Influence of Hydrocarbon Rocket Fuel Kerosene T-1 on the Physical and Geochemical Properties of Different Soil Types

Studies of the influence of hydrocarbon rocket fuel kerosene T-1 on the physical and geochemical properties were carried out in laboratory circumstances on different types of soils: brown semi-desert soil designated as zone (U-25) located in Central Kazakhstan, mountainous brown desert soil zone (U-30) located in East Kazakhstan, and a model soil standard (control soil). The soil was treated with various concentrations (0.002–150.0 g/kg) of hydrocarbon rocket fuel kerosene T-1, while the contact time was 3, 10, and 30 days. Pollution with kerosene T-1 in concentrations 5.0–15.0 g/kg affects the hydraulic characteristics of soils from the U-25 zone, and the filtration rate decreases by 4–5 times. For the mountainous brown desert soil from the U-30 zone, the concentration of kerosene up to 15.0 g/kg does not affect the mechanical composition of the soil, as well as the availability of the main nutrients (potassium, phosphorus, nitrogen). According to the mechanical composition, both soils belong to medium loamy soils. It has been established that when soil is contaminated from the U-25 zone in concentrations 15.0–150.0 g/kg, the fraction from 1.0 to 0.05 mm increases by 4–5%, and the silty and clay fractions in the soil decrease.


Introduction
Soil pollution will cause land degradation. Many pollutants are capable of further transport from local pollution sources and global dispersion (Seredina, 2015). With the increasing availability of space flights, the impact of rocket launches on soil contamination with rocket fuel components has become an environmental problem that seriously affects the ecological reconstruction and restoration of desert and semi-desert areas. Rocket and space activities carried out by mankind, like any other type of activity, hurt the environment. In recent decades, anthropogenic impacts have led to more severe soil pollution with hydrocarbon substances, becoming one of the world's environmental problems (Cachada et al., 2018;Dallas Khamehchiyan et al., 2007). If pollution with rocket fuel is mainly characteristic only for areas of rocket impact, then pollution with oil products such as kerosene and diesel fuel is widespread (Pepper, 2013;Shein et al., 2007).
Kerosene T-1 is a petroleum derivative, a complex compound of hydrocarbons (from C12 to C15), boiling away in the temperature range of 200-300 °C, transparent, slightly oily to the touch, and combustible liquid obtained by direct distillation or purification of oil (Koroleva et al., 2021;Moneke & Nwangwu, 2011). Hydrocarbon fuels are widely used in rocket and space technology due to the large supply of chemical energy, large-scale production, and relatively simple operation. Kerosene is used as fuel for rockets and in the lower stages of launch vehicles, cruise missiles, and spacecraft. There is information in the literature about the effect of gasoline, diesel fuel, kerosene, polycyclic aromatic hydrocarbons, and oil oxidation products on soil properties (Balachandran et al., 2012;Kolesnikov et al., 2006). However, only a few are dedicated to soil contamination with rocket kerosene. Also, there is no information about the studies maintained on the impact of kerosene T-1 pollution on soil properties in the areas of impact of the separating parts of the launch vehicle (IA SPLV) on the territory of the Republic of Kazakhstan (Akpambetova et al., 2001). Petroleum hydrocarbons seeping into the soil are primarily adsorbed by micropores or nanopores from non-aqueous fluids. Due to the absence of biological metabolic conditions such as air and water, biodegradation is difficult and natural decay is slow (Delogu, 2011;Khan et al., 2018;Wang et al., 2018). There are great risks and dangers after entering the human body through the food web (Ramadass et al., 2015); therefore, there is a deep need for fast and efficient recovery methods (Cheng et al., 2017). Physico-chemical methods for soil reclamation mainly use redox processes or high-temperature combustion, which are highly efficient (Lu et al., 2017).
The characteristic of soil quality is decided by the most significant chemical data for practical use, such as the total content of organic compounds (humus), nitrogen (ammonium, nitrate, and associated with organic matter), bound carbonic acid (calcium and magnesium carbonates), and plant nutrients-calcium, magnesium, potassium, phosphorus, and trace elements, as well as the ability for their biological assimilation. When determining soil quality, more superficial characteristics also play a role, for example, mechanical and fractional composition, pH value, dry weight, specific and bulk weight, moisture capacity, hygroscopicity, wetting heat, pore volume, and ion exchange capacity (Drugov, 2000).
The researchers studied the problems of the analytical management of environmental protection from pollution by rocket fuel kerosene jointly with heptyl components in the Ulytau Region (Akpambetova et al., 2001). Despite this, the level of soil pollution in these areas exceeds environmental standards. Thus, the study results will make it possible to obtain an ecological picture of the studied areas affected by rocket and space activities of the complexes and to develop measures for rehabilitating contaminated territories, which is supposed to be carried out within the framework of these studies. This work is aimed at exploring the influence of hydrocarbon rocket fuel kerosene T-1 on the physical and geochemical properties of different soil types.

Collection and Laboratory Characterization of Soil Samples
The studied soil samples were taken in the impact area of the launch vehicle (LV) "Soyuz" in Central Kazakhstan (zone U-25) 1st stage and impact area of the launch vehicle "Soyuz" East Kazakhstan (zone U-30) 2nd stage (Table 1 and Fig. 1). The "Soyuz" launch vehicle was designed to launch spacecraft from 1966 to 2000, which made more than 173 launches and used T-1 kerosene as a hydrocarbon rocket fuel. Zone U-25 is in the semi-arid landscapes of Central Kazakhstan in the Ulytau Region in a moderately humid zone. The environment is accurately continental, with large fluctuations in seasonal, daily temperatures and a small amount of precipitation (about 180 mm per year). On the territory of the U-25 zone, the soil type is brown semi-desert soils.
Zone U-30 is located within the vast intermountain plain between Altai and Saur-Tarbagatai. Numerous ranges and varied reliefs of Altai and Saur-Tarbagatai were formed consequently of mountain-building processes that began in the Tertiary and continued into the Quaternary, under the influence of the simultaneous impact of diverse exogenous strategies. The following types and subtypes of soils on the territory of the U-30 zone are mountain light chestnut soils, mountain meadow chestnut soils, and mountain brown desert soils.

Treatments and Experimental Conditions
In the present work, soil samples were accepted in two places: impact area of launch vehicles "Soyuz" 1st stage in the Ulytau region, zone (U-25), and impact area of launch vehicles "Soyuz" 2nd stage Altay and Saur-Tarbagatai region, zone (U-30), to study the effect of hydrocarbon rocket fuel kerosene T-1 (humidity 3% and pH 7.95) on the physical and geochemical of soil characteristics (Table 1). Process depends on its concentration (from 0.002 to 150 g/kg) and contact time from 1, 3, and 30 days. The soil sample was compiled on the surface layer 0-25 cm for laboratory experiments. Freshly selected soil is brought by drying in a wellventilated area for 3-4 days at room temperature in diffused light. The desiccated sample is released from foreign inclusions (stones, plant roots, etc.) and sieved through a sieve with a diameter of 2-3 mm. The soil thus prepared was used for experiments. The process photometry of chemical elements in a flame was used to study the geochemical properties of the samples. The trigonometric method for determining exchangeable calcium and exchangeable magnesium was also applied. The turbidimetric method was used to select mobile sulfur. Experimental studies on T-1 kerosene were carried out in the analytical laboratory of the branch of RSE "Infracos" in Almaty and Ltd "AspanTau" on a gas chromatograph with a flame ionization detector "Agilent-6890 N," an ionomer "I-160," and flame photometer PFA-378, all statistical analysis by Drugov (2000) and Kachinsky (1965).

Influence of Kerosene T-1 on the Physical
Properties of the Soil The results of studies' physical and water properties of soils after pollution are presented in Tables 2, 3, and 4. Determination of the mechanical compositions of soils by the "sieve" method showed that changes were observed in the granulomere composition of the studied soils for 1, 3, and 30 days from the moment of soil contamination with kerosene that was not significant (Table 2). This effect is manifested in a decrease in the filtration rate, with an increase in the load of kerosene starting from 5.0 g/kg, and with an increase in the cargo to 15.0 g/kg, the filtration rate decreases by 4-5 times. The outgrowth of the analysis shows that when the kerosene reaches 5.0-g/kg concentration of brown semi-desert soil (U-25), the fraction of more than 1.0 mm increases by almost three times. For mountain brown desert soil (U-30), the intro of kerosene up to 15.0 g/kg does not involve the mechanical components. Both soil types are classified as medium loamy in terms of mechanical composition (Table 3). According to the results of granulomere analysis, soils in the root layer vary within medium loamy soils. The main problem of soils of such mechanical composition can be their relatively low filtration capacity and possible oversaturation with moisture during periods of heavy rainfall. Brown semi-desert soils are more responsive to kerosene pollution in terms of hydraulic characteristics (Table 4). Data on hydraulic characteristics indicate that with an accumulation in the concentration of T-1 kerosene in the soil, the filtration coefficient decreases, and already with pollution of 5.0 g/kg, a significant decrease in water permeability is observed. The study was taken with samples at depths of 0-25 cm, and they were loosened and mixed. The responses of natural soils to contamination with kerosene T-1 can be assessed under the condition that their morphological structure is not disturbed and depends on the properties of each specific horizon, which differ significantly along the profile, i.e., based on the results of experiments in natural conditions.
Due to the weak influence of contaminated kerosene T-1 in soils, additional experimental studies were carried out with contamination of higher concentrations of kerosene T-1 (15.0 g/kg, 50.0 g/kg, and 150.0 g/kg). Based on the data, artificial pollution was carried out as follows: 215.0 g of soil was spread on a plastic container and then poured with the calculated volume of kerosene. Analyses were performed on days 3, 10, and 30 (Table 5). This research was conducted on soil from the U-25/ Ulytau Region, which is the most affected by launch vehicles powered by kerosene T-1.
The outcomes display that under the influence of kerosene T-1, the fraction from 1.0 to 0.05 mm increases by 4-5%, and the substance of dusty and clayey particles in the soil decreases. Pollution with kerosene in the indicated concentrations practically does not affect the hydraulic characteristics of the soil. From the data obtained, it is clear that an increase from 1.0 to 15.0 g/kg in the concentration of kerosene T-1 has little effect on the granulomere composition of soils and their basic water-physical properties. The impact of kerosene T-1 increases the fraction from 1.0 to 0.05 mm by 4-5% and reduces the content of silt and clay fractions in the soil (Tables 6 and 7). 3.2 Geochemical Study of the Impact of Kerosene T-1 on Soils Tables 8 and 9 show the results of determining mobile forms of phosphorus, potassium, and nitrogen, and analysis of soil availability with these elements in selected soils. Conducting studies on the geochemical composition, pollution with kerosene T-1 somewhat reduces the concentration of these elements in soils. As in the case of soil physical properties,  geochemical data show little effect of kerosene pollution on the content of mobile forms of phosphorus, potassium, and nitrogen (Table 8). Pollution with T-1 kerosene on mountain brown desert soils (U-30) up to 15.0 g/kg does not affect the supply of nutrients for potassium, and phosphorus intake decreases, and on brown semi-desert soils (U-25), the phosphorus intake increases with a magnification in the concentration of T-1 kerosene (Table 9). Further experiments were accepted on 15.0 g/kg, 50.0 g/kg, and 150.0 g/kg soils contaminated with high concentrations of kerosene T-1. The increasing content of the transportable structure of phosphorus reduces the number of mobile forms of potassium and significantly improves the measure of organic substances by more than 3 and 5 times (Table 10). The results show that high levels of availability of primary plant nutrients characterize the soil. According to the degree of salinity of the soil suspension (0.018-0.029 μS/cm), this soil is non-saline, which is confirmed by the analysis of soil water extract (Table 11).
An analysis of the cationic-anionic composition of the aqueous extract of soils showed that in the study area (initial soil without kerosene T-1), there is an increased content of the bicarbonate ion (the toxicity threshold of 0.8 mg-eq/100.0 g of soil was exceeded). The content of other salts is within acceptable limits. According to the number of salts, which is 0.06-0.10%, the soil in the study area is non-saline. The reaction of the aqueous soil solution is alkaline (pH-8.37-8.75) ( Table 12).
The results of soil analysis for the exchange of calcium, magnesium, and mobile sulfur are shown in Table 13 and analyses of soil nutrient levels are shown in Table 14. Thus, a solution of 15.0 g/kg of kerosene T-1 does not affect the supply of nutrients for mobile forms of potassium, and for mobile forms of phosphorus on mountain brown desert soils (U-30), the supply decreases, and on brown  semi-desert soils (U-25), the availability of mobile forms of phosphorus increases with an increase in the concentration of kerosene T-1. Soil contaminated with higher concentrations of kerosene (15.0-150.0 g/kg) is marked by high to high levels of exchangeable calcium, low to medium levels of ex-changeable magnesium, and medium to high levels of mobile forms of sulfur.

Discussion
Many countries around the globe are encountering oil pollution for many reasons, such as the leakage of hydrocarbon rocket fuel kerosene, due to accidents, in the impact area (IA) of the detached units of launch vehicles, which will be used to detect changes during their operation Shelyakin et al., 2022). The soil contaminated with kerosene lacks oxygen and minerals, which can lead to a complete change in the unique landscape. Due to the decrease in the permeability and gas exchange of soil contaminated with kerosene T-1, the size of the population and biomass of soil microflora decrease. Hydrocarbons in significant concentrations have a substantial impact on the main characteristics of the soil, the ability of the soil to support the need for plants in nutrients, and water and provide their root systems with sufficient air and heat for life. Soil is one of the primary natural resources on which man relies for survival, as a significant part of the human ecological environment, a reservoir of environmentally sensitive material biogeochemical cycles (Adriano et al., 1998;Shelyakin et al., 2022). Therefore, the safety and control of the soil's ecological environment have attracted general attention. Regarding the negative impact of oil products and reduction, many researchers have proposed various ways to clean the soil. (Rasheed et al., 2014;Shaheen, 2011). In addition to the extremely complex objective reasons for soil pollution itself, there are still many problems in people's subjective understanding of soil pollution and the choice of methods for studying soil pollution. In recent years, countries around the world have begun to pay attention to research on the technology of cleaning contaminated soil. In the current study, we studied the effect of the propellant component kerosene T-1 on the physical and geochemical properties of soils in order to better understand their behavior and detoxification. In the present work, soil samples such as brown semi-desert soil and mountain brown desert soil were taken from two habitats: areas where launch vehicle parts fell in the Ulytau Region zone (U-25) and Altay and Saur-Tarbagatai region, zone (U-25e). The experiment showed that the determination of soil contamination with hydrocarbon kerosene T-1 at a concentration of 1.0 to 15.0 g/kg does not affect the granulomere composition of soils. According to the mechanical components, the analyzed soils belong to medium loamy soils. The data on the filtration coefficient indicate that with increasing concentration of kerosene T-1, the filtration coefficient decreases, and soils have the lowest water permeability at pollution up to 5.0 g/kg. Similar results were obtained that hydrocarbon fuels (gasoline, kerosene) are stable in soils and persist for a long time (Akpambetova et al., 2001). After soil contamination, a rapid decrease in their concentrations is observed due to evaporation and weathering, as well as transport with surface and groundwaters. The maximum pollution during the year is contained in the surface of the 20-cm soil layer and will finally disappear only after a few decades. At concentrations from 0.7 to 50.0 ml/kg, there was a violation of microbiological processes in the soil, and at concentrations above 300.0 ml/kg, the death of microorganisms. The prior study indicated that when the soil was polluted with oil by-products, enzyme activity decreased after 4 days; increased on the eighth day at lower concentrations of kerosene, diesel fuel, and gasoline in the soil; and then began to fall 12 days after tillage (Achuba & Okoh, 2014). The outcome of this study showed that with artificial contamination of brown semi-desert soil (U-25) at concentrations of 15.0 g/kg, 50.0 g/kg, and 150.0 g/ kg, it was found that under the influence of kerosene, the fraction from 1.0 to 0.05 mm increases by 4-5% and the silt and clay fractions in the soil decrease. According to the mechanical components, the soil belongs to the heavy loamy type. However, another study showed that soil concentrations of kerosene up to 35,000 mg/kg were not toxic to the native microbial population (Malina & Grotenhuis, 2000).
In the current study, geochemical contamination with kerosene T-1 on soils showed that soils are characterized by phosphorus availability from high to very high, and soils are provided in high concentrations by potassium. Soils are characterized by low availability of easily hydrolyzable nitrogen. The soil is characterized by a high supply of basic plant nutrients, and according to the degree of soil suspension salinity (mS/cm-0.18-0.29), it belongs to nonsaline soils. Hydrocarbon propellant kerosene T-1 is in large quantities and should be recovered as much as possible, but in some cases, recovery is very difficult, and some of them will remain, causing environmental pollution (soil, surface, and groundwater). After it enters the soil, it will destroy the soil structure and dissipate the permeability of the soil. Its rich reactive groups can combine with inorganic nitrogen and phosphorus to limit nitrification and dephosphorization, thereby reducing available phosphorus and nitrogen in the soil. However, another study showed that the reduction in pollution levels is due to the action of kerosene, which provides a non-polar environment for soil ions, slowing down their movement and immobilizing them, which leads to a decrease in ion mobility, speed and, therefore, a decline in conductivity. The existence of kerosene in the soil reduces the number of available forms of phosphorus. (Okolo et al., 2005;Jørgensen et al., 2000;Devatha et al., 2019). According to the result of the granulomeres analysis of the soil in the root layer, they fluctuate within the medium loamy. The main problem of soils of such mechanical composition can be their relatively low filtration capacity and possible oversaturation with moisture during periods of heavy rainfall. Soil responses to kerosene T-1 contamination can be estimated under the proviso of their undisturbed morphological structure and depending on the possessions of each specific horizon, which differ significantly along the profile, i.e., based on the results of experiments in natural conditions. The results of this study can be a focus for designers and researchers to sufficiently apprehend the actions and detoxification of soils when infected with hydrocarbon kerosene T-1. Following the above research, the problem of detoxification of the soil cover under the action of the rocket fuel component kerosene T-1 remains relevant. To develop effective technologies for protecting land from pollution, re-cultivating contaminated land, and predicting the development of emergencies in case of spills of oil products, according to Maksimov and Golovanov (2006), it is necessary to have a clear understanding of the physics of the processes occurring in this case and be able to model them accordingly.

Conclusions
The work consists in studying the influence of hydrocarbon kerosene T-1 rocket fuel on the physical and geochemical properties of different types of soils, brown semi-desert soil, zone (U-25), and mountainous brown desert soil, zone (U-25). Hydrocarbon rocket fuel kerosene T-1 is most stable in mountainous brown desert soils and is associated with an increased (by 3%) porosity of mountainous brown desert soil. During the experiments, it was found that the introduction of T-1 kerosene into the soil at a concentration of 1.0 to 15.0 g/kg does not affect the granulomere composition of the soil. According to the mechanical composition, the studied soils belong to medium loamy soils.
Geochemical studies of the influence of kerosene on soils have shown that the input of kerosene up to 15.0 g/kg does not affect the supply of primary nutrients (potassium, phosphorus, nitrogen). According to the availability of phosphorus, the soils are characterized from high to very high, and in terms of potassium, they supplied high concentrations, and the availability of readily hydrolyzable nitrogen is low.
The input of kerosene in high concentrations (15.0-150.0 g/kg) increases the phosphorus content, reduces the amount of potassium, and significantly increases the organic matter content (more than 3.5 times). The soil is characterized by high levels of availability of primary plant supply, by the capacity of salinity of the soil suspension (mS/cm-0.18-0.29), and applied to not salted. According to the presence of exchangeable calcium, they are characterized by high to increased qualities, of magnesium from low to medium, and from medium to high supply of sulfur.
The results of this work are necessary to solve the most ambitious problem, such as the development of preparation for the detoxification of soil contaminated with hydrocarbon rocket fuel kerosene T-1. Based on the results obtained, it is planned to conduct detoxification studies, where laboratory and field tests will be performed on soil samples, brown semi-desert zone (U-25), and mountain brown desert soil zone (U-30).
This had only been preliminary research. Further work could be planned to conduct research work which will be using the results reflected in this article to develop a detoxification preparation. The research will be carried out in the laboratory and the field on soil samples contaminated with T-1 kerosene hydrocarbon rocket fuel from the launch vehicle impact area.