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Bulat Kenessov - One of the best experts on this subject based on the ideXlab platform.
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effects of oxidant and catalyst on the transformation products of Rocket Fuel 1 1 dimethylhydrazine in water and soil
Chemosphere, 2019Co-Authors: D S Kosyakov, N V Ulyanovskii, I. I. Pikovskoi, Bulat Kenessov, Nadezhda V Bakaikina, Zhailaubay K Zhubatov, A T LebedevAbstract:Abstract Existing methods for cleanup of wastewaters and soils polluted with the extremely toxic Rocket Fuel unsymmetrical dimethylhydrazine (UDMH) are mainly based on the treatment with various oxidative reagents. Until now, the assessment of their effectiveness was based on the residual content of UDMH and did not take into account the possibility of the formation of a large number of potentially dangerous nitrogen-containing transformation products (TPs). In this study, using the recently developed approach based on high-resolution Orbitrap mass spectrometry, the comprehensive characterization of UDMH TPs formed by the action of air oxygen and different oxidants (Fenton's reagent, KMnO4, HOCl, H2O2 in the presence of Cu2+ and [Fe (EDTA)]– catalysts) typically used to detoxify spill sites was performed. The range of the identified molecular formulas of TPs comprised 303 compounds of various classes. Among them, there is a number of major products not previously described in the literature. It was established that none of the investigated oxidative reagents ensures complete conversion of Rocket Fuel to safe compounds. The hydrogen peroxide based reagents, particularly H2O2 + Na [Fe (EDTA)] system currently used in Kazakhstan, give the greatest number of TPs, for many of which a toxicity was not characterized so far. The majority of the compounds found in model solutions was detected in extracts of soil from the crash site of the Proton carrier Rocket, which was subjected to the on-site reagent treatment. During successive treatments, along with the decrease in the number of detectable UDMH TPs, their ratios change in favor of amines.
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quantification of transformation products of Rocket Fuel unsymmetrical dimethylhydrazine in soils using spme and gc ms
Talanta, 2018Co-Authors: Nadezhda V Bakaikina, Bulat Kenessov, N V Ulyanovskii, D S KosyakovAbstract:Abstract Determination of transformation products (TPs) of Rocket Fuel unsymmetrical dimethylhydrazine (UDMH) in soil is highly important for environmental impact assessment of the launches of heavy space Rockets from Kazakhstan, Russia, China and India. The method based on headspace solid-phase microextraction (HS SPME) and gas chromatography-mass spectrometry is advantageous over other known methods due to greater simplicity and cost efficiency. However, accurate quantification of these analytes using HS SPME is limited by the matrix effect. In this research, we proposed using internal standard and standard addition calibrations to achieve proper combination of accuracies of the quantification of key TPs of UDMH and cost efficiency. 1-Trideuteromethyl-1H-1,2,4-triazole (MTA-d3) was used as the internal standard. Internal standard calibration allowed controlling matrix effects during quantification of 1-methyl-1H-1,2,4-triazole (MTA), N,N-dimethylformamide (DMF), and N-nitrosodimethylamine (NDMA) in soils with humus content
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Quantification of transformation products of unsymmetrical dimethylhydrazine in aqueous extracts from soil based on vacuum-assisted headspace solid-phase microextraction
al-Farabi Kazakh National University, 2018Co-Authors: Dina Orazbayeva, Bulat Kenessov, Aray ZhakupbekovaAbstract:Quantification of transformation products of unsymmetrical dimethylhydrazine (UDMH) in soil requires tedious, time- and labor-consuming sample preparation. The simple and fast method for quantification of transformation products of UDMH in aqueous extracts from soil using vacuum-assisted headspace solid-phase microextraction (Vac-HSSPME) was optimized in this work. The method is based on extraction of analytes from soil with water followed by Vac-HSSPME of the obtained aqueous extracts, and gas chromatography-mass spectrometry analysis. The target transformation products were: pyrazine, 1-methyl-1H-pyrazole, N-nitrosodimethylamine, N,N-dimethylformamide, 1-methyl-1Н-1,2,4-triazole, 1-methyl-imidazole and 1H-pyrazole. The effect of a sample pH on responses of target analytes was studied. It was negligible, and no pH adjustment was recommended before a subsequent extraction. The water amount was optimized to provide the best combination of analytes responses and their precision. Extraction by adding 7.00 mL of water to 2.0 g of soil ensured linear dependence of responses of the analytes on their concentrations in soil. The optimized method provided detection limits of target analytes in soil in the range from 0.2 to 9 ng/g. The spike recoveries obtained for model samples were in the range 90-103%. The developed method can be recommended for application in laboratories conducting routine analyses of soil samples potentially contaminated by Rocket Fuel residuals
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determination of 1 methyl 1h 1 2 4 triazole in soils contaminated by Rocket Fuel using solid phase microextraction isotope dilution and gas chromatography mass spectrometry
Talanta, 2015Co-Authors: Saltanat Yegemova, Bulat Kenessov, Nadezhda V Bakaikina, Jacek A Koziel, Mikhail NauryzbayevAbstract:Abstract Environmental monitoring of Central Kazakhstan territories where heavy space booster Rockets land requires fast, efficient, and inexpensive analytical methods. The goal of this study was to develop a method for quantitation of the most stable transformation product of Rocket Fuel, i.e., highly toxic unsymmetrical dimethylhydrazine – 1-methyl- 1H -1,2,4-triazole (MTA) in soils using solid-phase microextraction (SPME) in combination with gas chromatography–mass spectrometry. Quantitation of organic compounds in soil samples by SPME is complicated by a matrix effect. Thus, an isotope dilution method was chosen using deuterated analyte (1-(trideuteromethyl)- 1H -1,2,4-triazole; MTA-d3) for matrix effect control. The work included study of the matrix effect, optimization of a sample equilibration stage (time and temperature) after spiking MTA-d3 and validation of the developed method. Soils of different type and water content showed an order of magnitude difference in SPME effectiveness of the analyte. Isotope dilution minimized matrix effects. However, proper equilibration of MTA-d3 in soil was required. Complete MTA-d3 equilibration at temperatures below 40 °C was not observed. Increase of temperature to 60 °C and 80 °C enhanced equilibration reaching theoretical MTA/MTA-d3 response ratios after 13 and 3 h, respectively. Recoveries of MTA depended on concentrations of spiked MTA-d3 during method validation. Lowest spiked MTA-d3 concentration (0.24 mg kg −1 ) provided best MTA recoveries (91–121%). Addition of excess water to soil sample prior to SPME increased equilibration rate, but it also decreased method sensitivity. Method detection limit depended on soil type, water content, and was always below 1 mg kg −1 . The newly developed method is fully automated, and requires much lower time, labor and financial resources compared to known methods.
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transformation products of 1 1 dimethylhydrazine and their distribution in soils of fall places of Rocket carriers in central kazakhstan
Science of The Total Environment, 2012Co-Authors: Bulat Kenessov, Lars Carlsen, Svetlana Batyrbekova, Mereke Alimzhanova, Yerbolat Sailaukhanuly, Nassiba Baimatova, Madi Abilev, Akyl Tulegenov, Mikhail NauryzbayevAbstract:Abstract In our research, three fall places of first stages of Proton Rockets have been studied for the presence and distribution of transformation products of 1,1-dimethylhydrazine (1,1-DMH). Results of identification of transformation products of 1,1-DMH in real soil samples polluted due to Rocket Fuel spills allowed to detect 18 earlier unknown metabolites of 1,1-DMH being formed only under field conditions. According to the results of quantitative analyses, maximum concentrations of 1-methyl- 1H -1,2,4-triazole made up 57.3, 44.9 and 13.3 mg kg − 1 , of 1-ethyl- 1H -1,2,4-triazole — 5.45, 3.66 and 0.66 mg kg − 1 , of 1,3-dimethyl- 1H -1,2,4-triazole - 24.0, 17.8 and 4.9 mg kg − 1 in fall places 1, 2 and 3, respectively. 4-Methyl- 4H -1,2,4-triazole was detected only in fall places 2 and 3 where its maximum concentrations made up 4.2 and 0.66 mg kg − 1 , respectively. The pollution of soils with transformation products of 1,1-DMH was only detected in epicenters of fall places having a diameter of 8 to10 m where Rocket boosters landed. The results of a detailed study of distribution of 1,1-DMH transformation products along the soil profile indicate that transformation products can migrate down to the depth of 120 cm, The highest concentrations of 1,1-DMH transformation products were detected, as a rule, at the depth 20 to 60 cm. However, this index can vary depending on the compound, humidity and physical properties of soil, landscape features and other conditions. In the surface layer, as a rule, only semi-volatile products of transformation were detected which was caused by fast evaporation and biodegradation of volatile metabolites.
Lars Carlsen - One of the best experts on this subject based on the ideXlab platform.
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transformation products of 1 1 dimethylhydrazine and their distribution in soils of fall places of Rocket carriers in central kazakhstan
Science of The Total Environment, 2012Co-Authors: Bulat Kenessov, Lars Carlsen, Svetlana Batyrbekova, Mereke Alimzhanova, Yerbolat Sailaukhanuly, Nassiba Baimatova, Madi Abilev, Akyl Tulegenov, Mikhail NauryzbayevAbstract:Abstract In our research, three fall places of first stages of Proton Rockets have been studied for the presence and distribution of transformation products of 1,1-dimethylhydrazine (1,1-DMH). Results of identification of transformation products of 1,1-DMH in real soil samples polluted due to Rocket Fuel spills allowed to detect 18 earlier unknown metabolites of 1,1-DMH being formed only under field conditions. According to the results of quantitative analyses, maximum concentrations of 1-methyl- 1H -1,2,4-triazole made up 57.3, 44.9 and 13.3 mg kg − 1 , of 1-ethyl- 1H -1,2,4-triazole — 5.45, 3.66 and 0.66 mg kg − 1 , of 1,3-dimethyl- 1H -1,2,4-triazole - 24.0, 17.8 and 4.9 mg kg − 1 in fall places 1, 2 and 3, respectively. 4-Methyl- 4H -1,2,4-triazole was detected only in fall places 2 and 3 where its maximum concentrations made up 4.2 and 0.66 mg kg − 1 , respectively. The pollution of soils with transformation products of 1,1-DMH was only detected in epicenters of fall places having a diameter of 8 to10 m where Rocket boosters landed. The results of a detailed study of distribution of 1,1-DMH transformation products along the soil profile indicate that transformation products can migrate down to the depth of 120 cm, The highest concentrations of 1,1-DMH transformation products were detected, as a rule, at the depth 20 to 60 cm. However, this index can vary depending on the compound, humidity and physical properties of soil, landscape features and other conditions. In the surface layer, as a rule, only semi-volatile products of transformation were detected which was caused by fast evaporation and biodegradation of volatile metabolites.
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screening of transformation products in soils contaminated with unsymmetrical dimethylhydrazine using headspace spme and gc ms
Analytica Chimica Acta, 2010Co-Authors: Bulat Kenessov, Jacek A Koziel, Tim Grotenhuis, Lars CarlsenAbstract:Abstract The paper describes a novel SPME-based approach for sampling and analysis of transformation products of highly reactive and toxic unsymmetrical dimethylhydrazine (UDMH) which is used as a Fuel in many Russian, European, Indian, and Chinese heavy cargo carrier Rockets. The effects of several parameters were studied to optimize analyte recovery. It was found that the 85 μm Carboxen/polydimethylsiloxane fiber coating provides the highest selectivity for selected UDMH transformation products. Optimal sampling/sample preparation parameters were determined to be 1-h soil headspace sampling time at 40 °C. The GC inlet temperature was optimized to 170 °C held for 0.1 min, then 1 °C s −1 ramp to 250 °C where it was held for 40 min. Temperature programing resulted in a fast desorption along with minimal chemical transformation in the GC inlet. SPME was very effective extracting UDMH transformation products from soil samples contaminated with Rocket Fuel. The use of SPME resulted in high sensitivity, speed, small labor consumption due to an automation and simplicity of use. It was shown that water addition to soil leads to a significant decrease of recovery of almost all target transformation products of UDMH. The use of SPME for sampling and sample preparation resulted in detection of the total of 21 new compounds that are relevant to the UDMH transformation in soils. In addition, the number of confirmed transformation products of UDMH increased from 15 to 27. This sampling/sample preparation approach can be recommended for environmental assessment of soil samples from areas affected by space Rocket activity.
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a qsar qstr study on the human health impact of the Rocket Fuel 1 1 dimethyl hydrazine and its transformation products multicriteria hazard ranking based on partial order methodologies
Environmental Toxicology and Pharmacology, 2009Co-Authors: Lars Carlsen, Bulat Kenessov, Svetlana BatyrbekovaAbstract:The possible impact of the Rocket Fuel 1,1-dimethyl hydrazine (heptyl) (1) and its transformation products on human health has been studied using (Quantitative) Structure Activity/Toxicity ((Q)SAR/(Q)STR) modelling, including both ADME models and models for acute toxicity, organ specific adverse haematological effects, the cardiovascular and gastrointestinal systems, the kidneys, the liver and the lungs, as well as a model predicting the biological activity of the compounds. It was predicted that all compounds studied are readily bioavailable through oral intake and that significant amounts of the compounds will be freely available in the systemic circulation. In general, the compounds are not predicted to be acutely toxic apart from hydrogen cyanide, whereas several compounds are predicted to cause adverse organ specific human health effects. Further, several compounds are predicted to exhibit high probabilities for potential carcinogenicity, mutagenicity, teratogenicity and/or embryotoxicity. The compounds were ranked based on their predicted human health impact using partial order ranking methodologies that highlight which compounds on a cumulative basis should receive the major attention, i.e., N-nitroso dimethyl amine, 1,1,4,4-tetramethyl tetrazene, trimethyl, trimethyl hydrazine, acetaldehyde dimethyl hydrazone, 1, 1-formyl 2,2-dimethyl hydrazine and formaldehyde dimethyl hydrazone, respectively.
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a qsar qstr study on the environmental health impact by the Rocket Fuel 1 1 dimethyl hydrazine and its transformation products
Environmental health insights, 2008Co-Authors: Lars Carlsen, Bulat Kenessov, Svetlana BatyrbekovaAbstract:QSAR/QSTR modelling constitutes an attractive approach to preliminary assessment of the impact on environmental health by a primary pollutant and the suite of transformation products that may be persistent in and toxic to the environment. The present paper studies the impact on environmental health by residuals of the Rocket Fuel 1,1-dimethyl hydrazine (heptyl) and its transformation products. The transformation products, comprising a variety of nitrogen containing compounds are suggested all to possess a significant migration potential. In all cases the compounds were found being rapidly biodegradable. However, unexpected low microbial activity may cause significant changes. None of the studied compounds appear to be bioaccumulating. Apart from substances with an intact hydrazine structure or hydrazone structure the transformation products in general display rather low environmental toxicities. Thus, it is concluded that apparently further attention should be given to tri- and tetramethyl hydrazine and 1-formyl 2,2-dimethyl hydrazine as well as to the hydrazones of formaldehyde and acetaldehyde as these five compounds may contribute to the overall environmental toxicity of residual Rocket Fuel and its transformation products.
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gc ms determination of 1 methyl 1h 1 2 4 triazole in soils affected by Rocket Fuel spills in central kazakhstan
Chromatographia, 2008Co-Authors: Bulat Kenessov, Svetlana Batyrbekova, Mikhail Nauryzbayev, Timur Bekbassov, Mereke Alimzhanova, Lars CarlsenAbstract:The paper describes a method for the determination of 1-methyl-1H-1,2,4-triazole (MT) in soils contaminated due to space activities at the Baikonur Cosmodrome. MT is the main transformation product of the primary Rocket Fuel, 1,1-dimethylhydrazine (UDMH). The analytical procedure is based on gas chromatography in combination with mass-spectrometric detection. The detection limit of the method was determined to be 0.005 mg kg−1. A series of authentic samples from the fall regions of the burned out first stages of UDMH Fueled Rockets has been analyzed disclosing MT concentrations in the range of 0.020 to 100 mg kg−1.
Mikhail Nauryzbayev - One of the best experts on this subject based on the ideXlab platform.
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determination of 1 methyl 1h 1 2 4 triazole in soils contaminated by Rocket Fuel using solid phase microextraction isotope dilution and gas chromatography mass spectrometry
Talanta, 2015Co-Authors: Saltanat Yegemova, Bulat Kenessov, Nadezhda V Bakaikina, Jacek A Koziel, Mikhail NauryzbayevAbstract:Abstract Environmental monitoring of Central Kazakhstan territories where heavy space booster Rockets land requires fast, efficient, and inexpensive analytical methods. The goal of this study was to develop a method for quantitation of the most stable transformation product of Rocket Fuel, i.e., highly toxic unsymmetrical dimethylhydrazine – 1-methyl- 1H -1,2,4-triazole (MTA) in soils using solid-phase microextraction (SPME) in combination with gas chromatography–mass spectrometry. Quantitation of organic compounds in soil samples by SPME is complicated by a matrix effect. Thus, an isotope dilution method was chosen using deuterated analyte (1-(trideuteromethyl)- 1H -1,2,4-triazole; MTA-d3) for matrix effect control. The work included study of the matrix effect, optimization of a sample equilibration stage (time and temperature) after spiking MTA-d3 and validation of the developed method. Soils of different type and water content showed an order of magnitude difference in SPME effectiveness of the analyte. Isotope dilution minimized matrix effects. However, proper equilibration of MTA-d3 in soil was required. Complete MTA-d3 equilibration at temperatures below 40 °C was not observed. Increase of temperature to 60 °C and 80 °C enhanced equilibration reaching theoretical MTA/MTA-d3 response ratios after 13 and 3 h, respectively. Recoveries of MTA depended on concentrations of spiked MTA-d3 during method validation. Lowest spiked MTA-d3 concentration (0.24 mg kg −1 ) provided best MTA recoveries (91–121%). Addition of excess water to soil sample prior to SPME increased equilibration rate, but it also decreased method sensitivity. Method detection limit depended on soil type, water content, and was always below 1 mg kg −1 . The newly developed method is fully automated, and requires much lower time, labor and financial resources compared to known methods.
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transformation products of 1 1 dimethylhydrazine and their distribution in soils of fall places of Rocket carriers in central kazakhstan
Science of The Total Environment, 2012Co-Authors: Bulat Kenessov, Lars Carlsen, Svetlana Batyrbekova, Mereke Alimzhanova, Yerbolat Sailaukhanuly, Nassiba Baimatova, Madi Abilev, Akyl Tulegenov, Mikhail NauryzbayevAbstract:Abstract In our research, three fall places of first stages of Proton Rockets have been studied for the presence and distribution of transformation products of 1,1-dimethylhydrazine (1,1-DMH). Results of identification of transformation products of 1,1-DMH in real soil samples polluted due to Rocket Fuel spills allowed to detect 18 earlier unknown metabolites of 1,1-DMH being formed only under field conditions. According to the results of quantitative analyses, maximum concentrations of 1-methyl- 1H -1,2,4-triazole made up 57.3, 44.9 and 13.3 mg kg − 1 , of 1-ethyl- 1H -1,2,4-triazole — 5.45, 3.66 and 0.66 mg kg − 1 , of 1,3-dimethyl- 1H -1,2,4-triazole - 24.0, 17.8 and 4.9 mg kg − 1 in fall places 1, 2 and 3, respectively. 4-Methyl- 4H -1,2,4-triazole was detected only in fall places 2 and 3 where its maximum concentrations made up 4.2 and 0.66 mg kg − 1 , respectively. The pollution of soils with transformation products of 1,1-DMH was only detected in epicenters of fall places having a diameter of 8 to10 m where Rocket boosters landed. The results of a detailed study of distribution of 1,1-DMH transformation products along the soil profile indicate that transformation products can migrate down to the depth of 120 cm, The highest concentrations of 1,1-DMH transformation products were detected, as a rule, at the depth 20 to 60 cm. However, this index can vary depending on the compound, humidity and physical properties of soil, landscape features and other conditions. In the surface layer, as a rule, only semi-volatile products of transformation were detected which was caused by fast evaporation and biodegradation of volatile metabolites.
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gc ms determination of 1 methyl 1h 1 2 4 triazole in soils affected by Rocket Fuel spills in central kazakhstan
Chromatographia, 2008Co-Authors: Bulat Kenessov, Svetlana Batyrbekova, Mikhail Nauryzbayev, Timur Bekbassov, Mereke Alimzhanova, Lars CarlsenAbstract:The paper describes a method for the determination of 1-methyl-1H-1,2,4-triazole (MT) in soils contaminated due to space activities at the Baikonur Cosmodrome. MT is the main transformation product of the primary Rocket Fuel, 1,1-dimethylhydrazine (UDMH). The analytical procedure is based on gas chromatography in combination with mass-spectrometric detection. The detection limit of the method was determined to be 0.005 mg kg−1. A series of authentic samples from the fall regions of the burned out first stages of UDMH Fueled Rockets has been analyzed disclosing MT concentrations in the range of 0.020 to 100 mg kg−1.
Svetlana Batyrbekova - One of the best experts on this subject based on the ideXlab platform.
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transformation products of 1 1 dimethylhydrazine and their distribution in soils of fall places of Rocket carriers in central kazakhstan
Science of The Total Environment, 2012Co-Authors: Bulat Kenessov, Lars Carlsen, Svetlana Batyrbekova, Mereke Alimzhanova, Yerbolat Sailaukhanuly, Nassiba Baimatova, Madi Abilev, Akyl Tulegenov, Mikhail NauryzbayevAbstract:Abstract In our research, three fall places of first stages of Proton Rockets have been studied for the presence and distribution of transformation products of 1,1-dimethylhydrazine (1,1-DMH). Results of identification of transformation products of 1,1-DMH in real soil samples polluted due to Rocket Fuel spills allowed to detect 18 earlier unknown metabolites of 1,1-DMH being formed only under field conditions. According to the results of quantitative analyses, maximum concentrations of 1-methyl- 1H -1,2,4-triazole made up 57.3, 44.9 and 13.3 mg kg − 1 , of 1-ethyl- 1H -1,2,4-triazole — 5.45, 3.66 and 0.66 mg kg − 1 , of 1,3-dimethyl- 1H -1,2,4-triazole - 24.0, 17.8 and 4.9 mg kg − 1 in fall places 1, 2 and 3, respectively. 4-Methyl- 4H -1,2,4-triazole was detected only in fall places 2 and 3 where its maximum concentrations made up 4.2 and 0.66 mg kg − 1 , respectively. The pollution of soils with transformation products of 1,1-DMH was only detected in epicenters of fall places having a diameter of 8 to10 m where Rocket boosters landed. The results of a detailed study of distribution of 1,1-DMH transformation products along the soil profile indicate that transformation products can migrate down to the depth of 120 cm, The highest concentrations of 1,1-DMH transformation products were detected, as a rule, at the depth 20 to 60 cm. However, this index can vary depending on the compound, humidity and physical properties of soil, landscape features and other conditions. In the surface layer, as a rule, only semi-volatile products of transformation were detected which was caused by fast evaporation and biodegradation of volatile metabolites.
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a qsar qstr study on the human health impact of the Rocket Fuel 1 1 dimethyl hydrazine and its transformation products multicriteria hazard ranking based on partial order methodologies
Environmental Toxicology and Pharmacology, 2009Co-Authors: Lars Carlsen, Bulat Kenessov, Svetlana BatyrbekovaAbstract:The possible impact of the Rocket Fuel 1,1-dimethyl hydrazine (heptyl) (1) and its transformation products on human health has been studied using (Quantitative) Structure Activity/Toxicity ((Q)SAR/(Q)STR) modelling, including both ADME models and models for acute toxicity, organ specific adverse haematological effects, the cardiovascular and gastrointestinal systems, the kidneys, the liver and the lungs, as well as a model predicting the biological activity of the compounds. It was predicted that all compounds studied are readily bioavailable through oral intake and that significant amounts of the compounds will be freely available in the systemic circulation. In general, the compounds are not predicted to be acutely toxic apart from hydrogen cyanide, whereas several compounds are predicted to cause adverse organ specific human health effects. Further, several compounds are predicted to exhibit high probabilities for potential carcinogenicity, mutagenicity, teratogenicity and/or embryotoxicity. The compounds were ranked based on their predicted human health impact using partial order ranking methodologies that highlight which compounds on a cumulative basis should receive the major attention, i.e., N-nitroso dimethyl amine, 1,1,4,4-tetramethyl tetrazene, trimethyl, trimethyl hydrazine, acetaldehyde dimethyl hydrazone, 1, 1-formyl 2,2-dimethyl hydrazine and formaldehyde dimethyl hydrazone, respectively.
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a qsar qstr study on the environmental health impact by the Rocket Fuel 1 1 dimethyl hydrazine and its transformation products
Environmental health insights, 2008Co-Authors: Lars Carlsen, Bulat Kenessov, Svetlana BatyrbekovaAbstract:QSAR/QSTR modelling constitutes an attractive approach to preliminary assessment of the impact on environmental health by a primary pollutant and the suite of transformation products that may be persistent in and toxic to the environment. The present paper studies the impact on environmental health by residuals of the Rocket Fuel 1,1-dimethyl hydrazine (heptyl) and its transformation products. The transformation products, comprising a variety of nitrogen containing compounds are suggested all to possess a significant migration potential. In all cases the compounds were found being rapidly biodegradable. However, unexpected low microbial activity may cause significant changes. None of the studied compounds appear to be bioaccumulating. Apart from substances with an intact hydrazine structure or hydrazone structure the transformation products in general display rather low environmental toxicities. Thus, it is concluded that apparently further attention should be given to tri- and tetramethyl hydrazine and 1-formyl 2,2-dimethyl hydrazine as well as to the hydrazones of formaldehyde and acetaldehyde as these five compounds may contribute to the overall environmental toxicity of residual Rocket Fuel and its transformation products.
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gc ms determination of 1 methyl 1h 1 2 4 triazole in soils affected by Rocket Fuel spills in central kazakhstan
Chromatographia, 2008Co-Authors: Bulat Kenessov, Svetlana Batyrbekova, Mikhail Nauryzbayev, Timur Bekbassov, Mereke Alimzhanova, Lars CarlsenAbstract:The paper describes a method for the determination of 1-methyl-1H-1,2,4-triazole (MT) in soils contaminated due to space activities at the Baikonur Cosmodrome. MT is the main transformation product of the primary Rocket Fuel, 1,1-dimethylhydrazine (UDMH). The analytical procedure is based on gas chromatography in combination with mass-spectrometric detection. The detection limit of the method was determined to be 0.005 mg kg−1. A series of authentic samples from the fall regions of the burned out first stages of UDMH Fueled Rockets has been analyzed disclosing MT concentrations in the range of 0.020 to 100 mg kg−1.
D S Kosyakov - One of the best experts on this subject based on the ideXlab platform.
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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
Data in Brief, 2020Co-Authors: N V Ulyanovskii, I. I. Pikovskoi, D. E. Lakhmanov, Danil I. Falev, Mark S. Popov, Alexander Yu. Kozhevnikov, D S KosyakovAbstract:Abstract 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.
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effects of oxidant and catalyst on the transformation products of Rocket Fuel 1 1 dimethylhydrazine in water and soil
Chemosphere, 2019Co-Authors: D S Kosyakov, N V Ulyanovskii, I. I. Pikovskoi, Bulat Kenessov, Nadezhda V Bakaikina, Zhailaubay K Zhubatov, A T LebedevAbstract:Abstract Existing methods for cleanup of wastewaters and soils polluted with the extremely toxic Rocket Fuel unsymmetrical dimethylhydrazine (UDMH) are mainly based on the treatment with various oxidative reagents. Until now, the assessment of their effectiveness was based on the residual content of UDMH and did not take into account the possibility of the formation of a large number of potentially dangerous nitrogen-containing transformation products (TPs). In this study, using the recently developed approach based on high-resolution Orbitrap mass spectrometry, the comprehensive characterization of UDMH TPs formed by the action of air oxygen and different oxidants (Fenton's reagent, KMnO4, HOCl, H2O2 in the presence of Cu2+ and [Fe (EDTA)]– catalysts) typically used to detoxify spill sites was performed. The range of the identified molecular formulas of TPs comprised 303 compounds of various classes. Among them, there is a number of major products not previously described in the literature. It was established that none of the investigated oxidative reagents ensures complete conversion of Rocket Fuel to safe compounds. The hydrogen peroxide based reagents, particularly H2O2 + Na [Fe (EDTA)] system currently used in Kazakhstan, give the greatest number of TPs, for many of which a toxicity was not characterized so far. The majority of the compounds found in model solutions was detected in extracts of soil from the crash site of the Proton carrier Rocket, which was subjected to the on-site reagent treatment. During successive treatments, along with the decrease in the number of detectable UDMH TPs, their ratios change in favor of amines.
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quantification of transformation products of Rocket Fuel unsymmetrical dimethylhydrazine in soils using spme and gc ms
Talanta, 2018Co-Authors: Nadezhda V Bakaikina, Bulat Kenessov, N V Ulyanovskii, D S KosyakovAbstract:Abstract Determination of transformation products (TPs) of Rocket Fuel unsymmetrical dimethylhydrazine (UDMH) in soil is highly important for environmental impact assessment of the launches of heavy space Rockets from Kazakhstan, Russia, China and India. The method based on headspace solid-phase microextraction (HS SPME) and gas chromatography-mass spectrometry is advantageous over other known methods due to greater simplicity and cost efficiency. However, accurate quantification of these analytes using HS SPME is limited by the matrix effect. In this research, we proposed using internal standard and standard addition calibrations to achieve proper combination of accuracies of the quantification of key TPs of UDMH and cost efficiency. 1-Trideuteromethyl-1H-1,2,4-triazole (MTA-d3) was used as the internal standard. Internal standard calibration allowed controlling matrix effects during quantification of 1-methyl-1H-1,2,4-triazole (MTA), N,N-dimethylformamide (DMF), and N-nitrosodimethylamine (NDMA) in soils with humus content
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Modification of Hydrolysis Lignin by Hydrogen Peroxide to Obtain an Effective Adsorbent of Highly Toxic Rocket Fuel
al-Farabi Kazakh National University, 2017Co-Authors: Yu. A. Kozhevnikov, M. P. Semushina, E. A. Podrukhina, D S KosyakovAbstract:Lignin, a large scale by-product of papermaking and bioethanol production, is applied now in various fields. One of the main areas of use is in the development of different adsorbents, including those intended for detoxification of the spills of 1,1-dimethylhydrazine-based Rocket Fuel. The present work has shown the possibility of oxidative modification of hydrolytic lignin by hydrogen peroxide to improve the efficiency of the adsorbent. The change in functional composition of the modified adsorbent was studied by IR and NMR spectroscopy. It was shown that the oxidative treatment led to an increase in the content of carbonyl and carboxyl groups, which act as the active adsorption centres for hydrazine molecules. The optimum oxidation conditions were found. An increase in treatment duration from 15 to 120 min and in concentration of hydrogen peroxide from 6 to 30% did not have a significant effect on the functional composition and adsorption properties of lignin
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determination of transformation products of 1 1 dimethylhydrazine by gas chromatography tandem mass spectrometry
Journal of Analytical Chemistry, 2015Co-Authors: N V Ulyanovskii, D S Kosyakov, S A Pokryshkin, K G BogolitsynAbstract:A method is proposed for the highly sensitive simultaneous determination of eight major products of oxidative transformations of 1,1-dimethylhydrazine, widely used as a Rocket Fuel (formaldehyde dimethylhydrazone, acetaldehyde dimethylhydrazone, 2-furaldehyde dimethylhydrazone, 1,1,4,4-tetramethyl-2-tetrazene, N,N-dimethylformamide, N-nitrosodimethylamine, 1-methyl-1H-1,2,4-triazole and 1-formyl-2,2dimethylhydrazine) by gas chromatography–tandem mass spectrometry. The detection parameters in the MRM mode are optimized. The conditions for the efficient separation of analytes on an HP-INNOWAX polar stationary phase are chosen. The detection limits achieved are in the range 0.3–2.3 ng/mL, which is 1?2 orders of magnitude lower than those for the GC/MS method. The developed approaches are tested in the analysis of real samples, surface water of peaty swamp with high contents of organic substance taken at the place of impact of the first Rocket stage. It is found that N,N-dimethylformamide and 1-methyl-1H-1,2,4-triazole are predominant among the studied transformation products in natural waters. The results obtained are of great importance for the assessment of the environmental impacts of space Rocket activities.
