The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

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     

Ecosystem restoration in fire-managed savanna woodlands: Effects on biodiversity,local livelihoods and fire intensity

Ethiopia aims to restore 15 million ha degraded forests and woodlands, but effects on the potentially contrasting goals of long-term carbon storage, biodiversity and sustainable livelihoods are unknown. To quantify the effects of grazing exclusion on vegetation and fire behaviour, we established six 30 × 30 m fenced exclosures with grazed controls, in a mesic wooded savanna. Experimental burns were done after 1.5 years. Tree seedlings were few but more common inside fences. Field layer cover and biomass increased inside fences, and grass species increased in numbers and cover. Fire intensity was higher inside fences, killing shrubs and saplings but not mature trees. Interviews confirmed that overgrazing has resulted in “cool fires”, causing shrub encroachment. High-intensity fires occurred in the 1980s after a zoonotic disease killed most livestock. Short-term increase in carbon storage through fire and grazing exclusion may lead to loss of pasture, and in the long-term increased wildfire risk.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01343-7) contains supplementary material, which is available to authorized users.     

Simultaneous removal of emerging contaminants and disinfection for municipal wastewater treatment plant effluent quality improvement: a systemic analysis of the literature

Environmental Science and Pollution Research - This work presents a bibliographic review of the literature regarding the simultaneous removal of contaminants of emerging concern (CECs) and...     

Can we take the pulse of environmental governance the way we take the pulse of nature? Applying the Freshwater Health Index in Latin America

Quantitative assessments have long been used to evaluate the condition of the natural environment, providing information for standard setting, adaptive management, and monitoring. Similar approaches have been developed to measure environmental governance, however, the end result (e.g., numeric indicators) belies the subjective and normative judgments that are involved in evaluating governance. We demonstrate a framework that makes this information transparent, through an application of the Freshwater Health Index in three different river basins in Latin America. Water Governance is measured on a 0–100 scale, using data derived from perception-based surveys administered to stakeholders. Results suggest that water governance is a primary area of concern in all three places, with low overall scores (Guandu-26, Alto Mayo-38, Bogotá-43). We conclude that this approach to measuring governance at the river basin scale provides valuable information to support monitoring and decision making, and we offer suggestions on how it can be improved.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01407-8) contains supplementary material, which is available to authorized users.     

Inflammation biomarkers associated with arsenic exposure by drinking water and respiratory outcomes in indigenous children from three Yaqui villages in southern Sonora,México

Environmental Science and Pollution Research - Environmental arsenic exposure in adults and children has been associated with a reduction in the expression of club cell secretory protein (CC16) and...     

Heavy metal accumulation and distribution in Phragmites australis seedlings tissues originating from natural and urban catchment

The retention of heavy metal (HM) was studied in root and rhizomes (BLG), stems (ST), and leaves (LF) of Phragmites australis (common reed) seedlings collected from different locations, differing in the scale of anthropogenic interference. The analysis includes the reference samples of sediments in uncontaminated lake Garczonki and contaminated roadside ditch in Cieplewo. The concentrations of Zn, Cu, Pb, Cd, Ni, and Cr were analyzed in plant tissues and sediments using the atomic absorption spectrometry and inductively coupled plasma mass spectrometry. The general assessment of sediments collected in the Garczonki lake showed a good environmental status; while in the roadside ditch in Cieplewo, the sediments were considerably polluted with HM. In the first stage of plant growth, all of the analyzed HMs are mainly inhibited by BLG system. The decreasing trend of elements was as follows: BLG > ST > LF. The organs followed different decreasing trends of HM concentration; the trend Zn > Cu > Ni > Cr > Pb > Cd was found in ST and LF for the Garczonki lake seedlings and for BLG and LF for the roadside ditch in Cieplewo seedlings. Zn showed the highest concentration, while Cd the lowest concentration in each of the examined organs. The bioaccumulation factor indicated the higher mobility of HM in seedlings in the Garczonki lake than in the roadside ditch in Cieplewo. The morphological studies suggest the good state and health of seedling from both sites; however, the reduction of root hair surface was observed for the roadside ditch seedlings. The anatomical studies present changes in the size of the nucleus and count of chloroplasts in LF. No reaction on HM contamination sediments in the seedlings from the roadside ditch in Cieplewo in the aerenchyma was noted. Potentially, both types of seedlings can be used to decontaminate environments rich in HM. However, the level of HM absorbed by seedlings (in the first stage of growth) should be considered due to the behavior in the target phytoremediation site.

     

Innovations strategy for moving from created regional clusters to co-creation in life sciences for health care and well-being ecosystems

Environmental Science and Pollution Research - Over the last decades, the demographic changes have all altered the population structure and influenced the social, economic, and political...     

Dimethoate induces genotoxicity as a result of oxidative stress: in vivo and in vitro studies

Environmental Science and Pollution Research - Dimethoate ([O,O-dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate]) is an organophosphate insecticide and acaricide widely used for...     

Antioxidant activity and enzyme inhibitory potential of Euphorbia resinifera and E. officinarum honeys from Morocco and plant aqueous extracts

Natural products may be applied in a wide range of domains, from agriculture to food and pharmaceutical industries. In this study, the antioxidant properties and the capacity to inhibit some enzymatic activities of Euphorbia resinifera and Euphorbia officinarum aqueous extracts and honeys were assessed. The physicochemical characteristics were also evaluated. Higher amounts of iron, copper and aluminium were detected in E. officinarum honey, which may indicate environmental pollution around the beehives or inadequate storage of honey samples. This honey sample showed higher amounts of total phenols and better capacity for scavenging superoxide anion free radicals and DPPH free radicals as compared with E. resinifera honey, but poorer capacity for inhibiting lipoxygenase, acetylcholinesterase, tyrosinase and xanthine oxidase. The ratio plant mass:solvent volume (1:100) and extraction time (1 - 2 h) were associated with higher total phenols and better antioxidant activities and lipoxygenase, acetylcholinesterase and tyrosinase inhibitory activities, regardless of the plant species. The aqueous extracts had systematically higher in vitro activities than the respective honey samples.