JP6604017B2 - Application method of water area environmental conservation material - Google Patents

Description

  The present invention relates to an aquatic environment conservation material for supplying nutrient components to marine organisms such as algae and microorganisms that grow in coastal waters of freshwater, brackish water, and seawater, and a method for applying the aquatic environment conservation material.

  In recent years, in the water area, the production of organisms has been reduced due to the lack of iron necessary for the growth of organisms. For example, in coastal waters, seaweed disappears from rocky areas, and a burning phenomenon that is covered with lime algae progresses, and the reduction of coastal marine resources such as kombu, sea urchins, and abalone has become remarkable.

  The iron content of coastal waters is water soluble humic acid iron (complexed humic acid such as fulvic acid and humic acid complexed with iron ions) formed in forest humus. It is thought that it is supplied by flowing into the sea from the mountain. However, due to the recent devastation of forests, the supply of humic acid fertilizer to coastal waters has decreased, which may cause, for example, firewood burning.

  In order to deal with the problem of insufficient supply of iron in coastal waters, conventionally, a technology that deposits concrete or the like with minerals such as iron attached and / or mixed with coal ash (fly ash) etc. in the sea ( For example, the following patent documents 1 to 3) or a technique (for example, the following patent documents 4 to 6) in which a mineral supply material for supplying minerals such as iron is installed in the sea has been proposed. Furthermore, the technique (for example, the following patent documents 4 and 7) which installs a ferric fertilizer containing bivalent iron in a water area is proposed.

JP-A-6-217657 JP-A-8-89126 Japanese Patent Laid-Open No. 2002-45078 JP 2006-212036 A JP 2013-102743 A JP2013-126409A JP 2007-330254 A

Production Research, Vol. 45, No. 7, p. 2 (1993) http://www.humicsubstances.org/soilhafa.html Geotechnical Society “JGS T 232 Soil Humic Content Test” "Analytical method for organic matter such as compost" (Japan Soil Society) Marine Science Research, Vol. 22, No. 1, p. 19 (2009)

  In the techniques described in Patent Documents 1 to 3, since the elution of minerals such as iron from the concrete material is extremely slow and small, the effect of seaweed growth in seawater is small. In addition, in the techniques described in Patent Documents 2, 4 to 7, when a conventional mineral supply material is installed in the sea, in order to stabilize iron ions and the like in a dissolved state that can be easily taken up by living organisms, It must be mixed with an ion exchange material such as an organic acid. However, since these ion exchange materials are highly soluble in water and are quickly eluted in seawater, the ion exchange materials contained in the mineral supply material are rapidly depleted, so that the fertilizing effect on the sea does not continue. Furthermore, Patent Documents 2 and 4 to 7 do not disclose any requirements for maintaining the supply effect of iron or the like to the water area over a long period of time. Specifically, Patent Document 4 discloses that the mineral supply material contains a substance containing fulvic acid after fermentation and a fermentation accelerator, but sustains the effect of supplying iron or the like to the water area. The detailed requirements for the content and state of the substances contained in the mineral supply are not clarified.

  Then, the subject of this invention is providing the application method of the water area environmental conservation material which makes it possible to supply an iron ion to a water area continuously.

In order to solve the above-described problems, the present invention has the following configuration.
(1) A fermentation process of a humic acid supply substance that ferments a humic acid supply substance to produce humic acid, and the humic acid supply substance containing the humic acid after the fermentation process is mixed with an iron-containing substance to form a water area A method for applying an aquatic environment-preserving material, comprising: a process for producing an aquatic environment-preserving material for producing an environmentally-preserving material; and an application process for applying the aquatic environment-preserving material to a water area. Humus soil is contained, and in the fermentation step of the humic acid supply substance, the time-dependent changes in the contents of fulvic acid and humic acid are measured, and the fermentation period and the contents measured in advance are measured. Based on the relationship, obtaining the humic acid supply substance in the middle of fermentation containing more fulvic acid than the humic acid, the obtained humic acid supply substance in the fermentation in the production step, Mixed with iron-containing materials, A method of applying the frequency environmental protection material.

(2) The said humus soil is an application method of the water area environmental conservation material as described in said (1) containing at least any one of a waste wood chip | tip, a bark of a tree, a fallen leaf, a pruning waste, and a weed generating material.

(3) The application method of the water area conservation material according to (1) or (2), wherein the humic acid supply substance during fermentation is acquired before the content of the fulvic acid reaches a maximum amount.

(4) The method for applying an aquatic environment conservation material according to any one of (1) to (3) above, wherein the iron-containing substance contains steel slag.

  The aquatic environment conservation material of the present invention uses a mixture of an iron-containing substance (a substance capable of eluting iron ions) and a humic acid supply substance. Can be generated. As a result, water environment conservation can be achieved. In other words, not only iron humate as an initial component, but also after the installation of the water environment conservation material, the initial component is metabolized by the action of microorganisms, etc., and iron humate is newly and continuously generated. Thus, iron can be continuously supplied to the water area over a long period of time. If iron can be supplied to the water area, it will cause the growth of seaweeds that need it, and this will create a rich waterfront environment.

It is the figure which showed the time-dependent change of humic acid content in the fermentation process of the humic acid supply substance of Example 1, and organic substance content. It is a perspective view of the container for accommodating the water area environmental conservation material used in Examples 1-2 and sinking it in the sea. It is the figure which showed the time-dependent change of the dissolved iron concentration increase amount in seawater in Example A. It is the figure which showed the time-dependent change of the dissolved iron concentration increase amount in the seawater in the comparative example B. It is the figure which showed the time-dependent change of the fulvic acid content in the fermentation process of the humic acid supply substance used in Example 2, humic acid content, and organic substance content.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. First, materials used in the present embodiment will be described.

  In the following description, “aquatic environment conservation material” means a material that contributes to the conservation of the aquatic environment, and “aquatic environment conservation” means a broad concept that means having a positive impact on the aquatic environment. . Specifically, “aquatic environment conservation” includes the improvement of water quality through the absorption and removal of water-polluting nutrients and the improvement of the biological environment induced by the collection and inhabiting of seafood, triggered by the growth of seaweeds. The “water area” is a concept that means a place where water is related regardless of whether it is seawater or fresh water. For example, seas, rivers, lakes, and tidal flats are examples of water bodies.

(Water Environment Conservation Materials)
The water area environmental conservation material according to the present embodiment contains humic acid such as fulvic acid and humic acid, a humic acid supply substance capable of generating humic acid and the like, and an iron-containing substance capable of eluting iron ions. be able to. The water area environmental conservation material may further contain a low molecular organic acid such as formic acid or acetic acid.

(Humic acid)
Below, the humic acid which concerns on this embodiment is demonstrated. Although humic acid may be called humic acid in a narrow sense, in this embodiment, humic acid contains both fulvic acid and humic acid. Of the humic acids, the acid-soluble component is fulvic acid, and the organic substance that precipitates under acidic conditions is humic acid. As for the humic acid contained in the water environment conservation material, it is preferable that humic acid contains a large amount of fulvic acid because humic acid is low in water solubility, and therefore the supply amount of humic acid iron to the water area decreases. More preferably, the fulvic acid is contained more than the acid.

(Humic acid supply substance)
Next, the humic acid supply substance according to this embodiment will be described. The humic acid supply substance is an organic substance that can generate humic acid and organic acid by fermentation by metabolic reaction of microorganisms. It is preferable to use humus as the humic acid supply substance of this embodiment. Humus soil is fermented from fermented organic materials of plant-based materials. It produces the highest amount of humic acid, and more fulvic acid than other humic acid supply substances, and is easy to mature. It is less degraded, has a low possibility of environmental pollution, and is close to the composition of seaweeds, a kind of plant. As the humus soil, for example, waste wood chips, bark of trees, fallen leaves, pruning scraps, weed generating materials, fishery processing residues, fish cake, livestock dung, sewage sludge and the like can be used.

  As a humic acid supply substance of this embodiment, humus soil fermented naturally can also be used, and humus soil ripened by artificial fermentation can also be used. However, in this embodiment, in many natural humus soils, microorganisms are often transformed into organic substances that are difficult to metabolize, and therefore, humus aged by artificial fermentation rather than naturally fermented humus soil. It is preferable to use soil.

  Furthermore, when using humus soil that has been aged by artificial fermentation, if the fermentation of the humus soil proceeds too much, the humic acid produced from the fermentation of the humus soil is decomposed and the content of humic acid in the humic acid supply substance May decrease. Therefore, in this embodiment, it is preferable to use a humic acid supply substance that has been measured in advance to confirm that it contains sufficient humic acid.

  Therefore, in the present embodiment, in the step of fermenting the humic acid supply substance and generating humic acid, the relationship between the fermentation period and the humic acid content is previously grasped by measurement. Based on the relationship between the fermentation period and the humic acid content, the humic acid supply substance before the humic acid content reaches the maximum amount (that is, while the humic acid content is increasing) To get. Then, the humic acid supply substance and the iron-containing substance are mixed. By selecting such a humic acid supply substance in the middle of fermentation, the aging reaction proceeds and the humic acid can be continuously generated even after the aquatic environment conservation material is installed in the aquatic area. In addition, in this specification, before the content of humic acid reaches the maximum amount, it includes before the content of humic acid reaches the maximum amount and when the content of humic acid reaches the maximum amount. .

  Furthermore, in this embodiment, it is preferable to mix the humic acid supply substance in which the humic acid content is about the maximum amount with the iron-containing substance. The water area where the water environment conservation material is installed is, for example, a temperature lower than the optimum temperature for fermentation of the humic acid supply substance, or the salt concentration that inhibits fermentation is high. Often not the optimal environment. Therefore, depending on the water area where the aquatic environment conservation material is installed, the ripening reaction of the humic acid supply substance does not proceed sufficiently after installation, and the humic acid supply material that does not reach the aging reaction increases and is included in the aquatic environment conservation material There is a possibility that the amount of humic acid that the humic acid supply substance can originally supply cannot be supplied to the water area. Therefore, in the present embodiment, the humus obtained by sufficiently fermenting the humic acid supply substance in advance in the later-described fermentation process performed in an optimum environment for fermentation, and the humic acid content is about the maximum amount. By using the acid supply substance, an amount of humic acid that can be supplied by the humic acid supply substance can be supplied to the water area. And since it becomes possible to utilize more humic acids which can produce | generate a humic acid supply substance, an iron ion can be supplied to a water area effectively and continuously.

  That is, this embodiment considers the state of the humic acid supply material after the water environment protection material is installed in the water area, and selects the humic acid supply material to be used, thereby supplying the humic acid supply material to the humic acid supply material. It tries to maximize its capabilities. And in this embodiment, selection of a humic acid supply substance is performed by measuring the humic acid contained in a humic acid supply substance so that it may mention later.

  The content of humic acid can be measured by, for example, the method disclosed in Non-Patent Document 2 or the method disclosed in Non-Patent Document 3. Non-Patent Document 2 discloses a method of measuring the oil content of humic acid as a dry mass of humic acid after extracting humic acid from a test material by a designated method. In Non-Patent Document 3, after extracting humic acid from a test material by a specified method, humic acid is oxidized with an oxidizing agent containing potassium dichromate, and the amount of oxidizing agent used at that time is changed to oxidation. A measuring method for obtaining a necessary amount of oxygen and converting it to the amount of humic acid is disclosed.

  As explained above, the water area environmental conservation material according to the present embodiment preferably contains more fulvic acid, and more preferably contains more fulvic acid than humic acid. If the fermentation of the humic acid supply substance proceeds too much, for example, the decomposition / polymerization of the highly water-soluble fulvic acid generated from the fermentation into humic acid or humic acid having low water solubility proceeds (for example, Non-Patent Document 1). The fulvic acid content may be reduced. Therefore, by measuring the content of fulvic acid or humic acid in advance, select a humic acid supply substance that has been confirmed to contain a sufficient amount of fulvic acid and that humic acid produced by decomposition and polymerization of fulvic acid is low. It is preferable to do. In other words, in the present embodiment, the humic acid supply substance to be used is selected in consideration of the state of fulvic acid, so that the fulvic acid supply ability of the humic acid supply substance is maximized. And in this embodiment, selection of a humic acid supply substance is performed by measuring the fulvic acid and humic acid which are contained in a humic acid supply substance so that it may mention later.

  Therefore, in the present embodiment, in the step of fermenting the humic acid supply substance and generating humic acid, the relationship between the fermentation period and each content of fulvic acid and humic acid is previously grasped by measurement, and the grasped fermentation period and Based on the relationship between the contents of fulvic acid and humic acid, the humic acid supply substance before the fulvic acid content reaches the maximum is selected. More preferably, a humic acid supplying substance having a maximum content of fulvic acid is selected. By selecting such a humic acid supply substance during fermentation, the maturation reaction can proceed and the fulvic acid can be generated continuously even after the aquatic environment conservation material is installed in the aquatic area. And can be continuously supplied to the water area. In addition, in this specification, before the content of fulvic acid reaches the maximum amount, it includes before the fulvic acid content reaches the maximum amount and when the fulvic acid content reaches the maximum amount. .

  In addition, content of a fulvic acid and humic acid can be measured by the method disclosed by the said nonpatent literature 2, or the method disclosed by the said nonpatent literature 3, for example.

  In addition, when the water area environmental conservation material of the present embodiment is used in the sea area, the pH of seawater is generally about 8, and iron ions cannot be sufficiently dissolved. Therefore, in order to promote dissolution of iron ions from iron-containing substances. It is preferable to make the inside of the water area environmental conservation material acidic. Therefore, it is preferable to select a material with high acidity as the humic acid supply substance. Specifically, since the solubility of iron ions rapidly increases below pH 7, the pH inside the aquatic environment conservation material is below 7 It is more preferable to use a humic acid supplying substance that can be brought into a state. Moreover, when steel slag is employ | adopted as an iron-containing substance, the inside of water area environmental conservation material shows alkalinity. For this reason, even when steel slag is used as the iron-containing substance, it is preferable to use a humic acid supply substance in which the pH inside the water area environmental conservation material is lower than the pH of seawater. Furthermore, you may mix acidic materials, such as peat moss, a wood vinegar liquid, a fishery processing residue, or its fermented material with a humic acid supply substance with a water area environmental conservation material.

(Iron-containing substances)
As the iron-containing material of the present embodiment, as described above, iron or a material containing iron is used. Specifically, steelmaking slag can be used as the substance containing iron, and it is particularly preferable to use converter steelmaking slag with less harmful heavy metal contamination. Furthermore, as described above, it is preferable that the steelmaking slag is neutralized by carbonation treatment since the elution of iron is reduced when the pH of the water area around the water area environmental conservation material becomes alkaline.

(Application method)
The application method of the aquatic environment conservation material according to the present embodiment includes a fermentation process of a humic acid supply substance that ferments the humic acid supply substance to generate humic acid, and the humic acid supply substance after the fermentation process is converted into an iron-containing substance. It can have the manufacturing process of the water area environmental conservation material which mixes and manufactures a water area environmental protection material, and the application process which applies a water area environmental protection material to a water area.

(Fermentation process)
In the fermentation process of the present embodiment, one or more organic material raw materials such as waste wood chips, tree bark, fallen leaves, pruning waste, weeding material, fishery processing residue, fish meal, livestock dung, sewage sludge and the like are used. The humic acid supply substance obtained by mixing is subjected to fermentation of the humic acid supply substance by adding water as necessary and then allowing to stand. At this time, the organic matter in the humus soil is decomposed by the activity of microorganisms contained in the humus soil, for example, high molecular components such as cellulose and lignin are reduced in molecular weight, and further, the low molecular weight components are polymerized and various organic substances are polymerized. Acid and humic acid are produced. Although the temperature of the fermentation process of this embodiment will not be specifically limited if it is the temperature which can ferment a humic acid supply substance, It is preferable to set it as 60 degreeC or more. In addition, the fermentation period varies depending on the type and state of the humic acid supply substance, and the optimum fermentation period is selected based on the measurement results described later, but preferably from 3 months to 2 years. is there. Further, the humus soil may be turned over as needed during the fermentation to homogenize the state in the humus soil.

  In this embodiment, the relationship between a fermentation period and humic acid (fulvic acid, humic acid) content is grasped | ascertained by a measurement at a fermentation process. The time course of the content of humic acid (fulvic acid, humic acid) is measured by sampling a sample periodically during fermentation. The measurement method is as described above. In addition, since the fermentation rate and maturity period of the humic acid supply substance differ depending on the components in the humus soil and the environment (temperature, humidity, oxygen amount, etc.) in which fermentation takes place, the sampling interval of the sample varies with the content of humic acid. Can be set at an arbitrary interval that can be identified. And based on a measurement, the humic acid supply substance before content of humic acid reaches a peak is acquired, and this humic acid supply substance is used in the manufacturing process of the following water area environmental conservation material.

(Manufacturing process)
In the manufacturing process of the water area environmental conservation material of the present embodiment, the water area environmental protection material is manufactured by mixing the humic acid supply substance containing the humic acid obtained in the fermentation process and the iron-containing substance. The mixing ratio of the humic acid supply substance and the iron-containing substance can be selected at any ratio in view of the supply rate of humic acid iron and its sustainability. If the mixing ratio of the humic acid supply substance is too high, the mixing ratio of the iron-containing substance decreases, so the supply rate of humic acid iron in the initial stage of the installation of the aquatic environment conservation material to the water area increases, but the humic acid iron to the water area Supply is not sustainable. On the other hand, if the mixing ratio of the iron-containing substance is too high, the mixing ratio of the humic acid supply substance will be low, so the supply of humic acid will be insufficient with respect to the supply of iron. Less. Therefore, it is preferable to select an optimal mixing ratio in consideration of the supply amount of humic acid iron to the water area and its sustainability.

(Application process)
The water area environmental conservation material according to the present embodiment can be applied in various water areas. Moreover, there is no limitation in particular about the method of installing water area environmental conservation material in a water area, for example, containing water area environmental conservation material in a water-permeable bag shape, a bowl-shaped container, and subsiding in a water area, or including a waterside It is possible to embed water area environmental conservation material in the ground of the water area. In addition, in order to prevent loss due to waves and tidal currents, water environment protection materials can be fixed to the algal reef block and the fishing reef block. Furthermore, a water area environmental preservation material can be accommodated in the box-shaped structure drilled so that the water of the installed water area may circulate, and can be set in the water area.

  According to the water area environmental conservation material of the present embodiment, after the water area environmental conservation material is installed in the water area, the aging reaction proceeds to continuously generate humic acid, and the effect of supplying iron ions to the water area continuously. Obtainable. Furthermore, by continuously supplying iron ions to the water area, it is possible to induce the growth of seaweeds that require iron ions and to create a rich waterside environment. That is, according to the water area environmental conservation material of the present embodiment, water area environmental conservation can be achieved. In addition, the effect acquired by the water area environmental conservation material of this embodiment changes a little with water areas. For example, in a sea area where the iron content in seawater is low and the seawater exchange is low, a remarkable effect can be obtained by the water environment protection material of the present embodiment. On the other hand, in sea areas where seawater exchange by tides and tides is large, it is difficult to maintain the effective concentration of iron ions in the water due to dilution and diffusion, so it is difficult to expect significant effects from the water environment conservation material of this embodiment There is. Furthermore, in a water area that is not deficient in iron, it may be difficult to make the effect obtained by the water area environmental conservation material of the present embodiment noticeable.

  Hereinafter, the present invention will be described based on examples. In addition, this invention is not restrict | limited to the following Example.

(Example 1)
In order to confirm the effect of the present invention, a container containing an aquatic environment conservation material mixed with an iron-containing substance and a humic acid supply substance containing humic acid according to an embodiment of the present invention is installed in the sea, and the aquatic environment conservation material The supply performance of humic acid iron from was investigated.

  In Example 1, the artificial humus soil manufactured using waste wood chips as a raw material was used as the humic acid supply substance, and the fermentation process of the humic acid supply substance was performed as described above. In the fermentation process of the humic acid supply substance, the humic acid content and the organic substance content were measured over four times over time. The humic acid content of the humic acid supply substance conforms to Non-Patent Document 3, and the organic substance content of the humic acid supply substance conforms to the dry combustion method described in Non-Patent Document 4 and is measured. went. The measured organic substance content indicates the content of an organic substance capable of producing humic acid or an organic acid by fermentation due to a metabolic reaction of a microorganism, that is, a humic acid supply substance.

  FIG. 1 shows the measurement results. FIG. 1 is a diagram showing changes over time in the humic acid content and the organic substance content in the fermentation process of the humic acid supply substance of Example 1. FIG. In FIG. 1, the fermentation time increases as the sample number increases. As shown in FIG. 1, since the organic substance content decreased as the sample number increased, it can be seen that fermentation of the humic acid supply substance progressed with time. On the other hand, the content of humic acid is 6.9% by dry weight in Sample No. 1 and increases to 9.5% by dry weight in Sample No. 2. Reduced. From this, as the fermentation time elapses, the content of humic acid initially increases.However, as the fermentation time increases, the generated humic acid is decomposed and the content of humic acid decreases. It is estimated that From FIG. 1, for example, a humic acid supply substance in the middle of fermentation in a state between sample number 1 and sample number 2 and a humic acid in the state between sample number 2 and sample number 3 Since the amount of humic acid contained in the humic acid supplying substance may be the same, the amount of humic acid supplied to both water areas is expected to be the same. However, since the humic acid supply substance is fermented even after installation in the water area and humic acid may be generated, in this embodiment, the state between the sample number 1 and the sample number 2 out of the two. It is preferable to use the humic acid supply substance in the middle of fermentation. Moreover, even if it is a case where it installs in the environment where fermentation is difficult, since the time required for a fermentation process becomes short, among them, the humic acid in the middle of fermentation in the state between sample number 1 and sample number 2 It is preferred to use a feed material.

  Next, an aquatic environment conservation material was manufactured using the humic acid supply substance containing humic acid obtained above. Specifically, as the iron-containing substance, converter steelmaking slag having a particle size of 20 mm or less was used after being carbonized. Furthermore, as shown in Table 1 below, two types of humic acid supply substances (sample number 2 and sample number 4 in FIG. 1) having different humic acid contents were used. The iron-containing substance and the humic acid supply substance were mixed so that the ratio of the volume ratio was 50:50, and were produced as water area environmental conservation materials of Example A and Comparative Example B. In addition, as shown in FIG. 1, in the fermentation process of the humic acid supply substance, by measuring the contents of the generated humic acid and the organic substance with respect to the fermentation time of the humic acid supply substance in advance, as Example A The humic acid supply material containing the largest amount of organic substances that can be a humic acid supply source after installing the aquatic environment conservation material in the water area was selected as compared with Comparative Example B. .

  The water area environmental conservation materials of Example A and Comparative Example B prepared as described above were accommodated in the steel container 10 shown in FIG. 2 and submerged in the sea at a depth of about 5 m. In each of the steel containers 10, about 1 t of the water area environmental conservation material was filled in each 20 kg for each of Example A and Comparative Example B and stored. FIG. 2 is a perspective view of the container 10 for storing the water area environmental conservation material of Example 1 and setting it in the sea. The surface 11 of the container 10 is formed with a plurality of holes 12 for diffusing components of the water area environmental conservation material accommodated inside the container into the water area.

  After substituting the container 10 containing the water area environmental conservation material of Example A and Comparative Example B into the sea area, for 18 months, the water is periodically cleared at a position 1 m above the center of the upper surface of the container 10. The surrounding seawater was sampled to collect the humic acid iron contained in the seawater. The content of iron humate was measured as the dissolved iron concentration in accordance with the method described in Non-Patent Document 5. Furthermore, in the sea area close to the respective installation locations of the containers 10 of Example A and Comparative Example B, the sea area where there is no influence of humic acid iron elution from the water area environmental conservation material of Example A and Example B is regularly Seawater was collected and the same measurement was performed on the collected seawater to obtain a background (standard) of dissolved iron concentration. And each increase of humic acid iron was computed by subtracting the dissolved iron concentration as a background from each measured dissolved iron concentration of Example A and Comparative Example B.

  FIG. 3 shows the change over time in the amount of increase in dissolved iron, which is the difference between the dissolved iron concentration in seawater in Example A and the dissolved iron concentration in the background. In the surrounding seawater immediately after the installation of the container 10 containing the water environment conservation material of Example A, there is an increase of 15.7 μg / liter with respect to the dissolved iron concentration in the background. It was an increase of 25.3 μg / liter with respect to the dissolved iron concentration. Thereafter, after 9 months, the background dissolved iron concentration increased by 3 μg / liter, and the increase was reduced, but even after 18 months, the background dissolved iron concentration was 2.7 μg / liter. It was found that the effect of the water area environmental conservation material of Example A was sustained.

  On the other hand, FIG. 4 shows the change over time in the amount of increase in dissolved iron, which is the difference between the dissolved iron concentration in the seawater in Comparative Example B and the dissolved iron concentration in the background described above. In the surrounding seawater immediately after installing the container 10 containing the water environment protection material of Comparative Example B, there was an increase of 19.0 μg / liter with respect to the dissolved iron concentration in the background, but the increase amount quickly decreased. After 4 months of installation, it increased by 4.2 μg / liter, reached an increase of 1.6 μg / liter after 6 months, and became almost zero after 12 months. From this result, it was found that the effect of the water environment conservation material of Comparative Example B did not last as compared with Example A.

  Based on the results of FIGS. 3 and 4, humic acid iron by the water environment preservation material of Example A or Comparative Example B until 12 months after the water environment preservation material of Example A or Comparative Example B was installed in seawater The cumulative supply amount of each was calculated. Table 2 shows the ratio of the cumulative supply amount according to Example A when the cumulative supply amount according to Comparative Example B is 100%. As shown in Table 2, in the water environment conservation material of Example A, supply of humic acid iron 2.3 times that of the water environment conservation material of Comparative Example B during the same period for 12 months after installation. We were able to confirm that

  From this, according to the water area environmental conservation material of Example A, compared with the water area environmental conservation material of Comparative Example B, humic acid iron can be continuously supplied to seawater, and the accumulation of humic acid iron It was found that the supply amount was large. That is, it was found that the water area environmental conservation material of Example A can effectively and continuously supply iron humate, that is, iron ions, to the water area as compared with Comparative Example B.

(Example 2)
In order to confirm the effect of the present invention, a container containing an aquatic environment conservation material mixed with an iron-containing substance and a humic acid supply substance containing humic acid according to an embodiment of the present invention is installed in the sea, and the aquatic environment conservation material As a result, we investigated the effect of seaweed beds as

  In Example 2, as in Example 1, as the humic acid supply substance, artificial humus produced using waste wood chips as a raw material was used, and as described above, the fermentation process of the humic acid supply substance was performed. . In the fermentation process of the humic acid supply substance, the fulvic acid content, the humic acid content and the organic substance content of the humic acid supply substance were measured over four times over time. The fulvic acid content and the humic acid content were measured according to Non-Patent Document 3, and the organic substance content was measured according to the dry combustion method described in Non-Patent Document 4.

  FIG. 5 shows the measurement results. FIG. 5 is a diagram showing temporal changes in the humic acid content and the organic material content in the fermentation process of the humic acid supply material of Example 2. In FIG. 5, the fermentation time increases as the sample number increases. As shown in FIG. 5, the organic substance content of the humic acid supply substance decreased as the sample number increased, indicating that the fermentation of the humic acid supply substance progressed over time. On the other hand, the fulvic acid content is 4.4% by dry weight in Sample No. 1, increases to 6.1% by dry weight in Sample No. 2, and the fulvic acid content increases with Sample No. 3 and Sample No. 4. Reduced. Moreover, since the humic acid content showed an increasing tendency as the sample number increased, that is, consistently with time, it was confirmed that the humic acid content increased as the aging progressed. That is, it was confirmed that when ripening progresses too much, fulvic acid is transformed into humic acid and the content of humic acid is increased. As the humic acid supply substance used in the present embodiment, the humic acid tends to increase too much and the humic acid tends to increase. Is optimal.

  Next, an aquatic environment conservation material was manufactured using the humic acid supply substance containing fulvic acid obtained above. Specifically, as the iron-containing material, as in Example 1, converter steelmaking slag having a particle size of 20 mm or less was used after being carbonized. Furthermore, as shown in Table 3 below, two types of humic acid supply substances (sample number 2 and sample number 4 in FIG. 5) having different fulvic acid contents were used. The iron-containing substance and the humic acid supply substance were mixed so that the ratio of the volume ratio was 50:50, and were produced as water area environmental conservation materials of Example C and Comparative Example D. In addition, as shown in FIG. 5, in the fermentation process of the humic acid supply substance, the measurement was performed by measuring the contents of the generated fulvic acid, humic acid and organic substance with respect to the fermentation time of the humic acid supply substance. As Example C, the fulvic acid contained is the largest, and compared with Comparative Example D, the fulvic acid contained a lot of organic substances that could become a source of humic acid after the water environment protection material was installed in the water area. A humic acid feed material with a low content was selected.

  The water area environmental conservation materials of Example C and Comparative Example D prepared as described above are respectively stored in the steel container 10 shown in FIG. 2 and set in the sea at a water depth of about 5 m. did. In the steel container 10, about 1 t of water environment conservation material was filled in each 20 kg for each of Example C and Comparative Example D and stored.

  After the container 10 containing the water area environmental conservation material of Example C and Comparative Example D was set in the sea area, the state of overgrowth of seaweeds in the surrounding sea area where each container 10 was installed was periodically observed. Specifically, four 50 cm square survey zones are set on the seabed at a distance of 5 m along the direction of east, west, south, and north from the center of the container 10 containing the water area environmental conservation material of Example C and Comparative Example D. We observed the overgrowth of seaweeds in each district. In addition, the container 10 was sunk in October, and the survey was conducted approximately every three months after the sunk. As a result, as shown in Table 4, the growth of seaweeds was better in each section around the water environment conservation material of Example C than in each section around the water environment protection material of Comparative Example D.

  Furthermore, the seaweed coverage in each of the above-mentioned districts was examined. Seaweed coverage is the ratio of the area of the seabed covered with seaweed to the entire seabed of each section. As a result, in May, about half a year after the installation of the container 10, the average seaweed coverage of the section according to Example C is 55%, and the average seaweed coverage of the section according to Comparative Example D is 16%. Moreover, about the willow moku which is a prosperous main seaweed, as a result of measuring 30 leaf lengths from the division concerning Example C and the division concerning Comparative Example D, the average leaf length was 37 cm in Example C, compared In Example D, it was 23 cm. That is, according to the aquatic environment conservation material of Example C, the seaweed coverage is 3.4 times and the seaweed leaf length is 1.6 times that of the aquatic environment conservation material of Comparative Example C. It was. Therefore, according to Example C, it turned out that the proliferation of seaweed etc. which require iron ions can be induced effectively, and water area environmental conservation can be achieved effectively.

  From Example 1 and Example 2 demonstrated above, according to the Example concerning this invention, the effect which makes it possible to supply an iron ion to a water area continuously can be acquired. Furthermore, it is clear that iron ions can be effectively and continuously supplied to the water area, and as a result, water environment conservation represented by seaweed growth can be achieved.

  The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

10 Container 11 Surface 12 Hole

Claims (4)

Fermenting the humic acid supply substance to produce humic acid by fermenting the humic acid supply substance;
The process for producing an aquatic environment conservation material for producing the aquatic environment conservation material by mixing the humic acid supply substance containing the humic acid after the fermentation process with an iron-containing substance,
An application step of applying the water area environmental conservation material to the water area;
A method for applying a water area environmental conservation material comprising:
The humic acid supply substance contains humus soil,
In the fermentation process of the humic acid supply substance, the change over time in the content of each of fulvic acid and humic acid is measured, and the humic acid is based on the relationship between the fermentation period and the content measured in advance. To obtain a humic acid supply substance in the middle of fermentation containing a large amount of fulvic acid compared to
Wherein in the production step, the obtained said fermentation during the humic acid feed material was mixed with the iron-containing material, a method of applying the water zone environment preservation material. The method for applying an aquatic environment conservation material according to claim 1, wherein the humus soil includes at least one of waste wood chips, bark of trees, fallen leaves, pruning waste, and a weed generating material. The method for applying a water area conservation material according to claim 1 or 2, wherein the humic acid supply substance during fermentation is acquired before the content of the fulvic acid reaches a maximum amount. Wherein the iron-containing material includes steel slag, a method of applying the water conservation material according to any one of 請 Motomeko 1-3.

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