JP2010248457A - Method for reducing nitrogen in soil containing superfluous nitrate nitrogen or nitrite nitrogen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for reducing nitrogen in soil containing superfluous nitrate nitrogen or nitrite nitrogen in an agricultural field. <P>SOLUTION: A nitrogen reducing-soil treatment method is achieved by a means, wherein after sprinkling vegetable skin-fruit juice containing natural mineral ions extracted from minerals using vegetable organic acids into the soil containing superfluous nitrate nitrogen or nitrite nitrogen in the agricultural field, a denitrification method is performed by pouring calcium carbonate fine powders into the soil. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention, after spraying natural mineral ion-containing plant skin juice extracted with plant organic acid in excess nitrate nitrogen or nitrite nitrogen-containing soil of crop fields, put fine calcium carbonate, nitrate The present invention relates to a method for reducing nitrogen in soil containing excess nitrate nitrogen or nitrite nitrogen, which converts nitrogen or nitrite nitrogen into calcium nitrate.

Nitrate nitrogen in the soil is a nitrogen component indispensable for plant growth, but excess nitrate nitrogen remains in the plant body and may be harmful to people and animals who eat it.
In addition, it has been pointed out that groundwater and rivers are contaminated by underground infiltration and runoff, or that it is combined with nitrogen in the atmosphere to change to nitrous oxide, a global warming gas.
So far, a large amount of nitrogen source has been used in crop fields as immature compost of animal fertilizer and animal manure and organic fertilizer, but nitrogen that the plant could not absorb is excess nitrate nitrogen or nitrite nitrogen. Residual in the soil.
Regardless of whether it is domestic or overseas, the problem of excess nitrate nitrogen or nitrite nitrogen-containing soils is becoming more serious, causing plant germination failure and growth failure as well as desertification. Nitrogen reduction in soil containing nitrate nitrogen or nitrite nitrogen is an urgent issue.

So far, no countermeasures such as nitrogen reduction in soil containing excess nitrate nitrogen or nitrite nitrogen have been found.
Patent Document 1 discloses a proposal of a method for suppressing the generation of nitrite nitrogen from soil by spraying soil charcoal with added potassium, magnesium and sulfate radicals. Further, Patent Document 2 discloses a method for suppressing the production of nitrate nitrogen using microorganisms.
JP 2007-53966 A JP 2000-253868 A

  These proposals are intended to suppress the production of nitrate nitrogen and nitrite nitrogen using garbage charcoal and microorganisms, and excess nitrate nitrogen or nitrite nitrogen already accumulated in the soil. The challenge remains to reduce

Problems to be solved by the invention

  The object of the present invention is to disperse a plant skin juice containing natural mineral ions extracted with plant organic acid into excess nitrate nitrogen or nitrite nitrogen-containing soil in a crop field, and then add fine calcium carbonate. It is to establish a method for reducing excess nitrate nitrogen or nitrite nitrogen by converting nitrate nitrogen or nitrite nitrogen to calcium nitrate.

Means for solving the problem

  After spraying the natural mineral ion-containing plant skin juice extracted with plant organic acid into the soil containing excess nitrate nitrogen or nitrite nitrogen, the present inventors put in fine powdered calcium carbonate for a while. When the seeds of plants were sprouted in this soil, it was found to germinate and the nitrogen component in the soil was analyzed, and it was found that the nitrogen component was significantly reduced.

It is known that excess nitrate nitrogen or nitrite nitrogen-containing soil causes poor germination and growth failure of plants.
The inventors sprayed a diluted solution of organic acid or inorganic acid on the soil containing excess nitrate nitrogen or nitrite nitrogen, and then added fine powdered calcium carbonate to neutralize the soil, and several kinds of plant seeds were put on this soil. I did not see the germination of the seeds.
On the other hand, the inventors have confirmed over many years that natural mineral ion-containing plant skin juice extracted with plant organic acids has a remarkable effect on improving the green soil of golf courses and the healthy growth of turf. The plant skin juice containing natural mineral ions extracted with plant organic acid instead of organic acid or inorganic acid was considered to be applied to soil containing excess nitrate nitrogen or nitrite nitrogen. As seed germination was observed, the soil was analyzed, and as a result, it was found that the nitrogen content was significantly reduced, and the present invention was completed.

The natural mineral ion-containing plant skin juice extracted with the plant organic acid of the present invention will be described.
First, the vegetable organic acid will be described. In the present invention, as an organic acid, isovaleric acid [(CH ₃ ) ₂ CHCH ₂ COOH] or butyric acid [CH ₃ (CH ₂ ) ₂ COOH] contained in pineapple peel juice that is no longer used during food processing, And caproic acid [CH ₃ (CH ₂ ) ₄ COOH], caprylic acid [CH ₃ (CH ₂ ) ₆ COOH], capric acid [CH ₃ (CH ₂ ) ₈ COOH], lauric acid contained in coconut palm juice [CH ₃ (CH ₂ ) ₁₀ COOH], myristylic acid [CH ₃ (CH ₂ ) ₁₂ COOH] or limonene (C ₁₀ H ₁₆ ), ascorbic acid (C ₆ H ₈ O ₆ ) pantothene contained in citrus peel juice The use of a single or complex fruit juice such as an acid (C ₈ H ₁₇ NO ₅ ) is referred to as a plant organic acid in the present invention.

Next, the natural mineral ion-containing plant skin juice will be described. Examples of the mineral containing a group of mineral ions include zeolite, barleystone, leechite, and Ioishi. As a specific example, minerals of metal oxides such as calcium, magnesium, sodium, potassium, iron, manganese, and aluminum contained in diorite metamorphic biotite, which is leechite, are immersed in a vegetable organic acid in an ionized state. What was obtained by extraction is referred to as natural mineral ion-containing plant skin juice in the present invention, and has been confirmed to have oxidation and reduction ability.
The component composition values of the natural mineral ion-containing plant skin juice used in the present invention were generally those shown in [Table 1].

Furthermore, the oxidation ability and reduction ability of mineral ion-containing plant skin juice will be described.
The mineral composition of diorite alteration biotite is [K (Mg, Fe) ₃ (AlSiO ₁₀ ) (OH))]. These main components are eutectics of metal oxides or hydroxides such as K, Mg, Fe, Al and Si. The eutectic structure is composed of MgO, FeO, Mg (OH) ₂ , Fe (OH) ₂ , Al ₂ O ₃ , K ₂ O, SiO ₂ and various minerals.

When these metal oxides are leached and dissolved with isovaleric acid, which is a plant organic acid, and extracted in an ionized state, the excited water that is simultaneously generated is shown in formulas (1) and (2).

As described above, the excited hydroxyl group OH · of the excited water generated when the metal oxide of the mineral is extracted in an ionized state has an oxidizing ability and is adsorbed by the mineral ion or bound to the surrounding water (H ₂ O). Then, it becomes a hydroxy negative ion (H ₃ O ₂ ) ⁻ and maintains a stable state for a long time in a plant skin juice containing a mineral ion of a vegetable organic acid. On the other hand, excited hydrogen (H.) has a reducing ability, and combines with surrounding water (H ₂ O) to become a protonium ion (also referred to as hydronium ion) (H ₃ O) ⁺ , respectively (H ₃ O ₂ ). ^- it becomes a negative ion and (H 3 _O) ⁺ mineral ions containing plant bark juice solution and positive ions, characterized in that coexist, has been found to have a reducing action and oxidation simultaneously. In addition, the mineral ion-containing plant skin juice contains the hydrolysis product enzyme by self-fermentation.

The OH radical (OH.), Which is one of the active oxygens of the excited hydroxyl group, which is the oxidizing ability of the mineral ion-containing plant skin juice, was measured by the spin trap method of ESR (Electron Spin Resonance) measurement.
As a scavenger for OH radical (OH.), DMPO (5 dimethyl pyrrolline 1-oxide), which is generally used, was added to the diluted solution of the nellral ion-containing plant skin juice of the present invention. It was confirmed that a kind of OH radical (OH.) Was contained.

In addition, a copper dissolution test using metallic copper (Cu) was carried out for the presence of excited hydrogen (protonium ion H.) (also referred to as hydronium ion), which is the reducing ability of natural mineral ion-containing plant skin juice.
It is known that copper dissolves in a nitric acid acidic solution and becomes a blue copper ion solution. In the test, when a piece of copper was placed in a nitric acid acidic solution in which a small amount of nitric acid was added to a dilute sulfuric acid solution, the copper piece was dissolved into a blue liquid, but in a nitric acid acidic solution in which a small amount of nitric acid was added to the dilute sulfuric acid solution. When a small amount of the natural mineral ion-containing plant skin juice liquid of the present invention is added, the reduction potential (ORP) shows a positive value and shows a negative value, and the copper piece does not dissolve, The solution containing the copper pieces remained colorless.
This was confirmed to be evidence that excited hydrogen (H.) having reducing ability is contained in the natural mineral ion-containing plant skin juice.
Furthermore, when an iron piece was put into this solution, rust did not generate | occur | produce in the iron piece but kept metallic luster.
Incidentally, in the solution without adding the natural mineral ion-containing plant skin juice, iron pieces rusted, resulting in a reddish brown surface.

Based on the basic test described above, the present inventors have found that the excited hydrogen (H ·) trapping agent DPPH (1, 1Diphengl-2-picrylhydrazyl, max = 517 nm) The ESR (electron spin resonance) method using the peak reduction of the radical spectrum was further measured by an ESR measuring device (JES-FE3XG Spectrometer manufactured by JOEL), and the reducing ability was measured. Excited hydrogen (H.) having a hydrogen atom was detected and confirmed.
The method for detecting excited hydrogen (radical hydrogen H.) of the present invention is based on the following reaction. When DPPH radical captures H. (radical hydrogen) having a reducing ability, it reacts quantitatively and DPPH radical peak (517 nm) is generated. This is a detection method that uses the principle of disappearance.
It is shown in Reaction Formula (3) and [FIG. 1].

反応式（３）は、天然ミネラルイオン含有植物皮果汁液の５００倍希釈溶液を用いた場合について、ＤＰＰＨと励起水素（Ｈ・）とが反応しＤＰＰＨ−Ｈを生成し、ＤＰＰＨラジカルピークの減少（ｈ_１／ｈ_２）（［図１］）を示した検出ピーク図形である。ＤＰＰＨと反応した量は、２０．０μｇＨ・／ｌを検出した。

Reaction formula (3) shows a decrease in the DPPH radical peak when DPPH and excited hydrogen (H.) react with each other when a 500-fold diluted solution of plant skin juice containing natural mineral ions is used. _(h 1 _{/ h} 2) is a detected peak figure showing (FIG. 1). The amount reacted with DPPH was 20.0 μg H · / l.

Note that natural mineral ion-containing plant skin juice has been filed and proposed in Japanese Patent Application No. 2008-293888.
Regarding the oxidation ability and reduction ability of the natural mineral ion-containing plant skin juice described above, mineral ion-containing liquid extracted in an ionic state from minerals containing mineral groups using inorganic acids or plant organic acids other than the present invention If so, there is a similar effect.

Nitrate formation reaction by natural mineral ion-containing plant skin juice extracted from nitrate nitrogen or nitrite nitrogen and vegetable organic acid in the soil of the present invention, and fine powder calcium carbonate is added to the generated nitric acid The reaction for generating calcium is shown in equations (4), (5) and (6).

天然ミネラルイオン含有植物皮果汁液中に存在する励起水素および酵素の働きにより、炭酸カルシウムを添加して硝酸カルシウム（Ｃａ（ＮＯ_３）_２）が生成する際、炭酸ガス発生とともに窒素ガス（Ｎ_２）となり脱窒し、過剰硝酸態窒素ないし亜硝酸態窒素含有土壌中の窒素低減が行われることが考えられる。On the other hand, the nitrogen reduction reaction of nitrate nitrogen or nitrite nitrogen by the natural mineral ion-containing plant skin juice of the present invention is not complicated and simple, but in the natural mineral ion-containing plant skin juice of the present invention It is presumed that the reaction formulas (7), (8), and (9) shown below change depending on the active hydrogen and enzyme of excited hydrogen (protonium ion H ₃ O ⁺ ).

When calcium carbonate is added and calcium nitrate (Ca (NO ₃ ) ₂ ) is generated by the action of excited hydrogen and enzymes present in the natural mineral ion-containing plant skin juice, nitrogen gas (N ₂ ) is generated along with the generation of carbon dioxide. ) And denitrification to reduce nitrogen in soil containing excess nitrate nitrogen or nitrite nitrogen.

In addition to the vegetable organic acid according to the present invention, any organic acid or inorganic acid may be used as long as it exhibits the characteristics of the present invention. In order to enhance the oxidizing power, it is effective to use an oxidizing agent such as hydrogen peroxide (H ₂ O ₂ ) or ultrafine titanium dioxide in combination.

Nitric acid contained in the harvested Komatsuna grown in the field where excess nitrate nitrogen or nitrite nitrogen-containing soil of the present invention is nitrogen-reduced (denitrogenated) and cultivated Komatsuna, which is a representative vegetable that easily absorbs nitrate nitrogen When nitrogen was analyzed and measured, the content of nitrate nitrogen (NO ₃ -N) was 30 mg / 100 g or less.

The invention's effect

  After spraying natural mineral ion-containing plant skin juice from which mineral components of minerals have been extracted with the plant organic acid of the present invention to excess nitrate nitrogen or nitrite nitrogen-containing soil, fine powder calcium carbonate is added for denitrification treatment By applying it, the soil after the treatment is reduced in nitrogen content, and it becomes possible to exert a great effect on the regeneration of crop fields that have become waste cultivated land due to the presence of excess nitrate nitrogen or nitrite nitrogen. It was.

The invention is explained in more detail below by means of examples.
In the present invention, nitrogen reduction treatment in soil containing excess nitrate nitrogen or nitrite nitrogen was carried out in a crop field. The results of the confirmation test conducted over five months from May 2005 to September are disclosed.

Natural mineral ion-containing plant skin juice (isovaleric acid (free acid) 20 g / l, Al ³⁺ 20 g / l, Fe ²⁺ ) in about 450 m ^{2 of} excess nitrate nitrogen-containing soil (nitrate nitrogen 120 mg / 100 g). 0 g / l, Mg ²⁺ 4.10 g / l, K ⁺ 3.10 g / l, Mn 0.18 g / l, Ti 0.90 g / l, Si 0.07 g / l) After spraying 0.0 l / m ² , 3 hours later, 20 kg of fine calcium carbonate was mixed with 80 kg of dry sand and charged.
After 7 days, the soil was sampled and the residual nitrogen in the soil (nitrate nitrogen, nitrite nitrogen, calcium nitrate nitrogen) was measured. The results are shown in [Table 2].

実施例１の脱窒素率（▲１▼−▲２▼−▲３▼−▲４▼）／▲１▼＝６７％
硝酸・亜硝酸態窒素減少率（▲１▼−▲２▼−▲３▼）／▲１▼＝９７％As a comparative example, 20 kg of the same amount as [Example 1] was added to calcium carbonate containing excess nitrate nitrogen as in [Example 1], and the soil after 7 days was collected and analyzed for residual nitrogen. . The results are shown in [Table 2].

Denitrification rate of Example 1 ((1)-(2)-(3)-(4)) / (1) = 67%
Nitric acid / nitrite nitrogen reduction rate (▲ 1 ▼-▲ 2 ▼-▲ 3 ▼) / ▲ 1 ▼ = 97%

For a crop field having the same soil area of 450 m ² as in [Example 1] (pre-treatment nitrate nitrogen concentration 140 mg / 100 g), natural mineral ion-containing plant skin juice was diluted 500-fold with water to 0.5 to 1. Table 3 shows the results of measuring the nitrogen reduction amount of the treated soil when 6 l / m ² is applied.

From [Example 1] and [Example 2], the natural mineral ion-containing plant skin fruit juice 500-fold diluted solution of the present invention is diluted to about 2.0 liters per 1 m ² and further pulverized calcium carbonate in excess nitrate nitrogen-containing soil. It was found that 120 mg / 100 g of nitrate nitrogen in the soil was reduced to 3.2 mg / 100 g by applying an appropriate amount of.
In addition, from the test in the soil with nitrate nitrogen concentration of 140 mg / 100 g in [Example 3], when the application amount of the natural mineral ion-containing plant skin juice is less than 1.6 l / m ² , the nitrate nitrogen in the soil is reduced. I found it was not enough.

［表４］より、脱窒処理土壌を用いて実施した小松菜の栽培試験の結果、脱窒処理土壌においては、小松菜の生育状態も良好であり、収穫した小松菜の硝酸態窒素含有量は、３０ｍｇ／１００ｇ以下となり甘味を有したが、脱窒処理不足土壌による小松菜は多量の硝酸態窒素を含有し、非常に苦味が強く、カルシウム含有量も低い値を示した。[Example 1] and [Example 3] Using the soil after the denitrification treatment of excess nitrate nitrogen soil of Example No. 3-2, test cultivation was carried out with Komatsuna and confirmation analysis of nitrate nitrogen content of harvested Komatsuna Went. In untreated soil, seed germination of Komatsuna was poor. The component analysis of Komatsuna was conducted at the Japan Analysis Center. The results are shown in [Table 4].

From [Table 4], as a result of the cultivation test of Japanese mustard spinach carried out using the denitrified treated soil, the grown state of Japanese mustard spinach is good in the denitrified treated soil, and the nitrate nitrogen content of the harvested Japanese mustard spinach is 30 mg. / 100 g or less and had sweetness, but Komatsuna from the denitrification-deficient soil contained a large amount of nitrate nitrogen, had a very strong bitter taste and a low calcium content.

Industrial applicability

  The present invention is a method of spraying a plant mineral juice containing natural mineral ions into excess nitrate nitrogen or nitrate nitrogen-containing soil in a crop field, and adding and adding fine powdered calcium carbonate. It enabled denitrification treatment of soil containing nitrogen or nitrite nitrogen, and it was possible to regenerate fields that became waste cultivated land. This is expected to contribute greatly to the promotion of agricultural environment improvement measures such as poor germination, growth failure, desertification, etc. of plants occurring both inside and outside of the country, and at the same time, water caused by excess nitrate nitrogen. It is expected to contribute greatly to the improvement of global environmental problems such as pollution of resources and the increase of nitrous oxide, a global warming gas.

Decrease measurement diagram of DPPH radical peak that DPPH and excited hydrogen (H.) reacted to produce DPPH-H

Claims (3)

  After spraying plant skin juice liquid containing natural mineral ions extracted with plant organic acids into excess nitrate nitrogen or nitrite nitrogen-containing soil in the crop field, add fine calcium carbonate and add nitrate nitrogen or sub-nitrogen. Nitrogen reduction method for soil containing excess nitrate nitrogen or nitrite nitrogen by converting nitrate nitrogen to calcium nitrate   Plant mineral juice containing natural mineral ions is a vegetable organic acid such as pineapple peel, coconut coconut juice or citrus peel juice, or a single or complex peel juice, calcium, magnesium, sodium, potassium, iron It is a mineral group ionic liquid extracted in an ionized state from a mineral containing many kinds of mineral groups such as manganese, aluminum and the like. Nitrogen reduction method   In order to prevent the plant from absorbing excess nitrate nitrogen or highly toxic nitrite nitrogen, the method of claim 1 or 2 replaces excess nitrate nitrogen or nitrite nitrogen with calcium nitrate and absorbs it into the plant. A method for reducing nitrogen in soil containing excess nitrate nitrogen or nitrite nitrogen, characterized by activating the outer wall or cells of the plant

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