Lipophilicity and Metabolic Route Prediction of Imidazolium Ionic Liquids * (6 pp)

- Aims and Background. Ionic liquid application in industry will offer several excellent solutions, but it also means that they will enter the environment sooner or later. Responsible product design should always take into consideration not only technological demands, but also the risks arising out of possible toxicity and ecotoxicity. In our strategy we are aiming to understand the fate of these entities through their life cycle in the environment as a complimentary element of their design. This paper presents results on the lipophilicity of selected imidazolium ionic liquids, a parameter that plays a key role in environmental and biological distribution. Additionally, the prediction of the most stable metabolite of a 1-butyl-3-methylimidazolium (BMIM) cation – a congener representative of this group of compounds is presented. Materials and Methods Lipophilicity was evaluated by means of reversed phase and immobilized artificial membrane chromatography and further compared to calculated data. Theoretical prediction of lipophilicity was undertaken using fragmental methodology combined with manual calculations of the geometric bond factor for quaternary ammonium and the electronic bond factor due to the presence of a charge. Results and Discussion All the substances studied are characterized by very low partition coefficients, and lipophilicity varies linearly with elongation of the n-alkyl chain. Prediction of metabolic routes was based solely on thermodynamic data of the radical intermediates formed during the reaction with the cytochrome P450 system. The energetically most stable radical structure is generated by hydrogen abstraction from the gamma position of the BMIM cation. Conclusions and Recommendations. The experimentally measured and theoretically estimated lipophilicity coefficients obtained for all the compounds studied generally indicate a relatively low lipophilicity and thus preferable partition to the aqueous phase. By means of thermodynamic data, it was also confirmed that the energetically most stable radical structure is generated by hydrogen abstraction from the gamma position on the alkyl chain in the 1-alkyl-3-methylimidazolium cation, as a result of which the C1 atom is preferentially oxidized. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Differential sex- and age-related migration of Bluethroats Luscinia svecica at Eilat, Israel

This paper examines the phenology and biometrics of Bluethroats staging in the Eilat region. This is of special interest because of the extreme conditions with which this temperate zone breeding species has to contend because Eilat is a desert habitat and is the last green area before the crossing of the deserts in autumn or after it in spring. Data were collected during 20 spring and 18 autumn migration seasons in the years 1984–2003, and a total of 7,464 Bluethroat were recorded. The number of trapped birds was much higher in autumn than in spring. The majority of Bluethroats caught in both the autumn and spring migrations were juveniles. We found differences in sex ratio in the individual age classes only in the autumn wherein among both adults and juveniles, males were in greater numbers. We also found significant differences in the dates of ringed birds from different sex–age classes in the spring and in autumn migrations. In spring, males from both age classes were caught earlier than females. In autumn, adult birds arrived earlier than juveniles. We think that it is important to identify and conserve the high quality stopover habitats such as Eilat wherein not only Bluethroats have been shown to stopover but also several hundred other species.     

Ammoniacal leaching and recovery of copper from alloyed low-grade e-waste

The paper concerns a hydrometallurgical method for selective recovery of copper from low-grade electric and electronic wastes. The following consecutive stages were proposed: smelting of the scraps to produce Cu–Zn–Ag alloy, leaching of the alloy in ammoniacal solution, and selective copper electrowinning. Cu–Zn–Ag alloy was a polymetallic and five-phase system. It was leached in chloride, carbonate, sulfate and thiosulfate solutions. This resulted in the separation of the metals, wherein metallic tin and silver as well as lead salts remained in the slimes, while copper and zinc were transferred to the electrolyte. Copper was selectively recovered from the ammoniacal solutions by the electrolysis, leaving zinc ions in the electrolyte. The best conditions of the alloy treatment were obtained in the ammonia–carbonate system, where the final product was copper of high purity (99.9 %) at the current efficiency of 60 %. Thiosulfate solution was not applicable for the leaching of the copper alloy due to secondary reactions of the formation of copper(I) thiosulfate complexes and precipitation of copper(I) sulfide, both inhibiting dissolution of the metallic material.     

Evolution of within-colony distribution patterns of birds in response to habitat structure

It has long been suggested that habitat structure affects how colonial birds are distributed within their nesting aggregations, but this hypothesis has never been formally tested. The aim of this study was to test for a correlated evolution between habitat heterogeneity and within-colony distributions of Ciconiiformes by using Pagel’s general method of comparative analysis for discrete variables. The analysis indicated that central-periphery gradients of distribution (high-quality individuals occupying central nesting locations) prevail in species breeding in homogeneous habitats. These were mainly ground-nesting larids and spheniscids, where clear central-periphery patterns were recorded in ca. 80 % of the taxa. Since homogeneous habitats provide little variation in the physical quality of nest sites, central nesting locations should be largely preferred because they give better protection against predators by means of more efficient predator detection and deterrence. By contrast, central-periphery gradients tended to be disrupted in heterogeneous habitats, where 75 % of colonial Ciconiiform species showed uniform patterns of distribution. Under this model of distribution, edge nest sites of high physical quality confer higher fitness benefits in comparison to low-quality central sites, and thus, high-quality pairs are likely to choose nest sites irrespectively of their within-colony location. Breeding in homogeneous habitats and uniform distribution patterns were identified as probable ancestral states in Ciconiiformes, but there was a significant transition rate from uniform to central-periphery distributions in species occupying homogeneous habitats.     

Experimental and theoretical studies on formation and degradation of chloro organic compounds

Studies on oxidation of tert-butyl ethers in the presence of chloride ions proved that acid medium favoured formation of chloro organic compounds. 1,2-Dichloro-2-methylpropane, 3-chloro-2-chloromethylpropene were identified among the reaction products. Presence of these compounds was identified both in the case when methyl-tert-butyl ether (MTBE) and ethyl-tert-butyl ether (ETBE) were subjected to reaction. Reaction products were analysed by gas chromatography method with application of -FID, -MS and -AED detectors. On the basis of experimental data, the path of tert-butyl ethers conversion to dichloro products was proposed. It was found that the identified chloro derivatives could be formed both by ionic and radical reactions. In order to confirm this thesis for the proposed scheme of reaction, the theoretical calculations of molecular simulation of the reaction paths were performed.     

Relationships and bioaccumulation of chemical elements in the Baikal seal (Phoca sibirica)

Concentrations of Al, Ba, Cd, Cu, Fe, Mn, Mo, Si, Sr, Zn, Ca, K, Mg, Na and P in the livers of Baikal seal, plankton, zoobenthos, and fish, constituting the food sources for the seals, were determined by ICP-MS and ICP-AES. The accumulation of elements in the liver of seals, affected by internal and external (environmental) factors, was assessed by multidimensional (ANOVA, FA) and correlation analyses. FA has enabled identification of abiotic and biotic factors responsible for the accumulation of elements in the livers of Baikal seals. Significant influence of sex and development stage of the seals analysed on hepatic concentrations of some elements was found. The observed differences in element concentrations between pups, males and females could be attributable to the reproductive cycle of this species. ANOVA showed differences in concentrations of Fe, Zn, Cu and Cd in seals from the three separate basins of the lake. BMFs suggest biomagnification of Fe and Zn in the fish-seal trophic link.     

Management of adverse effects of a public water supply well field on the aquatic habitat of a stratified drift stream in eastern Connecticut.

A study was conducted to determine the effect of water withdrawals from the University of Connecticut's (Storrs) water supply wells on the fisheries habitat of the Fenton River adjacent to the well field. The study was designed to investigate the relationships between in-stream flow and selected fish habitat in the section of the Fenton River situated in the main zone of influence of the pumping field. With the aid of historical data, new data collection, and mathematical simulation modeling, the relation between the magnitude and timing of groundwater withdrawals on the stage and flow of water in the stream was derived. Fish sampling and habitat modeling were used to assess the effects of human influence on certain reaches of the Fenton River. Among the various water management scenarios studied, several are presented that would optimize water withdrawals, while minimizing adverse effects on the stream flow and in-stream habitat.     

The relationship between agricultural intensification and biological control: experimental tests across Europe

Agricultural intensification can affect biodiversity and related ecosystem services such as biological control, but large-scale experimental evidence is missing. We examined aphid pest populations in cereal fields under experimentally reduced densities of (1) ground-dwelling predators (-G), (2) vegetation-dwelling predators and parasitoids (-V), (3) a combination of (1) and (2) (-G-V), compared with open-fields (control), in contrasting landscapes with low vs. high levels of agricultural intensification (AI), and in five European regions. Aphid populations were 28%, 97%, and 199% higher in -G, -V, and -G-V treatments, respectively, compared to the open fields, indicating synergistic effects of both natural-enemy groups. Enhanced parasitoid: host and predator: prey ratios were related to reduced aphid population density and population growth. The relative importance of parasitoids and vegetation-dwelling predators greatly differed among European regions, and agricultural intensification affected biological control and aphid density only in some regions. This shows a changing role of species group identity in diverse enemy communities and a need to consider region-specific landscape management.     

Tailoring mesoporosity of poly(furfuryl alcohol)-based activated carbons and their ability to adsorb organic compounds from water

In this work it was shown that polymers can be recycled into a promising adsorbent for organic dyes and phenols waste removal. For this, a series of activated carbons (ACs) were produced from mixture of ferrocene or titanium acetylacetonate with poly(furfuryl alcohol) (PFA) by steam activation. The introduction of ferrocene as Fe precursor was found to be an efficient catalyst in mesoporosity development during carbonization and subsequent steam activation at 850 °C, whereas the polymer based only and titanium-doped ACs are typically microporous. The porous structure parameters were determined from nitrogen adsorption isotherms measured at 77 K. Scanning electron microscopy was applied to monitor the metal distribution of metal-loaded char and the surface morphology of activated carbons. The adsorption capacity was found to be dependent mainly on pore size distribution. In the case of phenol adsorption, the adsorption was defined by volume of pore with size 0.8–1.4 nm; whereas, for Congo red best fit was observed for volume of pore with size 2–5 nm.