Functional Activated Biocarbons Based on Biomass Waste for CO2 Capture and Heavy Metal Sorption.

Inexpensive porous activated biocarbons were prepared from biomass and agriculture waste following the method of thermal and hydrothermal carbonization and activation with superheated water vapor. The activated biocarbons were characterized by nitrogen adsorption-desorption at 77 K, SEM, XRD, Raman spectrometry, FTIR spectroscopy, determination of particle size, and elemental composition by XRF. The specific surface area was in the range of 240-709 m2/g, and the total pore volume was from 0.12 to 0.43 cm3/g. The percentage of microporosity in activated biocarbons was 89-92%. These activated biocarbons have been used for CO2 and heavy metal sorption. Activated biocarbons based on pine cones and birch prepared by thermal carbonization and activation with superheated water vapor had the highest ability to capture CO2 and amounted to 6.43 and 6.00 mmol/g at 273 K, as well as 4.57 and 4.22 mmol/g at 298 K, respectively. The best activated biocarbon was characterized by unchanged stability after 30 adsorption and desorption cycles. It was proved that the adsorption of CO2 depends on narrow micropores (<1 nm). Activated biocarbons have also been analyzed as effective adsorbents for removing Cu2+, Zn2+, Fe2+, Ni2+, Co2+, and Pb2+ ions from aqueous solutions. Activated biocarbons are effective adsorbents for the removal of lead and zinc ions from aqueous solutions.

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.

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 3h, 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.

Transformation products of 1,1-dimethylhydrazine and their distribution in soils of fall places of rocket carriers in Central Kazakhstan.

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.

GC-MS and GC-NPD Determination of Formaldehyde Dimethylhydrazone in Water Using SPME.

Formaldehyde dimethylhydrazone (FADMH) is one of the important transformation products of residual rocket fuel 1,1-dimethylhydrazine (1,1-DMH). Thus, recent studies show that FADMH toxicity is comparable to that of undecomposed 1,1-DMH. In this study, a new method for quantification of FADMH in water based on solid phase microextraction (SPME) in combination with gas chromatography (GC) with mass spectrometric (MS) and nitrogen-phosphorus detection (NPD) is presented. Effects of SPME fiber coating type, extraction and desorption temperatures, extraction time, and pH on analyte recovery were studied. The optimized method used 65 micron polydimethylsiloxane/divinylbenzene fiber coating for 1 min headspace extractions at 30 °C. Preferred pH and desorption temperature from the SPME fiber are >8.5 and 200 °C, respectively. Detection limits were estimated to be 1.5 and 0.5 µg L(-1) for MS and NPD, respectively. The method was applied to laboratory-scale experiments to quantify FADMH. Results indicate applicability for in situ sampling and analysis and possible first-time detection of free FADMH in water.