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JP2012039955A - Method for removing heavy metal in fish sauce - Google Patents

Method for removing heavy metal in fish sauce Download PDF

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JP2012039955A
JP2012039955A JP2010184585A JP2010184585A JP2012039955A JP 2012039955 A JP2012039955 A JP 2012039955A JP 2010184585 A JP2010184585 A JP 2010184585A JP 2010184585 A JP2010184585 A JP 2010184585A JP 2012039955 A JP2012039955 A JP 2012039955A
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heavy metals
soy sauce
fish soy
fish sauce
fish
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JP5386694B2 (en
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Tetsuya Sasaki
哲也 笹木
Shunei Michihata
俊英 道畠
Shizuo Nakamura
靜夫 中村
Toshiki Enomoto
俊樹 榎本
Toshiko Kurumada
寿子 車多
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SHATA SHUZO KK
Ishikawa Prefecture
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SHATA SHUZO KK
Ishikawa Prefecture
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Abstract

PROBLEM TO BE SOLVED: To solve the problem of a method for removing solid matters including heavy metals by adding tannin or a food additive containing tannin to a fish sauce, wherein liberated heavy metals can not be removed because the target of removal is heavy metals bound with protein only, and problems of a method for removal by eluding heavy metals in an acid treatment solution, wherein the taste is changed and therefore, the sauce can not be used in the state as a seasoning because it is necessary to treat the heavy metals in the solution at a low pH of 3-3.5 to increase the efficiency in removing the heavy metals and protein in the fish sauce is solubilized and eluded when treated in the solution at such a low pH.SOLUTION: Heavy metals are removed from the fish sauce without affecting the oxidation-reduction potential of the fish sauce and without impairing useful components such as flavor components in the fish sauce by adding a food additive filtration auxiliary agent to the fish sauce, separating the solid and liquid, and feeding the fish sauce into a column filled with a heavy metal adsorbent.

Description

本発明は魚醤油中に含まれる重金属類を除去し、魚醤油の安全性を高めかつ魚醤油の特徴(旨味等の有用成分)を損なうことのない食品とすることができる魚醤油の重金属除去方法に関する。   The present invention removes heavy metals contained in fish soy sauce, enhances the safety of fish soy sauce, and removes heavy metals from fish soy sauce that can be used as a food that does not impair the characteristics of fish soy sauce (useful ingredients such as umami). Regarding the method.

イワシ、イカ等の魚介類の内蔵等を利用する魚醤油中には重金属類が多量に含有されていることがある。
しかし、今日まで生産地域住民の食習慣として、恒常的に斯かる魚醤油を摂取してきたものであるが、特定疾患(イタイタイ病のような公害)の発症例は今までのところ報告されていない。
Fish soy sauce that uses built-in fish and shellfish such as sardines and squid may contain a large amount of heavy metals.
However, until now, as a habit of local residents in production areas, such fish soy sauce has been ingested constantly, but there have been no reports of cases of specific diseases (pollution such as Itai Thai disease). .

このような理由で、従来から魚醤油は重金属の除去処理が施されることなく商品化されているのが実情である。
しかしながら、魚醤油の有用成分の活用、調味料としての全国展開・海外輸出など消費拡大を目指すに際し、食の安全・安心の観点から重金属の含有が問題となり、その除去処理が必要となってくると予想される。
For these reasons, fish soy sauce has been commercialized without being subjected to heavy metal removal treatment.
However, when aiming to expand consumption, such as the use of useful ingredients in fish soy sauce, nationwide expansion as a seasoning, and overseas exports, the inclusion of heavy metals becomes a problem from the viewpoint of food safety and security, and its removal treatment is required It is expected to be.

魚醤油等の水産加工品から重金属類を除去することに着目した先行技術文献は1つ開示されている。特許文献1は、魚醤油にタンニン又はタンニンを含む食品添加物を添加し、重金属を含む固形物を除去する方法であり、うまみ成分等の有用成分が損なわれることがなく、食品加工用途が可能などの利点がある。
また、水産加工品自体ではないが、帆立貝やイカ等の内臓残渣を廃棄処分することなく有効利用するために、内臓残渣からの重金属の除去方法が開示されている。特許文献2には、蟻酸、乳酸、酢酸等の有機酸や、塩酸、硫酸、リン酸等の鉱酸を用いてpH3〜3.5の弱酸性とし、更に蛋白質分解酵素の作用によって重金属と結合した蛋白質を分解して重金属を蛋白質から解離させて重金属を酸処理液中に溶出させ、溶出した水溶液中の重金属類をキレート剤等によって分離する方法が記載されている。
One prior art document focusing on removing heavy metals from fishery processed products such as fish soy sauce is disclosed. Patent Document 1 is a method of adding tannin or food additives containing tannin to fish soy sauce and removing solids containing heavy metals, and useful ingredients such as umami ingredients are not impaired, and food processing applications are possible. There are advantages such as.
In addition, a method for removing heavy metals from visceral residues has been disclosed in order to effectively use visceral residues such as scallops and squids without being disposed of, although they are not processed fish products themselves. In Patent Document 2, it is weakly acidic at pH 3 to 3.5 using organic acids such as formic acid, lactic acid and acetic acid, and mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and further binds to heavy metals by the action of proteolytic enzymes. A method is described in which a heavy protein is dissociated from a protein by decomposing the produced protein, the heavy metal is eluted in an acid treatment solution, and the heavy metal in the eluted aqueous solution is separated by a chelating agent or the like.

特開2009−254274号公報JP 2009-254274 A 特開2001−137810 号公報JP 2001-137810 A

魚醤油にタンニン又はタンニンを含む食品添加物を添加し、重金属を含む固形物を除去する特許文献1の方法は、タンパク質に結合した重金属のみを除去対象としており、遊離した重金属は除去できない課題がある。   The method of patent document 1 which adds the food additive containing a tannin or a tannin to fish soy sauce, and removes the solid substance containing a heavy metal makes only the heavy metal couple | bonded with the protein removal object, and the subject which cannot remove the free heavy metal has the subject. is there.

重金属を酸処理液中に溶出させる特許文献2の方法では、重金属類の除去効率を高めるためにpH3〜3.5という低pHで処理することが必要となり、低pHで処理すると魚醤油中の蛋白質が可溶化して溶出し、味が変化するためそのまま調味料として使用できない。
すなわち、溶出しないで残存した蛋白質においても酵素活性が低下するため、水産エキスとしての利用は可能であっても、魚醤油のような発酵食品自体に対して利用すると、商品の品質低下を来たすという問題がある。
In the method of Patent Document 2 in which heavy metals are eluted in the acid treatment solution, it is necessary to treat at a low pH of 3 to 3.5 in order to increase the removal efficiency of heavy metals. The protein is solubilized and eluted, and the taste changes, so it cannot be used as a seasoning as it is.
In other words, since the enzyme activity decreases even in proteins that remain without elution, it can be used as a marine extract, but if used for fermented foods such as fish soy sauce, the quality of the product is reduced. There's a problem.

上記課題を解決するため、魚醤油に食品添加物のろ過助剤を添加、固液分離すること及び、重金属吸着剤を充填したカラムに魚醤油を通液させることで、魚醤油の酸化還元電位に影響されず、魚醤油のうまみ成分等の有用成分が損なわれることなく、魚醤油から重金属を除去するものである。   In order to solve the above-mentioned problems, the redox potential of fish soy sauce can be obtained by adding a filter additive for food additives to fish soy sauce, solid-liquid separation, and passing the fish soy sauce through a column filled with heavy metal adsorbent. It removes heavy metals from fish soy without being damaged by useful components such as umami components of fish soy.

魚醤油中の重金属は、魚醤油の酸化還元電位によりタンパク質との結合状態が決まる。
魚醤油の酸化還元電位を計測することによりろ過助剤を添加する方法、あるいは重金属除去剤を用いる方法の何れかを重点的に用いるようにすれば良く、両方の方法を組み合わせることにより魚醤油の酸化還元電位に拘わらず確実に魚醤中の重金属を除去することができる。
Heavy metals in fish soy sauce are bound to proteins by the redox potential of fish soy sauce.
Either the method of adding a filter aid by measuring the oxidation-reduction potential of fish soy or the method of using a heavy metal removing agent may be used intensively. By combining both methods, Heavy metals in fish sauce can be reliably removed regardless of the redox potential.

本発明方法によって魚醤油を処理すると、魚醤中のタンパク質に物理的・化学的吸着している重金属については食品添加物のろ過助剤を添加、固液分離することにより、また、タンパク質から遊離している重金属については重金属除去剤を用いて遊離している重金属をも除去することができ、魚醤油中の重金属類を効率よく所定濃度以下に低減化することができると共に、重金属類を除去した後の魚醤油は旨味を示すアミノ酸を損なうことなく品質を維持し、より安全性を高めた魚醤油として商品化することができる効果を有する。   When the fish soy sauce is treated by the method of the present invention, the heavy metal physically and chemically adsorbed to the protein in the fish sauce is added with a food additive filter aid and separated from the protein by solid-liquid separation. As for heavy metals that are used, heavy metals can be removed using a heavy metal remover, and heavy metals in fish soy sauce can be efficiently reduced to a predetermined concentration or less, and heavy metals can be removed. After the fish soy sauce has been obtained, the quality of the fish soy sauce is maintained without impairing the amino acid exhibiting umami, and it has the effect that it can be commercialized as a fish soy sauce with improved safety.

また、より安全性を高めた魚醤油としての調味料のみならず、これを原料に利用したサプリメント等への広範囲な利用が期待できる効果も有する。
そして、本発明方法は、pHを調整する必要もない等の処理条件が少ない簡易な処理方法となり、食品添加物を利用するため製品の安全性にも問題がなく、本方法の利用促進が図れる効果を有する。
Moreover, it has the effect that it can be expected to be used not only for seasoning as fish soy sauce with higher safety, but also for supplements using this as a raw material.
The method of the present invention is a simple processing method with few processing conditions such as no need to adjust the pH, and there is no problem in product safety because of the use of food additives, and the use of this method can be promoted. Has an effect.

本発明方法は、魚醤油をろ過助剤と混合させて処理した後、固形物を分離し、タンパク質と結合した重金属を除去する方法と、重金属吸着剤を充填したカラムに魚醤油を通液させる、もしくは重金属除去剤を魚醤油に添加して固液分離することで遊離した重金属を除去する方法を組み合わせて、魚醤油の酸化還元電位に影響されず処理するものである。   In the method of the present invention, after processing fish soy sauce with a filter aid, solids are separated and heavy metals bound to proteins are removed, and fish soy sauce is passed through a column filled with a heavy metal adsorbent. Alternatively, a combination of a method for removing heavy metals released by adding a heavy metal removing agent to fish soy sauce and performing solid-liquid separation, and processing is performed without being affected by the redox potential of fish soy sauce.

魚醤油中の重金属は、魚醤油の酸化還元電位によりタンパク質との結合状態が決まる。還元状態(例えば、酸化還元電位−100mV以下)の魚醤油では、重金属はタンパク質に結合しているものが多く存在し、酸化状態(例えば、−20mV以上)の魚醤油では、重金属は遊離しているものが多く存在する。   Heavy metals in fish soy sauce are bound to proteins by the redox potential of fish soy sauce. In fish soy sauce in a reduced state (for example, redox potential −100 mV or less), many heavy metals are bound to proteins, and in fish soy sauce in an oxidized state (for example, −20 mV or more), heavy metals are released. There are many things that exist.

魚醤油の酸化還元電位を計測することによりろ過助剤を添加する方法、あるいは重金属除去剤を用いる方法の何れかを重点的に用いるようにすれば良く、両方の方法を組み合わせることにより魚醤油の酸化還元電位に拘わらず確実に魚醤中の重金属を除去することができる。
酸化還元電位の調整は製造時の嫌気発酵、製造後の空気バブリングによる酸化、食品添加物の還元剤や酸化剤の添加などがある。
Either the method of adding a filter aid by measuring the oxidation-reduction potential of fish soy or the method of using a heavy metal removing agent may be used intensively. By combining both methods, Heavy metals in fish sauce can be reliably removed regardless of the redox potential.
Adjustment of the oxidation-reduction potential includes anaerobic fermentation at the time of production, oxidation by air bubbling after production, addition of a reducing agent or an oxidizing agent for food additives.

本発明方法において、ろ過助剤、および重金属除去剤は、食品への使用が許可をされており、調味料としての呈味性を損なうことのないものが望ましい。   In the method of the present invention, it is desirable that the filter aid and the heavy metal removing agent are permitted to be used in foods and do not impair the taste as a seasoning.

酸化還元電位が−40mVの魚醤油10mLに、5.0%タンニン水溶液を1mL加え、撹拌した後、遠心分離(8000rpm、15分)で固液分離した。このタンニン処理液を、キレート樹脂1mLを充填したガラス管に流速5mL/hで通液し、1時間毎に5mLずつ採取した。
原液、タンニン処理液および通液処理した魚醤油のCd濃度を表1に全窒素、遊離アミノ酸量、乳酸量、抗酸化性を表2示す。
Cd除去率は、処理前後のCd濃度から算出した。
1 mL of a 5.0% tannin aqueous solution was added to 10 mL of fish soy sauce with a redox potential of −40 mV, and the mixture was stirred and then solid-liquid separated by centrifugation (8000 rpm, 15 minutes). This tannin treatment solution was passed through a glass tube filled with 1 mL of a chelating resin at a flow rate of 5 mL / h, and 5 mL was collected every hour.
Table 1 shows the total nitrogen, free amino acid content, lactic acid content, and antioxidant properties of the Cd concentrations of the stock solution, the tannin treatment solution, and the fish soy sauce that had been passed through.
The Cd removal rate was calculated from the Cd concentration before and after the treatment.

Figure 2012039955
Figure 2012039955

Figure 2012039955
Figure 2012039955

魚醤油100mLを空気で数時間バブリングし、酸化還元電位−20mV以上になるまで酸化させた。
キレート樹脂1mLを充填したカラム管に、バブリングした魚醤油を流速5mL/hで通液した。
原液および通液処理した魚醤油のCd濃度を表3に全窒素、遊離アミノ酸量、乳酸量、抗酸化性を表4示す。
Cd除去率は、処理前後のCd濃度から算出した。
100 mL of fish soy sauce was bubbled with air for several hours and oxidized until the oxidation-reduction potential was −20 mV or higher.
Bubbled fish soy sauce was passed through a column tube filled with 1 mL of chelating resin at a flow rate of 5 mL / h.
Table 3 shows the total nitrogen, free amino acid content, lactic acid content, and antioxidant properties of the Cd concentrations of the stock solution and the fish soy sauce that had been passed through.
The Cd removal rate was calculated from the Cd concentration before and after the treatment.

Figure 2012039955
Figure 2012039955

Figure 2012039955
Figure 2012039955

Claims (2)

魚醤油に食品添加物のろ過助剤を添加、固液分離すること及び、重金属吸着剤を充填したカラムに魚醤油を通液させることで、魚醤油の酸化還元電位に影響されず、魚醤油のうまみ成分等の有用成分が損なわれることなく、魚醤油中の重金属を除去する方法。   Fish soy sauce is not affected by the redox potential of fish soy sauce by adding a food additive filter aid to fish soy sauce, solid-liquid separation, and passing fish soy sauce through a column filled with heavy metal adsorbent. A method of removing heavy metals in fish soy without damaging useful components such as umami components. 重金属吸着剤を充填したカラムに魚醤油を通液させることに代えて、重金属除去剤を魚醤油に添加し、固液分離する請求項1記載の魚醤油中の重金属を除去する方法。   The method for removing heavy metals in fish soy sauce according to claim 1, wherein a heavy metal removing agent is added to fish soy sauce and solid-liquid separated instead of passing the fish soy sauce through a column filled with a heavy metal adsorbent.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023042821A1 (en) * 2021-09-14 2023-03-23 キッコーマン株式会社 Soy sauce rich in organic acid

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JPH06106155A (en) * 1992-09-09 1994-04-19 Mutsumi Shoji Removal of heavy metals from amino acid solution of fishes and shellfishes
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JP2007282572A (en) * 2006-04-17 2007-11-01 Hokkaido Univ Method for removing heavy metal from organic substance containing heavy metal, and method for producing food obtained by the same
JP2009254274A (en) * 2008-04-16 2009-11-05 Ishikawa Pref Gov Method of removing heavy metals from fish sauce
JP2010057442A (en) * 2008-09-05 2010-03-18 Hokkaido Univ Method for removing heavy metal from fish and shellfish containing harmful heavy metal in short time, and manufacturing method of foodstuff obtained by the same

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* Cited by examiner, † Cited by third party
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JPH06106155A (en) * 1992-09-09 1994-04-19 Mutsumi Shoji Removal of heavy metals from amino acid solution of fishes and shellfishes
JP2001137810A (en) * 1999-11-10 2001-05-22 Kawabe Concrete Kk Method for removing heavy metal from unutilized organic resource containing hazardous heavy metal
JP2007282572A (en) * 2006-04-17 2007-11-01 Hokkaido Univ Method for removing heavy metal from organic substance containing heavy metal, and method for producing food obtained by the same
JP2009254274A (en) * 2008-04-16 2009-11-05 Ishikawa Pref Gov Method of removing heavy metals from fish sauce
JP2010057442A (en) * 2008-09-05 2010-03-18 Hokkaido Univ Method for removing heavy metal from fish and shellfish containing harmful heavy metal in short time, and manufacturing method of foodstuff obtained by the same

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JPN6013015418; 日本食品科学工学会第55回大会講演集, 2008年, 128ページ *
JPN6013015420; 日本農芸化学会大会講演要旨集, 2009年, 第2009巻, 56ページ *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023042821A1 (en) * 2021-09-14 2023-03-23 キッコーマン株式会社 Soy sauce rich in organic acid

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