New Insights into the Thermal Stability of 1-Butyl-3-methylimidazolium-Based Ionic Liquids.

One of the most promising applications of ionic liquids (ILs) with 1-butyl-3-methylimidazolium (bmim) cation is based on their unique ability to dissolve and fractionate lignocellulosic biomass, allowing for the development of green biorefining technologies. A complete dissolution of lignocellulose requires prolonged treatment at elevated temperatures, which can cause the partial degradation of ILs. In the present study, a combination of various analytical techniques (GC-MS, HPLC-HRMS, 2D-NMR, synchronous thermal analysis) was used for the comprehensive characterization of bmim acetate, chloride, and methyl sulfate degradation products formed at 150 °C during 6- and 24-h thermal treatment. A number of volatile and non-volatile products, including monomeric and dimeric alkyl substituted imidazoles, alcohols, alkyl amines, methyl and butyl acetates, and N-alkylamides, was identified. By thermal lability, ILs can be arranged in the following sequence, coinciding with the decrease in basicity of the anion: [bmim]OAc > [bmim]Cl > [bmim]MeSO4. The accumulation of thermal degradation products in ILs, in turn, affects their physico-chemical properties and thermal stability, and leads to a decrease in the decomposition temperature, a change in the shape of the thermogravimetric curves, and the formation of carbon residue during pyrolysis.

Gas Chromatography-Mass Spectrometry Quantification of 1,1-Dimethylhydrazine Transformation Products in Aqueous Solutions: Accelerated Water Sample Preparation.

The use of highly toxic rocket fuel based on 1,1-dimethylhydrazine (UDMH) in many types of carrier rockets poses a threat to environment and human health associated with an ingress of UDMH into wastewater and natural reservoirs and its transformation with the formation of numerous toxic nitrogen-containing products. Their GC-MS quantification in aqueous samples requires matrix change and is challenging due to high polarity of analytes. To overcome this problem, accelerated water sample preparation (AWASP) based on the complete removal of water with anhydrous sodium sulfate and transferring analytes into dichloromethane was used. Twenty-nine UDMH transformation products including both the acyclic and heterocyclic compounds of various classes were chosen as target analytes. AWASP ensured attaining near quantitative extraction of 23 compounds with sample preparation procedure duration of no more than 5 min. Combination of AWASP with gas chromatography-mass spectrometry and using pyridine-d5 as an internal standard allowed for developing the rapid, simple, and low-cost method for simultaneous quantification of UDMH transformation products with detection limits of 1-5 µg L-1 and linear concentration range covering 4 orders of magnitude. The method has been validated and successfully tested in the analysis of aqueous solutions of rocket fuel subjected to oxidation with atmospheric oxygen, as well as pyrolytic gasification in supercritical water modelling wastewater from carrier rockets launch sites.

Data on the spatial distribution of 1,1-dimethylhydrazine and its transformation products in peat bog soil of rocket stage fall site in Russian North.

The data set covers the results of a study of 96 samples of peat bog soil from the fall place of the first stage of the Cyclone-3 launch vehicle contained unburned toxic rocket fuel 1,1-dimethylhydrazine (UDMH) in the European North of Russia. Soil samples were taken during a helicopter expedition to the "Koida" fall region of Plesetsk Cosmodrome operation zone in October 2015 at different distances from the center of the fall site and from different soil horizons. Samples were analyzed by liquid chromatography with amperometric detection and gas chromatography - tandem mass spectrometry. The contents of UDMH and the ten most important products of its transformations (methylhydrazine, hydrazine, 1,1,4,4-tetramethyltetrazene, formaldehyde, acetaldehyde and furaldehyde N,N-dimethylhydrazones, 1-formyl-2,2-dimethylhydrazine, N,N-dimethylformamide, N-nitrosodimethylamine, and 1-methyl-1H-1,2,4-triazole) were determined. The obtained data reflect the spatial distribution, migration and transformation of UDMH in the fall places of rocket stages under conditions of subarctic which is discussed in related research article "Migration and transformation of 1,1-dimethylhydrazine in peat bog soil of rocket stage fall site in Russian North" [1]. They can be further used for understanding the UDMH transformation pathways in soils rich in organic matter and assessment of environmental impact of space rocket activities in high latitudes.

Migration and transformation of 1,1-dimethylhydrazine in peat bog soil of rocket stage fall site in Russian North.

An ingress of highly toxic rocket fuel 1,1-dimethylhydrazine (UDMH) and its transformation products into environment represents a serious negative impact on the ecosystem, as well as human health. The present research demonstrates the first data on the spatial distribution and quantification of UDMH and its main transformation products (methylhydrazine, hydrazine, 1,1,4,4-tetramethyltetrazene, formaldehyde, acetaldehyde and furaldehyde N,N-dimethylhydrazones, 1-formyl-2,2-dimethylhydrazine, N,N-dimethylformamide, N-nitrosodimethylamine, and 1-methyl-1H-1,2,4-triazole) in the peat bog soil of the fall site in subarctic region. One hundred samples of peat bog soil and one sample of surface water were analyzed by the developed earlier methodology. The considerable amounts of UDMH and most of its transformation products were found at distances of not >10 m from the center of the fall site. The maximum concentration of UDMH was found near the center, where maximal permissible concentration (MPC) was exceeded 2400-fold. The greatest pollution was observed in the surface soil layer, while methylhydrazine, 1-methyl-1H-1,2,4-triazole, 1-formyl-2,2-dimethylhydrazine, formaldehyde and acetaldehyde N,N-dimethylhydrazones, and N,N-dimethylformamide were the major UDMH transformation products. With increasing distance from the center, the composition of the transformation products changes in favor of the last three compounds. Formaldehyde N,N-dimethylhydrazone and N,N-dimethylformamide are present in all soil samples and can be considered as reliable markers of contamination with rocket fuel. The surface water of the peat bog contained four UDMH transformation products in considerable concentrations, including extremely toxic N-nitrosodimethylamine. The processes of migration and transformation of UDMH in peat bog soil differ considerably from those in sandy soils. This is due to cold climate of subarctic zone, the reducing environment of peat bog, and strong binding of hydrazines to organic matter of peat, which prevents migration of pollutants and contributes to the long-term maintenance of high levels of soil pollution.

Identification of novel disinfection byproducts in pool water: Chlorination of the algaecide benzalkonium chloride.

The maintenance of public swimming pools requires numerous technological steps. One of the most important issues involves microbiological safety. Benzalkonium chloride (BAC) encompasses homologous alkylbenzyldimethylammonium chlorides with various alkyl chains, in particular C12 and C14, and is known as a popular algaecide for keeping water clean. In addition to BAC, NaOCl and UV-irradiation are also used to treat pool water as additional technological steps. Therefore, BAC itself can become a precursor of disinfection byproducts (DBPs). High-performance liquid chromatography - tandem mass spectrometry (HPLC-MS/MS), with accurate mass measurements, has allowed the discovery of several groups of DBPs that are related to BAC in public pool water in Arkhangelsk (Russia). These DBPs include numerous isomeric monochlorinated derivatives ([C21H37ClN]+ and [C23H41ClN]+), hydroxyl derivatives ([C21H38NO]+ and [C23H42NO]), carbonyl ([C21H36NO]+ and [C23H40NO]+), and dicarbonyl derivatives ([C21H34NO2]+ and [C23H38NO2]+). In addition, chlorinated alcohols, ketones and ketoalcohols of BAC were also detected, including [C21H35ClNO]+, [C21H37ClNO]+ and [C21H35ClNO2]+ for BAC-12; and [C23H39ClNO]+, [C23H41ClNO]+ and [C23H39ClNO2]+ for BAC-14. MS/MS allowed reliable elucidation of the structures of novel DBPs, proving that chlorination starts via radical substitution in the long aliphatic chains of BAC. UV-irradiation dramatically accelerates the reaction completely destroying the original compounds in less than an hour, while the array of the intermediate products remains the same as in the dark. The formation of other DBPs proceeds due to further reactions of these primary products. The concentrations of novel DBPs in pool water reach µg L-1 levels. These conclusions were proved by conducting model reactions of BAC with NaOCl.

Halogenated fatty amides - A brand new class of disinfection by-products.

An array of similar halogenated nitrogen-containing compounds with elemental composition CnH2nNO2X, CnH2n-2NO2X and CnH2n-1NOX2 (X = Cl, Br; n = 16, 18, 22) was detected in drinking water with high performance liquid chromatography - high resolution mass spectrometry (HPLC-HRMS) method. Compounds of this type were never mentioned among disinfection by-products. Tandem mass spectrometry allowed referring them to halohydrines or dihalogenated fatty amides, the products of conjugated electrophilic addition of halogens to the double bonds of unsaturated fatty amides. The proposed structures were confirmed by conducting aqueous chlorination with standard solution of oleamide. These compounds may be considered as a brand new class of disinfection by products, while their toxicities require special study.