The sorption and desorption behaviour of samarium (Sm), an emerging contaminant, was examined in soil samples at varying Sm concentrations. The obtained sorption and desorption parameters revealed that soil possessed a high Sm retention capacity (sorption was higher than 99% and desorption lower than 2%) at low Sm concentrations, whereas at high Sm concentrations, the sorption-desorption behaviour varied among the soil samples tested. The fractionation of the Sm sorbed in soils, obtained by sequential extractions, allowed to suggest the soil properties (pH and organic matter solubility) and phases (organic matter, carbonates and clay minerals) governing the Sm-soil interaction. The sorption models constructed in the present work along with the sorption behaviour of Sm explained in terms of soil main characteristics will allow properly assessing the Sm-soil interaction depending on the contamination scenario under study. Moreover, the sorption and desorption Kd values of radiosamarium in soils were strongly correlated with those of stable Sm at low concentrations (r = 0.98); indicating that the mobility of Sm radioisotopes and, thus, the risk of radioactive Sm contamination can be predicted using data from low concentrations of stable Sm.

Propranolol (PRO), a human β-AR (β-adrenergic receptor) antagonist, is considered to result in specific effects in a non-target species, D. magna, based on our previous studies. The present study investigated the effects of β-AR agents, including an antagonist and agonist using pharmacologically relevant endpoints as well as a more holistic gene expression approach to reveal the impacts and potential mode of actions (MOAs) in the model non-target species. Results show that the responses in cardiac endpoints and gene expression in D. magna are partially similar but distinguishable from the observations in different organisms. No effect was observed on heart size growth in PRO and isoprenaline (ISO) exposure. The contraction capacity of the heart was decreased in ISO exposure, and the heart rate was decreased in PRO exposure. Time-series exposures showed different magnitudes of effect on heart rate and gene expression dependent on the type of chemical exposure. Significant enrichment of gene families involved in protein metabolism and biotransformation was observed within the differentially expressed genes, and we also observed differential expression in juvenile hormone-inducible proteins in ISO and PRO exposure, which is suspected of having endocrine disruption potential. Taken together, deviation between the effects of PRO and ISO in D. magna and other organisms suggests dissimilarity in MOAs or attributes of target bio-molecules between species. Additionally, PRO and ISO may act as endocrine disruptors based on the gene expression observation. Results in the present study confirm that it is challenging to predict ecological impact of active pharmaceutical ingredients (APIs) based on the available data acquired through human-focused studies. Furthermore, the present study provided unique data and a case study on the impact of APIs in a non-target organism.

The main objectives of this study were to evaluate global uncertainty in the prediction of Distribution coefficients (Kds) for several Trace Metals (TM) (Cd, Cu, Pb, Zn) through the probabilistic use of a geochemical speciation model, and to conduct sensitivity analysis in speciation modeling in order to identify the main sources of uncertainty in Kd prediction. As a case study, data from the Loire river (France) were considered. The geochemical speciation model takes into account complexation of TM with inorganic ligands, sorption of TM with hydrous ferric oxides, complexation of TM with dissolved and particulate organic matter (i.e. dissolved and particulate humic acids and fulvic acids) and sorption and/or co-precipitation of TM to carbonates. Probability Density Functions (PDFs) were derived for physico-chemical conditions of the Loire river from a comprehensive collection of monitoring data. PDFs for model parameters were derived from literature review. Once all the parameters were assigned PDFs that describe natural variability and/or knowledge uncertainty, a stepwise structured sensitivity analysis (SA) was performed, by starting from computationally ‘inexpensive’ Morris method to most costly variance-based EFAST method. The most sensitive parameters on Kd predictions were thus ranked and their contribution to Kd variance was quantified. Uncertainty analysis was finally performed, allowing quantifying Kd ranges that can be expected when considering all the sensitive parameters together.

Fate and transport of graphene oxide (GO) have received much attention recently with the increase of GO applications. This study investigated the effect of salt concentration on the transport and retention behavior of GO particles in heterogeneous saturated porous media. Transport experiments were conducted in NaCl solutions with three concentrations (1, 20, and 50 mM) using six structurally packed columns (two homogeneous and four heterogeneous) which were made of fine and coarse grains. The results showed that GO particles had high mobility in all the homogeneous and heterogeneous columns when solution ionic strength (IS) was low. When IS was high, GO particles showed distinct transport ability in six structurally heterogeneous porous media. In homogeneous columns, decreasing ionic strength and increasing grain size increased the mobility of GO. For the column containing coarse-grained channel, the preferential flow path resulted in an early breakthrough of GO, and further larger contact area between coarse and fine grains caused a lower breakthrough peak and a stronger tailing at different IS. In the layered column, there was significant GO retention at coarse-fine grain interface where water flowed from coarse grain to fine grain. Our results indicated that the fate and transport of GO particles in the natural heterogeneous porous media was highly related to the coupled effect of medium structure and salt solution concentration.

The predicted long lag time between a decrease in atmospheric deposition and a measured response in vegetation has generally excluded the investigation of vegetation recovery from the impacts of atmospheric deposition. However, policy-makers require such evidence to assess whether policy decisions to reduce emissions will have a positive impact on habitats. Here we have shown that 40 years after the peak of SOₓ emissions, decreases in SOₓ are related to significant changes in species richness and cover in Scottish Calcareous, Mestrophic, Nardus and Wet grasslands. Using a survey of vegetation plots across Scotland, first carried out between 1958 and 1987 and resurveyed between 2012 and 2014, we test whether temporal changes in species richness and cover of bryophytes, Cyperaceae, forbs, Poaceae, and Juncaceae can be explained by changes in sulphur and nitrogen deposition, climate and/or grazing intensity, and whether these patterns differ between six grassland habitats: Acid, Calcareous, Lolium, Nardus, Mesotrophic and Wet grasslands. The results indicate that Calcareous, Mesotrophic, Nardus and Wet grasslands in Scotland are starting to recover from the UK peak of SOₓ deposition in the 1970's. A decline in the cover of grasses, an increase in cover of bryophytes and forbs and the development of a more diverse sward (a reversal of the impacts of increased SOₓ) was related to decreased SOₓ deposition. However there was no evidence of a recovery from SOₓ deposition in the Acid or Lolium grasslands. Despite a decline in NOₓ deposition between the two surveys we found no evidence of a reversal of the impacts of increased N deposition. The climate also changed significantly between the two surveys, becoming warmer and wetter. This change in climate was related to significant changes in both the cover and species richness of bryophytes, Cyperaceae, forbs, Poaceae and Juncaceae but the changes differed between habitats.

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2′,4,4′,5,5′- hexachlorobiphenyl (PCB₁₅₃) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB₁₅₃ dechlorination activity (1.03 μM PCB₁₅₃ removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms’ metabolisms.

Ozone (O₃) and nitrogen dioxide (NO₂) are thought to play primary roles in aggravating air pollution-induced health problems. However, the effects of joint O₃/NO₂ on the allergenicity of pollen allergens are unclear. Humulus japonicus pollen allergen 1 (Hum j1) is a profilin protein that causes widespread pollinosis in eastern Asia. In order to study the effects of combined O₃/NO₂ on the allergenicity of Hum j1, tandem six-histidine peptide tag (His6)-fused recombinant Hum j1 (rHum j1) was expressed in a prokaryotic system and purified through His6 affinity chromatography. The purified rHum j1 was used to immunize SD rats. Rat sera with high titers of IgG and IgE antibodies against rHum j1 were used for allergenicity quantification. The rHum j1 was exposed to O₃/NO₂, and changes in allergenicity of the exposed rHum j1 were assayed using the immunized rat antibodies. Tandem LC-MS/LC (liquid chromatography-mass spectrometer/liquid chromatography spectrometer) chromatography and UV and circular dichroism (CD) spectroscopy were used to study the structural changes in rHum j1. Our data demonstrated that a novel disulfide bond between the sulfhydryl groups of two neighboring cysteine molecules was formed after the rHum j1 exposure to joint O₃/NO₂, and therefore IgE-binding affinity was increased and the allergenicity was reinforced. Our results provided clues to elucidate the mechanism behind air pollution-induced increase in pollinosis prevalence.

Sea ice decline is anticipated to increase human access to the Arctic Ocean allowing for offshore oil and gas development in once inaccessible areas. Given the potential negative consequences of an oil spill on marine wildlife populations in the Arctic, it is important to understand the magnitude of impact a large spill could have on wildlife to inform response planning efforts. In this study we simulated oil spills that released 25,000 barrels of oil for 30 days in autumn originating from two sites in the Chukchi Sea (one in Russia and one in the U.S.) and tracked the distribution of oil for 76 days. We then determined the potential impact such a spill might have on polar bears (Ursus maritimus) and their habitat by overlapping spills with maps of polar bear habitat and movement trajectories. Only a small proportion (1–10%) of high-value polar bear sea ice habitat was directly affected by oil sufficient to impact bears. However, 27–38% of polar bears in the region were potentially exposed to oil. Oil consistently had the highest probability of reaching Wrangel and Herald islands, important areas of denning and summer terrestrial habitat. Oil did not reach polar bears until approximately 3 weeks after the spills. Our study found the potential for significant impacts to polar bears under a worst case discharge scenario, but suggests that there is a window of time where effective containment efforts could minimize exposure to bears. Our study provides a framework for wildlife managers and planners to assess the level of response that would be required to treat exposed wildlife and where spill response equipment might be best stationed. While the size of spill we simulated has a low probability of occurring, it provides an upper limit for planners to consider when crafting response plans.

With the recent ban of triclosan (TCS) and triclocarban (TCC) from some personal care products, many replacement antimicrobial compounds have been used. Yet the potential health risk and environmental impact of these replacement compounds are largely unknown. Here we investigated the toxicological effects of three commonly used replacement antimicrobials, benzalkonium chloride (BAC), benzethonium chloride (BEC), and chloroxylenol (CX) to two model organisms, the nematode C. elegans and zebrafish (Danio rerio), and compared them to the banned TCS and TCC. We found that these replacement compounds are not any safer than the banned antimicrobials. In the worm, at least one of the three, BAC, showed comparable toxicity to TCS from organismal to molecular levels, with toxic effects occurring at lower hundred μg/L to lower mg/L levels. In the fish, all three compounds at the tested concentration ranges (0.05–5 mg/L) showed toxicity effects to zebrafish embryos, indicated by hatching delay or inhibition, embryonic mortality, morphological malformations, and neurotoxicity. BAC was the most toxic among the three, with acute lethal toxicity occurring at environmentally relevant concentrations (hundreds of μg/L), which is comparable to the banned TCC. However, the toxicity effects of BAC and TCC occurred within different time windows, potentially suggesting different mechanisms of toxicity. CX was the only compound that induced a “body curvature” phenotype among the five compounds examined, suggesting a unique mode of toxic action for this compound. Furthermore, all five compounds except TCS induced neurotoxicity in fish larvae, indicated by alterations in secondary motoneuron axonal projections. Such neurotoxicity has been largely understudied for these antimicrobials in the past years and calls for further investigations in terms of its underlying mechanisms and ecological significance. These findings strongly indicate that scrutiny should be put on these replacement compounds before their introduction into massive use in personal care products.

Pollution by microplastics in aquatic ecosystems is accumulating at an unprecedented scale, emerging as a new surface for biofilm formation and gene exchange. In this study, we determined the permissiveness of aquatic bacteria towards a model antibiotic resistance plasmid, comparing communities that form biofilms on microplastics vs. those that are free-living. We used an exogenous and red-fluorescent E. coli donor strain to introduce the green-fluorescent broad-host-range plasmid pKJK5 which encodes for trimethoprim resistance. We demonstrate an increased frequency of plasmid transfer in bacteria associated with microplastics compared to bacteria that are free-living or in natural aggregates. Moreover, comparison of communities grown on polycarbonate filters showed that increased gene exchange occurs in a broad range of phylogenetically-diverse bacteria. Our results indicate horizontal gene transfer in this habitat could distinctly affect the ecology of aquatic microbial communities on a global scale. The spread of antibiotic resistance through microplastics could also have profound consequences for the evolution of aquatic bacteria and poses a neglected hazard for human health.