A new procedure for the determination of 1,1-dimethylhydrazine (UDMH) in soil samples was developed. This involves the distillation of UDMH from an alkaline suspension of soil and ion chromatographic analysis of the distillate. The separation was performed on a silica cation-exchanger column with ammonium acetate buffer solution as mobile phase and amperometric detection at +1.2 V. Hydrazine (Hy) and methylhydrazine (MH), which are decomposition products of UDMH, can be determined simultaneously. The limits of detection in aqueous solutions were 0.2, 0.5 and 1 µg L−1 for Hy, MH and UDMH, respectively. The developed technique was used for investigating the behaviour of UDMH in spills of rocket fuels on soils. It was found that the addition of 4 kg m−2 UDMH resulted in a 0.02% residue one year after the soil treatment. The vertical migration of UDMH in soil was less than 50 cm.
One of the most important challenges for soil science is to determine the limits for the sustainable functioning of contaminated ecosystems. The response of soil microbiomes to kerosene pollution is still poorly understood. Here, we model the impact of kerosene leakage on the composition of the topsoil microbiome in pot and field experiments with different loads of added kerosene (loads up to 100 g/kg; retention time up to 360 days). At four time points we measured kerosene concentration and sequenced variable regions of 16S ribosomal RNA in the microbial communities. Mainly alkaline Dystric Arenosols with low content of available phosphorus and soil organic matter had an increased fraction of Actinobacteriota, Firmicutes, Nitrospirota, Planctomycetota, and, to a lesser extent, Acidobacteriota and Verrucomicobacteriota. In contrast, in highly acidic Fibric Histosols, rich in soil organic matter and available phosphorus, the fraction of Acidobacteriota was higher, while the fraction of Actinobacteriota was lower. Albic Luvisols occupied an intermediate position in terms of both physicochemical properties and microbiome composition. The microbiomes of different soils show similar response to equal kerosene loads. In highly contaminated soils, the proportion of anaerobic bacteria-metabolizing hydrocarbons increased, whereas the proportion of aerobic bacteria decreased. During the field experiment, the soil microbiome recovered much faster than in the pot experiments, possibly due to migration of microorganisms from the polluted area. The microbial community of Fibric Histosols recovered in 6 months after kerosene had been loaded, while microbiomes of Dystric Arenosols and Albic Luvisols did not restore even after a year.
The transformation of unsymmetrical dimethylhydrazine (UDMH, a propellant component) applied at a rate of 240 g/kg to different soils was studied. The kinetic regularities of a decrease in the UDMH concentration and the accumulation of its transformation products leached out from dry and wet soils were investigated 3, 10, 30, and 90 days after its application. As the UDMH enters the soil, it vaporizes, and the elevated moisture of the soils promotes an increase in the pollutant’s concentration at the initial moment; then, the concentration differences become leveled to the end of observation. It was also shown that the higher the organic matter content in the soil, the higher the UDMH concentration. However, at the end of the observations, on the 90th day, the total UDMH concentration did not exceed 0.5% of its initial content. In order to explain the UDMH behavior in the soils, one should take into account the existence of different forms of this substance and the changes in their ratios with time. The main portion of UDMH retained by the soil in the free form is transformed during the first few days. The products of the UDMH transformation, such as 1-methyl-1,2,4-triazole, formic acid dimethylhydrazide, dimethylguanidine, and dimethylamine are formed in considerable amounts, and their concentrations should be controlled in places of UDMH spills on soils.