22nd International Symposium on Plasma Chemistry July 5-10, 2015; Antwerp, Belgium Characteristics of soil treated with ozone generated by surface discharge T. Abiru1, F. Mitsugi1, T. Ikegami1 and K. Ebihara2 1 Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, JP-860-8555 Kumamoto, Japan 2 Environment and Energy Laboratory, 1-4-15, Otemon, JP-810-0074 Fukuoka, Japan Abstract: We have applied plasma technology to generate ozone. Ozone is expected as an alternative to agricultural chemicals such as pesticide and nitrogen fertilizer. In this study, ozone was generated by using the surface discharge injecting into soil directly in a quartz container. We investigated the influence of ozone treatment on physical properties of soil by evaluating acidity of soil. Keywords: ozone treatment, soil, nitrogen nutrient, pH(H 2 O), pH(KCl) 1. Introduction There are many kinds of studies about plasma with the development of science technology [1-4]. Plasma technology is applied in agricultural [5-8] and engineering field [9-11]. We have proposed to use plasma technology in agricultural field. Recently, chemical contamination of agricultural crop, water and soil has become a serious issue by the overuse of agricultural chemicals. There are many types of agricultural chemicals such as pesticide and nitrogen fertilizer. Pesticide has high effect of sterilization, however, it affects human body because it remains in agricultural crop, water and soil as residual toxic substances. Chemicals contained in pesticide penetrate into the underground, causing groundwater pollution. Nitrogen fertilizer has been used to advance the growth of crops. Nitrate nitrogen of nitrogen fertilizer proceeds acidification of soil, although it proceeds slowly. The acidification of soil and residual nitrogen oxides in groundwater have been observed all over the world by the overuse of nitrogen fertilizer. Therefore, alternatives to pesticide and nitrogen fertilizer are required from human health and environmental point of view. We propose the use of ozone in oxygen plasmas generated by surface discharge in agricultural applications, expecting the use of ozone to replace both pesticide and nitrogen fertilizer as alternative method because ozone can sterilize pathogens and virus in soil as well as increase nutrient composition of soil. We considered that ozone treatment affects physical properties of soil. There are many kinds of studies on application of ozone in agricultural field. Our previous study revealed that characteristics of soil such as inorganic nutrient (NO 3 -, NO 2 -, and NH 4 +), pH(H 2 O) were influenced after ozone treatment [12-14]. It also revealed that the value of pH(H 2 O) recovered to the initial value with time after ozone treatment. In this study, we measured the acidity of soil. Soil is generally consisted of soil solution and soil colloid. Acidity was evaluated by two different methods. One is pH(H 2 O) showing H+ in soil solution. The another is pH(KCl) showing H+ in soil solution as well as onto the surface of soil colloid because H+ which absorbs on soil colloid is P-III-9-2 replaced by K+. Therefore, pH(KCl) value is lower compared with pH(H 2 O). The difference between both values indicates to H+ absorbed onto soil colloids. Ozone was generated by oxygen plasma using a surface discharge and injected into andosol in a quartz container which is rotated by a motor. The concentration of ozone was 78 g/m3 with the flow rate of oxygen gas of 1.5 L/min. The treatment time was 90 min. We measured the change of pH(H 2 O) and pH(KCl) after ozone treatment. 2. Experimental Setup Fig. 1 shows the schematic illustration of the ozone treatment system for soil. This setup was used mainly for fundamental study because the use of the quartz container can avoid ozone consumption into unexpected organic matters. Ozone was generated by oxygen plasma using a surface discharge and injected into soil in a quartz container which is rotated by a motor. The concentration of ozone was 78 g/m3 with the flow rate of oxygen gas of 1.5 L/min. Exhaust ozone gas was monitored with an ozone monitor (Iwasaki electric., OZM-700GN). The soil used for treatment was andosol that was taken from field for cultivation of crops. The amount of andosol used for treatment was 100 g. The treatment time was 90 min. The ozone dose rate, which is defined as ozone does weight per unit weight of soil, was 11 %. We measured physical properties of soil such as inorganic nutrient (NO 3 -, NO 2 -, and NH 4 +), pH(H 2 O), pH(KCl), amount of soil DNA, amount of exchangeable bases (Ca2+, K+, Fe2+, and Al3+), fungi, and amount of nematodes before and after ozone treatment. Quantities of nitrate, nitrite and ammonium were evaluated using standard indices of NO 3 -, NO 2 -, and NH 4 + at mg/kg. Inorganic nutrients and bases were measured by colorimeter method with test reagent (Kanto Chemical Co. Inc., Reflrctoquant). After ozone treatment, we measured both pH(H 2 O) and pH(KCl) with time. One sample was a solution for pH(KCl) which the andosol (10 g) had been filtrated by potassium chloride solution (25 mL). Another sample was a solution for pH(H 2 O) which the andosol (10 g) had been filtrated by hyperpure water (25 mL). 1 pH(H2O)(90min) 7.0 Before treatment 6.5 pH(H2O) 6.0 5.5 5.0 4.5 0 1 2 3 4 Time (day) Fig. 1. Schematic illustration of ozone treatment system for soil. 3. Results and discussions We measured physical properties of soil before and after ozone treatment. In our previous study, inorganic nutrient in soil increased after ozone treatment, and kept at a constant value [14]. The pH(H 2 O) decreased after ozone treatment because organic matters in soil were decomposed by ozone. However, the pH(H 2 O) value recovered to the initial value with time [12, 13]. Fig. 2 shows the recovery curve of pH(H 2 O) after ozone treatment. There are also some studies about sterilizing effect of ozone in our previous studies. The almost of high molecular DNA in soil were decomposed and living bacteria were also sterilized after 11% ozone dose [15]. In this study, we measured H+ ions in soil solution as well as onto the surface soil colloid by pH(KCl), and H+ ions in soil solution by pH(H 2 O) after ozone treatment. Comparing between the recovery properties, as shown in Table 1, pH(H 2 O) and pH(KCl) decreased from 7.3 to 5.5 and 6.2 to 4.3, that increased 6.0 and 5.2 after 7 days passed from ozone treatment, respectively, increasing 7.4 and 6.4 after 14 days passed from ozone treatment. The pH(H 2 O) and pH(KCl) almost recovered to the initial value. The pH(H 2 O) indicated same recovery curve of our previous study. The pH(KCl) also indicated same recovery curve of pH(H 2 O). Both pH(H 2 O) and pH(KCl) value indicated that amount of H+ ions increased by a factor of hundred just after ozone treatment. The result suggested that amount of H+ ions changed only in soil solution. Subsequently amount of H+ ions decreased by one hundredth with time. From these results, it was found that H+ ions don’t migrate from soil solution to soil colloids. 4. Summary In this study, influence of ozone treatment on physical properties of soil was investigated. Ozone was generated by oxygen plasma using a surface discharge and injected into soil in a quartz container which is rotated by a motor. The concentration of ozone was 78 g/m3 with the flow rate of oxygen gas of 1.5 L/min. The treatment time was 2 Fig. 2. Recovery curve of pH(H 2 O) after ozone treatment. The dot line shows pH(H 2 O) value before treatment. Table 1. Changes in pH(H 2 O) and pH(KCl) of soil. Before ozone treatment Just after ozone treatment 7 days after ozone treatment 14 days after ozone treatment pH(H 2 O) pH(KCl) 7.3 6.2 5.5 4.3 6.0 5.2 7.4 6.4 90 min. We measured the change of pH(H 2 O) and pH(KCl) after ozone treatment. Comparing between the recovery curves, pH(H 2 O) and pH(KCl) decreased just after ozone treatment, subsequently recovered to the initial value. From the change of pH(H 2 O) and pH(KCl) value, it was found that H+ ions changed only in soil solution and don’t migrate from soil solution to soil colloids. 5. References [1] F. Mitsugi, T. Ohshima, H. Kawasaki, T. Kawasaki, S. Aoqui, T. Baba and S. Kinouchi. in: 21st International Symposium on Plasma Chemistry. 66, 1-4 (2013) [2] S. Aoqui, F. Mitsugi, H. Kawasaki, S. Kinouchi, T. Baba and T. Ikegami. in: 21st International Symposium on Plasma Chemistry. 353, 1-4 (2013) [3] F. Mitsugi, T. Ohshima, H. Kawasaki, T. Kawasaki, S. Aoqui, T. Baba and S. Kinouchi. IEEE Trans. Plasma Sci., 42, 12 (2014) [4] F. 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