Method for immobilizing nitrogen, immobilizing carbonic acid or synthesizing organic matter with air and light, at ordinary temperature and ordinary pressure, in coexistence of water, salt, metal or nature-derived material

Abstract

To provide a method for immobilizing nitrogen, immobilizing carbonic acid and producing an organic matter with only water, air and light by a simple device.SOLUTION: There is provided a method for immobilizing a carbonic acid, immobilizing nitrogen or producing an organic matter by existing only water in a container, or coexisting salt, metal or other nature-derived material with the water, and irradiating the substances with light including ultraviolet rays or sunlight in the air.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for performing nitrogen fixation, carbon dioxide fixation or organic synthesis using air and light in the presence of water or a mixture of water and salts, metals or naturally occurring materials at normal temperature and pressure. [Background technology]

[0002] It has been reported that water is decomposed by ultraviolet irradiation, and even amino acids and ribonucleosides are synthesized (Non-Patent Documents 1 and 2). Ultraviolet rays have strong energy, and when irradiated, they can break intermolecular bonds, ionize, or put molecules into a higher energy state. However, these reports assume the conditions when the Earth was first formed, and discuss interstellar ice and ice on the surface of comets. Since there was no oxygen in the Earth's atmosphere at that time, and there was no ozone layer, it is estimated that the intensity of ultraviolet rays was three orders of magnitude higher than today (Non-Patent Document 3). These are the results of experiments conducted in laboratories that reproduce the conditions of outer space and high vacuum conditions. The Earth settled into its modern form about 4 billion years ago, and life is said to have emerged about 3.8 billion years ago. There is much debate about the mechanism by which life emerged, but it is thought that the most important factor is that precursors that support the emergence of life were sufficiently formed.

[0003] Ammonia is a substance in which hydrogen is bonded to nitrogen (NH3), and is a valuable raw material used in a variety of fields. The annual demand for ammonia as a raw material for nitrogen-based fertilizers, medicines, food, etc. exceeds 170 million tons. Furthermore, NH3 gas can be combusted, and since no carbon dioxide is produced after combustion, only water is produced, it is a carbon-free substance. Although NH3 is a toxic gas, production, transportation, and storage have already been established, and safety measures and guidelines have been put in place. The Haber-Busch process, developed in Germany in 1913, is still the mainstream method for producing NH3. However, in order to effect the reaction, high temperatures (400 to 500°C) and high pressures (100 to 300 atm) are required, and the production energy consumption is large (Non-Patent Document 4). In recent years, a group from the Tokyo Institute of Technology has demonstrated that by supporting nano-sized ruthenium as a catalyst on the surface of C12A7 electride, it can be produced at low temperatures (340 to 400°C) and low pressures (1 atm) (Non-Patent Documents 5 and 6). Although the pressure is lower than that of the Haber-Busch method, it still requires high temperatures. [Non-patent literature] 1. Sarker, PK, J.-I. Takahashi, Y. Obayashi, T. Kaneko, and K. Kobayashi (2013). Advances in Space Research 51, 2235-2240. 2. Powner, MW, C. Anastasi, MACrowe, ALParkes, J. Raftery, and JDSutherland (2007). ChemBioChem 8(10),1170-9. 3.Ferris,JPand CTchen(1975).Chemical Evolution.XXVI.Journal of the American Chemical Society 97(11),2962-2967. 4.R.Schlogl,Angew.Chem.Int.Ed.2003,42,2004. 5.M.Kitano et al.Nature Communications 6:6731(2015) 6. A. Fujishima, K. Honda: Nature, 238, 37 (1972). The inventors succeeded in forming various substances by light irradiation using a very simple device. All they had to do was put water in a glass beaker and irradiate it with ultraviolet light.

[0004] [UV light irradiation on water] 20 mL of purified water was placed in a 50 mL quartz beaker and irradiated at room temperature in the dark, under an LED light (30 W) with an ultraviolet cut filter, and under UV lights (15 W, 4 lights). After about 20 hours, the irradiation was stopped and the water content was measured. The temperature rose due to the irradiation and the water evaporated, so the evaporated water was added to match the starting weight. In the nitrogen system, the ammonium ion (NH4 +Regarding the method for nitrite ion (NO2), the indophenol method (Non-Patent Document 7), the thymol-hypochlorite method (Non-Patent Document 8), and the Nessler method (Non-Patent Document 9) were used. - ) uses the naphthylethylenediamine method (Non-Patent Document 10) and nitrate ion (NO3 - For the saccharides, the phenol-disulfonic acid method (Non-Patent Document 11) was used, and for urea, the diacetyl monoxime method (Non-Patent Document 12) was used. For sugars, the Park-Johnson method (Non-Patent Document 13), sulfuric acid-silver nitrate method (Non-Patent Document 14), phenol-sulfuric acid method (Non-Patent Document 15), Somogyi method (Non-Patent Document 16), and Seliwanoff method (Non-Patent Document 17) were used. For amines and amino acids, the ninhydrin method (Non-Patent Document 18) was used, and for formyl groups, the Benedict solution (Non-Patent Document 19) and for carbonyl groups, the Fehling method (Non-Patent Document 20) were used. Furthermore, for ribose, the orcin reagent (Non-Patent Document 21) and for deoxyribose, the diphenylamine reaction (Non-Patent Document 22) were used. The results are shown in Table 1. [Table 1] As is clear from the TIFF2025018853000002.tif80160 table, NH4 + was only seen when exposed to ultraviolet light. Three methods were tried, and the generation was confirmed in all cases. NO2 - was not seen, but NO3 - Nitrogen fixation was confirmed by UV irradiation. Ninhydrin is produced by nitrification of not only amino acids and amines but also NH4 + This also reacts with NH4 + production was confirmed.

[0005] On the other hand, sugars have also been confirmed to be produced by UV irradiation, which indicates that carbon fixation is also taking place. In other words, nitrogen fixation and carbon dioxide fixation occur simultaneously when water is irradiated with UV light. However, when it comes to sugars in particular, some production has been confirmed with visible light, so UV irradiation cannot be said to be the only energy source. The amount produced, however, is extremely small. The confirmation of deoxyribose in particular is worthy of special mention, as it means that a nucleic acid precursor has been discovered. Ultraviolet rays are a type of electromagnetic wave found in sunlight in nature. Ultraviolet rays have the effect of breaking the bonds between molecules and ions, or putting them into a high-energy state. If it were possible to split water from sunlight and reduce nitrogen in the air, it would be possible to produce NH3 without consuming much energy. In addition, any container can be used during irradiation, but if the container is made of glass or quartz, no excess irradiation products will be produced from the container itself. [Non-patent literature] 7.JIS K 0102 Testing Methods for Industrial Wastewater, Japan Standards Association 148-149(2008) 8.W.Kh.Klibus,'TN Zarchuk:J.Anal.Chem USSR,16,80(1961) 9.JIS G 1228(1969) 10.JIS K 0102 Testing Methods for Industrial Wastewater(2008)43.1.1 11.Kato,Okinaka,Sakai Analytical Chemistry 3:231(1954) 12.Langenfeld,NJ,Payne,LE and Bugbee,B.(2021)PLoS ONE 16(11):e029760 13.Park,JTet al.J.Biol.Chem.,181,149(1949). 14. Kazuhiko Niwa, edited by the Chemistry Encyclopedia Editorial Committee (ed.), The Chemistry Encyclopedia, Volume 1 (reduced edition, 26th edition), Kyoritsu, 1981.10 15. Dubois, M. et al.: Anal.Chem., 28, 350 (1956). 16.Somogyi,M.:J.Biol.Chem.,125,399(1938) 17.Sanchez-Viesca,Francisco,and Reina Gomez.Modern Chemistry 6.1(2018):1-5 18.S.Lie.1nst.Brew.vo.179,p.37-41(1973) 19.BKSur et.al.:J.Clin.Path.25:892(1972) 20. Shuzo Fujita, Kazuhiko Yamada, Food Science Experiment Book 2nd Edition, Ishiyaku Shuppan, 2002. 21. W. Mejbaum, Z. Physiol. Chem. 258:117(1939) 22. Edited by the Biophysical Society of Japan: Continued Biophysics Lectures 6, Nucleic Acid and Protein Research Methods I: Nucleic Acids, Yoshioka Shoten (1968) DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0006] An object of the present invention is to carry out nitrogen fixation and carbon dioxide fixation by irradiating light including ultraviolet light using a simple device, thereby producing organic matter, etc. [Means for solving the problem]

[0007] As a result of extensive research into achieving the above-mentioned object, the inventors discovered that the above-mentioned problems could be solved by putting water in a container, mixing salts, metals, natural rocks, gravel, etc., and irradiating the mixture with light. Based on this finding, the present invention provides 1. A method for nitrogen fixation, carbon dioxide fixation or organic synthesis, characterized in that a container containing water is irradiated with light including ultraviolet light from a light source to produce ammonium ions, nitrite ions, nitrate ions, urea, organic acids, sugars, amines, nucleic acid precursors, etc. in the water; 2. The method for nitrogen fixation, carbon dioxide fixation or organic synthesis according to 1., characterized in that the water is pure water or a solution or suspension containing salts, metals, natural rocks or gravel, or naturally occurring materials. 3. The method for nitrogen fixation, carbon dioxide fixation or organic synthesis according to 1., wherein the naturally occurring material is silica gel, zeolite, talc, alumina, activated clay, florisil or a processed version of these. 4. The method for nitrogen fixation, carbon dioxide fixation or organic synthesis according to 1, wherein the light source is a fluorescent tube or LED that emits ultraviolet light, or sunlight. The present invention is characterized by the following points that are different from the conventional techniques. In other words, the process is simple: just put in water, salts, metals, natural gravel, rocks, or naturally occurring materials, and turn on the light using an ultraviolet light irradiation device or sunlight as the light source. The process is characterized by the fact that it proceeds at room temperature and pressure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Next, examples and comparative examples of the present invention will be described. Note that the examples shown below are for the purpose of facilitating understanding of the present invention, and the present invention is not limited to these examples. In other words, other examples or modifications based on the technical concept of the present invention are naturally included in the present invention. EXAMPLES

[0009] Salt water irradiation In nature, seawater accounts for a large proportion of the Earth's surface water, and is believed to make a large contribution to aquatic systems exposed to ultraviolet light. It is thought to be the largest source of materials for life. Therefore, we carried out similar ultraviolet light irradiation using seawater instead of pure water. As seawater contains many trace elements in addition to sodium chloride, we also used a sodium chloride solution with the same salt concentration as seawater. The results are shown in Figure 1. [Figure 1] As is clear from the figure, seawater contains approximately twice as much NH4 as pure water when exposed to ultraviolet light. + , NO2 - , NO3 - Ninhydrin is an amino acid detection reagent, but NH4 + It also reacts with NH4 + The sodium chloride solution had an intermediate value between pure water and seawater. However, the NH4 + The amount of nitrogen and carbon fixed in seawater was greater than that in other detection methods, suggesting that amino acids or amines were formed. This suggests that the materials necessary for the development of many forms of life were provided in the early Earth when the oceans were formed. EXAMPLES

[0010] Illuminating the collected gravel As seen in Experiment 1, if nitrogen fixation and carbon fixation can be carried out using only water and light, it is expected that they will be carried out more efficiently using water and rocks containing various substances on Earth. Therefore, gravel was collected from the coasts, harbors, and mountains around Hakodate City, and the products were examined by shining light on them. The gravel was collected from Omorihama, Yukawa Beach, Esan Beach, and Lake Onuma, as well as volcanic gravel from Esan, and gravel from Ofuna Fishing Port, Shionori Fishing Port, and Sumiyoshi Fishing Port. The collected gravel was thoroughly washed with purified water and dried, after which 4 g was weighed out, and 20 mL of purified water was added as in Example 1, and the gravel was left in the dark and exposed to LED and ultraviolet light for approximately 20 hours each. When irradiation of the gravel was completed, the water had evaporated, so the weight of each supernatant was measured after correcting the evaporated water to the initial weight. If the supernatant was cloudy, it was centrifuged as appropriate. The results are shown in Figure 2. [Figure 2] Although the amount varies, NH4 + is detected, and NO2 - , NO3 - Among these, the gravel from Sumiyoshi fishing port was especially rich in NH4 + It was found that sugar was produced in large quantities in the sand and gravel of Omorihama and Yukawa. EXAMPLES

[0011] Ultraviolet light exposure to silicon-containing materials The main component of sand and gravel found in nature is silicon dioxide (SiO2), with metals unique to the land likely mixed in. Therefore, we conducted the same light irradiation on silica sand, which is mainly composed of SiO2, and silica gel to investigate what reactions would occur. Silica gel was made by leaving an aqueous solution of sodium metasilicate (Na2SiO3) and dehydrating and drying the resulting silica gel. The results are shown in Figure 3. [Figure 3] SiO2 is a lot of NH4 + However, other products were few, and many products were confirmed in all the silica gel samples examined. Especially NO2 - and NO3 - Mostly. EXAMPLES

[0012] UV irradiation of natural materials In addition to the silica gel in Example 3, there are materials that are processed from natural rocks and used as adsorbents, reinforcing materials, fillers, etc. Of these, zeolite, talc, activated alumina, activated clay, and Florisil were each irradiated with ultraviolet light in the same manner and compared. Zeolite is a crystalline aluminosilicate with the formula M n+ 1 / n(AlO2)-(SiO2) x It is yH2O. Talc is a mineral composed of magnesium hydroxide and silicate, with the formula Mg3Si4O 10 (OH)2. Activated alumina is aluminum oxide and its composition is expressed as Al2O3. Activated clay is obtained by treating acid clay, the main component of which is montmorillonite, with hot acid. It contains 75-85% SiO2, 9-13% Al2O3, 1-2% Fe2O3, 1-3% MgO, and other components such as Ca, Na, and K. Florisil is a magnesium silicate with the formula MgO3Si. 2 g of each of these was placed in a beaker, 20 mL of pure water was added, and the mixture was irradiated with ultraviolet light for about 20 hours. The results are shown in Figure 4. [Figure 4] Zeolite and activated clay NH4 + High productivity, but NO3 - Activated clay and Florisil react well with ninhydrin and produce large amounts. When these are made alkaline and heated, NH4 + is converted to NH3 and volatilizes (ammonia stripping, (Non-Patent Document 23)). When reacted with ninhydrin, both produce color, suggesting that amino acids or amines may have been produced. [Non-patent literature] 23.PH.Liao,A.Chen,KVLo.1955.Bioresource Technology,54:17-20. EXAMPLES

[0013] UV irradiation of various metals As is clear from Example 4, nitrogen fixation and carbon dioxide fixation are observed when various metals are mixed into SiO2, but the effect of metals alone was examined. As metals alone, As (arsenic), Cd (cadmium), Se (selenium), and Zn (zinc) were used, and water-insoluble AgCl (silver chloride), SiC (silicon carbide), and TiO2 (titanium dioxide, anatase type) were also examined. TiO2 is a type of photocatalyst. The results are shown in Figure 5. [Figure 5] Both are NH4 + , NO2 - , NO3 - The production of arsenic was observed in very small amounts, but nothing noteworthy. However, the production of arsenic sugar in particular seems to be high, but compared to water, it is almost the same as water. EXAMPLES

[0014] UV irradiation of water containing phosphoric acid Since phosphoric acid was detected in natural gravel among the components that are not activated by light, a study was carried out using a phosphate buffer solution (Non-Patent Documents 24, 25) to examine whether phosphoric acid affects photoactivation. The results are shown in Figure 6. For comparison, the data for water only from Example 1 are also shown. [Figure 6] Compared to water, phosphate buffer solutions contain NH4 + The amount of NH4 produced is greater when the pH is acidic than when it is alkaline. + The amount of ninhydrin produced was found to be large. + However, the amount of NO2 - , NO3 - was lower than that of water, suggesting that phosphate ions act in the direction of nitrogen reduction. [Non-patent literature] 24. Gomori, after Sorensen. Meth. Enzymol. 1:143 (1955) 25. Data for biochemical research. British Library Cataloging in Publication Data (1968) EXAMPLES

[0015] UV irradiation of carbonated water Since it was clear from the above examples that CO2 is the raw material for carbon dioxide fixation, we compared the amount and pH not only of CO2 in the air but also of a carbonate buffer solution dissolved in water (Non-Patent Document 26). If the amount of CO2 in the air is 400 ppm, this concentration corresponds to 14 mM. The data for water only in Example 1 are also shown for comparison (Figure 7). [Figure 7] Contrary to expectations, the sugar content did not increase much even though the amount of carbonation increased, and rather the NH4 + , NO2 - , NO3 - The amount of sugar produced was lower than that of water, but the amount of sugar remained constant, suggesting that carbon dioxide contributed to the fixation of carbon dioxide. [Non-patent literature] 26. Delory and King.BJ39:245(1945) EXAMPLES

[0016] Irradiation of various salts In Example 2, since sodium chloride produced more nitrogen fixation and carbon dioxide fixation products than water, various salts were examined to search for substances that would activate the formation. The sulfates used were alum (potassium aluminum sulfate (AlK(SO4)2·12H2O)), cobalt sulfate (CoSO4·7H2O), copper sulfate (CuSO4·5H2O), ferrous sulfate (Fe(ll)SO4·7H2O), potassium sulfate (K2SO4), lithium sulfate (Li2SO4), magnesium sulfate (MgSO4·7H2O), and sodium hydrogen sulfate (NaHSO4). The results are shown in Figure 8A. Here, NH4 + Only the production of [Figure 8A] The amount of formation was often more than 1 mg / L. This amount can be used as an index. AlK(SO4)2·12H2O, MgSO4·7H2O, and NaHSO4 were found to be NH4 + It is a substance that increases the production of Chlorides include barium chloride (BaCl2) and calcium chloride. The following chlorides were used: CaCl2 2H2O, MgSO4 7H2O, cobalt chloride (CoCl2), ferrous chloride (FeCl2 4H2O), ferric chloride (FeCl3 6H2O), mercuric chloride (HgCl2), potassium chloride (KCl), lithium chloride (LiCl), magnesium chloride (MgCl2 6H2O), manganese chloride (MnCl2 4H2O), nickel chloride (NiCl2 6H2O), tin chloride (SnCl4), and palladium chloride (PdCl2). The results are shown in Figure 8B. Again, NH4 + Only the production of [Figure 8B] The chlorides were produced in smaller quantities overall than the sulfides, but the most abundant were MnCl2·4H2O, SnCl4, and PdCl2. Other salts used were sodium acetate (CH3COONa) and sodium hypochlorite (NaClO). The results are shown in Figure 8C. Again, NH4 + Only the production of [Figure 8C] NaClO and NH4 + Although the production was greater than that of chlorides and sulfides, the production of CH3COONa was found to exceed these and be extremely large. EXAMPLES

[0017] Detection of amines by thin-layer chromatography. An attempt was made to identify the substance using thin layer chromatography (TLC). The most characteristic substance production was observed in the sand and gravel from Hakodate Sumiyoshi fishing port, where ultraviolet light was irradiated, and it was examined whether amino acids or amines were produced and sugars were captured. UV light was irradiated for 20 hours on 4g of sand and gravel. As the concentration was low and it could not be detected by thin layer chromatography, it was heated and concentrated. The pH at this time was around 8, so NH4 + Most of it is converted to NH3, and when heated, NH4 + was removed (ammonia stripping). For TLC, the concentrated sample was divided into several portions and loaded onto a thin silica gel layer at 5μL and 10μL. The developing solvent was chloroform:methanol (40:2), and 0.4% ninhydrin (ethanol solution) was used for detection. The results are shown in Figure 9A. [Figure 9A] The amino acids glycine, alanine, tyrosine, and phenylalanine were used as markers, and three major bands were identified in the sample. The Rf of the bands in the sample was 0.95, 0.19, and 0.30, respectively. Although it did not match any of the markers used, it is likely that one of the amino acids or amines was formed. In addition, a similar TLC was performed independently on the same sample, but this time no band was observed, and instead, a smear was observed. The results are shown in Figure 9B. [Figure 9B] This indicates the presence of a variety of substances, and it was suggested that this was the result of the production of various amines or organic acids. EXAMPLES

[0018] Detection of sugars by thin-layer chromatography. Sugar TLC was performed on the same sample as in Example 9. The developing solution was 2-propanol: acetic acid: water (40:10:10), and the staining solution was a 5% ethanol solution of phosphomolybdic acid. The results are shown in FIG. [Figure 10] Two major bands appeared, but they did not match any of the markers glucose, fructose, galactose, and xylose used, suggesting that something different from the Rf of the marker sugars was produced. EXAMPLES

[0019] Hydrolysis of the produced substances Hydrolysis was performed on the sample of Example 10 because if nucleotides were formed, they would be broken down into nucleosides by hydrolysis, allowing for more precise identification of the constituents. Formic acid is used for hydrolysis, which is achieved by heating and pressurizing in a sealed container. 10 μL of the sample was placed in a glass tube, the same amount of formic acid was added, and both ends were heated and sealed. This was placed in a 175°C oven and heated for 30 minutes (Non-Patent Document 27). After heating, the tube was opened and 10 μL of the contents were analyzed by TLC. The developing solvent used was 0.5 M phosphate buffer (pH 7.0): 60 g / 100 mL ammonium sulfate: 2-propanol = 25 mL: 100 mL: 2.5 mL, and detection was recorded by applying ultraviolet light. The results are shown in FIG. [Figure 11] Although the bands were slightly distorted due to the influence of the acid, the Rf was 0.71, whereas in a literature study using the same developing solution (Non-Patent Document 23), the Rf was 0.8. In the same literature, the Rfs of cytosine, guanine, and adenine were 0.36, 0.16, and 0.24, respectively, which were smaller than the Rf of the detected band. From this, it was thought that the substance generated by hydrolysis was thymine. Therefore, it is suggested that nucleosides were formed in this sample. This experiment also revealed that nucleic acid precursors were formed. [Non-patent literature] 27.Akihiro Takemura Prot.Nucl.Enz.9:1342-1344(1964) EXAMPLES

[0020] Verification in sunlight It was found that ultraviolet light causes nitrogen fixation and carbon fixation, but we verified whether nitrogen fixation and carbon fixation actually occur when exposed to sunlight. On a clear day, sunlight is about 100,000 lux, of which the amount of ultraviolet light is about 5%, and the intensity is about 60 W / m 2 Of these, 90% is UV-A (315-400 nm). A beaker containing only water and a beaker containing silica gel in water were prepared, and a comparison was made between sunlight and an ultraviolet lamp. Sunlight exposure was chosen on a sunny day, and the exposure was for a total of 18 hours over two separate days. The ultraviolet lamp was also used for the same amount of time. The results are shown in Figure 12. [Figure 12] When irradiated to water, NH4 + The same experiment was carried out on silica gel, but the silica gel produced more NO2 than the water. - , NO3 - The productivity was good when using ultraviolet lamps, and this tendency was the same when using water or silica gel.

[0021] The present invention can be carried out using a simple device, so it can be verified for a variety of substances. Therefore, it can be applied to substances that are not covered in the examples. The nitrogen fixation method of the present invention proceeds at room temperature, and nitrogen in the air and NH4 are produced from water only by irradiating them with ultraviolet light. + It is an extremely energy-efficient method that can generate NH4 + To obtain NH3 gas from NH4, it is necessary only to make the pH alkaline, and it is possible to recover it. NH3 gas can be burned, and no carbon dioxide is emitted after combustion. + It has many uses as a material in various fields and is highly versatile. It can be stored by keeping the pH low, which is more stable and safer than converting it into NH3 gas. In addition, ordinary soil can fix nitrogen when exposed to ultraviolet light, so with just a little water, nitrogen fertilizer essential for plants is produced, which saves on fertilizer for cultivated land. Furthermore, this method detected amines, amino acids, sugars (including nucleosides), organic acids, and nucleic acid precursors, proving that carbon fixation was taking place. These phenomena suggest that organic matter can be formed relatively easily under normal temperature and pressure, which contributed greatly to the emergence of life on the primordial Earth, and may help us come closer to solving the mystery of the origin of life. [Brief description of the drawings]

[0022] [Table 1] UV irradiation of water This is a list of products produced by irradiating water with ultraviolet light. [Figure 1]UV irradiation of saltwater The results are shown for 20 mL each of pure water, 3.5% sodium chloride, and seawater, irradiated for approximately 18 hours under a UV lamp (15 W). [Diagram 2] UV irradiation of collected gravel 4 g of collected gravel was placed in 20 mL of pure water and exposed to a UV lamp for approximately 18 hours. The results are shown below. [Diagram 3] Ultraviolet light irradiation of silicon dioxide and silica gel 4g of silicon dioxide and silica gel were placed in 20mL of pure water and irradiated under an ultraviolet lamp for approximately 18 hours. The results are shown below. [Figure 4] UV irradiation of naturally derived materials 4g of zeolite, talc, activated alumina, activated clay and Florisil were placed in 20mL of pure water and exposed to a UV lamp for approximately 18 hours. The results are shown below. [Diagram 5] Ultraviolet light irradiation of single metals 4g each of silver chloride (AgCl), arsenic (As), cadmium (Cd), selenium (Se), silicon carbide (SiC), zinc (Zn) and titanium dioxide (TiO2, anatase type) were placed in 20mL of pure water and exposed to an ultraviolet lamp for approximately 18 hours. The results are shown below. [Figure 6] UV irradiation of water containing phosphoric acid The results are shown for 20 hours when 20 mL of 25 mM phosphate buffer (P-buffer) of pH 5.81, pH 7.0, and pH 8.0 was irradiated under a UV lamp. [Figure 7] UV irradiation of carbonated water The results are shown for 20 hours when 20 mL of 25 mM and 0.1 M carbonate buffer solutions (C-buffer) with pH 9.21 and pH 11.11, respectively, were irradiated under a UV lamp. [Figure 8A]UV irradiation of sulfates 20mL of each of the following substances, dissolved at a concentration of 1g / L, was placed in a beaker and exposed to UV light for approximately 18 hours. The results are shown below. [Figure 8B] UV irradiation of chlorides 20mL of each of the following substances were dissolved at a concentration of 1g / L: barium chloride (BaCl2), calcium chloride (CaCl2·2H2O), cobalt chloride (CoCl2), ferrous chloride (Fe(II)Cl2·4H2O), ferric chloride (Fe(III)Cl3·6H2O), mercury chloride (HgCl2), potassium chloride (KCl), lithium chloride (LiCl), magnesium chloride (MgCl2·6H2O), manganese chloride (MnCl2·4H2O), sodium chloride (NaCl), nickel chloride (NiCl2·6H2O), stannous chloride (Sn(II)Cl2), stannic chloride (Sn(IV)·5H2O) and palladium chloride (PdCl2). They were placed in a beaker and exposed to UV light for approximately 18 hours. The results are shown below. [Figure 9A] Thin-layer chromatography of substances produced by ultraviolet irradiation 4 g of Sumiyoshi Fishing Port gravel was placed in 20 mL of pure water, and the supernatant after ultraviolet irradiation was heated and concentrated. The sample was then loaded and developed in several batches, and the results of TLC stained with ninhydrin are shown below. [Figure 9B] Thin-layer chromatography of substances produced by UV irradiation The results of an independent TLC run are shown as in FIG. 9A. [Figure 10] Thin-layer chromatography of substances produced by ultraviolet irradiation. This shows the results of TLC using the sample in Figure 9B, stained with phosphomolybdic acid, and sugar detection. [Figure 11]Thin-layer chromatography of hydrolyzed sample 4 g of sand and gravel from Sumiyoshi fishing port was placed in 20 mL of pure water, irradiated with ultraviolet light, and the supernatant was heated and concentrated. The sample was then hydrolyzed with formic acid. This is the result of TLC. Detection was recorded by irradiating with ultraviolet light. [Figure 12] Comparison of irradiation with ultraviolet lamp and sunlight 20mL of pure water and pure water containing silica gel were placed under an ultraviolet lamp or sunlight, respectively. The ultraviolet lamp was used for 18 continuous hours, while sunlight was used over several days, for a total of 18 hours under clear skies. The results are shown below. [Explanation of symbols]

[0023] TIFF2025018853000003.tif19155. The horizontal axis shows the concentration in mg / L. TIFF2025018853000004.tif18156. The horizontal axis shows the concentration in mg / L. TIFF2025018853000005.tif18157. The horizontal axis shows the concentration in mg / L. TIFF2025018853000006.tif17161. The horizontal axis shows concentration in mg / L. TIFF2025018853000007.tif16164 is shown. The horizontal axis shows the concentration in mg / L. TIFF2025018853000008.tif17156. The horizontal axis shows concentration in mg / L. TIFF2025018853000009.tif15156. The horizontal axis shows concentration in mg / L. [Figure 8A] [Figure 8B] The horizontal axis indicates concentration in mg / L. [Figure 9A][Figure 9B] Thin-layer chromatography of amino acids or amines Gly: glycine, Ala: alanine, Tyr: tyrosine, Phe: phenylalanine, Leu: leucine, Tyr: tyrosine. Load 1: 5 μL and 2: 10 μL respectively. [Figure 10] Glu: glucose, Fru: fructose, Gal: galactose, Xyl: xylose, 1: sample [Figure 11] 1: before hydrolysis, 2: after hydrolysis. The arrows indicate the products after hydrolysis. TIFF2025018853000010.tif11154

Claims

1. A method for nitrogen fixation, carbon dioxide fixation or organic synthesis, characterized in that a container containing water is irradiated with light including ultraviolet light from a light source to generate ammonium ions, nitrite ions, nitrate ions, urea, organic acids, sugars, amines, nucleic acid precursors, etc. in the water.

2. 2. The method for nitrogen fixation, carbon dioxide fixation or organic synthesis according to claim 1, wherein the water is pure water or a solution or suspension containing salts, metals, natural rocks or gravel, or naturally occurring materials.

3. 2. The method for nitrogen fixation, carbon dioxide fixation or organic synthesis according to claim 1, wherein the naturally occurring material is silica gel, zeolite, talc, alumina, activated clay, florisil or a processed version of these.

4. 2. The method for nitrogen fixation, carbon dioxide fixation or organic synthesis according to claim 1, wherein the light source is a fluorescent tube or LED that emits ultraviolet light, or sunlight.

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