JP7392976B2 - mineral supplement - Google Patents

Description

The present invention relates to a mineral supplement containing a novel carbonate-based solid solution of essential minerals as an active ingredient. More specifically, the present invention relates to a mineral supplement containing a carbonate solid solution of Ca and/or Mg and trace essential minerals as an active ingredient.

It is gradually becoming recognized that minerals are important to all living things, whether animals or plants. Therefore, in addition to the three major elements of nitrogen, phosphorus, and potassium, fertilizers also use minerals such as Ca and Mg, which are required in medium amounts, as well as minerals that are required in trace amounts, such as Fe, Mn, Zn, Cu, B, and Mo. It is being done.

Human diets and animal feeds such as chickens, pigs, cows, and pets require medium amounts of Ca and Mg (approximately 200 to 600 mg per adult human) and trace amounts of Ca and Mg. Fe, Zn, Mn and Cu (approximately 2-15 mg per adult human) and ultra-trace amounts of Cr, Co, Se and Mo (approximately 20-40 μg per adult human). Some or all of the minerals are added as minerals.

Organic mineral substances used as mineral-containing substances include calcium lactate, peptide iron, peptide zinc, peptide copper, peptide manganese, DL-threonine iron, zinc sulfate methionine, iron citrate, succinic acid citric acid. Sodium iron, ferrous fumarate, etc., and inorganic mineral substances such as potassium chloride, magnesium oxide, aluminum hydroxide, zinc carbonate, cobalt carbonate, sodium hydrogen carbonate, magnesium carbonate, manganese carbonate, potassium iodide, and potassium iodate. , calcium iodate, zinc sulfate, cobalt sulfate, iron sulfate, copper sulfate, sodium sulfate, magnesium sulfate, manganese sulfate, potassium monohydrogen phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, etc. It is.

The inventor has developed the following formula (3)

（式中、Ｍ１^２＋はＣａおよび／またはＭｇを示し、Ｍ２^２＋は必須ミネラルＭｎ, Ｆｅ,ＣｕおよびＺｎの少なくとも一種以上を示し、ｘは０＜ｘ＜０．４の範囲を満足する正の数を示す）で表される金属水酸化物固溶体を有効成分として含有する植物のミネラル補給剤が提案されている。（特許文献１）

(In the formula, M1 ²⁺ represents Ca and/or Mg, M2 ²⁺ represents at least one of the essential minerals Mn, Fe, Cu and Zn, and x is a positive value satisfying the range of 0<x<0.4. A plant mineral supplement containing a metal hydroxide solid solution represented by the following numbers (indicating numbers) as an active ingredient has been proposed. (Patent Document 1)

JP2005-89237

In order for an essential mineral supplement to work effectively, it is necessary to ingest approximately the required amount of each mineral each day in the form of an easily absorbed compound. In order to be absorbed, it must be dissolved in water. Excessive intake can be harmful and even fatal. On the other hand, if the intake is too low, various problems will occur due to mineral deficiency. Therefore, a mineral supplement that gradually dissolves in water, releases the required amount of each mineral as ions, and is easily absorbed is ideal.

However, the existing mineral supplements are either poorly absorbed or absorbed too well. For example, CaCO ₃ and ZnCO ₃ are poorly soluble in water and therefore poorly absorbed. On the other hand, MgSO ₄ and FeSO ₄ are water-soluble, so they are absorbed too well resulting in excessive intake, or the amount exceeding the required amount is not absorbed and is excreted. Excretion occurs because the body absorbs only the required amount, even if it is supplied in excess of the maximum daily intake of minerals. In this way, conventional mineral supplements are either poorly soluble in water, resulting in under-intake, or easily soluble in water, resulting in excessive intake, and it is difficult to say that they are safe and effective mineral supplements. , the effects of minerals are not fully demonstrated.

As a sustained-release mineral supplement, there is a solid solution of calcium hydroxide and/or magnesium hydroxide and other essential minerals invented by the present inventor, but it has the disadvantage that the pH is too high at 12 to 13. (Patent Document 1)
Therefore, the problem to be solved by the present invention is to provide a mineral replenisher that is sustained-release and has a pH ranging from neutral to alkaline, from 7 to less than 12, particularly preferably from 7 to 10.

As a result of intensive research in order to solve the above problems, the present inventor has determined that the following formula (1)

（式中、Ｍは、Ｍｎ、Ｆｅ、Ｃｏ、ＣｕおよびＺｎから選ばれる少なくとも一種の２価金属，好ましくはＭｎ，Ｆｅ，ＣｕおよびＺｎを示し、ｘとｙはそれぞれ次の範囲、０＜ｘ＜０．４、好ましくは０．０２≦ｘ≦０．３、特に好ましくは０．０５≦ｘ≦０．２，０．０１＜ｙ≦１、好ましくは０．５≦ｙ≦１、特に好ましくは０．８≦ｙ≦１、を満足する正の数を示す）で表されるＣａおよび／またはＭｇと必須微量ミネラル２価金属イオンとの新規な炭酸塩系固溶体を共沈法で合成することにより、徐放性であり且つ温和なｐＨ範囲７～１２未満、特には７～１０を実現することに成功した。該炭酸塩系固溶体は、ＣａＣＯ_３やドロマイトよりも高い水溶性を示すだけでなく、難溶性のＭｎ，ＺｎおよびＣｕの炭酸塩の水溶性も大きく改善されている。
本明細書において固溶体のｐＨとは、固溶体１ｇの粉砕物を１００ｍＬの脱イオン水に加えて３０℃で５分間攪拌して得た分散液のｐＨを言う。

(In the formula, M represents at least one divalent metal selected from Mn, Fe, Co, Cu, and Zn, preferably Mn, Fe, Cu, and Zn, and x and y are each in the following range, 0<x <0.4, preferably 0.02≦x≦0.3, particularly preferably 0.05≦x≦0.2, 0.01<y≦1, preferably 0.5≦y≦1, particularly preferably is a positive number satisfying 0.8≦y≦1) A novel carbonate-based solid solution of Ca and/or Mg and essential trace mineral divalent metal ions is synthesized by coprecipitation method. As a result, we succeeded in achieving a sustained release and mild pH range of 7 to less than 12, particularly 7 to 10. The carbonate-based solid solution not only exhibits higher water solubility than CaCO ₃ and dolomite, but also greatly improves the water solubility of sparingly soluble Mn, Zn, and Cu carbonates.
In this specification, the pH of the solid solution refers to the pH of a dispersion obtained by adding 1 g of the solid solution to 100 mL of deionized water and stirring the mixture at 30° C. for 5 minutes.

CaCO ₃ is sparingly soluble with approximately 6 mg/L of Ca soluble in water, but by making it a solid solution with Mg etc., it is possible to significantly improve water solubility to 20 to 200 mg/L in terms of Ca, that is, improve absorption. It became. The pH of an aqueous solution containing the solid solution of the present invention can be lower than 8.6, which is the drinking water standard. This was not previously possible with CaCO ₃ and dolomite. By adding the carbonate-based solid solution of the present invention containing all divalent metals such as Ca, Mg, Mn, Fe, Zn, and Cu to chicken feed, it is possible to reduce mortality rate, reduce feed consumption, improve taste, and increase protein content. can increase weight and reduce fat. When the carbonate-based solid solution of the present invention is applied to growing agricultural products, an increase in yield, an increase in nutritional components, an improvement in sugar content and acidity can be obtained, and since the improvement in sugar content is greater than the improvement in acidity, the taste is also improved. When fed to mushroom media, it increases yield and mineral content.
Ca conversion refers to the total number of moles of all types of ions eluted during analysis, and the weight of Ca atoms corresponding to this number of moles.

XRD pattern of the product of Example 1 XRD pattern of the product of Example 2 XRD pattern of the product of Example 3 XRD pattern of the product of Example 4

（式中、Ｍは、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎから選ばれる少なくとも一種の２価金属を示し、ｘとｙはそれぞれ次の範囲、０＜ｘ＜０．４、０．０１＜ｙ≦１を満足する正の数を示す)で表される、２価金属炭酸塩系の固溶体を含有するミネラル補給剤である。
主成分であるＣａおよび／またはＭｇは、好ましくはＣａおよびＭｇである。好ましいＣａ：Ｍｇのモル比率は２５～７５：７５～２５、特に好ましくは４０～７０：６０～３０である。 The present invention is expressed by the following formula (1)

(In the formula, M represents at least one divalent metal selected from Mn, Fe, Co, Cu, and Zn, and x and y are in the following ranges, 0<x<0.4, 0.01<y, respectively. This is a mineral replenisher containing a divalent metal carbonate-based solid solution, expressed as a positive number satisfying ≦1.
The main components Ca and/or Mg are preferably Ca and Mg. The preferred Ca:Mg molar ratio is 25-75:75-25, particularly preferably 40-70:60-30.

The structure of the metal carbonate solid solution of the present invention belongs to any one of CaCO ₃ (calcite), MgCO ₃ (magnesite) and (Ca,Mg)CO ₃ (dolomite). When the Ca content is large, a calcite type structure is shown, when Mg is the main component, a magnesite type structure is shown, and when Ca and Mg are present in similar amounts, a dolomite type structure is shown. If the crystallinity is poor, it may be nearly amorphous. Since Ca and Mg are minerals that are required in moderate amounts, and the required amount of Ca is greater than that of Mg, the preferred structure of the solid solution of the present invention is dolomite type.

The solid solution of the present invention is neither poorly soluble nor easily soluble, and dissolves slowly while maintaining an appropriate concentration of 20 to 200 mg/L (calculated as Ca) (while compensating for absorption by the body). Shows radioactivity. In order for minerals to be absorbed by animals or plants, they must be dissolved in water. However, the solubility of calcium carbonate in water is extremely low at around 6 mg/L. In the present invention, calcium carbonate is dissolved in solid solution with magnesium carbonate or ferrous carbonate, which are relatively easily soluble, and the size of the crystals is controlled to be small by carrying out the carbonation reaction at less than 100°C without hydrothermal treatment. This makes it possible to achieve a solubility in water of 20 mg/L or more, preferably 30 mg/L or more, particularly preferably 50 mg/L to 200 mg/L in terms of Ca.

Furthermore, Mn and Fe, which are easily oxidized and become substantially insoluble in water when oxidized, are stabilized against oxidation by converting them into a solid solution in a divalent state, resulting in good water solubility. can be realized. At least two or more types, preferably seven or more types of minerals are dissolved in water at a composition ratio close to that of a solid solution.

The pH of the solid solution according to the invention is in the range from 7 to less than 12, preferably from 7 to 10, particularly preferably from 7 to 8.5. Therefore, it conforms to the pH standard of 5.8 to 8.6 for drinking water and can be used as a mineral supplement for drinking water.

An example of producing the solid solution of the present invention is to add Na ₂ CO ₃ , NaHCO ₃ , NH ₄ CO ₃ , NH ₄ HCO ₃ or the like to a mixed aqueous solution of water-soluble metal salts of Ca and/or Mg and the divalent metal M. This can be carried out by adding an alkaline carbonate to cause a coprecipitation reaction, followed by filtration, washing with water, and drying. At this time, if desired, the coprecipitated product is hydrothermally treated to enlarge the crystals, so that the pH is neutral to weakly alkaline and the amount of solubility in water is slightly reduced compared to amorphous products. can be obtained. The hydrothermal treatment is preferably carried out by treatment at 100 to 200°C, preferably 100 to 150°C for 1 to 10 hours after washing with water.

As another example of the method for producing the solid solution of the present invention, an alkaline compound such as NaOH, KOH, ammonia, Ca(OH) ₂ or the like is added in place of the alkaline carbonate in the coprecipitation reaction to cause the coprecipitation reaction. The carbonate-based solid solution of the present invention can be produced by producing a hydroxide solid solution, preferably washing the solid solution with water, dispersing it in water, and reacting it with CO ₂ . In this case as well, the same effect as described above can be achieved by further hydrothermally treating the carbonate solid solution.

The amount of the solid solution of the present invention used is 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, particularly preferably 0.02 to 0.2% by weight, based on the animal feed. For plants such as agricultural products, the amount is 0.5 to 20 g, preferably 1 to 10 g, particularly preferably 2 to 4 g per m ² of soil. The spraying time is before or after sowing or planting, and even just before fruiting and during fruiting. It is preferable to take the soil near the roots shallowly and cover the area with soil after spreading. For humans, the amount is 0.1 to 5 g, preferably 0.5 to 3 g, particularly preferably 0.7 to 2 g per day. For mushrooms it is 0.5-5 g per kg of medium.

When the solid solution of the present invention is used in animal feed, extremely small amounts of Mo, Se, Cr(3+) and Co(2+) are physically mixed with the solid solution of the present invention or reacted with the solid solution of the present invention. By doing so, the trace metal can be contained in a solid solution. Mo and Se can be prepared by physically mixing oxyacids or oxyacids of Mo(6+) and Se(6+) such as H ₂ MoO ₄ , Na ₂ MoO ₄ , H ₂ SeO ₄ , Na ₂ SeO ₄ or in an aqueous medium. It can be manufactured by mixing inside. In the case of Cr(3+) and Co(2+), an aqueous solution of water-soluble salts such as chlorides, nitrates, sulfates, etc. is mixed with an aqueous divalent metal ion solution of the carbonate-based solid solution synthesis raw material of the present invention to form an alkaline carbonate. By carrying out a coprecipitation reaction with Cr(3+) and Co(2+), it can be produced as a metal carbonate-based solid solution in which Cr(3+) and Co(2+) are further dissolved.

When the solid solution of the present invention is used for plants such as agricultural products and mushrooms, boron and Mo and Co, which are required in extremely small amounts, are physically mixed with the solid solution of the present invention or mixed in an aqueous medium. These metals can be contained in a solid solution. The boron source can be H ₃ BO ₃ or a borate such as Na ₂ B ₄ O ₇ . It is estimated that when these are mixed with a solid solution in an aqueous medium, boron ions replace carbonate ions. In animal feed, Mo and Co can be added to the solid solution of the present invention in a similar manner.

When intended for humans, the solid solution contains Ca and Mg, and further contains divalent metals such as Zn and/or Fe, and 1 g of the solid solution is added to 100 mL of deionized water and heated at 30°C. The pH of the dispersion obtained by stirring for 5 minutes is in the range of 6.5 to 8.6, and is preferably suitable for human drinking water.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

Mixed aqueous solution of calcium chloride, magnesium chloride, zinc chloride, ferrous chloride, manganese chloride and cupric nitrate (Ca = 0.75 mol/L, Mg = 0.6 mol/L, Zn = 0.06 mol/L) L, Fe = 0.045 mol/L, Mn = 0.03 mol/L, Cu = 0.015 mol/L) 2L, 0.9 mol/L sodium carbonate and 0.3 mol/L carbonate The mixture was added to 3 L of a mixed aqueous solution of sodium hydrogen under stirring, and a coprecipitation reaction was carried out at about 30°C. Thereafter, the cake was filtered and washed with water, and the resulting cake was dispersed in 3 L of water using a stirrer, and heated and aged at 80° C. for 2 hours. This was followed by filtration, drying (approximately 120°C), and grinding.

As a result of XRD measurement of the pulverized material, a diffraction pattern almost the same as that of dolomite was obtained, although it was slightly shifted to the lower angle side, indicating that it is a solid solution with a dolomite-type crystal structure (Figure 1). The pulverized material was dissolved in hydrochloric acid, and elemental analysis was performed by ICP method. The analysis of CO ₂ was performed using the AGK CO ₂ absorption method. As a result, the chemical composition was as follows.
[(Ca) _0.51 (Mg) _0.39 (Zn) _0.04 (Fe) _0.03 (Mn) _0.02 (Cu) _0.01 ] (CO ₃ ) _0.80 (OH) _{0. 40}

To examine the solubility in water and pH, 1 g of the pulverized material was added to 100 mL of deionized water, stirred at 30°C for 5 minutes using a magnetic stirrer, filtered, and the metal ion concentration in the filtrate was determined by ICP. It was measured by the method. The results were Ca=18 mg/L, Mg=9 mg/L, Zn=0.9 mg/L, Fe=0.7 mg/L, Mn=0.3 mg/L, and Cu=0.2 mg/L. pH was 9.3.

Add 0.9 mol/L of carbonic acid to 2 L of a mixed aqueous solution of calcium chloride, magnesium chloride, and zinc chloride (Ca=0.65 mol/L, Mg=0.35 mol/L, Zn=0.05 mol/L). 2 L of aqueous sodium solution was added under stirring, and then 2 L of 0.3 mol/L sodium hydrogen carbonate was added to cause a coprecipitation reaction. The temperature was approximately 25°C. A portion of the reaction product was placed in a 1 L autoclave and subjected to hydrothermal treatment at 120°C for 4 hours, followed by filtration, washing with water, drying (120°C), and pulverization.

The XRD of the pulverized material showed a diffraction pattern similar to that of dolomite, although it was slightly shifted to the higher angle side, indicating that Zn was dissolved in dolomite (FIG. 2). The chemical composition was measured in the same manner as in Example 1, and the results were as follows.
(Ca _0.66 Mg _0.335 Zn _0.05 ) CO ₃

As a result of measuring the amount dissolved in water and the pH using the same method as in Example 1, the respective elution amounts of Ca, Mg, and Zn were 22 mg/L, 9 mg/L, and 0.2 mg/L, and the pH was 7. It was .6.

To 1 L of a mixed aqueous solution of magnesium chloride and zinc chloride (Mg = 0.9 mol/L, Zn = 0.1 mol/L), 800 mL of a 1 mol/L sodium carbonate aqueous solution was added at about 30°C with stirring, followed by 400 mL of a 1.0 mol/L sodium hydrogen carbonate aqueous solution was added to carry out a coprecipitation reaction. A portion of the obtained reaction product was placed in a 1 L autoclave and hydrothermally treated at 120° C. for 4 hours. After that, it was filtered, washed with water, dried (120°C), and pulverized.

The XRD of the pulverized material shows a diffraction pattern that is slightly shifted toward higher angles, but almost the same as that of magnesite, indicating that it is magnesium carbonate containing Zn as a solid solution (Figure 3). The chemical composition was measured in the same manner as in Example 1, and the results were as follows.
(Mg _0.9 Zn _0.1 ) (CO ₃ ) _0.9 (OH) _0.2

As a result of measuring the solubility and pH in the same manner as in Example 1, the eluted amounts of Mg and Zn were Mg = 21 mg/L, Zn = 4.1 mg/L, and the pH was 7.5.

2 mol of calcium hydroxide was placed in a 5 L container, 2 L of water was added, and the mixture was dispersed using a stirrer. Add to this slurry a mixed aqueous solution of magnesium chloride, ferrous sulfate, manganese nitrate, zinc chloride, and cupric nitrate (Mg=0.5 mol/L, Fe=0.13 mol/L, Mn=0.09 mol/ L, Zn = 0.05 mol/L, Cu = 0.016 mol/L) was added under stirring to cause coprecipitation to produce a slurry containing a hydroxide solid solution, and then CO ₂ was added to the slurry from a carbon dioxide gas cylinder. Blowing was continued until the pH dropped to 10. This was followed by filtration, washing with water, drying (120°C), and pulverization.

The XRD of the pulverized material shows a diffraction image similar to that of calcite, although it is slightly shifted to the higher angle side, indicating that it is a calcite-type solid solution (FIG. 4). The chemical composition was measured in the same manner as in Example 1, and the results were as follows.
[(Ca) _0.612 (Mg) _0.25 (Fe) _0.065 (Mn) _0.045 (Zn) _0.02 (Cu) _0.008 ] (CO ₃ ) _0.7 (OH) _{0. 6}

As a result of measuring the dissolution amount and pH of the ground product in water in the same manner as in Example 1, the elution amount was Ca' = 36 mg/L, Mg = 22 mg/L, Fe = 8 mg/L, Mn = 6 mg/L, Zn=3 mg/L, Cu=1 mg/L, and pH was 9.8.
[Comparative example 1]

Regarding the crushed product of limestone (calcium carbonate, calcite type structure), the amount dissolved in water and the pH were measured in the same manner as in Example 1. As a result, the amount of elution Ca = 6 mg/L, and the pH was 9.6. Ta.
[Comparative example 2]

Regarding the pulverized dolomite, the amount dissolved in water and the pH were measured in the same manner as in Example 1, and the results were that eluted Ca = 7 mg/L, Mg = 5 mg/L, and pH = 9.3.
[Comparative example 3]

In Example 4, the amount dissolved in water and the pH of the powder obtained by filtering the obtained hydroxide, washing with water, drying (120°C), and pulverizing were measured, and the result was that the dissolved amount Ca = 220 mg/ L, Mg=6m, Fe=0.2mg/L, Mn=0.2mg/L, Zn=0.1mg/L, Cu=0.1mg/L, and pH=12.3.

The metal carbonate solid solution synthesized in Example 1 was mixed with commercially available feed (per 1 kg, corn: 580 g, soybean meal meal: 335 g, corn oil: 47 g, DL-methionine: 1.4 g, CaHPO ₄ : 20 g, CaCO ₃ : 6.6 g, NaCl: 5.0 g, mineral/vitamin mixture: 5.0 g) at a rate of 0.05% to make feed. The mineral/vitamin material contained minerals, Mg = 120 g, Fe = 16 g, Mn = 12 g, Zn = 8 g, Cu = 1.6 g, and I (iodine) = 0.07 g per 1 kg. The feed was administered to 18,000 120-day-old chickens for 60 days. As a control, chickens fed a feed supplemented with 0.05% of a commercially available mineral/vitamin mixture instead of the metal carbonate solid solution synthesized in Example 1 were used as a control, and the mortality rate, feed intake, and egg production after 60 days were evaluated. I checked the taste. As a result, mortality rate decreased from 0.3% to 0.06%, feed consumption decreased from 110g per day to 105g per bird, and the taste of eggs greatly improved.

To the slurry of the metal carbonate solid solution of the present invention synthesized by the method of Example 4 before drying, 70 g and 1 g of boric acid and sodium molybdate, respectively, calculated as 1 kg of the dry solid solution, were added under stirring and mixed for about 30 minutes. After that, it was filtered, dried and ground.

For every 40 ^m2 of farmland where the crushed product was sprayed together with base fertilizer (nitrogen, phosphorus, and potassium at 4, 8, and 6 kg per 10 ares) at a rate of 3 g per ¹ m2, radish (Spring Capital), potato (Baron), Eggplant (grafted seedlings) and corn (sweet corn) were planted, and yields were measured using 40 m ² of adjacent farmland, which was not sprayed with pulverized material, as a control plot. The results are shown in Table 1.

Claims (9)

The following formula (1)

(In the formula, M represents at least one divalent metal selected from Mn, Fe, Co, Cu, and Zn, and x and y are in the following ranges, 0<x<0.4, 0.01<y, respectively. A mineral replenisher containing a divalent metal carbonate solid solution represented by a positive number satisfying ≦1. The mineral supplement according to claim 1, wherein the solid solution contains Ca and Mg. The mineral supplement according to claim 1 or 2, wherein the solid solution contains divalent metals such as Mn, Fe, Cu, and Zn as M in formula (1). The mineral supplement according to any one of claims 1 to 3, wherein in formula (1) of claim 1, x and y are in the range of 0.02≦x≦0.3 and 0.5≦y≦1, respectively. agent. The mineral supplement according to any one of claims 1 to 4, which has a dissolved amount in water of 20 mg/L or more in terms of Ca. The solid solution contains all divalent metals of Ca, Mg, Mn, Fe, Cu, and Zn, and adsorbs boron and molybdenum oxyacids and/or oxyacids, and is for plants. The mineral supplement according to any one of Items 1 to 5. The solid solution contains all divalent metals of Ca, Mg, Mn, Fe, Cu, and Zn and trivalent Cr, and adsorbs selenium and molybdenum oxyacid and/or oxyacid, The mineral supplement according to any one of claims 1 to 5, which is for animals. The solid solution contains Ca and Mg, and further contains divalent metals such as Zn and/or Fe, and is obtained by adding 1 g of the pulverized solid solution to 100 mL of deionized water and stirring at 30 ° C. for 5 minutes. The mineral supplement according to any one of claims 1 to 5, wherein the dispersion has a pH in the range of 6.5 to 8.6 and is suitable for human drinking water. The following formula (2)

(However, in the formula, M represents at least one divalent metal selected from Mn, Fe, Co, Cu, and Zn, and x and y are in the following ranges 0<x<0.4, 0.01< A divalent metal carbonate solid solution represented by a positive number satisfying y≦1.

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