Ecological monitoring of the impact of agrochemical plant protection products on the adjacent areas of farming enterprises in Ternopil region

The article presents the results of ecological soil monitoring on the territories adjacent to agricultural storage facilities used for storing agrochemical plant protection products in the village of Vyshnivchyk, Ternopil region. The article is based on the study of the ecological monitoring of soil conditions on the territories adjacent to the areas where agrochemical plant protection products are stored. In most cases, these areas do not meet environmental and sanitary standards, posing a potential threat to the environment and the community's health. Inadequate storage conditions, which do not comply with the existing standards, release toxic residues from unused agrochemicals into the soil, water sources, and the air. Consequently, there is a risk of poisoning for both humans and animals. This study also includes an analysis of the composition of agrochemical substances from previous years on the territory of Vyshnivchyk village, Ter-nopil region (the territory of 'Denys K' Farm). A sheltered storage space near the village of Vyshnivchyk has been operating for more than 30 years. It was constructed in 1978 according to the standards of that time. Both bulk and liquid chemicals have been discharged into the quarry. The problem is further complicated because the landfill has no owner. It is unknown which specific toxic chemicals are present in the abandoned landfill. According to the accompanying documents, 465 tons of dichlorodiphenyltrichloroethane (DDT), over 200 tons of hexachlorane, and 7 tons of mercury and arsenic substances have been accumulated there. According to the results of the conducted agrochemical survey, the soil is characterized by a weakly acidic reaction (soil type – leached chernozem (black soil), coarse-silty, light-loamy, soil pH = 5.9; humus content – 3.6 %). Due to wind and water diffusion (pollutant dispersion up to 30 meters from the storage was detected), agrochemicals near the storage facility had the following content: 2,4-D amine salt (0.35), simazine (0.01–0.05 mg/kg), HCH (0.02-0.14), DDT (0.03–0.10), no detected methaphos, but present in the composition (0.19), no detected trichlorfon, but present in the composition (0.10) mg/kg. The productivity and stability of the ecosystems are significantly disrupted within a radius of up to 50 meters from the storage facility site, which hurts the biogeochemical cycling of substances. Therefore, the low presence of plant protection chemical residues near the storage facility in the village of Vyshnivchyk can be attributed to the fact that these pesticides were initially stored in the adjusted facility. However, over time (since the warehouse was established in 1978, and the containers have deteriorated), they have migrated into the soil beyond the storage area.


Glovyn, N. M., & Pavliv, O. V. (2023). Ecological monitoring of the impact of agrochemical plant protection products on the adjacent areas of farming enterprises in Ternopil region. Scientific Messenger of Lviv National University of Veterinary Medicine and Biotechnologies. Series: Agricultural sciences, 25(99), 89-93. doi: 10.32718/nvlvet-a9915
The article presents the results of ecological soil monitoring on the territories adjacent to agricultural storage facilities used for storing agrochemical plant protection products in the village of Vyshnivchyk, Ternopil region.The article is based on the study of the ecological monitoring of soil conditions on the territories adjacent to the areas where agrochemical plant protection products are stored.In most cases, these areas do not meet environmental and sanitary standards, posing a potential threat to the environment and the community's health.Inadequate storage conditions, which do not comply with the existing standards, release toxic residues from unused agrochemicals into the soil, water sources, and the air.Consequently, there is a risk of poisoning for both humans and animals.This study also includes an analysis of the composition of agrochemical substances from previous years on the territory of Vyshnivchyk village, Ternopil region (the territory of 'Denys K' Farm).A sheltered storage space near the village of Vyshnivchyk has been operating for more than 30 years.It was constructed in 1978 according to the standards of that time.Both bulk and liquid chemicals have been discharged into the quarry.The problem is further complicated because the landfill has no owner.It is unknown which specific toxic chemicals are present in the abandoned landfill.According to the accompanying documents, 465 tons of dichlorodiphenyltrichloroethane (DDT), over 200 tons of hexachlorane, and 7 tons of mercury and arsenic substances have been accumulated there.According to the results of the conducted agrochemical survey, the soil is characterized by a weakly acidic reaction (soil type -leached chernozem (black soil), coarse-silty, light-loamy, soil pH = 5.9; humus content -3.6 %).Due to wind and water diffusion (pollutant dispersion up to 30 meters from the storage was detected), agrochemicals near the storage facility had the following content: 2,4-D amine salt (0.35), simazine (0.01-0.05 mg/kg), HCH (0.02-0.14),DDT (0.03-0.10), no detected methaphos, but present in the composition (0.19), no detected trichlorfon, but present in the composition (0.10) mg/kg.The productivity and stability of the ecosystems are significantly disrupted within a radius of up to 50 meters from the storage facility site, which hurts the biogeochemical cycling of substances.Therefore, the low presence of plant protection chemical residues near the storage facility in the village of Vyshnivchyk can be attributed to the fact that these pesticides were initially stored in the adjusted facility.However, over time (since the warehouse was established in 1978, and the containers have deteriorated), they have migrated into the soil beyond the storage area.(тип ґрунту -чорнозем вилугуваний, грубопилуватий, легкосуглинковий, рН сольове = 5,9; гумус -3,6 %).За рахунок вітрової та водної дифузій хімічних сполук (виявлено розсіяння забруднення до 30 м від складу) біля складу вміст 2,4-Д-амінна сіль (0,35), симтриазин -0,01 -0,05 мг/кг, ГХЦГ -0,02 -0,14; ДДТ -0,03 -0,10.Від обстежуваної території об'єкту дослідження до 50 метрів виявлено занижену продуктивність і стійкість екосистем, що відповідно негативно відбивається на біогеохімічний колообіг речовин.Тобто, виявлена кількість залишків токсинів навколо території приміщення складування агрохімзасобів с.Вишнівчик виправдовується, що агрохімзасоби раніше зберігалися в адаптованому складі, але за тривалий період (склад створений у 1978 році, контейнери протерміновані, методом міграції розчиняються у ґрунт за межі сховища.

Introduction
Studies on monitoring soil condition in the areas adjacent to agricultural enterprises, where the use of inappropriate or banned agrochemicals is prevalent, have been the focus of research by various scientists, including Akimov V. I., Andrusenko M. I., Holik Y. S., Krainov I. P., Biletska H. A., Petruk R. V., Petruk V. H., Bereziuk A. P., Baliuk S. A., Zhukorskyi O. M., Liuta N. H., Polkovnychenko S. A., Romanchenko I. S., Fedulova I. V., Mokliachuk L. I., Lokhanska V. Y. (Zakon Ukrainy…, 1995;Alekperova, 2005;Mykytas, 2008).In order to restore environmental stability, preserve biodiversity of flora and fauna, and protect agrocenoses, it is essential to unite the efforts of specialists from various fields, including ecologists, microbiologists, biologists, biotechnologists, agrochemists, and others, and initiate comprehensive research on the detection of the residues of outdated agrochemicals and their impact on soil microflora, flora, and fauna.Informed individuals are more likely to be cautious when facing potential dangers (Petruk et al., 2013;Ramos et al., 2017).
This research aimed to conduct the ecological monitoring of soil conditions around the storage facilities containing unusable agrochemicals in the village of Vyshnivchyk, Ternopil region.Thus, the research task was to substantiate ecological safety and profitability factors concerning the disposal of storage facilities and warehouses containing unusable agrochemicals.

Materials and methods
Research methods included information and bibliographic research, analytical methods (literature analysis, results synthesis), chromatographic techniques, and statistical methods (assessing the likelihood of obtained results and determining correlation relationships).The inventory was carried out following the requirements of the norma-  (Alekperova, 2005;Mykytas, 2008;Petruk & Petruk, 2010).Soil samples were collected according to the methodology of integrated soilagrochemical monitoring of agricultural lands in Ukraine (1994) (Mykytas, 2008;Petruk et al., 2013;Ramos et al., 2017).Soil agrochemical indicators were determined using commonly accepted methods: humus (organic matter) content was determined using Simakov's modification of the Tiurin method (DSTU 4289: 2004); soil pH was determined potentiometrically using the CINAU method (GOST 26483-85).The soil samples collected in the area of the storage facility of prohibited and unusable chemicals located in the village of Vyshnivchyk, Terebovlya district, were investigated.The soil type was leached chernozem (coarse-silty, light-loamy, pH salt = 5.9; humus -3.6 %) (Alekperova, 2005;Mykytas, 2008).Data on the number of pesticide residues in the soil were obtained based on the research data of Ternopil Soil Research Laboratory "Oblderzhrodiuchist" by the officially established methodological guidelines (Klysenko, 1983) (Velychko & Yurchenko, 2017).

Results and discussion
The research on conducting a comprehensive inventory of storage sites for prohibited agrochemical plant protection products in the Ternopil region began in 2004, and the assessment of their environmental condition and the organization of soil remediation efforts on these sites continues to this day.The research was conducted on the territory of the Terebovlia community in the Ternopil region, focusing on the storage facilities for unusable agrochemical substances located in the village of Rizdviany (TzOV "Karier Plus" territory) and the village of Vyshnivchyk (the territory of "Denys K" Farm).This article also covers the method agrochemical substances in the village of Vyshnivchyk, Terebovlia community.Concerns about storing unusable pesticides in inadequate conditions and violating sanitary protection zones around the toxic chemical warehouse could further lead to environmental contamination.The toxic chemical landfill near Vyshnivchyk has existed for over 30 years.It was built in 1978 according to the standards of that time.When the former quarry, where bulk and liquid chemicals were disposed of, was filled, it was decided to preserve it.The problem is further complicated because the landfill has no owner.Currently, it is unknown which specific toxic chemicals are located in the preserved landfill.According to accompanying documents, it is believed that approximately 465 tons of dichlorodiphenyltrichloroethane (DDT) and over 200 tons of hexachloride, as well as 7 tons of substances containing mercury and arsenic, are accumulated in the landfill (Mokliachuk et al., 2012;Lokhanska et al., 2012;Petruk et al., 2013).These substances are located beneath a layer of concrete and are covered with soil.However, this does not eliminate the problem since material tends to deteriorate over time, especially when exposed to harmful chemicals.If there are liquid toxic chemicals present, they could seep into the groundwater.
Additionally, it is crucial to maintain the safety of the toxic landfill and prevent any moisture from entering, as it could lead to its destruction.The results of the conducted selective soil investigations of the storage facility indicate significant contamination with residues of chlororganic, phosphororganic, and simazine pesticides.Within the scope of our research, we focused on the most dangerous and persistent chlororganic compounds, which constitute approximately 80 % of the total volume of industrial pesticides.This is because chlorine-containing agrochemicals are highly bioactive (Migliorini et al., 2014;Mahmood et al., 2017;Yurchenko & Velychko, 2018).The combination of chlorine ions with organic molecules synthesizes a biologically active compound that blocks more than 16 physiological processes in microorganisms, plants, and animals, including photosynthesis, cell division, and respiratory processes, and; therefore, modern plant protection chemicals are produced based on bioactive chlorine-containing organic compounds (Ivankiv et al., 2014;Shah et al., 2016).Chlorinated cyclic hydrocarbons with hazardous toxic properties with a high half-life period characterize the chemical properties of chlorinecontaining organic pesticides.Their degradation resistance increases with higher chlorine atom concentrations.These substances have hydrophobic properties and can accumulate in the soil for an extended period.They participate in trophic chains in the soil-plant-animalhuman system and can persist in living organisms long.
Monitoring soil studies regarding the distribution of agrochemicals in the soil profile in the vertical direction show that toxicants accumulate in the soil up to a depth of 0.8 meters.This is because these toxic substances accumulate in the soil, especially in the root-containing horizon.Several literature sources confirm that soils, especially clay, and organic colloidal components, serve as excellent sorbents for 14 pesticides and heavy metals and can permanently or temporarily store these substances (Wiśniewski et al., 2015;Shah et al., 2016).The rates of soil fertility loss and soil degradation have become so high that a well-known soil scientist, H. V. Dobrovolskyi, notes the following: among the vast number of xenobiotics entering the soil, only a few dozen are registered, and their transformation products, which are often more toxic than the original substance itself, are not considered at all.When these compounds accumulate in the soil, they can undergo unpredictable reactions with each other, leading to chemical mutations and the emergence of substances unknown to humanity, the impact of which on the human body is unpredictable.Newly formed chemical compounds, such as heptachlor, are relatively less toxic.However, under the action of soil microorganisms, heptachlor can transform into heptachlor epoxide, which has a toxicity of 4-5 times higher (Yavorov & Nikitin, 2010).In addition, the accumulation of pesticide residues in the soil can also be explained by their persistence -the ability of agrochemicals to remain locally in the soil for an extended period.The evidence of this phenomenon is the detection of active DDT residues in the investigated area near the storage facility, indicating the significant persistence of this compound, which does not degrade under the influence of any factors.Any active substance typically degrades either through a chemical or a biological process.In other words, it reacts with specific soil chemical compounds, undergoes metabolic reactions, and loses activity.Alternatively, it becomes a food source for bacteria that break down the substance molecules into smaller fragments with their enzymes and then absorb them.Persistence is the inability to engage in such chemical interactions or the "inappropriateness" of bacteria consumption (Ivankiv et al., 2014).An integral part of ecological monitoring research is the detection of residues of agrochemicals within the local ecosystem, specifically in plants collected from the areas near the storage facilities under study.Therefore, the levels of these residues in plants from the areas near the storage facilities were de-termined (Yavorov & Nikitin, 2010;Mokliachuk et al., 2012).It was observed that as the distance from the storage site increased, the accumulation of toxic compounds in the plants decreased.Such studies were necessary because these areas were used for livestock grazing and haymaking (Table 2).
According to the analysis of the previous research conducted by scientists directly at the site to determine the residues of unused and prohibited substances, it is evident that this area has the highest level of contamination (Table 3) (Yavorov & Nikitin, 2010).The maximum allowable concentration of toxicants in the soil: simazine -0.2 mg/kg of soil; HCH -0.1; DDT -0.1; metaphos -0.1; trichlorfon -0.5; 2,4-D-amine salt -0.25 mg/kg of soil (Ivankiv et al., 2014).

Conclusions
The storage facility was constructed using outdated technologies (1978), and therefore, it cannot guarantee suitability for further preservation of unsuitable agrochemi-cals.Finding alternative methods to remove these substances, such as utilization through modern specialized technologies, is necessary.The highest concentration of toxicant residues was found near the storage facility (1-5 meters).Contamination was practically not detected within a distance of up to 100 meters.Therefore, it is necessary to inspect the condition of containers in old landfills, as this could cause contamination of the nearby ecosystems.
Prospects for further research.The conducted research serves as a warning signal to continue the study of the condition inside the storage facility the containers filled with agrochemical substances.
tive and methodological document "Procedure for Comprehensive Inventory of Locations Accumulating Prohibited and Unusable Plant Protection Chemicals in Agriculture", approved by the order of the Ministry of Agrarian Policy, Ministry of Ecology and Natural Resources, Ministry of Health on 18.10.2001No. 315/376/412, registered with the Ministry of Justice of Ukraine on 14.11.2001under No. 951/6142

Table 1
Storage and Disposal Status of Banned and Unsuitable for Use Agrochemical Substances in Ternopil Region (as of October 1, 2022)

Table 2
Content of toxic compound residues in the soil and plants in the areas near the storage facilities, µg/kg, M±m Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected Not detected

Table 3
Content of agrochemical substances in the soil (depth of samples 0-30 cm) depending on the distance from the toxic chemicals storage facility, mg/kg