JPH06335330A - Algal field proliferating material and artificial fish reef - Google Patents

Abstract

PURPOSE:To provide an algal field proliferating material affording algal field effective for proliferating sea algae or phytoplankton growing undersea, and to provide an artificial fish reef enabling such algal field to be proliferated and thus enabling fish and shellfish gathering there to be bred and proliferated. CONSTITUTION:The algal field proliferating material consisting of a vitreous material composed of (A) 30-70wt.% of silicon in terms of SiO2, (B) 10-50wt.% of sodium and/or potassium in terms of Na2O and/or K2O and (C) 5-50wt.% of iron in terms of Fe2O3 with the content of divalent iron being >=1wt.%. The other objective artificial fish reef can be obtained by arranging such algal field proliferating material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a seaweed bed growth material capable of forming a seaweed bed that is effective for growing organisms such as seaweeds and phytoplankton that grow in the sea. The present invention also relates to an artificial fish reef that makes it possible to grow such a seaweed bed and thereby grow and grow seafood that gathers at the seaweed bed.

[0002]

2. Description of the Related Art Conventionally, as a method for artificially growing and multiplying seafood, a fish reef space is formed by immersing steel, stone, wood, etc. in water to form a fish reef space, and seaweed in this space. A method of forming a seaweed bed by inhabiting species and phytoplankton is widely used. Such an artificial fish reef does not protect eggs of seafood or protects or raises young larvae in a floating life period, but collects seafood that has grown to some extent to form an artificial fishing ground. However, in the fishing ground thus formed, the algae settlement on the fish reef tends to be extremely reduced within a few years after the fish reef is deposited. Therefore, there is a demand for the development of artificial fish reef materials that can sustain epiphytes such as algae and phytoplankton for a long period of time.

On the other hand, according to a study by Professor Matsunaga of Hokkaido University, the growth of seaweed organisms such as seaweeds and phytoplankton requires components such as iron, manganese, silicon and phosphorus dissolved in seawater. It has been reported that the proliferative effect is extremely high especially when iron is dissolved as a divalent ion (Nikkan Seikei Information January 1, 1988 issue).

It is also empirically known that seagrass organisms are densely present on iron fish reefs formed by sunken ships or abandoned ships in the sea, and seafoods that feed on them are collected. It is speculated that this phenomenon is due to the fact that part of the iron, which is the material for sunken ships, is dissolved in the sea in the state of divalent iron ions, which can be directly used by seaweed beds. . This estimation is based on the data that the concentration of iron contained in seaweeds grown on iron fish reefs and the concentration of iron in seaweeds grown on reefs are measured and compared, the iron concentration of the former is more than twice that of the latter. It is also supported by.

[0005]

Accordingly, if the material forming the seaweed bed breeding material such as artificial fish reef contains particularly divalent iron, and further components such as manganese, silicon and phosphorus, the seaweed bed It is fully predicted that it will be possible to grow organisms. However, conventionally used steel, stone, wood, and other seaweed bed breeding materials contain divalent iron, and further manganese, silicon, phosphorus, etc., and their components are stable in seawater for a long period of time. Up to now, no method for continuous elution has been found.

[0006]

SUMMARY OF THE INVENTION The present invention firstly comprises silicon,
Sodium and / or potassium, and iron, in terms of SiO ₂ , are each 30 to 70% by weight (preferably,
35 to 60% by weight), 10 to 50% by weight (preferably 20 to 30% by weight) in terms of Na ₂ O and / or K ₂ O, and 5 to 50% by weight (preferably, in terms of Fe ₂ O ₃ ). 10 to 35% by weight) and the content of divalent iron is 1% by weight or more (preferably 3% by weight or more, more preferably 5% by weight or more, most preferably 8% by weight).
It is a seaweed bed breeding material made of a glassy material in an amount of at least 1% by weight, preferably 30% by weight or less. In addition, these weight% means the ratio with respect to the whole amount of the seaweed bed growth material (glassy material).

In the present invention, silicon, sodium and / or potassium and iron are added in an amount of 30 to 70% by weight (preferably 35 to 60% by weight) in terms of SiO ₂ , Na ₂ O and / or K _{2 respectively.} 10-50 in O conversion
Wt% (preferably 20-35 wt%), and Fe
5 to 50% by weight in terms of ₂ O ₃ (preferably 10 to 35%
(% By weight) and the content of divalent iron is 1
There is also an artificial fish reef coated with a glassy material in an amount of not less than 5% by weight (preferably not less than 3% by weight, more preferably not less than 5% by weight, most preferably not less than 8% by weight, preferably not more than 30% by weight). .

The present invention focuses on the characteristics of a glassy amorphous structure different from metal materials and concrete materials, and by using this glassy material as a matrix material, the iron content containing a certain amount or more of divalent iron is confined. Completed based on the new finding of the present inventor that it becomes possible to stably and slowly release iron ions such as divalent iron ions generated from the divalent iron into the sea for a long period of time. Is.

The vitreous material constituting the seaweed bed breeding material and artificial fish reef of the present invention is further composed of phosphorus and / or
Alternatively, manganese is 1 to 30% by weight in terms of P ₂ O ₅ , and manganese is 0.1 to 5% by weight in terms of MnO.
It is preferable to contain.

The vitreous material is a network-forming atom centered on silicon and oxygen forming the amorphous network structure,
And it contains network modifying atoms such as sodium and potassium that enter into the network structure, and iron that functions as a network forming atom or a network modifying atom. When such a glassy material is immersed in seawater, water molecules become glass. In order to gradually and slowly cut the mesh of the quality material mesh structure,
The vitreous component gradually elutes over a long period of time (water elution property). If the vitreous material further contains phosphorus that functions as a network-forming atom and manganese that functions as a network-forming atom or a network-modifying atom, it will gradually elute over a long period of time as the network is cut. . Therefore, if the kind and amount of the constituent element components of the seaweed bed growing material of the present invention are adjusted at the time of manufacturing the seaweed bed growing material, the target component can be eluted at a target rate.

In order to produce the seaweed bed growth material of the present invention,
A known material containing an elemental component such as silicon, iron, sodium and / or potassium is used, which is heated to a high temperature (for example, heated at 1300 to 1500 ° C. for about 10 minutes or more), melted, and then cooled. Vitrification methods can be used. During the vitrification process, the melting atmosphere is reduced by using a reducing agent such as coke or reducing gas such as carbon monoxide gas. It is possible to increase the content of divalent iron. Also, when introducing additional elemental components such as manganese and phosphorus into the glass,
Similarly, a method may be used in which a raw material containing those elemental components is prepared, the raw material is mixed with the above-mentioned glassy raw material, and then the raw material is melted by heating at high temperature. The glassy material seaweed bed multiplying material of the present invention can be made porous if desired. That is, by forming the seaweed bed breeding material with porous glass, the contact area between the seaweed bed breeding material and seawater increases, so that the elution of the constituent element components in the seaweed bed breeding material is promoted.

Used waste glass can also be used as a raw material for the seaweed bed growing material of the present invention. That is, even if a method such as crushing a used glass bottle, adding a raw material containing additional elemental components necessary for this, and then heating and melting the same in a reducing atmosphere is used, A seaweed bed breeding material can be manufactured.

Further, the vitreous material to be used as the seaweed bed breeding material of the present invention may be applied to the surface of other structures (concrete structures, steel materials, stone materials, construction wastes, natural rock fields, etc.) as it is or other materials. An artificial fish reef can also be obtained by mixing the material and disposing it by a method such as coating. Such an artificial fish reef having a seaweed bed breeding material, which is made of glass containing elemental components such as silicon, iron, sodium and / or potassium, and has an increased content of divalent iron, on all or part of its surface is , It is effective not only for collecting fish and shellfish around it to stably elute silicon and divalent iron into sea water for a long time, but also for growing seaweed and phytoplankton, which is also effective for the growth of fish and shellfish. Becomes Therefore, it can be used for a long time as an artificial fish reef.

[0014]

【Example】

[Example 1] As a glassy raw material, 10 parts of hematite powder (parts by weight, the same applies hereinafter), 50 parts of silica sand, 50 parts of potassium phosphate.
Parts, 15 parts of orthophosphoric acid, 2 parts of manganese dioxide and 2 parts of coke were thoroughly mixed and then placed in a crucible. Then, this crucible was placed in a furnace preheated to 1400 ° C., the vitreous raw material was heated and melted for 1 hour in a reducing atmosphere with city gas, and then cooled to room temperature, and the vitreous compact A (seaweed bed growth of the present invention). Material A) was obtained.

As a glassy raw material, hematite powder 30
Parts (parts by weight, the same hereinafter), 50 parts of silica sand, 25 parts of sodium carbonate, 15 parts of potassium phosphate, 2 parts of manganese dioxide, and 5 parts of coke were taken and mixed well, and then put in a crucible. The crucible is then placed at 1400 ° C
The glassy raw material was heated and melted for 1 hour under a reducing atmosphere with city gas, and then cooled to room temperature to obtain a glassy molded body B (seaweed bed breeding material B of the present invention).

Example 2 As a glassy raw material, 30 parts of hematite powder (parts by weight, the same applies hereinafter), 50 parts of silica sand, 25 parts of soda ash, 15 parts of potassium phosphate, and 5 parts of coke were taken, and these were thoroughly mixed. After that, I put it in the crucible. Then, this crucible was placed in a furnace preheated to 1400 ° C., the vitreous raw material was heated and melted for 1 hour in a reducing atmosphere with city gas, and then cooled to room temperature to obtain a vitreous compact C
(The seaweed bed growth material C of the present invention) was obtained.

As a glassy raw material, 9 parts of hematite powder (weight part, the same applies hereinafter), 50 parts of silica sand, 20 parts of soda ash,
After taking 18 parts of potassium phosphate and 4 parts of coke and mixing them well, they were put in a crucible. Then, this crucible was placed in a furnace preheated to 1400 ° C., the vitreous raw material was heated and melted for 1 hour in a reducing atmosphere with city gas, and then cooled to room temperature, and the vitreous compact D (seaweed bed growth of the present invention). Material D) was obtained.

As a glassy raw material, hematite powder 20
Parts (parts by weight, the same applies hereinafter), 50 parts silica sand, 3 potassium phosphates
7.3 parts, potassium carbonate 44.1 parts, and coke 1
Parts were taken, these were mixed well and then placed in a crucible. The crucible was then placed in a furnace preheated to 1400 ° C,
The glassy raw material was heated and melted for 1 hour in a reducing atmosphere with city gas, and then cooled to room temperature to obtain a glassy molded body E (seaweed bed breeding material E of the present invention).

[Evaluation of glassy molded body (seaweed breeding material)]
Table 1 shows the respective elemental component compositions (expressed as oxides) of the glassy molded products (algae bed growth materials) A, B, C, D and E obtained in Examples 1 and 2.

[0020]

[Table 1] Table 1 ──────────────────────────────────── Breeding material glass composition (weight %) Fe ₂ O ₃ SiO ₂ Na ₂ OK ₂ OP ₂ O ₅ MnO Al ₂ O ₃ ────────────────────────────── ──────── A 8.8 44.8 --23.7 21.6 1.1 0.04 B 27.2 46.4 13.5 7.4 3.7 1.1 0.04 C 27.7 47.2 13.8 7.5 3.8 --0.04 D 10.4 58.9 13.8 11.3 5.7 --0.04 E 15.1 38.6 --38.5 7.7- -0.03 ─────────────────────────────────────

Further, a glassy molded body (algal bed growth material) A,
For each of B, C, D, and E, divalent iron (Fe ²⁺ ) was quantified by the Mossbauer spectroscopy. The results were as follows. A (Fe ²⁺ : 4.9
Wt%), B (Fe ²⁺ : 15.2 wt%), C (F
e ²⁺ : 15.5% by weight), D (Fe ²⁺ : 5.8% by weight), E (Fe ²⁺ : 8.5% by weight)

Next, a glassy molded body (seaweed breeding material) A,
For each of B, C, D, and E, an elution test of iron and silicon was performed by the following method. The vitreous molding was crushed in an agate mortar, and the crushed sample was passed through a sieve No. 18 (850 μm).
Particle No. 0 (300 μm) was passed through to remove fine particles passing therethrough. The particles remaining on the sieve No. 50 are washed with the sieve in water with gentle sieving for 1 minute, further washed with ethanol for 1 minute, and then dried at 100 ° C. for 30 minutes.
Then, it was placed in a desiccator and cooled to obtain a test sample.
10 g of this test sample was placed in a 200 mL hard glass Erlenmeyer flask, 100 mL of pure water was added thereto, the lid was covered with a watch glass, and the mixture was heated in a water bath for 2 hours. Immediately after the heating, the sample eluate was obtained by cooling in running water. The above dissolution test method corresponds to the dissolution that occurs in about 7 months when converted to the dissolution in water at room temperature. Using the sample eluate obtained by the above method, the elution amount of iron (total iron amount), divalent iron, manganese, and silicon dioxide was measured by the following method. For comparison, the casting powder (chemical composition (% by weight) C: 3.6, Si: 2.0, Mn: 0.
6, Ni: 1.0, Fe: 92.0, balance P, S, C
r) and electric furnace steelmaking slag (chemical composition (% by weight) Fe ₂ O ₃ : 44.
_{7, FeO: 14.4, SiO 2} : 8.2, CaO: 11.0, MgO: 4.3, MnO: 4.7,
Al ₂ O ₃ : 6.8 and Cr ₂ O ₃ : 2.1) were also pulverized and eluted in the same manner to obtain a control sample eluate, and the same measurement was performed. The measurement results are shown in Table 2.

(1) Quantification of iron (quantification of the total amount of iron) 25 mL of sample eluate (1 when the sample eluate is colored)
(0 mL) in a 100 mL volumetric flask, 5 w / V
(Weight / volume)% ascorbic acid solution (2 mL) was added, and then 0.1 W / V% o-phenanthroline aqueous solution (10 mL) was added, and further 20 W / V% ammonium acetate aqueous solution (15 mL) was added. Dilute to the marked line with and leave for 30 minutes. A part of this solution is put into a photometric cell, the absorbance is measured at a measurement wavelength of 510 nm, and the concentration of iron is calculated from the absorbance and the absorbance of control water.

(2) Determination of divalent iron 25 mL of the sample eluate was placed in a 100 mL volumetric flask, to which was added 10 mL of 0.1 W / V% o-phenanthroline aqueous solution, and further 20 W / V% ammonium acetate. After adding 15 mL of the aqueous solution, dilute to the marked line with water and leave for 30 minutes. A part of this solution is put into a photometric cell, the absorbance is measured at a measurement wavelength of 510 nm, and the concentration of iron is calculated from the absorbance and the absorbance of control water.

(3) Quantification of manganese The atomic absorption spectrometry is used to measure the absorbance of the sample eluate at a wavelength of 279.5 nm to calculate the manganese concentration.

(4) Quantification of silicon dioxide 25 mL of the sample eluate was placed in a 100 mL plastic beaker, and 2 mL of an aqueous solution of hydrofluoric acid (1 part by volume of hydrofluoric acid + 9 parts by volume of water) was added and left for 10 minutes. After that, 50 mL of boric acid aqueous solution is added. Next, 2 mL of ammonium molybdate is added and stirred, and then left for 10 minutes. Next, after adding 5 mL of a tartaric acid aqueous solution, 5
Add 2 mL of w / V% ascorbic acid aqueous solution, transfer this to a 100 mL volumetric flask, dilute to the marked line with water, and leave for 30 minutes. A part of this solution is put into a photometric cell, the absorbance is measured at a measurement wavelength of 650 nm, and the concentration of silicon dioxide is calculated from the absorbance and the absorbance of control water.

[0027]

[Table 2] Table 2 ──────────────────────────────────── Breeding material elution amount (μg / 10g) Total iron divalent iron manganese silicon dioxide ───────────────────────────────────── A 56100 1530 290 1100 B 1120 330 330 70 11400 C 1120 410 -10100 D 1810 540-72500 E 22800 690-15700 ─────────────────────────── ───────── Cast powder 86 29 − − Electric furnace steelmaking slag 14 3 − − ───────────────────────────── ────────

From the above results, the seaweed bed growth material of the present invention is
It can be seen that a sufficient amount of iron (especially divalent iron), silicon dioxide, etc. are eluted over a long period of time as compared with casting powder and electric furnace steel slag. Therefore, it is expected to be very effective as a seaweed bed growth material.

[Example 3] As a glassy raw material, 50 parts of hematite powder (parts by weight, the same applies hereinafter), 50 pieces of soda-lime glass having a size of several millimeters to several centimeters (fragment of bottle glass) 50
Parts, and 5 parts of coke were taken, mixed well and then put in a crucible. Next, this crucible was placed in a furnace and heated from room temperature to 1200 ° C. over 2 hours and then cooled to room temperature to obtain a glassy molded body F (seaweed bed growth material F of the present invention).

The glass molded article F was subjected to an elution test of iron, divalent iron and silicon dioxide by the method described above. The results are shown in Table 3.

[0031]

[Table 3] Table 3 ──────────────────────────────────── Amount of leachable breeder (μg / 10g) Total iron amount Divalent iron Silicon dioxide ──────────────────────────────────── F 59 12 1060 ─────────────────────────────────────

From the above results, the seaweed bed growth material of the present invention is
It can be seen that iron (especially divalent iron), silicon dioxide, etc. can be eluted over a long period without using fine particles. Therefore, it is expected to be effective as a seaweed bed growth material.

[Algal bed growth test using glassy molded product (algal bed growth material)] Control culture solution: NaNO ₃ : 75 mg, NaH _{2
PO 4 · 2H 2 O: 6mg} , Na 2 SiO 3 · 9H
_{2 O: 10mg, CoSO 4 ·} 7H 2 O: 12μg, Z
_{nSO 4 · 7H 2 O: 21μg} , MnCl 2 · 4H
₂ O: 180 μg, CuSO ₄ .5H ₂ O: 7 μg, N
a ₂ MoO ₄ · 2H ₂ O: 7 μg, and seawater 1000
Prepared by mixing mL.

(1) Preparation of sample culture solution Sample culture solution G: Only the above-mentioned control culture solution Sample culture solution H: 10 mg of the above-mentioned growth material C (particle size: 300 to 850 μm) was added to 100 mL of the control culture solution Sample culture solution I : 10 mg of the proliferation material D (particle size: 300 to 850 μm) was added to 100 mL of the control culture medium Sample culture fluid J: 10 mg of the proliferation material E (particle size: 300 to 850 μm) was added to the 100 mL of the control culture fluid

(2) Cultivation test of sample culture solution I In the sample culture solution, diatom (Chaetocerros) was used as plankton.
sociale) was added so that the cell concentration would be 300 cells / mL, the culture temperature was maintained at 5 ° C, and the first 1
After culturing was continued for 21 days in a cycle of lighting at 3000 lux for 2 hours and no lighting for the next 12 hours, the cell concentration of diatom was measured, and the results shown in FIG. 1 were obtained.

(3) Cultivation test of sample culture solution II In the sample culture solution, flagellates (Gymnodiniu) as plankton were used.
m mikimotoi) with a cell concentration of 100 cells / mL
After maintaining the culture temperature at 5 ° C, the culture was continued for 22 days under the cycle of 3000 lux illumination for the first 12 hours and no illumination for the next 12 hours. When the cell concentration of was measured, the results shown in FIG. 2 were obtained.

(4) Evaluation As is clear from FIG. 1 and FIG. 2, in the control culture solution (culture solution G), the cell concentrations of diatom and flagella were almost increased even after 21 days and 22 days of culture, respectively. But not
On the other hand, in the culture fluids (culture fluids H, I, and J) to which the algae bed growth material of the present invention was added, the cell concentration of diatoms increased to about 130 to 300 times that of the initial culture after 21 days of culture. On the other hand, the cell concentration of flagella was increased about 3 to 8 times as much as the initial concentration after 22 days of culture. Therefore, it is understood that the material for growing seaweed beds of the present invention is extremely effective for growing seaweed beds such as plankton. Similarly, it is apparent that the artificial fish reef having the seaweed bed breeding material layer of the present invention on the surface is also extremely effective for growing seaweed bed organisms such as plankton.

[Test for Transferring Iron Content to Kombu by Glassy Molded Body (Algae Bed Growth Material)] 10 samples of the seaweed bed growth material C (particle size: 300 to 850 μm) were added to 1 liter of seawater to obtain four samples. A liquid was prepared. For each of these four sample liquids, kelp K of about 20 cm in length immediately after collection,
Add L, M, N respectively and maintain the temperature at 10 ° C.
For the first 12 hours, under the lighting of 3000 lux, the next 12 hours
The kelp culture experiment was continued for 10 days in a cycle of no illumination. After that, iron was quantified by the method described above with respect to the kelp solution obtained by dissolving each kelp with sulfuric acid. In addition, about the above kelp K, L, M, N,
Before the start of the above experiment, iron was similarly quantified.
The results obtained are shown in Table 4.

[0039]

[Table 4] Table 4 ──────────────────────────────────── Including iron in the components Amount (μg / g dry weight) Kelp K L M N Average ──────────────────────────────────── ─ Immediately after collection 7.3 8.9 9.4 8.8 8.6 After culture experiment 16.5 15.5 16.3 17.4 16.4 ────────────── ──────────────────────

As is clear from the results shown in Table 4, the iron content in each kelp increases on average about twice after the culture experiment as compared to immediately after the collection. From this result, it was found that the iron eluted from the material for growing seaweed beds of the present invention is efficiently incorporated into seaweeds such as kelp. It is reported in the January 1, 1988 issue of Nikkan Seikei Information that the iron content efficiently incorporated into seaweed is effective for the growth of seaweed. Similarly, it is clear that the artificial fish reef having the seaweed bed propagation material layer of the present invention on the surface is also effective for the growth of seaweeds.

[0041]

By using the seaweed bed breeding material or artificial fish reef of the present invention, iron (particularly divalent iron) and silicon can be obtained.
When phosphorus and manganese are further contained, phosphorus and manganese are also stably eluted into the sea for a long period of time, which is effective for the growth of organisms such as seaweeds and phytoplankton that grow in the sea. Can be formed, and by proliferating such a seaweed bed, it becomes possible to grow and grow seafood that gathers at the seaweed bed. Further, the seaweed bed breeding material and artificial fish reef of the present invention can be produced by using waste materials such as waste bottle glass and waste plate glass as raw materials, and adjusting the necessary components to them, so that the waste is effectively used. Is also useful. The seaweed bed breeding material and artificial fish reef of the present invention also have an advantage that the elemental components to be eluted can be easily adjusted.

[Brief description of drawings]

FIG. 1 is a graph showing the results of an experiment in which the growth amount of diatoms was investigated after culturing diatoms as plankton with a culture solution to which a seaweed bed growth material according to the present invention was added and a culture solution to which the material was not added.

FIG. 2 is a graph showing the results of an experiment in which the growth amount of flagellates was investigated after cultivating flagellates as plankton using a culture solution containing the algal bed growth material according to the present invention and a culture solution containing no material. .

[Explanation of symbols]

G sample culture solution (control culture solution) H sample culture solution (control culture solution + seaweed bed growth material C of the present invention) I sample culture solution (control culture solution + seaweed bed growth material D of the present invention) J sample culture solution ( Control culture solution + seaweed bed growth material E of the present invention)

Claims (6)

[Claims] 1. Silicon, sodium and / or potassium, and iron in an amount of 30 to _{7 in} terms of SiO ₂ , respectively.
0% by weight, 10 in terms of Na ₂ O and / or K ₂ O
A seaweed bed multiplying material comprising a glassy material containing 50% by weight and 5 to 50% by weight in terms of Fe ₂ O ₃ and having a divalent iron content of 1% by weight or more. 2. Further, phosphorus is contained in an amount of 1 to 30 in terms of P ₂ O _5.
The seaweed bed growth material according to claim 1, wherein the material is contained in a weight percentage. 3. Manganese is further converted into MnO in an amount of 0.1.
The seaweed bed growth material according to claim 1 or 2, wherein the content is 5 wt%. 4. Silicon, sodium and / or potassium, and iron in an amount of 30 to _{7 in} terms of SiO ₂ , respectively.
0% by weight, 10 in terms of Na ₂ O and / or K ₂ O
An artificial fish reef coated with a glassy material containing 50% by weight and 5 to 50% by weight in terms of Fe ₂ O ₃ and having a divalent iron content of 3% by weight or more. 5. Further, phosphorus is contained in an amount of 1 to 30 in terms of P ₂ O _5.
The artificial fish reef according to claim 4, wherein the artificial fish reef is contained in a weight percentage. 6. Manganese is further converted into MnO in an amount of 0.1.
The artificial fish reef according to claim 4 or 5, containing 5 to 5% by weight.