Perfluorododecanoic acid (PFDoA), a kind of perfluorinated carboxylic acid (PFCA) with 12 carbon atoms, has an extensive industrial utilization and is widespread in both wildlife and the water environment, and was reported to have the potential to cause a disruption in the thyroid hormone system homeostasis. In this study, zebrafish embryos/larvae were exposed to different concentrations of PFDoA (0, 0.24, 1.2, 6 mg/L) for 96 h post-fertilization (hpf). PFDoA exposure caused obvious growth restriction connected with the reduced thyroid hormones (THs) contents in zebrafish larvae, strengthening the interference effect on the growth of fish larvae. The transcriptional level of genes within the hypothalamic-pituitary-thyroid (HPT) axis was analyzed. The gene expression levels of thyrotropin-releasing hormone (trh) and corticotrophin-releasing hormone (crh) were upregulated upon exposure to 6 mg/L of PFDoA, and iodothyronine deiodinases (dio2) was upregulated in the 1.2 mg/L PFDoA group. The transcription of thyroglobulin (tg) and thyroid receptor (trβ) were significantly downregulated upon exposure to 1.2 mg/L and 6 mg/L of PFDoA. PFDoA could also decrease the levels of sodium/iodide symporter (nis) and transthyretin (ttr) gene expression in a concentration-dependent manner after exposure. A significant decrease in thyroid-stimulating hormoneβ (tshβ), uridinediphosphate-glucuronosyltransferase (ugt1ab) and thyroid receptor (trα) gene expression were observed at 6 mg/L PFDoA exposure. Upregulation and downregulation of iodothyronine deiodinases (dio1) gene expression were observed upon the treatment of 1.2 mg/L and 6 mg/L PFDoA, respectively. All the data demonstrated that gene expression in the HPT axis altered after different PFDoA treatment and the potential mechanisms of the disruption of thyroid status could occur at several steps in the process of synthesis, regulation, and action of thyroid hormones.

Iodination of dissolved organic matter (DOM) initiated by manganese oxide may represent an important source of organoiodine compounds (OICs) for iodide-containing waters. Here, Suwannee River natural organic matter was selected as model DOM, the OICs formation in simulated freshwater samples from iodinated DOM induced by manganese oxide (δ-MnO2) was investigated at different pHs and concentrations of iodide and δ-MnO2 by using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). While no OIC was observed in DOM control samples without δ-MnO2, hundreds of OICs were detected in the presence of δ-MnO2, suggesting the enhanced role of δ-MnO2 played in DOM iodination. The relative abundance was defined as the value of dividing the peak intensity of OICs by the highest m/z peak intensity constantly occurred in each mass spectrum, and selected as a parameter for partly reflecting the real level of OICs. The relative abundance of most OICs were around or greater than 1%, and several OICs with higher relative abundance were identified as diiodo-5-hydroxy-4-cyclopentene-1,3-dione, diiodomethane and diiodoacetic acid. The numbers of the formed OICs increased with the increase concentrations of iodide/δ-MnO2 and the decrease of pH, and nearly all OICs formed at lower levels of iodide/δ-MnO2 and/or higher pH were overlapped by that at higher levels of iodide/δ-MnO2 and/or lower pH, indicating the reliability of FT-ICR MS analysis techniques and data processing method. The OICs were formed mainly from the iodination of typical lignin-like and tannin-like compounds, as well as the precursor compounds with higher relative abundance through substitution reactions. Our findings demonstrate that the OICs formation by δ-MnO2-initiated DOM iodination should receive more attention and the concentration, exact structure and toxicity of the OICs need to be further investigated.

Perchlorate (ClO4−) interferes with uptake of iodide in humans. Emission inventories do not explain observed distributions. Ozone (O3) is implicated in the natural origin of ClO4−, and has increased since pre-industrial times. O3 produces ClO4−in vitro from Cl−, and plant tissues contain Cl− and redox reactions. We hypothesize that O3 exposure may induce plant synthesis of ClO4−. We exposed contrasting crop species to environmentally relevant O3 concentrations. In the absence of O3 exposure, species exhibited a large range of ClO4− accumulation but there was no relationship between leaf ClO4− and O3, whether expressed as exposure or cumulative flux (dose). Older, senescing leaves accumulated more ClO4− than younger leaves. O3 exposed vegetation is not a source of environmental ClO4−. There was evidence of enhanced ClO4− content in the soil surface at the highest O3 exposure, which could be a significant contributor to environmental ClO4−.

The cationic degradable polymer poly(lactic acid) choline iodide ester methacrylate, poly(PLA₄ChMA), can be used to flocculate particles and dewater sediments from tailings ponds and wastewater. A suitable bioaccessibility method is required to characterize the interactions of this novel flocculant in the human gastrointestinal system. To this end, a physiologically based extraction test (PBET) was modified to evaluate the bioaccessibility of flocculants. Bioaccessibility (bioaccessible fraction) is a measure of the solubility of a contaminant in gastrointestinal fluids and that may be available for systemic absorption. The flocculants poly(PLA₄ChMA), SNF C3276, and FLOPAM A3338 were tested at a solid-to-liquid ratio of 1:200 in the absence and presence of kaolin clay, which is used as a model sediment compound. Bioaccessible fractions were characterized by proton nuclear magnetic resonance spectroscopy and estimated by gravimetry. The bioaccessibility of poly(PLA₄ChMA) in gastric and intestinal PBET solutions decreases from 78% and 100%, respectively, in the absence of kaolin to approximately 0% with kaolin, indicating that poly(PLA₄ChMA) remains adsorbed onto the clay surface throughout the PBET, a result confirmed by thermogravimetric analysis. The bioaccessibility of cationic SNF C3276 and anionic FLOPAM A3338 in gastric solution is approximately 76% and 26%, respectively, and is not affected by the presence of kaolin. However, in intestinal solutions, the bioaccessibility of SNF C3276 and FLOPAM A3338 (60–85% in the absence of kaolin) changes to 0% and 100%, respectively, in the presence of kaolin. These results, interpreted in terms of solution pH and surface charge, demonstrate that interactions with kaolin influence the solubility of flocculants and must be considered in the evaluation of bioaccessibility. In future works, such bioaccessibility methods can be applied to assess the human-health safety of using flocculants in wastewater treatments.

The abnormality in thyroid hormone modulation in developmental fish, vulnerable to per- and polyfluorinated substances, is of particular concerns for the alternative substances. Juvenile rare minnows, were exposed to chlorinated polyfluoroalkyl ether sulfonates (Cl-PFESAs), the novel alternatives to perfluorooctane sulfonate (PFOS), for 4 weeks followed by 12 weeks of depuration. Half lives were determined to be 33 d, 29 d, and 47 d for total Cl-PFESAs, C8 Cl-PFESA and C10 Cl-PFESA, respectively. Preliminary toxicity test suggested that Cl-PFESAs are moderately toxic to Rare minnow with a LC50 of 20.8 mg/L (nominal concentration） after 96 h of exposure. In the chronic toxicity test, fishes were exposed to Cl-PFESAs at geometric mean measured concentrations of 86.5 μg/L, 162 μg/L and 329 μg/L. In juvenile fishes exposed to Cl-PFESAs for 4 weeks, gene profile sequencing analysis identified 3313 differentially expressed genes, based on which pathways regulating thyroid hormone synthesis and steroid synthesis were enriched. Both whole body total and free 3,5,3′-triiodothyronine (T3) levels were significantly increased. mRNA expression of genes regulating thyroid hormone synthesis (corticotropin-releasing hormone (CRH), thyroid-stimulating hormone (THS), sodium/iodide symporter (NIS), thyroglobulin (TG), and thyroid peroxidase (TPO), transport (transthyretin,TTR), deiodinase (Dio1, Dio2) and receptor (TRα and TRβ) were decreased. Uridinediphosphate glucoronosyl-transferases (UGT1A) gene, regulating THs metabolism, was also decreased. In adult fish, thyroid hormone and genes expression in hypothalamic-pituitary-thyroid axis remained at disturbed levels after 12 weeks of depuration without exposure. Chronic developmental exposure to Cl-PFESAs caused persistent thyroid hormone disrupting effects in fish, highlighting a necessity of comprehensive ecological risk assessment.

A two-step method was developed to extract microplastics from sediments. First, 1 kg sediments was pre-extracted using the air-induced overflow (AIO) method, based on fluidisation in a sodium chloride (NaCl) solution. The original sediment mass was reduced by up to 80%. As a consequence, it was possible to reduce the volume of sodium iodide (NaI) solution used for the subsequent flotation step. Recoveries of the whole procedure for polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polystyrene and polyurethane with sizes of approximately 1 mm were between 91 and 99%. After being stored for one week in a 35% H2O2 solution, 92% of selected biogenic material had dissolved completely or had lost its colour, whereas the tested polymers were resistant. Microplastics were extracted from three sediment samples collected from the North Sea island Norderney. Using pyrolysis gas chromatography/mass spectrometry, these microplastics were identified as PP, PVC and PET.

Perchlorate is a widespread contaminant in the aquatic environment. In the present work, the expressions of deiodinase enzymes (d1, d2, and d3) and sodium iodide symporter (nis) genes were determined after larval and adult rare minnow (Gobiocypris rarus) exposed to 5 and 50μg/L perchlorate for 21days. The results showed that deflation of swim bladder development was observed in larvae at 50μg/L perchlorate treatment. An up-regulation of the d2 and nis mRNA levels were observed in the larve and in brain of adults. Meanwhile the expressions of d3 mRNA levels were significantly down-regulated in the liver. These results indicate the changes in d2, nis, and d3 mRNA expression brings about increased outer-ring deiodination, idodine uptake, and a further decrease of inner-ring deiodination, respectively reflecting auto-regulation of hypothalamic-pituitary-thyroid (HPT) axis in adult after perchlorate exposure. The larval fish development could be affected by perchlorate at environmentally relevant concentrations.

The ecological relevance of polychaetes coupled with their easy culture and maintenance in the laboratory, has led them to become increasingly used in marine ecotoxicological studies, raising the need to validate frequently applied monitoring tools at various biological levels. The present study was aimed to characterize the cholinesterases (ChE) activity in the polychaete Capitella teleta, using three substrates (acetylthiocholine iodide, propionylthiocholine iodide, and S-butyrylthiocholine iodide) and four known inhibitors (eserine hemisulfate, BW284c51, iso-OMPA and chlorpyrifos-oxon). Results showed that most of the measured cholinesterase activity was acetylcholinesterase (AChE). Inhibition of enzyme kinetic experiments denoted that sensitivity of C. teleta’s ChE to the organophosphorous metabolite chlorpyrifos-oxon (IC50=60.72nM) was analogous to some fish species. This study highlights the relevance of ChE characterization before its use as a biomarker in ecotoxicology and biomonitoring studies.

The reduction of commonly used X-ray contrast iohexol (IOX) by the electrooxidation process is presented in this study. To begin with, the effect of anode material was examined, and different mixed metal oxide electrodes (MMOs) such as Ti/RuO₂, Ti/Pt, Ti/IrO₂-RuO₂, Ti/IrO₂-Ta₂O₅, Ti/Ta₂O₅-SnO₂-IrO₂, and Pt/SnO₂ were used. To assess experimental conditions at Ti/RuO₂ anode, provided the highest removal efficiency, the response surface method was applied and the key influencing parameter was the process time. The determined optimal conditions were triplicated with real wastewater samples, and the average degradation efficiency of IOX was found to be 99%. By-products of the IOX degradation on the Ti/RuO₂ anode have been identified using density functional theory and LC/MS-MS analysis. The results showed that IOX degradation opened with OH group detachment and resulted in the formation of a by-product with a molecular mass of 804 g mol⁻¹. Further degradation mechanism took place due to the breakup of C₄-C₁₀ and C₅-I₇ bonds with a by-product formed as 603 g mol⁻¹. Iodide atom replacement by OH groups caused the formation of a molecular fragment with 375 g mol⁻¹ molecular weight. The further disintegration of C₂-C₁₁ and C₆-N₁₆ σ- bonds led to the formation of molecular masses of 133, 126, and 119 g mol⁻¹, respectively.

Regarding the cost-effective degradation of diazinon (DIZ), the present study was conducted to develop and UV/iodide process in a photo catalyst reactor. CCD modeling applied and the results shows that the highest R-squared value (adjusted R-squared: 0.9987), the lowest P-value (2.842 e − 10), the lowest AIC (14.54), and the most insignificant lack-of-fit (0.73) belonged to the second-order model. Based on second-order model, the stationary points for time, iodide: DIZ (molar ratio %), DIZ concentration, and pH were 6.99 min, 80.15% iodide: DIZ (molar ratio %), 3.34, mg L⁻¹, and pH 7.34 (− log₁₀[H⁺]), respectively. The maximum reduction efficiency of 97.22% was obtained at the experimental conditions. The LC–MS analyses from optimal condition implied that all the DIZ molecules and its intermediates breaking to simple compounds during 15 min of processing. The data shown UI process reduced the BOD and COD levels by about 66% and 86.29% within 80 min of photoreaction, respectively. Furthermore, in kinetic investigation, with the increase in DIZ concentration, kₒbₛ and rₒbₛ increased and secondly, the conventional and PCBR reactor kₒbₛ increased by about respectively 17% and 50% with an increase in DIZ concentration from 5 to 15 mgL⁻¹. Additionally, when the DIZ concentration increase from 5 to 15 mg L⁻¹, rₒbₛ increased in the conventional and PCBR reactors respectively about 4.9 and 6 times. Figure-of-merit EEₒ changed from 12.66–17.41 to 7.26–10.15 kWhm³ for the conventional reactor, and 8.66–13.61 to 5.24–8.12 kWhm³ in PCBR, when the DIZ concentration increasing from 5 to 15 mg L⁻¹. Consequently, in the PCBR reactor, the energy consumption reduced by 14% at 5 mg L⁻¹ DIZ concentration and by 60% at 15 mg L⁻¹ DIZ concentration. Also, total cost of the system (TCS) decreases from 4.52 to 1.46 $ in conventional reactor and 1.47 to 0.42 $ in PCBR reactor when the DIZ concentration increase from 5 to 15 mg L⁻¹.