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231.
Siedlecka EM Stepnowski P 《Environmental science and pollution research international》2009,16(4):453-458
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 相似文献
232.
233.
Minero C Maurino V Bono F Pelizzetti E Marinoni A Mailhot G Carlotti ME Vione D 《Chemosphere》2007,68(11):2111-2117
The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging. 相似文献
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235.
Mercury concentrations have been analysed in bream (Abramis brama L.) and zebra mussels (Dreissena polymorpha) collected at 17 freshwater sites in Germany from 1993-2009 and 1994-2009, respectively, within the German Environmental Specimen programme. Mercury concentrations in bream ranged from 21 to 881 ng g−1 wet weight with lowest concentrations found at the reference site Lake Belau and highest in fish from the river Elbe and its tributaries. Statistical analysis revealed site-specific differences and significant decreasing temporal trends in mercury concentrations at most of the sampling sites. The decrease in mercury levels in bream was most pronounced in fish from the river Elbe and its tributary Mulde, while in fish from the river Saale mercury levels increased. Temporal trends seem to level off in recent years. Mercury concentrations in zebra mussels were much lower than those in bream according to their lower trophic position and varied by one order of magnitude from 4.1 to 42 ng g−1 wet weight (33-336 ng g−1 dry weight). For zebra mussels, trend analyses were performed for seven sampling sites at the rivers Saar and Elbe of which three showed significant downward trends. There was a significant correlation of the geometric mean concentrations in bream and zebra mussel over the entire study period at each sampling site (Pearson’s correlation coefficient = 0.892, p = 0.00002). A comparison of the concentrations in bream with the environmental quality standard (EQS) of 20 ng g−1 wet weight set for mercury in biota by the EU showed that not a single result was in compliance with this limit value, not even those from the reference site. Current mercury levels in bream from German rivers exceed the EQS by a factor 4.5-20. Thus, piscivorous top predators are still at risk of secondary poisoning by mercury exposure via the food chain. It was suggested focusing monitoring of mercury in forage fish (trophic level 3 or 4) for compliance checking with the EQS for biota and considering the age dependency of mercury concentrations in fish in the monitoring strategy. 相似文献
236.
Here we investigated whether the assay system (10-d) in Caenorhabditis elegans can be used to evaluate chronic toxicity of chromium (Cr(VI)) at environmental relevant concentrations ranging from 5.2 μg L−1 to 260 μg L−1. The results indicated that lethality, locomotion behavior as revealed by head thrash, body bend, and forward turn, metabolism as revealed by pumping rate and mean defecation cycle length, intestinal autofluorescence, and ROS production were severely altered in Cr chronically exposed nematodes at environmental relevant concentrations. The most surprising observations were that head thrash, body bend, intestinal autofluorescence, and ROS production in 13 μg L−1 Cr exposed nematodes were significantly influenced. The observed adverse effects of Cr on survival, locomotion behavior, and metabolism were largely due to forming severe intestinal autofluorescence and ROS production. Therefore, our findings demonstrate the usefulness of chronic toxicity assay system in C. elegans in evaluating the chronic toxicity of toxicants at environmental relevant concentrations. 相似文献
237.
We report results of a multigenerational experiment with Chironomus riparius. Two strains with a high and a low level of genetic variability were exposed to a low, environmentally relevant TBT concentration of 80 μg Sn kg−1 sediment dw nominally (time weighted mean, based on measured concentrations: 4.5 μg Sn kg−1 sediment dw), and various life history traits as well as genetic diversity were monitored for eleven consecutive generations. While TBT effects are hardly visible in the outbred and genetically diverse strain, the inbred and genetically impoverished strain shows a clearly reduced population growth rate compared to the control. Moreover, the impoverished strain shows an increase in fitness over time. Analyses of variation at five microsatellite loci revealed that the level of genetic variation is strongly reduced in the inbred compared to the outbred strain. Moreover, genetic diversity increases over time in the inbred strain. This finding explains the observed increase in fitness in both inbred lineages (control and TBT exposed). The results document that inbreeding and the level of genetic diversity might be of crucial importance in populations under pollution stress. Furthermore, ecotoxicological bioassays have to consider genetic diversity if results between laboratories should be comparable. Our data provides evidence that genetic diversity strongly contributes to the survival of a population exposed to chemical pollution. 相似文献
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