport of FLG in aqueous systems. This study also provides the first evidence that interaction of graphene with natural polysaccharides affected the uptake of FLG in the snails, which may alter the fate of FLG in aquatic environments.

While determining the uranium concentration in the rock (background level) and soils on the Iberian Massif of western Spain, several geochemical anomalies were observed. The uranium concentration was much higher than the geochemical levels at these locations, and several uranium minerals were detected. The proposed uranium background levels for natural soils in the west of Salamanca Province (Spain) are 29.8 mg kg−1 in granitic rock and 71.2 mg kg−1 in slate. However, the soil near the tailings of abandoned mines exhibited much higher concentrations, between 207.2 and 542.4 mg kg−1.The calculation of different pollution indexes (Pollution Factor and Geo-accumulation Index), which reveal the conditions in the superficial horizons of the natural soils, indicated that a good percentage of the studied samples (16.7–56.5%) are moderately contaminated. The spatial distribution of the uranium content in natural soils was analysed by applying the inverse distance weighted method.The distribution of uranium through the horizons of the soils shows a tendency to accumulate in the horizons with the highest clay content. The leaching of uranium from the upper horizons and accumulation in the lower horizons of the soil could be considered a process for natural attenuation of the surface impacts of this radiogenic element in the environment. Environmental restoration is proposed in the areas close to the abandoned mining facilities of this region, given the high concentration of uranium. First, all the tailings and other mining waste would be covered with a layer of impermeable material to prevent leaching by runoff. Then, a layer of topsoil with organic amendments would be added, followed by revegetation with herbaceous plants to prevent surface erosion.

Mining in the Athabasca Oil Sands Region (AOSR) has contributed extensively to increased exposure of wildlife to naturally occurring polycyclic aromatic compounds (PACs), yet little is known about the toxicity of PACs to wildlife in this region. We identified reproductive and developmental changes in tree swallows (Tachycineta bicolor) breeding in close proximity to mining-related activities in the AOSR, and determined these changes in relation to the birds' exposure and accumulation of 41 PACs (parent-, alkylated-PAHs), dibenzothiophenes (DBTs; previously published), diet (carbon (δ13C), nitrogen (δ15N)), volatile organic compounds, and weather variables. Tree swallow pairs (N = 43) were compared among mining-related (OS1, OS2) and reference (REF1, REF2) sites. At OS2, clutch initiation was slightly advanced (2012) but reproductive success (65%) was much lower than at the other sites (≥ 79%). Fledgling production by each pair was influenced by the timing of clutch initiation (years combined); in a highly inclement brood rearing period (2013), additional influences included the nestlings' exposure to ΣDBTs, accumulation of C1-naphthalene, the trophic position of the prey in their diet (δ15N), and record-breaking rainfall. Nestlings at OS2 were significantly lighter at day (d) 9 and d14, and in poorer body condition (d9). Nestling body mass was influenced by multiple stressors that varied by site: mass of younger nestlings (d9) was related to dietary source (δ13C; e.g., wetlands, terrestrial fields), exposure and/or accumulation of C1-phenanthrenes, C2-fluorenes, Σalkyl-PAHs and ΣDBTs, while for older nestlings (d14), body mass was related to sex, hatch date and/or rainfall during brood rearing. The swallows' exposure and accumulation of parent-PACs, alkyl-PACs and DBTs, the timing of hatching, their diet and exposure to highly inclement rains, contributed to their reproductive and developmental changes.

The effect of titanium dioxide nanoparticles (nano-TiO2) on the bioaccumulation and biotransformation of arsenic (As) remains largely unknown. In this study, we exposed two freshwater algae (Microcystis aeruginosa and Scenedesmus obliquus) to inorganic As (arsenite and arsenate) with the aim of increasing our understanding on As bioaccumulation and methylation in the presence of nano-TiO2. Direct evidence from transmission electron microscope (TEM) images show that nano-TiO2 (anatase) entered exposed algae. Thus, nano-TiO2 as carriers boosted As accumulation and methylation in these two algae species, which varied between inorganic As speciation and algae species. Specifically, nano-TiO2 could markedly enhance arsenate (As(V)) accumulation in M. aeruginosa and arsenite (As(III)) accumulation in S. obliquus. Similarly, we found evidence of higher As methylation activity in the M. aeruginosa of As(III) 2 mg L−1 nano-TiO2 treatment. Although this was also true for the S. obliquus (As(V)) treatment, this species exhibited higher As methylation compared to M. aeruginosa, being more sensitive to As associated with nano-TiO2 compared to M. aeruginosa. Due to changes in pH levels inside these exposed algae, As dissociation from nano-TiO2 inside algal cells enhanced As methylation. Accordingly, the potential influence of nanoparticles on the bioaccumulation and biotransformation of their co-contaminants deserves more attention.

Previous aquaria-based experiments have shown dissolution and leaching of metals, especially copper (Cu), from the simulated sediment plumes generated during mining activities resulting in a pronounced increase of Cu contamination in the surrounding seawater. Metals are bioavailable to corals with food, through ingestion (particulate phase) and through tissue-facilitated transport (passive diffusion). With corals being particularly vulnerable to metal contamination, resuspension of metal-bearing sediments during mining activities represents an important ecological threat. This study was undertaken to evaluate the impact of acute copper exposure (LC50;96 h) on the survival of the cold-water octocoral Dentomuricea aff. meteor. The experimental design was divided in two stages. In stage one, a Cu range-finding toxicity test was performed using Cu dilutions in filtered seawater with concentrations of 0 (control); 60; 150; 250; 450; 600 μg/L. Coral mortality was investigated visually based on the percent surface area of tissue changing from natural yellow colour to black colour indicative of tissue necrosis and death. In stage two, we used the results obtained in the range-finding experiment, to define sub-lethal Cu exposure treatments and exposed D. meteor to Cu concentration of 0 (control); 50; 100; 150; 200; 250 μg/L for 96 h. The corals physical conditions were inspected daily and seawater conditions recorded. Corals were considered dead when all of their tissue turned black. The LC50 value was calculated with regression analysis following Probits methodology. Our results indicate that Cu LC50;96 h for the octocoral D. meteor is 137 μg/L.

Mariculture activities including enclosure, raft and cage cultures employ a variety of plastic gear such as fishing nets, buoyant material and net cages. The plastic gear poses a potential source of microplastics to the coastal environment, but relevant data on the impacts of mariculture are still limited. To this end, a semi-enclosed narrow bay (i.e., Xiangshan Bay, China) with a long-term mariculture history was investigated to assess how mariculture activities affect microplastics in seawater and sediment. The results indicated that mariculture-derived microplastics accounted for approximately 55.7% and 36.8% of the microplastics in seawater and sediment, respectively. The average microplastic abundances of seawater and sediment were 8.9 ± 4.7 (mean ± SD, n = 18) items/m³ seawater and 1739 ± 2153 (n = 18) items/kg sediment, respectively. The types of mariculture-derived microplastics included polyethylene (PE) foam, PE nets, PE film, polypropylene (PP) rope, polystyrene (PS) foam and rubber. PE foam had the highest proportion (38.6%) in the seawater samples. High usage rates and the porous structure of PE foam led to the high abundance. The average microplastic sizes of seawater and sediment are 1.54 ± 1.53 mm and 1.33 ± 1.69 mm, respectively. The spatial variations in the abundance and size of microplastics implied that the mariculture-derived microplastics in Xiangshan Bay were transported along the Bay to the open sea. The results of this study indicate that mariculture activity can be a significant source of microplastics. Further research is required to investigate how the high microplastic abundance in mariculture zone affects marine organisms, especially cultured seafood.