STUDY OF THE PROCESS OF DESTRUCTION OF HARMFUL MYCOBACTERIA IN SURFACE WATER WITH ENVIRONMENTAL PROBLEMS USING OZONE TECHNOLOGY

Journal: Water Conservation and Management (WCM)
Author: Askar Abdykadyrova,b, Palvan Kalandarovb, Sunggat Marxulya*, Aruzhan Sabyrovac, Kanat Zhunusova*, Anar Khabaya, Nurzhigit Smailova,Alisher Tereka
Print ISSN : 2523-5664
Online ISSN : 2523-5672

This is an open access article distributed under the Creative Commons Attribution License CC BY 4.0, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited

Doi: 10.26480/wcm.03.2024.331.351

Abstract

The scientific research work is based on the process of destroying harmful microbacteria in surface water with the help of ozone technology, which are exposed to environmental problems. In general, this research paper carried out a comprehensive review of the literature published in scientific journals in the world in recent years on the process of neutralizing surface waters with traditional disinfectant reagents, which are subject to environmental problems. For example, we have highlighted the disadvantages and advantages of oxidizing agents and disinfectant reagents such as chlorine (Cl), chloramin (NH2Cl), chlorine dioxide (ClO2), ozone (O3) and ultraviolet (UV). However, among these reagents, considering the advantages of ozone technology, according to the research work, there is a special Current to ozone technology. The scientific novelty of the research work was the creation of a modern ozonator unit Etro – 02 based on an electric corona discharge with a frequency of 13 kHz, a voltage of 21 kV. For testing the installation, surface water was taken from the Kapshagai and Vyacheslav reservoirs, where aranai was exposed to environmental problems, and expert samples were carried out. The number of microbiological indicators that do not meet the standards found in the composition of water is as follows: total number of microbes 130-160 (1 ml of CFU (Colony-forming unit)), TCB (Thermotolerant coliform bacteria) 270-370 (100 ml of CFU), CCB (Common Coliform Bacteria) 650-800 (100 ml of CFU), coliphages 135-170 (100 ml of PFU (plaque – forming units)). To completely neutralize and clean these bacteria, the amount of ozone consumed per 1m3 of water was enough for 0.5 – 0.8 g/hour of ozone. And it turned out that the decontamination time will be enough 20 – 25 minutes. In addition, the obtained data were used to compile a mathematical model using the programs “Mathcad 14” and “SMath Solver”.

 

Keywords

Electric discharge, ozone, UV radiation, primary water, purified water, sorption.

1. INTRODUCTION

Depending on the human development strategy, it is estimated that by 2030 and 2040, water reserves in 167 countries will be 40% less than today (World Economic Forum, 2022). According to such statistics, water scarcity can have a negative impact on overall economic development (Maddocks et al., 2015). This issue is also relevant for Kazakhstan. After all, in the 1950s in Kazakhstan 120 billion. there are about 100 billion cubic meters of water reserves. there are also assumptions that the Cube was reduced to a meter (UN., 2022). This is because drinking water is obtained in most cases through surface reservoirs. Therefore, it is necessary to protect the environment and restore resources (Estévez et al., 2022). One of the reservoirs affected by environmental problems is Kapshagai and Vyacheslav reservoir (KZ News, 2022). On the shore of the kapshagai reservoir is the “training and drilling test site” of the Satbayev University. Due to the scarcity of drinking water in the landfill, surface water is used for drinking purposes. The content of harmful microbacteria in water is higher than the maximum permissible concentration (MPC) established by sanitary rules and norms [Ministry of Justice of the Republic of Kazakhstan, 2015; Siberian Ecology company, 2022). For example, the total number of microbes (TNM) i.e. the number of colony – forming bacteria in 1 ml 130 – 160 met. Modern articles on the effectiveness of the destruction of such harmful bacteria are currently published in foreign and domestic publications. For example, the effectiveness of technologies for disinfection of harmful bacteria in water by chlorine, ozone and ultraviolet rays is being considered (Diana and Yuly, 2021). However, these mentioned reagents have their own advantages and disadvantages (Figure 1) (Novikov and Prodous, n.d)

Figure 1: The main types of water disinfection methods

1.1 Chlorination of water
Advantages: effective against many types of microorganisms, widely used in large water treatment systems (Novikov and Prodous, n.d.; Limarenko and Novikov, 2014)
Disadvantages: chlorides and trichloromethane can form, which are dangerous to health. The taste and smell of chlorine in the water will appear (Limarenko and Novikov, 2014).
1.2 UV light treatment
Advantages: effective against bacteria, viruses and simple organisms without chemical additives. Does not change the chemical composition of water (Seleznev et al., 2007).
Disadvantages: does not remove particles and toxins, requires electricity and is effective only under direct radiation.
1.3 Ozone disinfection
Advantages: Ozone is effective against bacteria, viruses, fungi and organic pollution (Dan Kroll, 2007; Draginsky et al., 2007). Leaves no residue in the water.

Disadvantages: ozone requires special equipment to produce. The formation of some nitrogen oxides is possible.
Water disinfection is selected depending on the scope of the task (Bakhir, 2003;2007). Also, by water content and quality requirements (Dan Kroll, 2007 Zheldakova and Tulskaya, 2010). Chlorination is suitable for large water systems, UV treatment is suitable for small water systems and home use, and ozone disinfection is more environmentally friendly than chlorine (Bonnelye and Richard, 1997).

In recent years, there has been significant research and notable advancements in plasma disinfection technologies (Takuya Kuwahara, 2018). Ozone (O3) is an effective disinfectant in the process of destroying viruses among the reagents mentioned above (Figure 1) (Lin et al., 2007; Wigginton and John 2012). Therefore, it is widely used as a strong oxidizer of water. Ozone is usually formed in a cold plasma (NTP) with a dielectric barrier discharge from oxygen (O2) (Suan Tial and Mistugi, 2022). Therefore, when designing the design of ozonators, it is worth considering the cooling system of the electrodes in it. Considering the unique properties of ozone, we’ve embarked on a new ozonator project, with a keen focus on integrating ozone technology based on scientific research.

2. MATERIALS AND METHODS

The elimination of harmful microbacteria contained in surface water, which are subject to environmental problems, by means of an electric discharge is currently under rapid development (Tian et al., 2015; Parpiev et al., 2021). Overall, surface water is vital for supporting life on Earth. However, the existence of microorganisms like bacteria and viruses can endanger human health (Bakhir 2003;2007). Utilizing ozone generated through electric discharge emerges as one of the most efficient methods for eradicating microorganisms in water. (Khainatsky et al., 2018; Abdelaziz, 2016). In a scientific study, we will consider the mechanisms of action of ozone, the tendency of its formation in an electric discharge, and also evaluate the effectiveness of this method in the destruction of microorganisms in water [24]. In order to effectively remove harmful microorganisms contained in water in general with ozone, it is advisable to first thoroughly analyze the solubility and self-distribution of ozone in water.

2.1 The solubility and self-distribution of ozone in water
As ozone dissolves in water, its concentration steadily rises until it reaches the required threshold for a specific condition (Egorova et al., 2015).
The solubility of ozone in water depends on different conditions, i.e. the volume of water (voz/vw),), the temperature of the water (Т,0С) and the value of рН (Draginsky et al., 2007; Lunin, 2015). The concentration volume of dissolved ozone (measured in mg/l) in water is determined by the Bunsen coefficient. (Eike Breitbarth et al., 2004). At the same time, the tendency of ozone to dissolve in water can be explained by Henry’s law, which is proportional to the pressure of dissolved ozone and gaseous ozone in solution (Egorova et al., 2015). This pattern is written as:

C=β⋅М⋅Рγ,g/l

Where, C is the solubility of ozone in water, g/l; β-Bunsen coefficient, M is the density of ozone 2.14 g/l [16.31], Рγ – is the partial pressure of ozone in the melting gas medium. The solubility of ozone in water is very high compared to oxygen and nitrogen in the atmosphere (Battino,1983; Wei et al., 2017). Its solubility property in water increases with a decrease in water temperature (Egorova et al., 2015). Such research works Horvath M.L., Bilitrki Land Hutter., W. J. Considered in the experimental research works of Masschelein and B. F. Kogan (Table 1) (Draginsky et al., 2007).

Figure 2: Distribution of published study locations related to Ephemeroptera as bioindicator for surface water habitat in Indonesia

This can be seen from the experimental research work in Table 1 Above: as the water temperature (Т,оС) increases, the solubility of ozone in water (g/l) and the Bunsen coefficient β (l O3/ l H2O) decrease. Ozone is less soluble in acidic and salt water than in distilled water (Epelle et al., 2022). Sander R. on questions about the stability of Henry’s law, from the research work, it was also considered in connection with pH (Sander, 2015). In this research paper, the change in Henry’s constant due to pH at different temperatures can be expressed by the following equation.

Where, Ha is the Henry coefficient at the molar amount of ozone; T is the absolute temperature (K). It is observed that at a temperature of 300 K or 270С, the solubility property of ozone in water is very poor. That is, it is determined that LnHa =8.9 at pH=2 and LnHa =8.5 at pH=7 (Epelle et al., 2022; Sander, 2015).

During the dissolution of ozone in water, there is not only a tendency to react with chemical (Lim et al., 2022) substances present in the water, but also its own distribution (Yudianto et al., 2023). These two processes occur simultaneously and depend on the water temperature, pH environment (Sofia, 2020; Galdeano, 2018). At this point, it begins to affect microbiological indicators in drinking water (Sofia, 2020).
In general, the rate of propagation of ozone in water can be written as (Draginsky et al., 2007; Li et al., 2022).

where, Кр is the constant of the rate at which ozone is dissipated in water.

The quantitative characteristic and important feature of dissolved ozone to improve the process of decontamination and purification of surface waters can be seen in some studies (Jin et al., 2022):

О_3+Н_2 О→2ОН^*+О_2

О_3+ОН^-→〖О_2〗^(-*)+НО_2

О_3+ОН^*→О_2+Н〖О_2〗^*⇔〖О_2〗^(-*)+Н^±

О_3+Н〖О_2〗^*→2О_2+ОН^*

2Н〖О_2〗^*→О_2+Н_2 О_2

This can be traced to the formation of the OH* radical and hydrogen oxide from the above expressions.
The electrochemical decomposition of ozone by ozone occurs faster in an alkaline medium than in an acid (Bavasso et al., 2020), the rate of its dissolution under such conditions is expressed as:

where, Кр and Кa are stability in a wide range of pH in water. The ionic strength of the stabilized phosphate buffer is 0.15(mole/m3) (Judah et al., 2020).

the presence and tendency to decay of OH- – ions at or below pH=3 does not matter. OH- – ions have a faster tendency to dissolve in self – water in the region of a value of pH=7÷10. Most often, at such pH values, the ozone propagation time in water is taken into account as about 10 – 25 minutes (Von Sonntag et al., 2012).

Currently, the Staehelin et Hoigne scheme is a scheme that takes into account all the main trends in the dissolution of ozone in water (Figure 2) (Draginsky et al., 2007; Von Sonntag et al., 2012).

Figure 2: General cyclic scheme of ozone dissolution in water (Draginsky et al., 2007)

The ozone dissociation reaction and the mechanism of interaction with hydrogen at high temperatures hydrogen oxide can accelerate the reaction of self-decomposition of ozone, giving rise to intermediate radical parts (Jian et al., 2023; Yang et al., 2023).Н_2 О_2⇔Н^++Н〖О_2〗^-

Н〖О_2〗^-+О_3→Н〖О_2〗^*+〖О_3〗^*

The equilibrium constant is 11.6.
Various solutes interact with ozone and the OH* radical, at which time the acceleration of the self-decomposition of ozone occurs (Guo et al., 2021).

Given the large number of water pollutants, understanding a fully accurate image of ozone dissolving in water is a difficult task (Abdykadyrov et al., 2023). There is a certain experimental assessment of the main ways of ozone dissolution. In the simplest case, half of the ozone is molecular, and the rest is transformed into radicals. However, the transformed  radicals act on harmful microorganisms contained in water by different mechanisms.

2.2 Mechanisms of action of ozone by microorganismsr
Ozone (O3) in water is a powerful oxidizing agent capable of destroying the cellular structures of microorganisms (Abdykadyrov et al., 2023). In the process of introducing ozone into water, the oxidation of proteins, lipids and nucleic acids contained in water, as a result of which microorganisms are destroyed (Abdykadyrov et al., 2023; Rangel et al., 2021). This mechanism is an effective solution for disinfecting water with ozone. In general, the effectiveness of the destruction of harmful microorganisms contained in surface water is currently one of the most pressing problems (Gorito et al., 2021). However, in the data of recent scientific publications, the treatment of water with ozone based on an electric discharge provides a high degree of disinfection (Qasim et al., 2022). Efficiency in research work depends on parameters such as ozone concentration, processing time and characteristics of microorganisms (Tao et al., 2021, Xue et al., 2023). The high reactivity of ozone ensures the destruction of a wide range of pathogens, including bacteria, viruses and fungi (Rangel et al., 2021).

The tendency to remove microorganisms with ozone can expose water to oxidizing agents (Rangel et al., 2021; Xue et al., 2023). Which can also affect water quality. Therefore, it is important to balance the ozone concentration and monitor the quality of water after treatment (Spiliotopoulou et al., 2018).

A study of the process of destruction of microorganisms in water using ozone based on electric discharge shows the prospects for this method in ensuring the safety of Water Resources (Abdykadyrov et al., 2023; Qasim et al., 2022). Mechanisms of action and optimization of process parameters help to develop effective and sustainable methods of disinfection of water and other products in various situations (Botondi et al., 2023; Seridou and Kalogeraki, 2021). In general, below is a diagram of the mechanism of action of ozone by microorganisms (Figure 3).

Figure 3: Diagram of the mechanism of action of ozone by microorganisms

As we conclude from the diagram presented in the figure, it can be seen that it is worth paying special attention to the factors that affect the destruction of microorganisms with the help of ozone.

2.3 Factors affecting the destruction of microorganisms using ozone
The effectiveness of ozone in killing microbes is influenced by various
factors, including water quality parameters, ozone dose, contact time, and organic matter availability (Rangel et al., 2021; Davidson et al., 2011). The type and concentration of microorganisms also play an important role in determining the effectiveness of ozone treatment (Rangel et al., 2021; Takizawa et al., 2023; Thanomsub et al., 2002). The interaction of these factors and their general tendency to destroy microorganisms can be observed in Table 2 (Epelle et al., 2022).

What we can see from this table is that ozone can be a powerful disinfectant, but it is important not to forget that it is essential to use it correctly and that it works optimally. Therefore, before applying in the technological process, it is better to conduct a comparative analysis of ozone technology with traditional methods.

2.4 Comparative analysis of ozone technology with traditional methods
Comparison of ozone treatment with traditional water disinfection methods such as chlorination (Al-Abri et al., 2019). And ultraviolet irradiation, filtration works gives an idea of the benefits and limitations of the destruction of microorganisms by ozone (Soboksa et al., 2020; Cescon and Jiang, 2020; Zinn et al., 2018; Castro et al., 2023). Ozone’s ability to quickly inactivate a wide range of microorganisms without leaving harmful byproducts makes it a suitable option for surface water treatment (Castro et al., 2023; García-Araya and Beltrán, 2023). To compare ozone technology with traditional methods, let’s divide it into the main categories (Table 3).

Figure 4: Strategic future directions of water ozonation technology

The table showed a comprehensive comparative analysis of ozonation technology and traditional methods in various aspects (chlorine and UV). What we can see here is the peculiarity of ozone technology. However, special attention should be paid to the strategic future directions of water ozonation technology.

2.4 Strategic future directions of water ozonation technology

Disinfection of water from microbes, ozone has a very high property in the process of purification (Ngwenya et al., 2012; Muzafarov et al., 2021). It also aims to break down organic pollutants and improve the overall water quality (Mouele et al., 2015). The elimination of microorganisms through ozone is a promising method for improving the quality of surface water (Santos et al., 2021). The process contributes to the development of strategies for active water treatment, solving mechanisms and factors. Some research papers consider a solution to the strategy of increasing the activity of photocatalytic ozonation of g-C3N4 by halogen doping for water purification (Tan et al., 2022). A diagram of the strategic future directions of total water ozonation technology is presented in Figure 4 below

This figure presents a simplified diagram of the strategic future direction of water ozonation technology. It highlights the interrelated strategic directions of water ozonation technology for the future, highlighting key areas such as the improvement of ozone production, integration with intelligent systems, safety measures, environmental sustainability, integration with other technologies, miniaturization, study of ozone reaction kinetics, public awareness, education and cooperation. Each cell here represents a strategic direction, and the language lines indicate the relationships and influence between these directions.

Taking into account the previously studied scientific information in the above materials and methods, we paid special attention to the process of destroying harmful microbacteria in surface water with the help of ozone technology, which is subject to environmental problems.

3. RESULTS AND DISCUSSIONS

In the process of decontaminating surface water from harmful microorganisms, a number of advantages of ozone (O3) over traditional methods such as chlorine (Cl) and ultraviolet (UV) radiation have been identified (Summerfelt, 2003). For instance, ozone exhibits a significantly faster effect on harmful microorganisms in water, approximately 15 to 20 times faster than chlorine. Specifically, while ozone at a concentration of 0.45 mg/l can destroy the polio virus within 2 minutes, chlorine requires a dose of 2 mg/l and takes 3 hours to achieve the same result. Consequently, the necessary amount of ozone is approximately 2.5 times less than chlorine. Overall, the advantages of ozone over chlorine and UV radiation are as follows (Ishaq et al., 2018; Voukkali and Zorpas., 2015).
– High oxidation potential: Ozone has a high oxidation potential compared to chlorine and ultraviolet radiation. This allows ozone to effectively degrade and oxidize a wide range of organic and inorganic pollutants in water, including bacteria, viruses, and pollutants (Voukkali and Zorpas., 2015).

– Absence of harmful by-products after the oxidation process: unlike chlorine, which can form potentially harmful disinfectant by-products when interacting with organic substances, ozone does not form such by-products (Sassi et al., 2005).
– Effectively destroys pathogens: Ozone is a more powerful disinfectant than chlorine or ultraviolet radiation, capable of destroying a wide range of pathogens, including bacteria, viruses, and parasites. This makes ozone a reliable solution to prevent water-borne diseases (Ishaq et al., 2018).
– Lack of residual taste and smell: Ozone does not give the treated water a residual taste or smell, which is especially effective when treating drinking water, as consumers prefer water with a stable taste and no smell (Voukkali and Zorpas., 2015; Sassi et al., 2005)

– Wide range of pollution removal: Ozone effectively decomposes and removes a wide range of pollutants, including organic pollutants, pesticides, and pharmaceutical waste. UV radiation may not be effective against certain types of pollutants, and chlorine may require additional treatment steps for complete removal (Ishaq et al., 2018).
– Short contact time: Ozone disinfection usually requires a shorter contact time compared to chlorine. This can lead to more efficient water treatment processes and a shorter overall treatment time, which contributes to energy savings (Voukkali and Zorpas., 2015).
– PH flexibility: Ozone remains effective in a wider pH range compared to chlorine. This provides flexibility when treating water at different pH levels without compromising disinfection efficiency (Sassi et al., 2005).

– Eco-friendly: Ozone decomposes into oxygen without leaving harmful waste, making it an environmentally friendly disinfectant. On the contrary, disinfection with chlorine can lead to the formation of chlorinated by-products that can affect the environment. Although UV radiation is effective in disinfection, it does not provide a residual disinfecting effect. Ozone, on the other hand, can have a residual disinfectant effect that provides permanent protection against the regrowth of microorganisms in the distribution system (Draginsky et al., 2007; Sassi et al., 2005).

Thus, the advantages of ozone over chlorine and UV radiation in water treatment include high disinfection capabilities, the absence of harmful by-products, flexibility in the pH range and an integrated approach to removing pollutants. These factors contribute to an increase in the preference for ozone in various areas of water preparation.

3.1 The tendency to destroy harmful microorganisms contained in water with ozone
Ozone destruction of microorganisms involves oxidative reactions in which ozone reacts with various components of microbial cells (Martinelli et al., 2017; Rosenblum et al., 2012). Specific chemical reactions can vary depending on the nature of microorganisms and the composition of cells (Ngwenya et al., 2013; Banach et al., 2015). The ozone concentration can be determined according to the stage of the technological process as follows (Chasanah et al., 2019):

d[O_3 ]/dt=-k_1 [O_3]
Where k1 is a constant rate due to the decay of ozone.

The concentration of lipids in the total [L] microbial cell membranes can be determined as follows (Barák and Muchová, 2013; Lakey et al., 2017).

d[L]/dt=-k_2 [O_3][L]
Where k2 is the constant reaction rate between ozone and lipids.

Similarly ,the concentration of proteins in [P] microbial cells can be determined as follows (Cataldo, 20005).

d[P]/dt=-k_3 [O_3][P]
Where k3 is the constant reaction rate between ozone and proteins.

Reaction equation with nucleic acids (Hoigné and Bader, 1983, Portjanskaja, 2010):

d[NA]/dt=-k_4 [O_3][NA]
Where [NA] is the concentration of nucleic acids (DNA/RNA) in microbial cells. k4 is a constant reaction rate between ozone and nucleic acids.

Microbial inactivation equation (Brodowska, 2017):

d[M]/dt=-k_5 [O_3][M]
Where [M] refers to the concentration of microorganisms. k5 is a constant rate of total inactivation of microorganisms by ozone.

These equations describe changes in the concentration of ozone and the concentration of lipids, proteins, nucleic acids and microorganisms over time. Based on these theoretical data, a system for eliminating harmful microorganisms contained in water with ozone was identified below (Figure 5). Let us consider the algarity of the basic system of equations that take into account the reactions in which ozone and various components of microorganisms are involved during the general technological process.

Figure 5: The system of equations of contact of ozone with the destruction of microorganisms.

3.2 Design of a new pilot ozonator installation Etro-02
Based on the theoretical data and methodological instructions given in the previous sections, a special installation of the Etro – 02 ozonator was developed at the K. I. Satpayev Kazakh National Research Technical University (KazNRTU) based on an electric corona discharge with a frequency of 13kHz and a voltage of 21 kV (Abdykadyrov et al., 2014). The general sketch scheme of the installation is presented in Figure 6 a,b below. For practical testing, the unit was installed in a scientific laboratory located near the Kapshagai reservoir, which was exposed to environmental problems. There, scientific research was carried out on the process of destroying harmful microbacteria contained in surface water using ozone technology.

The Etro-02 unit belongs to ozone extraction devices and can be used in the field of Ecology, in the treatment and disinfection of drinking water and wastewater, as well as in medicine, water channels, drainage, food industry, etc. The voltage between the corona electrodes in the ozonator is 21 kV, the length of the electrodes in it is 40 m, and the cooling system is carried out using nitrogen or transformer oil. The generator produces an ozone-air mixture with a capacity of 30g/m3 per hour.

The technological scheme for cleaning water from harmful bacteria is based on the Etro – 02 ozonator device operating at a special frequency of 13 kHz and a voltage of 21 KV to carry out the process of disinfection and purification of harmful microorganisms found in the reservoir water (Figure 7).

Figure 7: Technological scheme of the process of destruction of harmful microorganisms in water.

With the help of the Etro-02 ozonator, the process of neutralizing and cleaning harmful microorganisms found in surface waters of the Kapshagai and Vyacheslav reservoirs is effective.

The Etro – 02 ozonator unit was used to decontaminate surface water from the warehouse. In the course of the general process, our goal in using ozone in reagents (chlorine and UV radiation, etc.) was to find that the oxidizing and disinfecting properties of ozone are higher than others. This is because it was effective for disinfecting surface water from harmful microorganisms, removing odors, changing the color of water, and removing impurities (Ding et al., 2019; Morrison et al., 2022). For example the elimination of bacteria, spores, germs and viruses in water (inactivation). To do this, a disinfectant reagent (ozone, chlorine, UV, etc.) is usually introduced into the water (Abdykadyrov et al., 2023). The dose of reagent in water treatment processes and disinfectants varies depending on the content of organic matter in the water, the temperature of the water, and the time of active reaction of the water with the disinfectant (Collivignarelli et al., 2018). When using chlorine, the higher the dose, the fewer bacteria will live, but at the same time unpleasant side effects will occur (Morrison et al., 2022). Heavy metals and bactericidal effects with the use of ozone begin when a certain critical dose is reached, equal to 0.3 – 0.6 mg per liter of treated water (Abdykadyrov et al., 2023). In addition, complete inactivation (disinfection) of water occurs.

The mechanism of action of ozone in general consists in the breakdown of bacterial proteins and is carried out by the diffusion of ozone through the cell membrane into the cytoplasm, after which the life centers are damaged. The action takes place quickly-if its required concentration in water is maintained. If ozone has an effective effect on almost all bacteria, then chlorine selectively poisons the life centers of bacteria due to the low rate of diffusion in the cytoplasm (Broséus et al., 2009). The time it takes to reduce the concentration of bacteria to the allowable amount is called the inactivation (disinfection) time. For chlorine, the inactivation time is 30 min. when the chlorine content in water is in the range of 0.05 – 0.2 mg/l. For ozone, this time is 12 min. when the ozone content in water is 0.2 – 0.3 mg/l. In France, a time equal to 4 min is taken for water inactivation (ozone concentration 0.4 mg/l) [16].

According to the technological scheme, the process begins with the formation of ozone. Ozone (O3) is formed by passing oxygen molecules through a high – voltage electrical discharge(as can be seen in Figure 6 (B)). The ozone then enters the water through a tube using a compressor. That is, at this time, there is a process of neutralization of harmful microorganisms contained in the water. When ozone comes into contact with pollutants in water, such as organic matter, bacteria, viruses, and other impurities, it breaks them down by giving them highly reactive oxygen atoms. This process effectively neutralizes and removes these pollutants. In general, ozone in water not only fights microorganisms, but also helps to remove particles and turbidity. The oxidizing power of ozone causes aggregation of small particles, making them easier to settle or filter during subsequent water treatment steps.

3.3 Testing the unit
For testing the installation, special research works were carried out on the Kapshagai reservoir located on the coast of the city of Kunaev and on the Vyacheslav reservoir located on the coast of Astana (Republic of Kazakhstan) (Wikipedia; ADB, 2021; CAWater-info).
During the technological process, the amount of ozone (0.3 – 0.6 g/hour) is consumed depending on the content of surface water in the warehouse. The treated water from the facility retained a residual ozone concentration ranging from approximately 0.09 to 0.3 mg/l. Presently, ozone technology stands as one of the contemporary approaches to water disinfection and purification. Ozone exerts both organoleptic and chemical effects on harmful bacteria present in water throughout the technological process. Its impact on waterborne microorganisms varies depending on factors such as pH level (pH = 6 – 10) and temperature (ranging from 0°C to 37°C). It’s challenging to assert that ozone selectively targets microorganisms in water: initially, it acts on dissolved organic impurities before affecting microorganisms (Abdykadyrov et al., 2023).

Among the methods of surface water disinfection, ozone technology is very effective. For example, it can be observed in Figure 8 and Table 4 below (Draginsky et al., 2007; Abdykadyrov et al., 2023). Table 4 uses various disinfection methods (temperature 220C. pH = 6.8 – 7.0) from microorganisms (E. coli) and viruses can be observed with a decontamination efficiency of up to 97 – 99% percent.

Figure 8: K·T (concentration·time) values of various disinfectants for virus disinfection

What we see in Figure 8 is that chlorine is suitable for neutralizing bacteria and viruses, but should not be used to deactivate protozoa. And the process of ozonation is able to destroy all known bacteria and viruses. When ozonating water, first of all, the contact time and the concentration of ozone in the water are taken into account.

Table 5 and Figure 9 below show the disinfection rate of “Giardia cysts”. In
this table, it can be observed that total chlorine and chloramine have a low K·T (concentration·time) value. In general, ozone is a powerful disinfectant to neutralize the microorganism. The protozoa contained in water (Cryptosporidium) actually react slowly with chlorine and chloramine. The K·T (concentration·time) values for chlorine deactivation are equal to 3000 – 4000 mg·min/l for 1 – log deactivation (90% deactivations.

“Giardia cysts” refer to an intestinal infection caused by Giardia parasites, characterized by symptoms such as stomach cramps, bloating, nausea, and episodes of watery diarrhea. This infection arises from a microscopic parasite prevalent worldwide, particularly in regions lacking proper sanitation and having unsafe water sources.

Figure 9: Speed of disinfection of “Giardia cysts” using various disinfectants

This can be seen in the figures 8 and 9 above, the advantage of ozone. Here ozone has little effect on ph and temperature. However, as the temperature increases, the solubility of ozone decreases, the level of disinfection increases at 10°C, in the range of 0 – 30°C, these two factors reduce each other. in the pH = 6 – 8.5 range, the ozone disinfection rate hardly changes. For some resistant microorganisms (such as Giardia Muris), the disinfection rate increases when the pH is high. For other types of microorganisms, the opposite is true.

To determine the efficiency of oxidizing agents and destruction of microorganisms contained in surface water in the warehouse, it was necessary to develop a sanitary reliability criterion, taking into account
various reagents, their doses, the length of the water supply network, quality indicators. Such research work has already been adopted in the United States in previous centuries, that is, in the 1960s (Корко, 2020).

According to scientific research, the ozonator plant was tested, special water was removed from the surface reservoirs of Kapshagai (Kunayev city) and Vyacheslav (Astana city), ozonation was carried out. Scientific research was carried out in the “sanitary and hygienic Laboratory” of the RSE (Republican State enterprise) of Almaty and in the scientific laboratories “Astana Su Arnasy” of Astana. The microbial parameters of water quality do not align with the Maximum Permissible Concentration (MPC), as demonstrated in the table provided below (Table 6).

It is evident that the initial water samples contain microbiological indicators within the ranges of 130-160 CFU (total coliform bacteria), 270-370 CFU (thermotolerant coliform bacteria), and 135-170 PFU (coliphages) per 100 ml. Upon introducing varying ozone amounts ranging from 0.3 to 0.8 g/h into the water, there is a gradual reduction in microbiological indicators, as illustrated in Figures 10 and 11. Notably, when the ozone concentration reaches 0.5 to 0.8 g/h, the total microbe
count in the water meets the predetermined criteria set by the MPC. This indicates a 99.9% elimination of harmful microorganisms from the water.

Option 2. In this version, we change the decontamination time to 5 – 25 minutes, keeping the ozone concentration constant (C = 0.8 g/hour). The results of the research work are presented in Table 9 (Kapshagai reservoir), table 10 (Vyacheslav reservoir) and figures 12 and 13 below.

Figures 12 and 13 demonstrate that with an ozone concentration of C = 0.8 g/hour, and a decontamination duration of 20-25 minutes, the levels of thermotolerant coliform bacteria (TCB), coliform bacteria (CCB), and coliphages in the water align with the maximum permissible concentrations outlined in the drinking water standard MEST 2.1.4.1074 – 01 [7]. However, for the sake of standardizing experimental procedures and determining ozone consumption per 1m3 of water, it is recommended to develop a mathematical model that incorporates relevant physical parameters (Звонарев, 2019).

3.4 Mathematical model of the technological process

To construct a mathematical representation of the process wherein ozone eliminates harmful microorganisms in surface water it is necessary to first analyze the technology of ozonation of water (Figure 14) (Loeb, 2011). From this figure 14, let’s denote the ozone concentration in water as C_0 (t), depending on the time. Then the rate of change in ozone concentration ((dC_o)/dt) can be described by the following differential equation (Draginsky et al., 2007; Shin et al., 2020):
(dC_o)/dt=R_0-Q_i·C_0-k_ow·C_0 (21)

Where: Ro is the rate of ozone formation; Qi is the rate of ozone injection; kow is the constant rate of ozone+water reaction.
Through this (21) expression, one predicts first-order kinetics for the ozone + water reaction, and one can observe the rate at which ozone and injection occur.

The main factors influencing surface water disinfection processes include concentration of disinfectant reagents, mechanical work, time and temperature (Richardson and Postigo, 2012, Pérez-Lucas, 2022). When using disinfectants, you should be guided by the manufacturer’s recommendations. For example, when using highly concentrated solutions during the process, it can lead to the formation of insoluble compounds and the activation of corrosive processes (Wei et al., 2017).

High temperatures can lead to chemical decomposition of the active substance, loss of hard water salts, polymerization of proteins and fats (Epelle et al., 2023). But this negatively affects the quality of disinfection. Another important factor in the process of disinfection of vegetables in any agriculture, including drinking water, is the time of contact. For example, the greater the contact time of ozone, the lower the number of microorganisms (Sukarminah et al., 2017).

There are many mathematical models that describe the process of inactivation of microorganisms found in the drinking water and food industries (Hafsan et al., 2023). Difficulties arise when using these models, because it involves complex parameters that are determined experimentally. One of the models used more often than others is the Chika-Watson linear-logarithmic model (Mecha et al., 2020):

Log(Nt/N0) = – ĸCnt (22)
Or this (22) expression can also be written as:
N_t=N_0 e^(-kC^n t) (23)
Nt is the number of microorganisms that survived during the process; N0 this refers to the initial quantity of microorganisms.; k is the constant of the disinfection rate; C this denotes the concentration of the disinfectant.; n is the dilution factor; t is the contact time.

The dilution factor (n) here depends on the type of disinfectant. For example, for quaternary ammonium salts n = 1. this means that the exposure time must be doubled when the concentration of n is halved. For ethanol, n = 10, which means that when the ethanol concentration is halved, the processing efficiency decreases by 210, that is, by 1024 times.

Based on the experimental data presented in figures 10, 11 and 12, 13 of the previous section, mathematical calculations were carried out to determine the amount of ozone consumed per 1m3 of water. Mathematical calculations were performed using the Mathcad 14 and SMath Solver programs (SMath Studio, 2010).

According to the research work, the process of complete disinfection of 1m3 of water from harmful microorganisms was carried out according to two options:

Option 1: according to this option, let’s determine the number of survivors of harmful microorganisms during the Nt – process in water by changing the concentration of ozone in the range of C = 0.3 – 0.8 g/hour? Where time constant t = 5 minutes; dilution coefficient n=2; disinfection rate constant ĸ = 0.12 – 4.00; N0 – the initial number of microorganisms is given in Table 11 below. Based on this data, let’s write from the expression (23) the number of microorganisms eliminated by the concentration of ozone (Nt) in Table 11.

And now let’s draw the destruction of microorganisms contained in water in the interval C = 0.3 – 0.8 g/hour, depending on the amount of ozone, according to the data in Table 11. Where time constant is t = const. The algorithm for the destruction and contact characteristics of microbiological indicators of the water content of 1m3 are presented in figures 15 a and b below.

Figure 15 of the aforementioned equation (22,23) illustrates that the method for eliminating harmful microorganisms in water through the algorithm is most effective with an ozone concentration of C = 0.8 g/h. Throughout the technological process, it’s feasible to counterbalance the water composition from detrimental compounds by adjusting the time constant at a specific juncture. By maintaining a constant ozone level in the water (C = const) while altering the decontamination duration, we can ascertain the effective time constant.

Option 2: according to this option, let’s determine the number of microorganisms that survived during the Nt process by keeping the ozone concentration constant C = 0.8 g/hour, and accordingly changing the decontamination time from T = 5 to 25 minutes? Where the dilution coefficient is n=2; the constant of the disinfection rate is ĸ = 0.12 – 4.00; N0 – the initial number of microorganisms is given in Table 12 below. Based on this data, let’s write from the expression (23) to table 12 of the number of microorganisms (Nt) that have been removed due to time.

It is possible to determine the time (t, minutes) and the amount of ozone concentration (C, g/hour) of the process of destruction of harmful microorganisms (Nt) in water using the algorithm presented above in figures 15 a, b and 16.

4. DISCUSSION OF SCIENTIFIC RESEARCH WORK

Microorganisms present in surface waters can pose various threats to human health. The damage they cause is primarily due to diseases and infections transmitted through water. Here are some common microorganisms found in surface waters and their potential health effects:

Bacteria: pathogenic bacteria like E. coli, Salmonella, and Vibrio cholerae can induce gastrointestinal infections, resulting in symptoms such as diarrhea, abdominal cramps, nausea, and vomiting

Viruses: Intestinal viruses such as norovirus and rotavirus are responsible for viral gastroenteritis. They can cause severe diarrhea, dehydration, and sometimes more serious complications, especially in vulnerable groups such as children and the elderly.

Parasites: Protozoa such as” Giardia lamblia “and” cryptosporidium parvum ” can cause gastrointestinal problems. Cryptosporidia, in particular, are resistant to traditional disinfection methods and can lead to long-term diarrhea, especially in people with weakened immune systems.

Algae: Toxic algae can cause harmful algae blooms (HABs) that release toxins into the water. Ingestion or contact of these toxins with the skin can cause various health problems, including respiratory problems, skin irritation, and in severe cases, neurotoxic effects.

Mushrooms: Although some water-carrying fungi are rare in surface water, they can cause infections, especially in people with weakened immune systems. Examples are the species” Aspergillus “and” Fusarium”.

The health risks associated with these microorganisms highlight the importance of proper water treatment and disinfection. Contaminated surface water, especially in areas with insufficient sanitation and water treatment facilities, can lead to the widespread spread of waterborne diseases. In addition, extreme weather events such as heavy rain and floods can increase the chances of contamination. However, currently, the main widespread methods of water disinfection are the following methods (figure 17).

Figure 17: Speed of disinfection of “Giardia cysts” using various disinfectants

Proper water disinfection methods such as chlorination, UV sterilization or ozonation are very effective in reducing the microbial load in surface water and preventing water-borne diseases. Constant monitoring of water quality and compliance with water safety standards is essential to ensure the health and well-being of communities that use surface water sources.

Among the listed methods, we paid special attention to ozone technology during our scientific research work. Figure 18 below shows the effectiveness of ozone technology in eliminating harmful microorganisms contained in surface water.

Figure 17: Efficiency of the process of neutralization of harmful microorganisms in water using ozone technology

In Figure 18, the efficacy of ozone technology in neutralizing harmful microorganisms present in water was thoroughly examined. The study also delved into the technological and design aspects of the ozonation process for Kapshagai and Vyacheslav surface waters, utilizing the Etro-02 ozonator unit featuring a pilot, innovative electric Crown discharge of 21 kV with a frequency of 13 kHz. However, a drawback of ozone technology is that water treated with ozone may traverse many kilometers of pipelines before reaching consumers, potentially encountering secondary contamination along the way. To mitigate this issue, a high-quality water filter was incorporated into the technological scheme. Among the filters examined, the research highlighted membrane filters as the most effective option. These filters are safe for human consumption and yield water that can be consumed without further treatment.

4. CONCLUSIONS

Over the past 5 years, a comprehensive review of modern scientific literature has been carried out on the process of destroying harmful microbacteria in surface water with the help of ozone technology, which is subject to environmental problems. Based on the review of the scientific literature at the Department of “Electronics, Telecommunications and space technologies” of the Satbayev University, the Etro-02 ozonator unit based on the electric Crown discharge was developed. According to scientific research, the ozonator plant was tested, special water was removed from the surface reservoirs of Kapshagai (Kunayev) and Vyacheslav (Astana), ozonation was carried out. Scientific research was carried out in the “sanitary and hygienic Laboratory” of the RSE of Almaty and in the scientific laboratories “Astana Su Arnasy” of Astana. During the research work, the following results were revealed:

– for testing the installation, surface water was taken from the Kapshagai and Vyacheslav reservoirs, where aranai was exposed to environmental problems, and expert samples were carried out. The number of microbiological indicators that do not meet the standards found in the composition of water is as follows: total number of microbes 130-160 (1 ml of CFU), TCB 270-370 (100 ml of CFU), CCB 650-800 (100 ml of CFU), coliphages 135-170 (100 ml of PFU). To completely neutralize and clean these bacteria, the amount of ozone consumed per 1m3 of water was enough for 0.6– 0.8 g/hour of ozone. And it turned out that the decontamination time will be enough 20 – 25 minutes;

• There was a decrease in toxicological indicators found in water, i.e. Inorganic compounds with a high toxicity indicator such as nitrates, nitrites, fluorine, etc.;

• Toxicological indicators found in the composition of water were observed in which there was a decrease in organic compounds.
This proposed scientific research work was carried out using the Etro – 02 ozonator unit based on an electric corona discharge with a special frequency of 13 kHz and a voltage of 21 kV. Research work was carried out in the period from 2020 to 2023, and the performance of the unit, its power and other technological indicators were determined.

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Pages 331-351
Year 2024
Issue 3
Volume 8

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