The effects of the ionic liquid 1-octyl-3-methylimidazolium chloride ([OMIM]Cl) was studied in hydroponically grown rice seedlings. Observed effects included increased root length and weight at concentrations of 0.1 mg/L [OMIM]Cl, however, as concentrations increased a reversed response was observed where roots and stems grew shorter and the weight decreased. The inhibitory concentration 50 (IC50,5d) values for root length and stem length were 0.59 mg/L and 0.70 mg/L, respectively. The Hill reaction activity and root system activity in [OMIM]Cl-treated rice seedlings were observed to be lower than the controls, however, root membrane permeability increased. The antioxidant enzyme activity in roots decreased, while in leaves there was an initial stimulation followed by a decrease. Malondialdehyde (MDA) content was found to be greater in seedlings subjected to [OMIM]Cl treatment. The cellular structures, such as chloroplasts, mitochondria and rough endoplasmic reticulum in rice root and leaf cells were affected at concentrations of 0.6 mg/L [OMIM]Cl.

Ionic liquids (ILs) are extensively used in several chemistry fields. And research about the effects of ILs on soil microbes is needed. In this study, brown soil was exposed to 1-butyl-3-methylimidazolium bromide ([C₄mim]Br), 1-hexyl-3-methylimidazolium bromide ([C₆mim]Br) and 1-decyl-3-methylimidazolium bromide ([C₁₀mim]Br). The toxicities of the three ILs are evaluated by measuring the soil culturable microbial number, enzyme activity, microbial diversity and, abundance of the ammonia monooxygenase (amoA) genes of ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA). Results showed that all tested ILs caused a decrease in culturable microbial abundance. Tested ILs exposure inhibit urease activity and promote acid phosphatase and β-glucosidase activities. Tested ILs reduced soil microbial diversity and the abundances of AOB-amoA and AOA-amoA genes significantly. After a comparison of the integrated biomarker response (IBR) index, the toxicities of tested ILs to soil microorganisms were as follows: [C₁₀mim]Br > [C₆mim]Br > [C₄mim]Br. Among all collected biomarkers, the abundance of the AOA-amoA gene was the most sensitive one and was easily affected after ILs exposure.

Lange's metalmark butterfly, Apodemia mormo langei Comstock, is in danger of extinction due to loss of habitat caused by invasive exotic plants which are eliminating its food, naked stem buckwheat. Herbicides are being used to remove invasive weeds from the dunes; however, little is known about the potential effects of herbicides on butterflies. To address this concern we evaluated potential toxic effects of three herbicides on Behr's metalmark, a close relative of Lange's metalmark. First instars were exposed to recommended field rates of triclopyr, sethoxydim, and imazapyr. Life history parameters were recorded after exposure. These herbicides reduced the number of adults that emerged from pupation (24–36%). Each herbicide has a different mode of action. Therefore, we speculate that effects are due to inert ingredients or indirect effects on food plant quality. If these herbicides act the same in A. mormo langei, they may contribute to the decline of this species.

Structural and functional responses of a benthic macroinvertebrate assemblage to pulses of the insecticide imidacloprid were assessed in outdoor stream mesocosms. Imidacloprid pulses reduced invertebrate abundance and community diversity in imidacloprid-dosed streams compared to control streams. These results correlated well with effects of imidacloprid on leaf litter decomposition and feeding rates of Pteronarcys comstocki, a stonefly, in artificial streams. Reductions in oxygen consumption of stoneflies exposed to imidacloprid were also observed in laboratory experiments. Our findings suggest that leaf litter degradation and single species responses can be sensitive ecotoxicological endpoints that can be used as early warning indicators and biomonitoring tools for pesticide contamination. The data generated illustrates the value of mesocosm experiments in environmental assessment and how the consideration of functional and structural endpoints of natural communities together with in situ single species bioassays can improve the evaluation and prediction of pesticide effects on stream ecosystems. Combining organism-level responses with community-level processes for the evaluation and prediction of pesticide effects on stream ecosystems.

Ammonia (NH3) gas-aging of secondary organic aerosol (SOA) results in the formation of organonitrogen compound is an important class of brown carbon. The particulate products of aged 1,3,5-trimethylbenzene (135-TMB) SOA in the presence of NH3 were measured by UV–Vis spectrophotometer, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), and aerosol laser time-of-flight mass spectrometer (ALTOFMS) in present study. Experimental results indicated that NH3 has significant promotion effect on 135-TMB SOA formation. Organic ammonium salts, such as ammonium methyl glyoxylate, ammonium 3,5-dimethylbenzoate, which are formed from NH3 reactions with gaseous organic acids were detected as the principal particulate products of NH3-aged 135-TMB SOA. 4-methyl-imidazole-2-acetaldehyde, 4-methyl- 1H-imidazole and other imidazole products via the heterogeneous reactions between NH3 and dialdehydes of 135-TMB SOA were newly measured. The formation of imidazole products suggests that some ambient particles contained organonitrogen compounds may be come from this mechanism. The results of this study may provide valuable information for discussing SOA aging mechanisms and new route for NH3 deposition.

We developed a new hybrid material resulting from an innovative supramolecular tripartite association between an ionic liquid covalently immobilized on primary β-cyclodextrins rim and an anionic water-soluble polymer. Two hydrophilic ternary complexes based on native and permethylated β-cyclodextrins substituted with an ionic liquid and immobilized on poly(styrene sulfonate) (CD-IL⁺PSS⁻ and CD(OMe)IL⁺PSS⁻) were obtained by simple dialysis with a cyclodextrin maximal grafting rate of 25% and 20% on the polymer, respectively. These polyelectrolytes are based on electrostatic interactions between the opposite charges of the imidazolium cation of the ionic liquid and the poly(styrene sulfonate) anion. The inclusion properties of the free cavities of the cyclodextrins and the synergic effect of the polymeric matrix were studied with three reference guests such as phenolphthalein, p-nitrophenol, and 2-anilinonaphthalene-6-sulfonic acid using UV-visible, fluorescent, and NMR spectroscopies. The support has been applied successfully in dialysis device to extract and concentrated aromatic model molecule. This simple and flexible synthetic strategy opens the way to new hybrid materials useful for fast and low-cost ecofriendly extraction techniques relevant for green analytical chemistry.

The degradation of nitroaromatics/toxic energetic compounds contaminated water is a major cause of concern. W-doped TiO₂ nanoparticles (NPs) were synthesized in ionic liquid, ethyl methyl imidazolium dicyanamide (EMIM-DCA) by a solvothermal method. The developed NPs were sintered at 500 °C and characterized by UV-Vis-DRS, FT-IR, FE-SEM, XRD, XPS, and BET techniques. The 30–40-nm-sized NPs were subjected to photocatalytic degradation of the toxic energetic compound, tetryl (2,4,6-trinitrophenylmethylnitramine) under UV-Vis light. Various operating parameters such as the effect of concentration of catalyst, pH of feed phase, oxidizing agents, and recycling of catalyst were studied in detail. For the first time, the degradation-mechanism pathway and kinetics of tetryl were evaluated. The degradation products were precisely analyzed by using HPLC, GC-MS, and TOC techniques. The USEPA has prescribed a drinking water limit of 0.02 mg L⁻¹, and it was found that 0.5 g of 4% W-TiO₂ could totally degrade tetryl (50 mg L⁻¹) within 8 h. The kinetic rate constant of 4% W-TiO₂ was 0.356 h⁻¹, whereas pure TiO₂ showed 0.207 h⁻¹.

The effect of coexisting pesticide on adsorption/desorption and mobility of another one was investigated with carbendazim (CBD), imidacloprid (IDP), and atrazine (ATR). The data indicated that adsorption of CBD, ATR, and IDP on the tested soil was fitted well by Freundlich equation and increased with an order of IDP < ATR ≪ CBD. Adsorption of a pesticide was decreased by the coexistence of another one through their competitive adsorption. The presence of coexisting solute of the more adsorbability played a more important role than that of the lesser adsorbability. The adsorption of IDP and ATR was easier to be affected by 28.9-52.0 % and 31.1-60.7 % with the addition of CBD, while that of CBD was much less influenced by 3.4-18.1 % and 6.9-31.8 % with the presence of ATR and IDP, respectively. An adsorbability-related enhancement in desorption of the three pesticides by the co-adsorbed solute was also observed. As a result of competitive adsorption/desorption, the mobility of the pesticides estimated from soil thin-layer chromatography was altered. The results clearly illustrated that adsorbability and concentration-related alteration in adsorption/desorption and mobility will be caused by the coexistence of pesticides.

Background, aim, and scope Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57-84% to 87-100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals.

Persulfates are recognized as promising oxidants and an alternative to Fenton reaction for water treatment. However, activation methods in hand restrict the practical application. Herein, we explore the possibility of Fe-N complexes being a catalyst for persulfate activation for the first time. The catalyst denoted as Fe-Im-SBA was synthesized from ferric chloride, imidazole, and SBA-15 at high temperature. The internal pore structure of Fe-Im-SBA was maintained well; Fe, N and C elements are evenly distributed on the catalyst. This catalyst presents an extraordinarily catalytic activity for Rh B removal by PMS activation with a removal rate of Rh B that reached up to 97.0% in the first 5 min. It also performed well in a wide pH range with complete removal of Rh B in pH ranged from 0.5 to 10, suggesting the stability of this catalyst in both acidic and alkaline conditions. It also showed high adaptability to degrade different kinds of pollutants, which could give an attractive advantage of Fe-Im-SBA for environmental implications. Through X-ray absorption spectroscopies analysis, it shows that the active sites of Fe-Im-SBA are composed of Fe-N₄ sites and Fe₂–N₂ sites. ¹O₂ were proved to generate in the Fe-Im-SBA/PMS system and serve as the major ROS. Meanwhile, graphitic carbon can accelerate the transfer of electrons, which may also be the reason for its high catalytic performance.