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     

砒霜生产化工厂危险废物处置工程设计

通过对砒霜生产化工厂原场址废渣及污染场地调查的基础上,进行了处置方案比选及技术经济比较,确定了就地安全填埋的处置方案。根据区域性危险废物集中安全填埋场的设计经验,本工程采用先进的HDPE双层防渗的安全填埋方式,并设置了雨水分流系统、渗滤液收集系统、封场处理和填埋气体导排系统,整个场区布置合理,对周围环境的影响小,投资少,取得了良好的社会效益和环境效益,并对危险废物处理处置工程设计中应注意的问题提出了建议。     

An analysis of assessment outcomes from eight years' operation of the Australian border weed risk assessment system

The majority of Australian weeds are exotic plant species that were intentionally introduced for a variety of horticultural and agricultural purposes. A border weed risk assessment system (WRA) was implemented in 1997 in order to reduce the high economic costs and massive environmental damage associated with introducing serious weeds. We review the behaviour of this system with regard to eight years of data collected from the assessment of species proposed for importation or held within genetic resource centres in Australia. From a taxonomic perspective, species from the Chenopodiaceae and Poaceae were most likely to be rejected and those from the Arecaceae and Flacourtiaceae were most likely to be accepted. Dendrogram analysis and classification and regression tree (TREE) models were also used to analyse the data. The latter revealed that a small subset of the 35 variables assessed was highly associated with the outcome of the original assessment. The TREE model examining all of the data contained just five variables: unintentional human dispersal, congeneric weed, weed elsewhere, tolerates or benefits from mutilation, cultivation or fire, and reproduction by vegetative propagation. It gave the same outcome as the full WRA model for 71% of species. Weed elsewhere was not the first splitting variable in this model, indicating that the WRA has a capacity for capturing species that have no history of weediness. A reduced TREE model (in which human-mediated variables had been removed) contained four variables: broad climate suitability, reproduction in less or than equal to 1year, self-fertilisation, and tolerates and benefits from mutilation, cultivation or fire. It yielded the same outcome as the full WRA model for 65% of species. Data inconsistencies and the relative importance of questions are discussed, with some recommendations made for improving the use of the system.     

Forecasting the outbreak of moorland wildfires in the English Peak District

Warmer, drier summers brought by climate change increase the potential risk of wildfires on the moorland of the Peak District of northern England. Fires are costly to fight, damage the ecosystem, harm water catchments, cause erosion scars and disrupt transport. Fires release carbon dioxide to the atmosphere. Accurate forecasts of the timing of fires help deployment of fire fighting resources.     

An Approach for Evaluating the Repeatability of Rapid Wetland Assessment Methods: The Effects of Training and Experience

We sampled 92 wetlands from four different basins in the United States to quantify observer repeatability in rapid wetland condition assessment using the Delaware Rapid Assessment Protocol (DERAP). In the Inland Bays basin of Delaware, 58 wetland sites were sampled by multiple observers with varying levels of experience (novice to expert) following a thorough training workshop. In the Nanticoke (Delaware/Maryland), Cuyahoga (Ohio), and John Day (Oregon) basins, 34 wetlands were sampled by two expert teams of observers with minimal protocol training. The variance in observer to observer scoring at each site was used to calculate pooled standard deviations (SD_pool), coefficients of variation, and signal-to-noise ratios for each survey. The results showed that the experience level of the observer had little impact on the repeatability of the final rapid assessment score. Training, however, had a large impact on observer to observer repeatability. The SD_pool in the Inland Bay survey with training (2.2 points out of a 0–30 score) was about half that observed in the other three basins where observers had minimal training (SD_pool = 4.2 points). Using the results from the survey with training, we would expect that two sites assessed by different, trained observers who obtain DERAP scores differing by more than 4 points are highly likely to differ in ecological condition, and that sites with scores that differ by 2 or fewer points are within variability that can be attributed to observer differences.     

Comparison of Function of Created Wetlands of Two Age Classes in Central Pennsylvania

Hydrogeomorphic (HGM) functional assessment models were used to assess whether function in created wetlands of two ages (1 year old and >12 years old) was equivalent to that of natural (reference) mainstem floodplain wetlands. Reference wetlands scored higher than both created age classes for providing energy dissipation and short-term surface water storage. Reference wetlands scored higher in maintaining native plant community and structure than 1-year-old sites, and 12-year-old wetlands scored higher than reference sites for providing vertebrate habitat structure. Analysis of individual model variables showed that reference wetlands had greater vegetative biomass and higher soil organic matter content than both created wetland age classes. Created wetlands were farther from natural wetlands and had smaller mean forest patch sizes within a 1-km-radius circle around the site than did the reference sites, indicating less hydrologic connectivity. Created wetlands also had less microtopographic variation than reference wetlands. The 1-year-old created sites were placed in landscape settings with greater land use diversity and road density than reference sites. The 12-year-old sites had a higher gradient and a higher percentage of their surrounding area in urban land use. These results show that the created wetlands were significantly structurally different (if not functionally so) from reference wetlands even after 12 years. The most profound differences were in hydrology and the characteristics of the surrounding landscape. More attention needs to be focused on placing created wetlands in appropriate settings to encourage proper hydrodynamics, eliminate habitat fragmentation, and minimize the effects of stressors to the site.     

Ecoregions in the Southern Balkans: Should Their Boundaries Be Revised?

Ecoregion delineations have gained increased attention in Europe, especially following the Water Framework Directive 2000/60/EC (WFD), which provides the European Union’s first policy-relevant ecoregion map. However, the WFD’s ecoregions were created through a minor adaptation of Illies’ (Limnofauna Europaea. Gustav Fisher Verlag, Stuttgart, 1967/1978) freshwater zoogeographic regions, and the map’s specific boundaries have not been widely evaluated with respect to the WFD’s uses or their biogeographic accuracy. We examined the WFD ecoregion boundaries in Greece and its neighboring Balkan states by comparing them with the most prominent freshwater biogeographic boundaries as shown by riverine freshwater fish assemblages. Classification and ordination analyses of 23 river basin fish assemblages helped delineate natural faunal break boundaries in freshwater species assemblage distributions depicting major biogeographic barriers to aquatic biota dispersal. However, these biogeographic boundaries differ from those delineated in the WFD map, suggesting boundary errors and inconsistencies in the delineation method of the WFD ecoregions. We reviewed specific boundary disagreements and produced a map showing the region’s most prominent freshwater biogeographic boundaries by charting them on watershed borders among the four biotically dissimilar river basin groups in the southern Balkans. This regional evaluation reveals both a need to reconcile disparate approaches to ecoregion mapping and to promote the development of a new policy-relevant inland waters ecoregion framework that would support broad-scale water management and aquatic conservation.     

Monitoring Environmental Impact in the Upper Sonoran Lifestyle: A New Tool for Rapid Ecological Assessment

Characterized by expensive housing, high socioeconomic status, and topographic relief, Upper Sonoran Lifestyle communities are found primarily along the Wildland-Urban Interface (WUI) in the Phoenix, Arizona metro area. Communities like these sprawl into the wildlands in the United States Southwest, creating a distinct urban fringe. This article, through locational comparison, introduces and evaluates a new field assessment tool for monitoring anthropogenic impact on soil–vegetation interactions along the well-maintained multi-use recreational trails in Upper Sonoran Lifestyle region. Comparing data from randomly selected transects along other multi-use trails with data from a control site revealed three key indicators of anthropogenic disturbances on soil–vegetation interactions: soil disturbance, vegetation disturbance, and vegetation density. Soil and vegetation disturbance displayed an average distance decay exponent factor of −0.60, while vegetation density displayed a reverse decay average of 0.60. Other important indicators of disturbance included vegetation type, biological soil crusts, and soil bulk density. The predictive ability of this new field tool enhances its applicability, offering a powerful rapid ecological assessment method for monitoring long-term anthropogenic impact in the Upper Sonoran Lifestyle, and other sprawling cities along the WUI.