The oxidation of magnetite into maghemite and its coating by natural organic constituents are common changes that affect the reactivity of iron oxide nanoparticles (IONP) in aqueous environments. Certain ubiquitous compounds such as humic acids (HA) and phosphatidylcholine (PC), displaying a high affinity for both copper (Cu) and IONP, could play a critical role in the interactions involved between both compounds. The adsorption of Cu onto four different IONP was studied: magnetite nanoparticles (magnNP), maghemite NP (maghNP), HA- and PC-coated magnetite NP (HA-magnNP and PC-magnNP, respectively). According to the results, the percentage of adsorbed Cu increases with increasing pH, irrespective of the IONP. Thus, protonation/deprotonation reactions are likely involved within Cu adsorption mechanism. Contrary to the other studied IONP, HA-magnNP favor Cu adsorption at most of the pH tested including acidic pH (pH = 3), suggesting that part of the active surface sites for Cu²⁺ were not grabbed by protons. The Freundlich adsorption isotherm of HA-magnNP provides the highest sorption constant KF (bonding energy) and n value which supports a heterogeneous sorption process. The heterogeneous adsorption between HA-magnNP and Cu²⁺ can be explained by both the diversity of the binding sites HA procured and the formation of multidendate complexes between Cu²⁺ and some of the HA functional groups. Such favorable adsorption process was neither observed on PC-coated-magnNP nor on maghNP, whose behaviors were comparable to that of magnNP. On another hand, HA and PC coatings considerably reduced iron (Fe) dissolution from magnNP as compared with magnNP. It was suggested that HA and PC coatings either provided efficient shield against Fe leaching or fostered dissolved Fe re-adsorption onto the functional groups at the coated magnNP surfaces. Thus, this study can help to better understand the complex interfacial reactions between cations-organic matter-colloidal surfaces which are relevant in environmental and agricultural contexts.This work showed that magnetite NP properties can be affected by surface modifications, which drive NP chemical stability and Cu adsorption, thereby affecting the global water chemistry.

Despite the widespread use of the antiviral drug, Tamiflu®, little is known about the long-term toxic effects of drug or its metabolites in an aquatic ecosystem. This study integrated epidemiological and ecotoxicological methods to determine environmentally relevant concentrations of Tamiflu. A model based on the species medaka (Oryzias latipes) was then used to determine the health status and reproductivity of adults exposed to the drug as well as the embryonic development of offspring. The proposed ecotoxicological model was also used to quantitatively and qualitatively evaluate the toxicodynamic parameters related to egg production, hatchability, and development. Our results revealed that at an environmentally relevant exposure, Tamiflu and its metabolites had no adverse effects on growth, survival, or fecundity of adult medaka. Nonetheless, we observed a reduction in hatchability under exposure to 300 μg L⁻¹ and a reduction in body length under exposure exceeding 90 μg L⁻¹. Under exposure to 300 μg L⁻¹, the estimated spawning time to reach 50% of the maximum percentage of cumulative egg production (ET50) far exceeded that of the control group (without exposure to Tamiflu). We also observed a ∼ 3-fold decrease in maximum egg hatching (Eₘₐₓ). Based on an integrated epidemiological and ecotoxicological model, predictions of environmental concentrations of Tamiflu and its metabolites revealed that the influenza subtypes associated with increases in environmental concentrations: A(H3N2) > A(H1N1) > type B (in order of their effects). We also determined that A(H3N2) posed a potential risk to hatchability and development. Note however, the environmental concentrations of Tamiflu and its metabolites in most countries are lower than the effect concentrations derived in this study, indicating no hazards for aquatic environments. We recommend the use of hatchability and embryonic development as indicators in assessing the effects of long-term parental exposure to Tamiflu metabolites.

Zearalenone (ZEA), an estrogen-like mycotoxin, is commonly detected in animal feeds including improperly stored grains. It has been well demonstrated that ovarian granulosa cells (GCs) perform vital roles during follicular development, however, the competing endogenous RNA (ceRNA) network in GCs after ZEA exposure remains to be well described. Here, for the first time, we adopted whole-transcriptome sequence technology to explore the molecular mechanism of ZEA toxicology on porcine GCs. The results provide evidence that the cell cycle of porcine GCs is arrested in the G2/M phase after exposure to ZEA. Furthermore, bioinformation analysis found that cell cycle arrest related genes were perturbed, including CDK1, CCNB1, CDC25A, and CDC25C, which was consistent with the results of RT-qPCR, immunofluorescence, and Western Blotting. Based on the whole-transcriptome sequence data, by constructing ceRNA networks related to cell cycle arrest, we observed that ZEA exposure arrested cell cycle progression at the G2/M phase in porcine GCs, and non-coding RNAs (ncRNAs) played an important role in this process via regulating the expressions of cell cycle arrest related genes. Taken together, our data here provides strong data to support that the toxicological mechanism regarding the widely distributed toxicant ZEA acts through ceRNA networks in porcine granulosa cells.

Inhalation of size-dependent particle-bound polycyclic aromatic hydrocarbons (PAHs) has been extensively studied, whereas dermal absorption has not been adequately investigated. To address this knowledge gap, dermal absorption of size-dependent particle-bound PAHs was characterized through the collection of indoor air and forearm wipe samples in the setting of an indoor barbecue. The mass of size-fractioned PAHs associated with particulate matter was greater in fine particles (<1.8 μm) than in coarse particles (>1.8 μm). Gas-particle distribution of specific PAHs from barbecue fume was ascribed to both adsorption and absorption which would probably be close to equilibrium, while that from background air was dominated by absorption. Forearm-deposited amounts of particulate PAHs suggested that removal of coarse and fine particles could minimize exposure to low and high molecular-weight (MW) PAHs, respectively. Besides, the concentrations of particulate PAHs in forearms wipe were significantly correlated to their dry deposition fluxes with coarse particles, but weakly correlated to those with fine particles. This indicated that particle size would influence dermal absorption efficiency of particle-bound PAHs with fine particles prolonging dermal exposure to PAHs. Overall, higher MW particle-bound PAHs derived from barbecue fume may pose higher risk to human health by dermal absorption than lower MW PAHs.

Marine deposit feeders are of ecological significance in transferring sedimentary Cd along aquatic food chains. A key process for this transfer is these organisms’ dietary uptake of Cd via solubilization of Cd present in ingested contaminated sediment. To better understand the bioavailability of sedimentary Cd to deposit feeders, the present study used in vitro extraction experiments to explore the contribution of different digestive agents (proteins, amino acids and surfactants) to the solubilization of Cd from sediment collected in a highly-contaminated Chinese bay. This was done for various commercially-available mimetic digestive agents (the protein BSA, a mixture of amino acids, and the surfactants rhamnolipid and SDS), and for proteins and surfactants collected from the gut juice of a sipunculan worm. The Cd mobilization capacity of BSA was significantly higher than that of the amino acids and the commercial surfactants. In the presence of BSA, > 70% of the released Cd became associated with this protein. In contrast, the digestive proteins from the sipunculan had a lower Cd mobilization capacity than was the case for the other digestive agents and the majority of the released Cd (∼80%) was associated with small molecular weight fractions. The differences in Cd mobilization between the BSA and the digestive proteins were attributed to differences in their sediment-adsorption tendencies and their Cd-complexing capacities. While the digestive surfactants had minor effects on the release of sedimentary Cd, they significantly enhanced Cd mobilization by the digestive proteins when both were present simultaneously. Our results suggest that the characteristics of proteins should be considered when using commercially-available mimetic digestive agents to explore Cd bioavailability in sediments. Furthermore, digestive surfactants seem to have important effects on the solubilization of Cd during gut passage by reducing the adsorption of the digestive proteins to the sediments.

Di(2-ethylhexyl) phthalate (DEHP), the most extensively used plasticizer in plastic formulations, is categorized as a priority environmental contaminant with carcinogenic, teratogenic, and mutagenic toxicities. Many isolated microorganisms exhibit outstanding performance as pure cultures in the laboratory but are unable to cope with harsh environmental conditions in the field. In the present study, a microbial consortium (CM9) with efficient functionality was isolated from contaminated farmland soil. CM9 could consistently degrade 94.85% and 100.00% of DEHP (1000 mg/L) within 24 h and 72 h, respectively, a higher efficiency than those of other reported pure and mixed microorganism cultures. The degradation efficiencies of DEHP and di-n-butyl phthalate were significantly higher than those of dimethyl phthalate and diethyl phthalate (p < 0.05). The primary members of the CM9 consortium were identified as Rhodococcus, Niabella, Sphingopyxis, Achromobacter, Tahibacter, and Xenophilus. The degradation pathway was hypothesized to include both de-esterification and β-oxidation. In contaminated soil, bioaugmentation with CM9 and biochar markedly enhanced the DEHP removal rate to 87.53% within 42 d, compared to that observed by the indigenous microbes (49.31%) (p < 0.05). During simulated bioaugmentation, the dominant genera in the CM9 consortium changed significantly over time, indicating their high adaptability to soil conditions and contribution to DEHP degradation. Rhodococcus, Pigmentiphaga and Sphingopyxis sharply decreased, whereas Tahibacter, Terrimonas, Niabella, Unclassified_f_Caulobacteraceae, and Allorhizobium-Neorhizobium-Pararhizobium-Rhizobium showed considerable increases. These results provide a theoretical framework for the development of in situ bioremediation of phthalate (PAE)-contaminated soil by composite microbial inocula.

Owing to environmental health concerns, a number of per- and polyfluoroalkyl substances (PFAS) have been phased-out, and increasingly replaced by various chemical analogs. Most prominent among these replacements are numerous perfluoroether carboxylic acids (PFECA). Toxicity, and environmental health concerns associated with these next-generation PFAS, however, remains largely unstudied. The zebrafish embryo was employed, in the present study, as a toxicological model system to investigate toxicity of a representative sample of PFECA, alongside perfluorooctanoic acid (PFOA) as one of the most widely used, and best studied, of the “legacy” PFAS. In addition, high-resolution magic angle spin (HRMAS) NMR was utilized for metabolic profiling of intact zebrafish embryos in order to characterize metabolic pathways associated with toxicity of PFAS. Acute embryotoxicity (i.e., lethality), along with impaired development, and variable effects on locomotory behavior, were observed for all PFAS in the zebrafish model. Median lethal concentration (LC₅₀) was significantly correlated with alkyl chain-length, and toxic concentrations were quantitatively similar to those reported previously for PFAS. Metabolic profiling of zebrafish embryos exposed to selected PFAS, specifically including PFOA and two representative PFECA (i.e., GenX and PFO3TDA), enabled elaboration of an integrated model of the metabolic pathways associated with toxicity of these representative PFAS. Alterations of metabolic profiles suggested targeting of hepatocytes (i.e., hepatotoxicity), as well as apparent modulation of neural metabolites, and moreover, were consistent with a previously proposed role of mitochondrial disruption and peroxisome proliferator-activated receptor (PPAR) activation as reflected by dysfunctions of carbohydrate, lipid and amino acid metabolism, and consistent with a previously proposed contribution of PFAS to metabolic syndrome. Taken together, it was generally concluded that toxicity of PFECA is quantitatively and qualitatively similar to PFOA, and these analogs, likewise, represent potential concerns as environmental toxicants.

Atmospheric levels of chlorinated paraffins (CPs) at five remote, six rural and four urban sites in Australia were measured using XAD-2 passive air samplers (XAD-PAS). While long-chain CP (LCCP, C>₁₇) levels were below method detection limits (MDLs), short-chain CPs (SCCPs, C₁₀₋₁₃) and, for the first time, medium-chain CPs (MCCPs, C₁₄₋₁₇) and CPs with a carbon chain length of nine (CP–C9) were found at many sites (88%, 81% and 88%, respectively) across the Australian continent, representing a range of environmental conditions. Applying preliminary sampling rates of the XAD-PAS for CPs, gaseous CP levels in Australian air were <MDL-1.3 and <MDL-1.8 ng/m³ for ΣSCCPs and ΣMCCPs, respectively, with a significant decreasing trend from more densely to less densely populated areas. Atmospheric median levels in this study (0.37 and 0.47 ng/m³ for SCCPs and MCCPs, respectively) were at the lower end of the median range (0.32–10 and 3.0–4.2 ng/m³ for SCCPs and MCCPs, respectively) reported for CPs at predominantly urban or industrial sites elsewhere (apart from China and extremely remote sites such as Antarctica). Principal component analysis matched the SCCP and MCCP congener group patterns in samples with those found in commercial mixtures, indicating a prevalence of less chlorinated congener groups in the Australian atmosphere. Information about the Australian production, use and disposal of CPs as well as their levels in other environmental matrices, including humans, is needed for assessing their emissions, behaviour, fate and potential exposure.

A wide variety of sampling techniques and strategies are needed to analyze polycyclic aromatic compounds (PACs) and interpret their distributions in various environmental media (i.e., air, water, snow, soils, sediments, peat and biological material). In this review, we provide a summary of commonly employed sampling methods and strategies, as well as a discussion of routine and innovative approaches used to quantify and characterize PACs in frequently targeted environmental samples, with specific examples and applications in Canadian investigations. The pros and cons of different analytical techniques, including gas chromatography – flame ionization detection (GC-FID), GC low-resolution mass spectrometry (GC-LRMS), high performance liquid chromatography (HPLC) with ultraviolet, fluorescence or MS detection, GC high-resolution MS (GC-HRMS) and compound-specific stable (δ¹³C, δ²H) and radiocarbon (Δ¹⁴C) isotope analysis are considered. Using as an example research carried out in Canada’s Athabasca oil sands region (AOSR), where alkylated polycyclic aromatic hydrocarbons and sulfur-containing dibenzothiophenes are frequently targeted, the need to move beyond the standard list of sixteen EPA priority PAHs and for adoption of an AOSR bitumen PAC reference standard are highlighted.