JP6459495B2 - How to determine the sea area of wakame - Google Patents
How to determine the sea area of wakame Download PDFInfo
- Publication number
- JP6459495B2 JP6459495B2 JP2014259686A JP2014259686A JP6459495B2 JP 6459495 B2 JP6459495 B2 JP 6459495B2 JP 2014259686 A JP2014259686 A JP 2014259686A JP 2014259686 A JP2014259686 A JP 2014259686A JP 6459495 B2 JP6459495 B2 JP 6459495B2
- Authority
- JP
- Japan
- Prior art keywords
- wakame
- seaweed
- log
- discriminant
- sea area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 241001261506 Undaria pinnatifida Species 0.000 title claims description 177
- 241001474374 Blennius Species 0.000 claims description 130
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 58
- 239000011777 magnesium Substances 0.000 claims description 55
- 239000011575 calcium Substances 0.000 claims description 51
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 49
- 229910052788 barium Inorganic materials 0.000 claims description 48
- 229910052793 cadmium Inorganic materials 0.000 claims description 47
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 47
- 229910052785 arsenic Inorganic materials 0.000 claims description 44
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 44
- 239000011701 zinc Substances 0.000 claims description 39
- 229910052720 vanadium Inorganic materials 0.000 claims description 37
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 36
- 229910052749 magnesium Inorganic materials 0.000 claims description 36
- 229910052701 rubidium Inorganic materials 0.000 claims description 36
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 34
- 239000011574 phosphorus Substances 0.000 claims description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims description 34
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 32
- 229910052791 calcium Inorganic materials 0.000 claims description 32
- 229910052712 strontium Inorganic materials 0.000 claims description 31
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 31
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims 3
- 238000004458 analytical method Methods 0.000 description 42
- 241000195493 Cryptophyta Species 0.000 description 32
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 11
- 238000012790 confirmation Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000000491 multivariate analysis Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 244000048199 Hibiscus mutabilis Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000012850 discrimination method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 238000012886 linear function Methods 0.000 description 2
- 238000003947 neutron activation analysis Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 241000173735 Undaria peterseniana Species 0.000 description 1
- 241001641748 Undaria undarioides Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007621 cluster analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000513 principal component analysis Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Description
本発明は、ワカメに含まれる元素量を用いたワカメの生育海域を判別する方法に関する。 The present invention relates to a method for discriminating a growing sea area of seaweed using the amount of elements contained in seaweed.
従来、日本国内で流通している湯通し塩蔵ワカメ、乾燥ワカメなどのワカメ加工品は、主に日本国内(三陸、瀬戸内など)、中国(大連、山東など)、韓国(莞島、釜山、機張など)などの海域で生育した原藻ワカメを原料としている。そして日本国内で流通しているワカメ加工品は、原料となる原藻ワカメの原産地名を記載することが義務付けられている。 Traditionally, seafood processed products such as boiled salted wakame and dried wakame that are distributed in Japan are mainly in Japan (Sanriku, Setouchi, etc.), China (Dalian, Shandong, etc.), South Korea (Yeouido, Busan, Gijang) The raw algae wakame grown in the sea area. And for processed wakame products distributed in Japan, it is obliged to describe the place of origin of the raw seaweed wakame as a raw material.
原藻ワカメの原産地(生育海域)の確認は、原藻ワカメの収穫者、ワカメ加工者などが取引する際に生じる帳票による確認、漁協などが発行する産地証明書による確認、などによって行われているが、その確認方法として、科学的手法によりワカメの生育海域を判別する方法も求められている。 Confirmation of the origin (growing area) of the original algae wakame is done by checking the forms generated when the original algae wakame harvester, wakame processor, etc. trades, or by the confirmation of the place of origin issued by the fishery cooperative. However, as a method for confirming this, a method for discriminating the sea area where wakame is growing by a scientific method is also required.
原藻ワカメの原産地(生育海域)を判別する従来技術としては、ワカメに含まれる特定元素の安定同位体比を測定する方法、ワカメに含まれる特定元素の量を分析する方法、あるいは上記の方法を組合わせなどによる方法などが開示されている。 Conventional techniques for discriminating the origin (growing sea area) of the original alga wakame include a method for measuring the stable isotope ratio of the specific element contained in the seaweed, a method for analyzing the amount of the specific element contained in the wakame, or the above method A method based on a combination of the above is disclosed.
上記方法の中で、ワカメに含まれる特定元素の量を分析することによる原藻ワカメの原産地(生育海域)を判別する方法としては、(1)原藻生ワカメに含まれるアルミニウム、リン、マンガン、鉄およびバリウムの5元素、または原料用湯通し塩蔵ワカメに含まれるマグネシウム、アルミニウム、リン、カリウム、カルシウム、マンガン、鉄、ストロンチウムおよびバリウムの9元素、の量の違いにより日本産であるか中国産であるかの判別方法(非特許文献1)、(2)湯通し塩蔵ワカメに含まれるアルミニウム、リン、マンガン、鉄およびバリウムの5元素の量の違いにより日本産であるか中国産であるかの判別方法(非特許文献2)、(3)湯通し塩蔵わかめに含まれるルビジウム、イットリウム、カドミウム、バリウムおよびネオジムの量の違いにより三陸、鳴門、中国および韓国のいずれかを判別方法(非特許文献3)、(4)湯通し塩蔵ワカメに含まれるマンガンおよびバリウムの量の違いにより日本産であるか中国産であるかの判別方法(非特許文献4)などが開示されている。 Among the above methods, as a method of discriminating the origin (growing area) of the original alga seaweed by analyzing the amount of the specific element contained in the seaweed, (1) aluminum, phosphorus, manganese contained in the raw seaweed raw seaweed , Japan and China depending on the amount of 5 elements of iron and barium, or 9 elements of magnesium, aluminum, phosphorus, potassium, calcium, manganese, iron, strontium and barium contained in the boiled salted seaweed for raw materials (2) Whether it is made in Japan or in China depending on the amount of aluminum, phosphorus, manganese, iron and barium contained in the boiled salted seaweed Discrimination method (Non-patent Document 2), (3) Rubidium, yttrium, cadmium, barium and neo contained in boiled salted seaweed A method for distinguishing between Sanriku, Naruto, China and Korea depending on the amount of mud (Non-patent Document 3), (4) Is it made in Japan or in China depending on the amount of manganese and barium contained in the boiled salted seaweed? (Non-Patent Document 4) and the like are disclosed.
しかし、上記(1)(2)(4)の方法では、ワカメの生育海域が日本であるか中国であるかを判別できるが、日本の三陸または瀬戸内であるか、また韓国産であるかの判別はできないという問題点がある。また、上記(3)では、4原産地を判別することができるものの、ワカメの形態が湯通し塩蔵ワカメのみであるという問題点があり、さらにより良いワカメの生育海域を判別する方法が求められている。 However, with the methods (1), (2) and (4) above, it is possible to determine whether the sea area where the seaweed grows is Japan or China, but whether it is Japan's Sanriku or Setouchi, or whether it is from Korea There is a problem that it cannot be distinguished. In the above (3), although the four origins can be discriminated, there is a problem that the form of the seaweed is only a boiled salted seaweed, and there is a demand for a method for discriminating a better growing sea area of seaweed. .
本発明の目的は、ワカメに含まれる元素量の分析情報を用いて、ワカメの生育海域を判別する方法を提供することである。詳しくは、ワカメに含まれる元素量の分析情報を用いて、ワカメの生育海域が、三陸、瀬戸内、中国、韓国のいずれかであるかを判別する方法を提供することである。 The objective of this invention is providing the method of discriminating the growth sea area of a seaweed using the analysis information of the element amount contained in a seaweed. Specifically, it is to provide a method for discriminating whether the sea area where the seaweed is growing is Sanriku, Setouchi, China, or Korea using the analysis information of the amount of elements contained in the seaweed.
本発明者らは、上記課題を解決する為に鋭意研究を重ねた結果、ワカメに含まれる少なくともヒ素、カドミウム、バリウムの元素量の分析情報を用いることにより、上記課題を解決することを見出した。本発明者らは、これらの知見に基づきさらに研究を重ね、本発明を完成するに至った。
すなわち、本発明は、以下の構成からなっている。
[1]ワカメに含まれるヒ素、カドミウム、バリウムの元素量を分析し、それらの分析情報を用いてワカメの生育海域を判別する方法。
[2]さらに、ワカメに含まれるマグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素から選択される1種以上の元素量を分析し、それらの分析情報を用いてワカメの生育海域を判別することを特徴とする上記[1]に記載の方法。
[3]ワカメの形態が原藻ワカメであって、さらにマグネシウム、バナジウム、亜鉛、ルビジウム、ストロンチウムの元素量を分析し、分析情報を用いてワカメの生育海域を判別することを特徴とする上記[1]に記載の方法。
[4]ワカメの形態が湯通し塩蔵ワカメであって、さらにマグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素量を分析し、分析情報を用いてワカメの生育海域を判別することを特徴とする上記[1]に記載の方法。
[5]ワカメの形態が乾燥ワカメであって、さらにマグネシウム、リン、カルシウム、バナジウム、マンガン、ルビジウムの元素量を分析し、分析情報を用いてワカメの生育海域を判別することを特徴とする上記[1]に記載の方法。
[6]ワカメの生育海域が、三陸、瀬戸内、中国、韓国のいずれかであるかを判別することを特徴とする上記[1]〜[5]のいずれかに記載の方法。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using analysis information of element amounts of at least arsenic, cadmium and barium contained in seaweed. . The present inventors have further studied based on these findings and have completed the present invention.
That is, the present invention has the following configuration.
[1] A method of analyzing the amount of elements of arsenic, cadmium and barium contained in wakame and discriminating the growing sea area of wakame using those analysis information.
[2] Further, the amount of one or more elements selected from the elements of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, and strontium contained in the seaweed is analyzed, and the wakame is analyzed using the analysis information. The method according to [1] above, wherein the growing sea area is discriminated.
[3] The wakame is a proto-algae wakame, and further analyzes the elemental amounts of magnesium, vanadium, zinc, rubidium, and strontium, and uses the analysis information to determine the sea area where the wakame grows. 1].
[4] Wakame is a boiled salted wakame, and further analyzes the elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, and strontium, and uses the analysis information to determine the sea area of wakame The method according to [1] above, wherein:
[5] The form of wakame is dried wakame, and further, elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, and rubidium are analyzed, and the growing sea area of wakame is discriminated using the analysis information The method according to [1].
[6] The method according to any one of [1] to [5] above, wherein it is determined whether the sea area where the seaweed is grown is Sanriku, Setouchi, China, or Korea.
ワカメに含まれるヒ素、カドミウム、バリウムの元素量を分析し、それらの分析情報を用いることによりワカメの生育海域、特に三陸、瀬戸内、中国、韓国のいずれかであるかを判別することができる。また、ワカメが原藻ワカメ、さらに原藻ワカメに各種処理を施したワカメ加工品などの各形態のワカメであっても、各形態のワカメに含まれる上記3元素の分析情報を用いることによりワカメの生育海域を判別することができる。さらに、ワカメに含まれる上記3元素に加え、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素から選択される1種以上の元素量を分析し、それらの分析情報を用いることによりワカメの生育海域を精度よく判別することができる。 By analyzing the amount of arsenic, cadmium, and barium contained in the seaweed and using the analysis information, it is possible to determine whether the seaweed is in the sea area, especially Sanriku, Setouchi, China, or Korea. Moreover, even if the wakame is a wakame of various forms such as a raw algae wakame and a wakame processed product obtained by applying various treatments to the original algae wakame, the wakame can be obtained by using the analysis information of the above three elements contained in the wakame of each form. The growing sea area can be determined. Furthermore, in addition to the above three elements contained in seaweed, the amount of one or more elements selected from the elements of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, and strontium is analyzed, and analysis information thereof is obtained. By using it, it is possible to accurately determine the sea area where the seaweed grows.
本発明でいうワカメとは、ワカメが生育する海域から収穫した原藻ワカメ、さらに原藻ワカメに各種処理を施して得たワカメ加工品などの各形態のワカメを意味する。 The wakame used in the present invention means wakame of various forms such as a raw algae wakame harvested from the sea area where the wakame grows, and a processed wakame product obtained by subjecting the raw algae wakame to various treatments.
上記原藻ワカメの品種としては、コンブ目チガイソ科ワカメ属に属するものが挙げられ、その種類としてはワカメ(Undaria pinnatifida)、ヒロメ(U.undarioides)、アオワカメ(U.peterseniana)などである。一般市場では、味わいが良好である点で、ワカメ(Undaria pinnatifida)が好ましく用いられている。 Examples of the varieties of the original algae wakame include those belonging to the genus Wakame of the order of the Coleoptera, and the types thereof include wakame (Undaria pinnatifida), hirome (U.undarioides), Aowakame (U. peterseniana) and the like. In the general market, wakame (Undaria pinnatifida) is preferably used because it has a good taste.
原藻ワカメは、自生または養殖場などで生産されたものが挙げられる。原藻ワカメの生育海域としては特に制限はないが、主な生育海域としては、例えば、日本(三陸、瀬戸内など)、中国、韓国などの沿岸が挙げられる。 Examples of the raw algae wakame include those grown on their own or in farms. Although there is no restriction | limiting in particular as a growth sea area of the original algae seaweed, As a main growth sea area, coasts, such as Japan (Sanriku, Setouchi, etc.), China, and Korea, are mentioned, for example.
原藻ワカメに施す各種処理としては、従来公知の処理であれば特に制限はなく、例えば、湯通し、冷蔵、冷凍、塩蔵、乾燥などの各処理およびその組合わせなどが挙げられる。
本発明でいうワカメ加工品とは、原藻ワカメに各種処理を施したものであれば特に限定するものではないが、例えば、原藻ワカメを加温した海水などでボイルし、さらに冷蔵または冷凍した湯通し冷蔵・冷凍ワカメ、湯通しワカメに食塩を添加して脱水した湯通し塩蔵ワカメ、湯通しワカメに食塩を添加して脱水し、水洗いをして脱塩などの処理をした後に乾燥処理した乾燥ワカメなどの各形態のワカメが挙げられる。
Various treatments applied to the raw alga seaweed are not particularly limited as long as they are conventionally known treatments. Examples thereof include boiled water, refrigeration, freezing, salt storage, drying, and combinations thereof.
The wakame processed product as used in the present invention is not particularly limited as long as the raw algae wakame has been subjected to various treatments. For example, the raw algae wakame is boiled with warmed seawater and further refrigerated or frozen. Boiled chilled / frozen seaweed, salted seaweed wakame that has been dehydrated by adding salt to watered seaweed, dried wakame that has been dehydrated by adding salt to watered seaweed, dehydrated, washed with water, desalted, etc. The wakame of each form is mentioned.
本発明のワカメの生育海域を判別する方法は、ワカメに含まれるヒ素、カドミウム、バリウムの元素量、より好ましくは前記3元素量と、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素から選択される1種以上の元素量を分析し、それらの分析情報を用いてワカメの生育海域を判別するものであればよく、その判別する方法に特に制限はない。 The method for discriminating the growing sea area of the seaweed of the present invention is based on the amounts of arsenic, cadmium and barium contained in the seaweed, more preferably the three elements, and magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc and rubidium. Any method may be used as long as it analyzes the amount of one or more elements selected from the elements of strontium and discriminates the sea area where the seaweed grows using the analysis information.
本発明で判別するワカメの生育海域は、原藻ワカメの主要な生育海域である三陸(岩手県沿岸:普代、広田、小友など、宮城県沿岸:歌津、塩釜など)、瀬戸内(徳島県沿岸:北灘、北泊、鳴門町など、兵庫県沿岸:南あわじ、浅野浦など)、中国(渤海湾の海域:遼寧省大連、山東省煙台、山東省威海など)、韓国(西南部の全羅南道海域:莞島郡、珍島郡、長興郡、高興郡など、南東部の慶尚南道海域:釜山、機張郡など)が挙げられる。 The sea areas where wakame is identified in the present invention are Sanriku (Iwate coast: Fuyo, Hirota, Otomo, etc., Miyagi coast: Utatsu, Shiogama, etc.), Setouchi (Tokushima coast) : Hokuto, Kitadomari, Naruto, etc., Hyogo coast: Minamiawaji, Asanoura, etc.), China (Sea area of Bohai Bay: Liaoning Dalian, Shandong Yantai, Shandong Weihai, etc.), South Korea : Yeouido-gun, Jindo-gun, Changxing-gun, Gaoxing-gun, etc.
上記元素量を分析する方法としては、公知の微量元素分析方法、例えば、誘導結合プラズマ質量分析法(ICP‐MS)、誘導結合プラズマ発光分光分析(ICP−AES)、原子吸光分析(AAS)、蛍光エックス線分析(XRF)、中性子放射化分析(NAA)などが挙げられ、好ましくは多くの元素に対して高感度で分析することができる誘導結合プラズマ質量分析法(ICP‐MS)が挙げられる。 As a method for analyzing the element amount, a known trace element analysis method, for example, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), atomic absorption analysis (AAS), Examples thereof include fluorescent X-ray analysis (XRF) and neutron activation analysis (NAA), and inductively coupled plasma mass spectrometry (ICP-MS) capable of analyzing with respect to many elements with high sensitivity is preferable.
上記分析する方法のうち、誘導結合プラズマ質量分析法(ICP‐MS)、誘導結合プラズマ発光分光分析(ICP−AES)、原子吸光分析(AAS)は、通常ワカメを前処理して得た溶液を測定に用いることが好ましい。蛍光エックス線分析(XRF)、中性子放射化分析(NAA)は、通常ワカメを酸分解することなく個体試料として測定に用いることが好ましい。 Among the above analysis methods, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), and atomic absorption spectrometry (AAS) are usually prepared by pre-treating seaweed. It is preferable to use for measurement. Fluorescence X-ray analysis (XRF) and neutron activation analysis (NAA) are usually preferably used for measurement as an individual sample without acid decomposition of seaweed.
本発明は、以下の工程を含む判別する方法であることが好ましい。即ち、[工程1:ワカメを酸分解する工程]、[工程2:ワカメに含まれる元素量を測定する工程]、および[工程3:元素量の分析情報を利用してワカメの生育海域を判別する工程]を例示することができる。 The present invention is preferably a determination method including the following steps. That is, [Step 1: Acid-decomposing wakame], [Step 2: Measuring the amount of element contained in seaweed], and [Step 3: Analyzing element amount analysis information to determine the sea area where wakame grows. Can be illustrated.
上記[工程1:ワカメを酸分解する工程]は、ワカメを酸分解して無機成分を主に含む溶液を調整する工程である。本工程は、ワカメに酸を加えて分解すれば特にその方法に制限はなく、例えば、ワカメに硝酸を加えマイクロウェブで分解するマイクロウェブ酸分解法、ワカメに硝酸を加えてホットプレート上で加熱して分解する開放系酸分解法などが挙げられる。 The above [Step 1: Acid-decomposing wakame] is a step of preparing a solution mainly containing inorganic components by acid-decomposing wakame. This process is not particularly limited as long as acid is added to the seaweed and decomposed. For example, a microweb acid decomposition method in which nitric acid is added to seaweed and decomposed with a microweb, nitric acid is added to seaweed and heated on a hot plate. And an open acid decomposition method that decomposes in this way.
また、上記工程1を行う前に、ワカメを乾燥、粉砕する前処理を行うことが好ましい。例えば、原藻ワカメおよび乾燥ワカメの場合、適度な大きさにカットした後に乾燥し、該乾燥物を粉砕する前処理方法が挙げられ、湯通し塩蔵ワカメの場合、適度な大きさにカットした後に乾燥し、該乾燥物に付着している食塩を取り除き、該乾燥物粉砕する前処理方法が挙げられる。 Moreover, before performing the said process 1, it is preferable to perform the pretreatment which dries and grinds a seaweed. For example, in the case of raw algae wakame and dried wakame, there is a pretreatment method in which the dried product is cut after being cut to an appropriate size and then dried, and in the case of boiled salted wakame, it is dried after being cut to an appropriate size. And a pretreatment method for removing salt attached to the dried product and crushing the dried product.
上記[工程2:ワカメに含まれる元素量を測定する工程]は、前述した公知の微量元素分析方法、好ましくは工程1で得られた試料を誘導結合プラズマ質量分析法(ICP‐MS)でワカメに含まれるヒ素、カドミウム、バリウムの元素量、好ましくは前記3元素量と、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素量を測定する工程である。 The above-mentioned [Step 2: Measuring the amount of elements contained in seaweed] is the known trace element analysis method described above, preferably the sample obtained in step 1 is subjected to inductively coupled plasma mass spectrometry (ICP-MS). Is a step of measuring elemental amounts of arsenic, cadmium and barium, preferably the three elemental amounts, and elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium and strontium.
上記[工程3:元素量の分析情報を利用してワカメの生育海域を判別する工程]は、上記工程1、工程2に従って、判別したい海域で生育したことがわかっているワカメに含まれるヒ素、カドミウム、バリウムの元素量を複数検体測定してワカメ生育海域ごとのデータベースを構築し、該データベースと、上記工程1、工程2に従って生育海域が不明なワカメに含まれるヒ素、カドミウム、バリウムの元素量とを比較することで生育海域を判別することができる。 The above-mentioned [Step 3: Step of discriminating sea area where wakame grows using elemental analysis information] includes arsenic contained in seaweed that is known to have grown in the sea region to be discriminated according to Step 1 and Step 2 above, Establishing a database for each seaweed growing area by measuring multiple amounts of elemental elements of cadmium and barium, and amounts of arsenic, cadmium and barium contained in wakame where the growing sea area is unknown according to the database and steps 1 and 2 above The growing sea area can be determined by comparing with.
データベースを構築する際は、判別したい海域で生育したワカメを、海域ごとに広範囲で偏りなく、複数年にわたり数多くの検体からデータを収集しデータベースを構築することが好ましい。また、ワカメの形態として、例えば、原藻ワカメ、湯通し塩蔵ワカメ、乾燥ワカメなど、形態ごとにデータを収集しデータベースを構築することが好ましい。 When constructing a database, it is preferable to construct a database by collecting data from a large number of specimens over a period of several years without wakame grown in the sea area to be discriminated over a wide range for each sea area. In addition, as a form of wakame, for example, it is preferable to collect data for each form such as raw algae wakame, boiled salted wakame, and dried wakame to construct a database.
構築したデータベースから分析情報を得る方法としては、データベースの各元素を多変量解析する方法が挙げられる。本発明で用いる多変量解析としては、特に制限はないが、例えば、判別分析、主成分分析、クラスター分析などが挙げられ、好ましくは判別分析である。
判別分析としては、例えば、すべての変数を使用するか、あるいは変数選択法としてステップワイズ後進法、ステップワイズ前進法、変数増加法、変数減少法、などのいずれの方法を用いてもよい。
As a method of obtaining analysis information from the constructed database, there is a method of multivariate analysis of each element of the database. The multivariate analysis used in the present invention is not particularly limited, and examples thereof include discriminant analysis, principal component analysis, cluster analysis, and the like, and preferably discriminant analysis.
As the discriminant analysis, for example, all variables may be used, or any method such as a stepwise backward method, a stepwise forward method, a variable increase method, a variable decrease method, or the like may be used as a variable selection method.
例えば、多変量解析として判別分析を用いる場合、構築したデータベース中のヒ素、カドミウム、バリウムを説明変数として判別分析することで、判別関数と分類関数が得られ、これらの分析情報を用いてワカメの生育海域を判別することができる。 For example, when discriminant analysis is used as multivariate analysis, discriminant function and classification function are obtained by discriminating and analyzing arsenic, cadmium, and barium in the constructed database as explanatory variables. The growing sea area can be identified.
ワカメの生育海域を判別する方法としては、例えば下記の2つの方法などが挙げられる。
1つとしては構築したデータベース中のヒ素、カドミウム、バリウムの元素量を説明変数として判別分析を行って判別関数を得た後に、該判別関数に各形態ごとのワカメのヒ素、カドミウム、バリウムの元素量を代入することで得られた得点のプロット図を作成して各形態ごとのワカメの生育海域を視覚的に表現することができる。
Examples of the method for discriminating the sea area where the wakame grows include the following two methods.
One is that after the discriminant analysis is performed using the amounts of arsenic, cadmium and barium in the constructed database as explanatory variables to obtain the discriminant function, the wakame arsenic, cadmium and barium elements for each form are included in the discriminant function. A plot of the score obtained by substituting the quantity can be created to visually represent the sea area where the wakame grows.
さらにもう一つとしては、構築したデータベース中のヒ素、カドミウム、バリウムの元素量を説明変数として判別分析を行って得られた分類関数を各形態のワカメに対応した生育海域判別式とする方法などが挙げられる。得られた生育海域判別式に、生育海域が不明なワカメに含まれるヒ素、カドミウム、バリウムの元素量を代入することによりワカメの生育海域を判別することができる。 In addition, the classification function obtained by performing discriminant analysis using the amounts of arsenic, cadmium, and barium in the constructed database as explanatory variables is used as a growing sea area discriminant corresponding to each form of seaweed, etc. Is mentioned. By substituting the elemental amounts of arsenic, cadmium, and barium contained in wakame whose growth area is unknown, the growth area of wakame can be determined.
判別精度を高めるためには、ヒ素、カドミウム、バリウムの元素量以外に、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素量のいずれか1種以上を比較する要素に加えることが好ましい。前記9元素のいずれを選択するかは、多変量解析により得られた判別寄与率により決定すればよい。
例えば、多変量解析として判別分析を用いる場合、ヒ素、カドミウム、バリウムの元素量に加えて、原藻ワカメの生育海域を判別する際は、さらにマグネシウム、バナジウム、亜鉛、ルビジウム、ストロンチウムの元素量を要素として加えることが好ましく、湯通し塩蔵ワカメのワカメ生育海域を判別する際は、さらにマグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素量を要素として加えることが好ましく、乾燥ワカメのワカメ生育海域を判別する際は、さらにマグネシウム、リン、カルシウム、バナジウム、マンガン、ルビジウムの元素量を要素として加えることが好ましい。
In order to improve discrimination accuracy, in addition to the elemental amounts of arsenic, cadmium, and barium, as an element to compare one or more of the elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, and strontium It is preferable to add. Which of the nine elements is selected may be determined by the discriminant contribution rate obtained by multivariate analysis.
For example, when discriminant analysis is used as a multivariate analysis, in addition to the elemental amounts of arsenic, cadmium, and barium, when determining the growth area of the original alga wakame, the elemental amounts of magnesium, vanadium, zinc, rubidium, and strontium It is preferable to add as an element, and when discriminating the seawater growth area of boiled salted seaweed, it is preferable to add elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, strontium as elements, and dry When discriminating sea areas where wakame grows, it is preferable to add elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese and rubidium as elements.
各形態のワカメから得られた各元素量を用い、各形態のワカメに共通した生育海域判別式を作成し、ワカメの生育海域を判別することも可能である。
該生育海域判別式を得る方法としては、構築したデータベースの元素から、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの群のいずれか1元素、好ましくはストロンチウムを選択し、選択した1元素量(濃度)で他の元素量(濃度)をそれぞれ割り、次いで対数をとり、該数値を多変量解析することにより分類関数が得られる。得られた分類関数は各形態のワカメに共通した生育海域判別式とすることができる。
By using the amount of each element obtained from each form of seaweed, it is possible to create a growth sea area discriminant common to each form of seaweed and discriminate the sea area of seaweed.
As a method of obtaining the growing sea area discriminant, from the elements of the constructed database, select one element of the group of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, strontium, preferably strontium, A classification function is obtained by dividing each other element amount (concentration) by the selected one element amount (concentration), then taking a logarithm, and performing multivariate analysis on the numerical value. The obtained classification function can be a growing sea area discriminant common to each form of seaweed.
以下に本発明を実施例で説明するが、これは本発明を単に説明するだけのものであって、本発明を限定するものではない。 The present invention will now be described by way of examples, which are merely illustrative of the invention and do not limit the invention.
≪各形態のワカメの収集≫
生育海域がわかっている各形態のワカメを収集した。ワカメの形態としては、原藻ワカメ(保管のため、生の原藻ワカメをそのまま冷凍して保管したもの、または乾燥して保管したもの)、湯通し塩蔵ワカメ、乾燥ワカメ(湯通し塩蔵ワカメを乾燥したもの)とし、生育海域は、三陸、瀬戸内、中国、韓国とした。収集したワカメは、2012年、2013年に収穫した原藻ワカメ267検体(三陸:66検体、瀬戸内:105検体、中国:24検体、韓国72検体)、2012年、2013年に収穫した原藻ワカメを用いた湯通し塩蔵ワカメ358検体(三陸:57検体、瀬戸内:123検体、中国:44検体、韓国:134検体)、2011年、2013年、2014年に収穫した原藻ワカメを用いた乾燥ワカメ56検体(三陸:22検体、瀬戸内:17検体、中国:8検体、韓国:9検体)である。
≪Collecting various types of seaweed≫
Each form of wakame with known growing area was collected. As for the form of wakame, the raw algae wakame (the raw raw algae wakame was stored frozen or stored for storage), the boiled salted wakame, the dried wakame (dried salted wakame dried) )), And the growing area was Sanriku, Setouchi, China, and Korea. The collected seaweeds were 267 raw algae wakame harvested in 2012 and 2013 (Sanriku: 66 specimens, Setouchi: 105 specimens, China: 24 specimens, 72 Korean specimens), raw algae wakame harvested in 2012, 2013 358 specimens of boiled salted seaweed wakame (Sanriku: 57 specimens, Setouchi: 123 specimens, China: 44 specimens, Korea: 134 specimens), dried seaweed 56 using raw algae wakame harvested in 2011, 2013, 2014 Samples (Sanriku: 22 samples, Setouchi: 17 samples, China: 8 samples, Korea: 9 samples).
上記収集した各形態のワカメの生育海域は、三陸としては、普代、広田、小友、歌津の海域、瀬戸内としては、北灘、北泊、鳴門町、浅野浦の海域、中国としては、凌水、金石灘、柏嵐子の海域、韓国としては明川、薬山の海域である。 The collected sea areas of the wakame collected above are Sanyo, Fuyo, Hirota, Otomo, Utatsu, Setouchi, Hokuto, Kitadomari, Naruto, Asanoura, China, Ryosui , The area of Jinshi Pass and Saga Arashi, and the South of Korea is Myokawa and Yakusan.
上記原藻ワカメのうち、生の原藻ワカメをそのまま冷凍して保管したものは、海から収穫した原藻ワカメの表面の水分を軽く振って水切りした後、約−20℃の冷凍庫で冷凍保管したものである。
上記原藻ワカメのうち、生の原藻ワカメをそのまま乾燥して保管したものは、海から収穫した原藻ワカメの表面の水分を軽く振って水切りした後、常温(約25℃)で72時間乾燥したものである。
Of the above-mentioned raw algae wakame, raw raw algae wakame that has been frozen and stored as it is is stored in a freezer at about -20 ° C after lightly shaking the surface water of the raw algae wakame harvested from the sea. It is a thing.
Among the above-mentioned raw algae wakame, raw raw algae wakame that has been dried and stored as it is is drained by gently shaking the surface water of the raw algae wakame harvested from the sea, and then at room temperature (about 25 ° C.) for 72 hours. It is dry.
上記湯通し塩蔵ワカメは、収穫地域、加工業者によって加工方法が若干異なるが、海から収穫した原藻ワカメを、約90℃に加温した海水に、約1分間湯通しした後に海水につけて冷却、脱水した後に、湯通しワカメに対して約40質量%の食塩を添加し、1〜2日程度塩漬して脱水したものである。 該湯通し塩蔵ワカメは、各種ワカメ加工品の原料として用いられ、例えば、該湯通し塩蔵ワカメの食塩量を調整することにより一般市場で販売される湯通し塩蔵ワカメが得られ、あるいは該湯通し塩蔵ワカメを後述する加工を施して乾燥ワカメが得られる。 The processing method of the boiled salted wakame is slightly different depending on the harvesting area and the processor. However, the raw alga wakame harvested from the sea is boiled in seawater heated to about 90 ° C for about 1 minute, and then cooled and dehydrated. After that, about 40% by mass of salt is added to the boiled seaweed, dehydrated by salting for about 1-2 days. The boiled salted wakame is used as a raw material for various wakame processed products. For example, by adjusting the salt amount of the boiled salted wakame, a boiled salted wakame sold in the general market is obtained, or the boiled salted wakame is described later. A dried seaweed is obtained by performing the processing.
上記乾燥ワカメは、収穫地域、加工業者によって加工方法が若干異なるが、以下の方法によって得られたものが挙げられる。即ち、湯通し塩蔵ワカメを原料とし、水による洗浄により食塩量を調整したものを乾燥して得たものである。 Although the processing method of the dried wakame is slightly different depending on the harvesting area and the processor, those obtained by the following method can be mentioned. That is, it is obtained by drying a salted wakame made from boiled water and having a salt amount adjusted by washing with water.
≪各形態のワカメの元素分析方法およびデータベース構築≫
[原藻ワカメをそのまま冷凍して保管したものの前処理]
原藻ワカメをそのまま冷凍して保管したものは、常温で解凍した後、各検体の葉部をセラミック製の包丁を用いて約0.5×0.5cmの大きさにカットし、乾燥機(型式:DK400;ヤマト化学社製)を用いて105℃、10時間乾燥させ、室温まで放冷した後、セラミック製ミル(型式:CM−45CF;京セラ社製)を用いて10分間粉砕して粉末化した。
≪Element analysis method and database construction of wakame of each form≫
[Pretreatment of raw alga wakame frozen and stored]
After freezing the raw seaweed wakame, it thawed at room temperature, and then the leaves of each specimen were cut into a size of about 0.5 x 0.5 cm using a ceramic knife and dried ( (Model: DK400; manufactured by Yamato Chemical Co., Ltd.), dried at 105 ° C. for 10 hours, allowed to cool to room temperature, and then pulverized for 10 minutes using a ceramic mill (Model: CM-45CF; manufactured by Kyocera). Turned into.
[湯通し塩蔵ワカメの前処理]
湯通し塩蔵ワカメの各検体の葉部をセラミック製の包丁を用いて約0.5×0.5cmの大きさにカットし、乾燥機(型式:DK400;ヤマト化学社製)を用いて105℃、10時間乾燥させ、室温まで放冷した後、目開き5メッシュのプラスチック製篩で約30秒間振い付着する食塩を除去した後、セラミック製ミル(型式:CM−45CF;京セラ社製)を用いて10分間粉砕して粉末化した。
[Pretreatment of boiled salted seaweed]
The leaves of each specimen of the boiled salted seaweed were cut into a size of about 0.5 × 0.5 cm using a ceramic knife, and 105 ° C. using a dryer (model: DK400; manufactured by Yamato Chemical Co., Ltd.) After drying for 10 hours and allowing to cool to room temperature, the salt attached by shaking for about 30 seconds with a 5-mesh plastic sieve was removed, and then a ceramic mill (model: CM-45CF; manufactured by Kyocera Corporation) was used. And pulverized for 10 minutes.
[原藻ワカメをそのまま乾燥して保管したもの、乾燥ワカメの前処理]
原藻ワカメをそのまま乾燥して保管したもの、および乾燥ワカメの各検体の葉部(約0.5×0.5cm)を、乾燥機(型式:DK400;ヤマト化学社製)を用いて105℃、1時間乾燥させ、室温まで放冷した後、セラミック製ミル(型式:CM−45CF;京セラ社製)を用いて10分間粉砕して粉末化した。
[Dry seaweed wakame dried and stored as it is, pretreatment of dried wakame]
The raw algae wakame was dried and stored as it was, and the leaves (about 0.5 × 0.5 cm) of each sample of the dried wakame were dried at 105 ° C. using a dryer (model: DK400; manufactured by Yamato Chemical Co., Ltd.). After drying for 1 hour and allowing to cool to room temperature, it was pulverized for 10 minutes using a ceramic mill (model: CM-45CF; manufactured by Kyocera Corporation).
[酸分解処理]
テフロン容器(型式:HPV100;マイルストーンゼネラル社製)に得られた各検体の粉末品のそれぞれを0.5gと硝酸8mLを入れて密封し、マイクロウェブ分解装置(型式:ETHOST TC;マイルストーンゼネラル社製)を用いて下記分解温度プログラム(時間、温度、ワット数)で分解し、検体溶液を得た。
(分解温度プログラム)
ステップ1: 2分間 50℃ 1000W
ステップ2: 3分間 30℃ 0W
ステップ3:15分間 210℃ 1000W
ステップ4: 1分間 190℃ 0W
ステップ5: 4分間 210℃ 1000W
ステップ6:40分間 210℃ 1000W
[Acid decomposition treatment]
Each sample powder obtained in a Teflon container (model: HPV100; manufactured by Milestone General) was sealed with 0.5 g and 8 mL of nitric acid, and the microweb decomposition apparatus (model: ETHOST TC; milestone general). The sample solution was obtained using the following decomposition temperature program (time, temperature, wattage).
(Decomposition temperature program)
Step 1: 2 minutes 50 ° C 1000W
Step 2: 3 minutes 30 ° C 0W
Step 3: 15 minutes 210 ° C 1000W
Step 4: 1 minute 190 ° C 0W
Step 5: 4 minutes 210 ° C 1000W
Step 6: 40 minutes 210 ° C 1000W
[誘導結合プラズマ質量分析法(ICP‐MS)による元素分析]
酸分解処理した各検体溶液を誘導結合プラズマ質量分析計(型式:Agilent7700;アジレントテクノロジー社製)を用いて測定した。測定に際し、500ppbのインジウム溶液を内標準としてオンラインで添加し、下記条件で12元素量(マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウム)を内標準法により測定した。
(ICP−MS分析条件)
・プラズマ条件
RFパワー :1550W
キャリアーガス :1.03L/min
プラズマガス :15L/min
ヘリウムガス :4.3mL/min
・ペリポンプ条件
測定時回転速度 :0.1rps
・データ採取条件
データポイント :3点/質量数
繰り返し回数 :3回
[Elemental analysis by inductively coupled plasma mass spectrometry (ICP-MS)]
Each sample solution subjected to the acid decomposition treatment was measured using an inductively coupled plasma mass spectrometer (model: Agilent 7700; manufactured by Agilent Technologies). At the time of measurement, 500 ppb indium solution was added online as an internal standard, and 12 element amounts (magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, arsenic, rubidium, strontium, cadmium, barium) were used as internal standards under the following conditions. Measured by the method.
(ICP-MS analysis conditions)
・ Plasma condition RF power: 1550W
Carrier gas: 1.03 L / min
Plasma gas: 15 L / min
Helium gas: 4.3 mL / min
・ Peri-pump condition Measurement rotation speed: 0.1 rps
・ Data collection conditions Data point: 3 points / mass number Repeat count: 3 times
上記方法によって得られた各形態のワカメに含まれる12元素量(マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウム)をデータベースとした。 The amount of 12 elements (magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, arsenic, rubidium, strontium, cadmium, barium) contained in each form of seaweed obtained by the above method was used as a database.
≪ヒ素、カドミウム、バリウムの元素量を用いたデータベースの解析≫
(1)判別分析
データベース中の各形態のワカメごとに含まれるヒ素、カドミウム、バリウムの元素量を説明変数として判別分析を行い、各形態のワカメごとの判別関数1(原藻ワカメ:判別関数1−1、1−2、湯通し塩蔵ワカメ:判別関数1−3、1−4、乾燥ワカメ:判別関数1−5、1−6)および4群を判別する分類関数1(ワカメの生育海域判別式1)を得た。前記判別分析としては、ステップワイズ判別分析の後進法によって行った。なお、上記「4群を判別する」とは、「ワカメの生育海域が三陸、瀬戸内、中国および韓国のいずれかであるかを判別する」、という意味である。
≪Analysis of database using element amounts of arsenic, cadmium, and barium≫
(1) Discriminant analysis Discriminant analysis is performed using the amounts of arsenic, cadmium, and barium contained in each form of wakame in the database as explanatory variables, and discriminant function 1 for each form of wakame (raw algae wakame: discriminant function 1 -1, 1-2, boiled salted seaweed: discriminant functions 1-3, 1-4, dried seaweed: discriminant functions 1-5, 1-6) and classification function 1 for discriminating the four groups (seaweed growing sea area discriminant 1) was obtained. The discriminant analysis was performed by the backward method of stepwise discriminant analysis. The above “determining the four groups” means “determining whether the sea area where the seaweed is growing is Sanriku, Setouchi, China, or Korea”.
得られた各形態ごとのワカメの判別関数1の一般式を下記に示す。式中のH’、K’、L’は各元素の係数であり、M’は定数である。ここで、「[ ]」内は、各元素量(濃度)であり、ヒ素およびバリウムの濃度単位はppm、カドミウムの濃度単位はppbである。下記式に用いる係数および定数を表1に示す。
各形態のワカメの判別関数1=H’[As]+K’[Cd]+L’[Ba]+M’
The general formula of the wakame discriminant function 1 obtained for each form is shown below. In the formula, H ′, K ′, and L ′ are coefficients of each element, and M ′ is a constant. Here, “[]” indicates the amount (concentration) of each element, the arsenic and barium concentration units are ppm, and the cadmium concentration unit is ppb. Table 1 shows coefficients and constants used in the following formula.
Wakame discriminant function 1 for each form = H ′ [As] + K ′ [Cd] + L ′ [Ba] + M ′
(2)各形態のワカメごとの判別関数1を用いたプロット図
得られた各形態のワカメごとの判別関数1(原藻ワカメ:判別関数1−1、1−2、湯通し塩蔵ワカメ:判別関数1−3、1−4、乾燥ワカメ:判別関数1−5、1−6)に、データベースに蓄積された各形態のワカメごとのヒ素、カドミウム、バリウムの元素量を代入して得た判別得点を用いて、縦軸に判別関数1−2、1−4、1−6より得られた判別得点2、横軸に判別関数1−1、1−3、1−5より得られた判別得点1をプロットして各形態のワカメごとのプロット図を作成した。得られたプロット図は、プロットした点が判別したい海域ごと、具体的には三陸、瀬戸内、中国、韓国の4海域に分かれることが確認された。
(2) Plot diagram using discriminant function 1 for each form of seaweed Discriminant function 1 for each form of seaweed obtained (raw algae seaweed: discriminant functions 1-1, 1-2, boiled salted seaweed: discriminant function 1-3, 1-4, dried seaweed: discriminant scores obtained by substituting the elemental amounts of arsenic, cadmium, and barium for each form of wakame accumulated in the database into discriminant functions 1-5, 1-6) , The discriminant score obtained from discriminant functions 1-2, 1-4, 1-6 on the vertical axis, and the discriminant score obtained from discriminant functions 1-1, 1-3, 1-5 on the horizontal axis 1 was plotted to create a plot for each form of seaweed. It was confirmed that the plots obtained were divided into four sea areas, namely, Sanriku, Setouchi, China, and South Korea, according to the sea areas that the plotted points wanted to be identified.
一例として、乾燥ワカメのデータベースに蓄積されたヒ素、カドミウム、バリウムの元素量を乾燥ワカメの判別関数に代入して得た判別得点を用いて作成したプロット図を図1に示す。なお、乾燥ワカメの判別関数1−5、1−6の計算式を下記に示す。
乾燥ワカメの判別関数1−5=−0.1045[As]+0.0018[Cd]+0.5991[Ba]−6.2099
乾燥ワカメの判別関数1−6=0.1540[As]+0.0017[Cd]−0.1162[Ba]−6.8105
As an example, FIG. 1 shows a plot created using the discriminant score obtained by substituting the elemental amounts of arsenic, cadmium, and barium accumulated in the dry wakame database into the discriminant function of dry wakame. In addition, the calculation formulas of the discriminant functions 1-5 and 1-6 for dried seaweed are shown below.
Discriminant function for dried seaweed 1-5 = −0.1045 [As] +0.0018 [Cd] +0.5991 [Ba] −6.2099
Discriminant function for dried seaweed 1-6 = 0.1540 [As] +0.0017 [Cd] -0.1162 [Ba] -6.8105
乾燥ワカメに含まれるヒ素、カドミウム、バリウムの元素量を用いることにより、図1に示す通り、三陸、瀬戸内、中国、韓国の4海域の分布を確認することができた。データベースのわかめの生育海域の判別率は三陸90.9%、瀬戸内94.1%、中国100.0%,韓国100.0%であった。 By using the amounts of arsenic, cadmium, and barium contained in the dried seaweed, we were able to confirm the distribution of the four sea areas of Sanriku, Setouchi, China, and Korea as shown in FIG. The distinction rate of the sea area where the seaweed grows in the database is 90.9% for Sanriku, 94.1% for Setouchi, 100.0% for China, and 100.0% for Korea.
(3)4群を判別する分類関数1(ワカメの生育海域判別式1)
ヒ素、カドミウム、バリウムの元素量を用いた4群を判別する分類関数1(ワカメの生育海域判別式1)は、各海域に対して構築される一次関数であり、下記にそれらを示すことができる。式中のH、K、Lは各元素の係数であり、Mは定数である。ここで、「[ ]」内は、各元素量(濃度)であり、ヒ素およびバリウムの濃度単位はppm、カドミウムの濃度単位はppbである。下記式に用いる係数および定数を表2〜4に示す。
(ワカメの生育海域判別式1)
三陸 =H[As]+K[Cd]+L[Ba]+M
瀬戸内=H[As]+K[Cd]+L[Ba]+M
中国 =H[As]+K[Cd]+L[Ba]+M
韓国 =H[As]+K[Cd]+L[Ba]+M
(3) Classification function 1 for discriminating 4 groups (Wakame's growing sea area discriminant 1)
Classification function 1 for discriminating four groups using elemental amounts of arsenic, cadmium, and barium (Wakame's growing sea area discriminant 1) is a linear function constructed for each sea area, and is shown below. it can. In the formula, H, K, and L are coefficients of each element, and M is a constant. Here, “[]” indicates the amount (concentration) of each element, the arsenic and barium concentration units are ppm, and the cadmium concentration unit is ppb. The coefficients and constants used in the following formulas are shown in Tables 2-4.
(Wakame growth area discriminant 1)
Sanriku = H [As] + K [Cd] + L [Ba] + M
Setouchi = H [As] + K [Cd] + L [Ba] + M
China = H [As] + K [Cd] + L [Ba] + M
Korea = H [As] + K [Cd] + L [Ba] + M
上記ワカメの生育海域判別式1に、対象となるワカメに含まれるヒ素、カドミウム、バリウムの元素量(濃度)をそれぞれ代入し、得られた値が最も大きい海域が生育した海域であると判別する。 Substituting the elemental amounts (concentrations) of arsenic, cadmium and barium contained in the target seaweed into the seaweed growing sea area discriminant 1 above, it is determined that the sea area where the obtained value is the largest is the sea area where it grew. .
≪わかめの生育海域を判別する方法の有用性確認1≫
(1)ワカメの生育海域が明確な各形態のワカメの元素量分析
生育海域が三陸(歌津)、瀬戸内(北灘)、中国(正明寺)および韓国(明川)である、原藻ワカメの冷凍保管品、湯通し塩蔵ワカメ、および生育海域が三陸、瀬戸内、中国および韓国である乾燥ワカメに含まれる12元素量(マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウム)を、≪各形態のワカメの元素分析方法およびデータベース構築≫に記載の元素分析方法で測定した。分析結果を表5〜8に示す。
≪Confirmation of usefulness 1 of the method to determine the sea area where seaweed grows≫
(1) Elementary analysis of wakame in various forms with clear wakame growing area Freeze storage of raw seaweed wakame with growing areas in Sanriku (Utatsu), Setouchi (Hokuto), China (Shomei-ji) and Korea (Mingcheon) 12 elements in magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, arsenic, rubidium, strontium, strontium, cadmium, Barium) was measured by the elemental analysis method described in << Elemental analysis method and database construction of wakame of each form >>. The analysis results are shown in Tables 5-8.
(2)各形態のワカメに対応した生育海域判別式1を用いた判別する方法の有用性確認
得られた各生育海域および各形態のワカメに含まれる12元素量(マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウム)を用いて、各形態のワカメに対応した生育海域判別式1に必要な元素量をそれぞれ代入した。結果として、全ての産地が正しく判別することができた。
(2) Confirmation of the usefulness of the method of discriminating using the growing sea area discriminant 1 corresponding to each form of seaweed 12 amounts of elements (magnesium, phosphorus, calcium, vanadium) contained in each obtained sea area and each form of seaweed , Manganese, iron, zinc, arsenic, rubidium, strontium, cadmium, barium), and the necessary element amounts were substituted into the growing sea area discriminant 1 corresponding to each form of seaweed. As a result, all production areas were correctly identified.
(3)生育海域判別式1を用いた判別する方法の有用性確認例
一例として、原藻ワカメの生育海域が三陸である乾燥ワカメに含まれるヒ素、カドミウム、バリウムを用いた乾燥ワカメに対応した生育海域判別式1の計算式を下記に示す。
三陸 =1.5645[As]+0.0125[Cd]+1.9402[Ba]−50.1725
瀬戸内=1.3828[As]+0.0042[Cd]+2.3270[Ba]−38.9848
中国 =0.1891[As]+0.0302[Cd]+9.4542[Ba]−165.6611
韓国 =2.0509[As]+0.0139[Cd]+3.5210[Ba]−93.6806
(3) Example of confirming the usefulness of the method of discriminating using the growing sea area discriminant 1 As an example, it corresponds to dry wakame using arsenic, cadmium, and barium contained in dried seaweeds where the growing sea area of the original alga wakame is Sanriku. The calculation formula of the growing sea area discriminant 1 is shown below.
Sanriku = 1.5645 [As] + 0.0125 [Cd] + 1.9402 [Ba]-50.1725
Setouchi = 1.3828 [As] + 0.0042 [Cd] + 2.3270 [Ba]-38.9848
China = 0.1891 [As] + 0.0302 [Cd] + 9.4542 [Ba]-165.6611
Korea = 2.0509 [As] + 0.0139 [Cd] + 3.5210 [Ba]-93.6806
上記式に、原藻ワカメの生育海域が三陸である乾燥ワカメ(表5)に示した、ヒ素、カドミウム、バリウムの各元素量を代入したところ、三陸=49.5、瀬戸内=42.2、中国=−42.2、韓国=39.8となり、三陸の値が他の海域の数値より大きく、三陸で生育した原藻ワカメを用いた乾燥ワカメであると判別することができた。 Substituting the amount of each element of arsenic, cadmium, and barium shown in the dry wakame (Table 5) where the growth area of the original alga wakame is Sanriku into the above formula, Sanriku = 49.5, Setouchi = 42.2, China = −42.2, Korea = 39.8, and the value of Sanriku was larger than that of other sea areas, and it was possible to discriminate that it was dry wakame using the original alga wakame grown in Sanriku.
≪マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウムの元素量を用いたデータベースの解析≫
(1)判別分析
データベース中の各形態のワカメごとに含まれるヒ素、カドミウム、バリウムの元素量に加え、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素のいずれか1種以上の元素量を追加した各元素量を説明変数として判別分析を行い、各形態のワカメごとの判別関数2(原藻ワカメ:判別関数2−1、2−2、湯通し塩蔵ワカメ:判別関数2−3、2−4、乾燥ワカメ:判別関数2−5、2−6)および4群を判別する分類関数2(ワカメの生育海域判別式2)を得た。前記判別分析としては、原藻ワカメおよび乾燥ワカメに関してはステップワイズ判別分析の後進法によって行った。また、湯通し塩蔵ワカメに関してはすべての変数を使用した判別分析によって行った。
≪Analysis of database using elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, arsenic, rubidium, strontium, cadmium, and barium≫
(1) Discriminant analysis In addition to the amounts of arsenic, cadmium, and barium contained in each form of wakame in the database, any one of the elements magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, and strontium Discriminant analysis is performed with each elemental amount added with the amount of element or more as an explanatory variable, and discriminant function 2 for each form of wakame (raw algae wakame: discriminant functions 2-1, 2-2, boiled salted wakame: discriminant function 2-3, 2-4, dried seaweed: discriminant functions 2-5, 2-6) and classification function 2 for discriminating 4 groups (seaweed growing sea area discriminant 2) were obtained. The discriminant analysis was performed by the backward method of stepwise discriminant analysis for the raw alga seaweed and dried seaweed. For boiled salted seaweed, we conducted a discriminant analysis using all variables.
上記各形態のワカメごとの判別関数2(原藻ワカメ:判別関数2−1、2−2、湯通し塩蔵ワカメ:判別関数2−3、2−4、乾燥ワカメ:判別関数2−5、2−6)および4群を判別する分類関数2(ワカメの生育海域判別式2)を得る際の判別分析に用いるヒ素、カドミウム、バリウムの元素量以外の元素量は、各形態のワカメによって異なる。原藻ワカメの生育海域を判別する場合は、マグネシウム、バナジウム、亜鉛、ルビジウム、ストロンチウムの元素量であり、湯通し塩蔵ワカメのワカメ生育海域を判別する場合は、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素量であり、乾燥ワカメのワカメ生育海域を判別する場合は、さらにマグネシウム、リン、カルシウム、バナジウム、マンガン、ルビジウムの元素量である。 Discriminant function 2 for each form of wakame (original algae wakame: discriminant functions 2-1, 2-2, boiled salted wakame: discriminant functions 2-3, 2-4, dry wakame: discriminant functions 2-5, 2- The amount of elements other than the amounts of arsenic, cadmium, and barium used in the discriminant analysis when obtaining the classification function 2 (Wakame growth area discriminant 2) for discriminating between 6) and 4 groups varies depending on the wakame of each form. When discriminating the growing sea area of the raw alga wakame, it is the element amount of magnesium, vanadium, zinc, rubidium, strontium, and when discriminating the wakame growing area of the boiled salted wakame, magnesium, phosphorus, calcium, vanadium, manganese, The elemental amounts of iron, zinc, rubidium, and strontium. When determining the sea area where dried wakame is grown, the elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, and rubidium are further included.
得られた各形態ごとのワカメの判別関数2の一般式を下記に示す。式中のA’、B’、C’、D’、E’、F’、G’、H’、I’、J’、K’、L’は各元素の係数であり、M’は定数である。ここで、「[ ]」内は、各元素量(濃度)であり、バナジウムおよびカドミウムの元素量の濃度単位はppb、他の元素量の濃度単位はppmである。下記一般式に用いる係数および定数を表9に示す。
各形態のワカメの判別関数2=A’[Mg]+B’[P]+C’[Ca]+D’[V]+E’[Mn]+F’[Fe]+G’[Zn]+H’[As]+I’[Rb]+J’[Sr]+K’[Cd]+L’[Ba]+M’
The general formula of the obtained wakame discriminant function 2 for each form is shown below. In the formula, A ′, B ′, C ′, D ′, E ′, F ′, G ′, H ′, I ′, J ′, K ′, and L ′ are coefficients of each element, and M ′ is a constant. It is. Here, “[]” represents the amount (concentration) of each element, the concentration unit of the element amounts of vanadium and cadmium is ppb, and the concentration unit of the other element amounts is ppm. Table 9 shows the coefficients and constants used in the following general formula.
Wakame discriminant function 2 of each form = A ′ [Mg] + B ′ [P] + C ′ [Ca] + D ′ [V] + E ′ [Mn] + F ′ [Fe] + G ′ [Zn] + H ′ [As] + I '[Rb] + J' [Sr] + K '[Cd] + L' [Ba] + M '
(2)各形態のワカメごとの判別関数2を用いたプロット図
得られた各形態のワカメごとの判別関数2(原藻ワカメ:判別関数2−1、2−2、湯通し塩蔵ワカメ:判別関数2−3、2−4、乾燥ワカメ:判別関数2−5、2−6)に、データベースに蓄積された各形態のワカメごとのヒ素、カドミウム、バリウムの元素量に加え、マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素のいずれか1種以上の元素量を追加した各元素量を代入して得た判別得点を用いて、縦軸に判別関数2−2、2−4、2−6より得られた判別得点4、横軸に判別関数2−1、2−3、2−4より得られた判別得点3をプロットして各形態のワカメごとのプロット図を作成した。得られたプロット図は、プロットした点が判別したい海域ごと、具体的には三陸、瀬戸内、中国、韓国の4海域に精度よく分かれることが確認された。
(2) Plot diagram using discriminant function 2 for each form of seaweed Obtained discriminant function 2 for each form of seaweed (original algae wakame: discriminant functions 2-1, 2-2, boiled salted seaweed: discriminant function 2-3, 2-4, dried seaweed: discriminant functions 2-5, 2-6), in addition to the elemental amounts of arsenic, cadmium, and barium for each form of seaweed accumulated in the database, magnesium, phosphorus, calcium Discriminant function 2-2 on the vertical axis using the discriminant score obtained by substituting the amount of each element to which one or more of the elements of vanadium, manganese, iron, zinc, rubidium and strontium are added. 2-4, the discrimination score 4 obtained from 2-6, the discrimination score 3 obtained from the discriminant functions 2-1, 2-3, 2-4 on the horizontal axis, and a plot diagram for each type of seaweed It was created. It was confirmed that the plots obtained were accurately divided into four areas, namely Sanriku, Setouchi, China, and Korea, where the plotted points were to be identified.
一例として、乾燥ワカメのデータベースに蓄積されたヒ素、カドミウム、バリウムの元素量およびマグネシウム、リン、カルシウム、バナジウム、マンガン、ルビジウムの元素量を乾燥ワカメの判別関数に代入して得た判別得点を用いて作成したプロット図を図2に示す。なお乾燥ワカメの判別関数2−5、2−6の計算式を下記に示す。
乾燥ワカメの判別関数2−5=0.0022[Mg]−0.0004[P]−0.0012[Ca]−0.0162[V]−0.0935[Mn]+0.1790[As]+4.7036[Rb]+0.0000[Cd]+0.4567[Ba]−9.1462
乾燥ワカメの判別関数2−6=−0.0010[Mg]+0.0002[P]−0.0001[Ca]+0.0011[V]+0.2552[Mn]−0.2387[As]+0.4304[Rb]+0.0011[Cd]+0.5522[Ba]+2.9443
As an example, using the discriminant score obtained by substituting the elemental amounts of arsenic, cadmium and barium and the elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese and rubidium accumulated in the dry wakame database into the discriminant function of dry wakame FIG. 2 shows the plot created in this way. Formulas for discriminant functions 2-5 and 2-6 for dried seaweed are shown below.
Discriminant function of dried seaweed 2-5 = 0.0002 [Mg] −0.0004 [P] −0.0012 [Ca] −0.0162 [V] −0.0935 [Mn] +0.1790 [As] +4 7036 [Rb] +0.0000 [Cd] +0.4567 [Ba] -9.1462
Discriminant function of dry seaweed 2-6 = −0.0010 [Mg] +0.0002 [P] −0.0001 [Ca] +0.0011 [V] +0.2552 [Mn] −0.2387 [As] +0. 4304 [Rb] +0.0011 [Cd] +0.5522 [Ba] +2.9443
乾燥ワカメに含まれるヒ素、カドミウム、バリウムの元素量およびマグネシウム、リン、カルシウム、バナジウム、マンガン、ルビジウムの元素量を用いることにより、図2に示す通り、三陸、瀬戸内、中国、韓国の4海域の分布をより明確に確認することができた。データベースのわかめの生育海域の判別率は、三陸100.0%、瀬戸内100.0%、中国100.0%,韓国100.0%であった。 By using the amounts of arsenic, cadmium, and barium contained in dried seaweed and the amounts of elements of magnesium, phosphorus, calcium, vanadium, manganese, and rubidium, as shown in Fig. 2, four areas in Sanriku, Setouchi, China, and Korea The distribution could be confirmed more clearly. The distinction rate of the sea area where the seaweed grows in the database was Sanriku 100.0%, Setouchi 100.0%, China 100.0%, and Korea 100.0%.
(3)4群を判別する分類関数2(ワカメの生育海域判別式2)
ヒ素、カドミウム、バリウムの元素量に加え、さらにマグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ルビジウム、ストロンチウムの元素から選択される1種以上の元素量を用いた4群を判別する分類関数2(ワカメの生育海域判別式2)は、各海域に対して構築される一次関数であり、下記にそれらを示すことができる。式中のA、B、C、D、E、F、G、H、I、J、K、Lは各元素の係数であり、Mは定数である。ここで、「[ ]」内は、各元素量(濃度)であり、バナジウムおよびカドミウムの元素量の濃度単位はppb、他の元素量の濃度単位はppmである。下記一般式に用いる係数および定数を表10〜12に示す。
(ワカメの生育海域判別式2)
三陸 =A[Mg]+B[P]+C[Ca]+D[V]+E[Mn]+F[Fe]+G[Zn]+H[As]+I[Rb]+J[Sr]+K[Cd]+L[Ba]+M
瀬戸内=A[Mg]+B[P]+C[Ca]+D[V]+E[Mn]+F[Fe]+G[Zn]+H[As]+I[Rb]+J[Sr]+K[Cd]+L[Ba]+M
中国 =A[Mg]+B[P]+C[Ca]+D[V]+E[Mn]+F[Fe]+G[Zn]+H[As]+I[Rb]+J[Sr]+K[Cd]+L[Ba]+M
韓国 =A[Mg]+B[P]+C[Ca]+D[V]+E[Mn]+F[Fe]+G[Zn]+H[As]+I[Rb]+J[Sr]+K[Cd]+L[Ba]+M
(3) Classification function 2 for discriminating 4 groups (Wakame's growing sea area discriminant 2)
Classification that distinguishes four groups using one or more elements selected from elements of magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, rubidium, and strontium in addition to the elements of arsenic, cadmium, and barium Function 2 (Wakame's growing sea area discriminant 2) is a linear function constructed for each sea area, and can be shown below. In the formula, A, B, C, D, E, F, G, H, I, J, K, and L are coefficients of each element, and M is a constant. Here, “[]” represents the amount (concentration) of each element, the concentration unit of the element amounts of vanadium and cadmium is ppb, and the concentration unit of the other element amounts is ppm. The coefficients and constants used in the following general formula are shown in Tables 10-12.
(Wakame growth area discriminant 2)
Sanriku = A [Mg] + B [P] + C [Ca] + D [V] + E [Mn] + F [Fe] + G [Zn] + H [As] + I [Rb] + J [Sr] + K [Cd] + L [Ba] + M
Setouchi = A [Mg] + B [P] + C [Ca] + D [V] + E [Mn] + F [Fe] + G [Zn] + H [As] + I [Rb] + J [Sr] + K [Cd] + L [Ba] + M
China = A [Mg] + B [P] + C [Ca] + D [V] + E [Mn] + F [Fe] + G [Zn] + H [As] + I [Rb] + J [Sr] + K [Cd] + L [Ba] + M
Korea = A [Mg] + B [P] + C [Ca] + D [V] + E [Mn] + F [Fe] + G [Zn] + H [As] + I [Rb] + J [Sr] + K [Cd] + L [Ba] + M
上記ワカメの生育海域判別式2に、対象となるワカメに含まれる各元素量(濃度)をそれぞれ代入し、得られた値が最も大きい海域が生育した海域であると判別する。 Each element amount (concentration) contained in the target seaweed is substituted into the seaweed growing sea area discriminant 2, and it is determined that the sea area having the largest obtained value is the sea area where the seaweed has grown.
≪わかめの生育海域を判別する方法の有用性確認2≫
(1)ワカメの生育海域が明確な各形態のワカメの元素量分析
「≪わかめの生育海域を判別する方法の有用性確認1≫」で得られた生育海域が明確な原藻ワカメの冷凍保管品、湯通し塩蔵ワカメおよび乾燥ワカメに含まれる12元素量(マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウム)の測定結果を用いた。
≪Verification of usefulness of the method to determine wakame's growing area 2≫
(1) Elementary analysis of wakame in various forms with clear wakame growth area The frozen storage of the original seaweed wakame with a clear growth area obtained in “<< Availability confirmation method for discriminating wakame growth area 1 >>” The measurement results of 12 element amounts (magnesium, phosphorus, calcium, vanadium, manganese, iron, zinc, arsenic, rubidium, strontium, cadmium, barium) contained in the product, boiled salted seaweed and dried seaweed were used.
(2)各形態のワカメに対応した生育海域判別式2用いた判別する方法の有用性確認
得られた各生育海域および各形態のワカメに含まれる12元素量(マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウム)を用いて、各形態のワカメに対応した生育海域判別式2に必要な元素量をそれぞれ代入した。結果として、全ての産地が正しく判別することができた。
(2) Confirmation of the usefulness of the discrimination method using the growing sea area discriminant 2 corresponding to each form of seaweed Each amount of 12 elements contained in each growing sea area and each form of seaweed (magnesium, phosphorus, calcium, vanadium, Using manganese, iron, zinc, arsenic, rubidium, strontium, cadmium, barium), the necessary element amounts were substituted into the growing sea area discriminant 2 corresponding to each form of seaweed. As a result, all production areas were correctly identified.
(3)生育海域判別式2を用いた判別する方法の有用性確認例
一例として、原藻ワカメの生育海域が三陸である乾燥ワカメに含まれるヒ素、カドミウム、バリウムの元素量に加えマグネシウム、リン、カルシウム、バナジウム、マンガン、ルビジウムの元素量を用いた乾燥ワカメに対応した生育海域判別式2の計算式を下記に示す。
三陸 =−0.0018[Mg]+0.0168[P]+0.0291[Ca]−0.2133[V]−2.8511[Mn]+1.6303[As]+44.6330[Rb]+0.0148[Cd]+3.3564[Ba]−215.8717
瀬戸内=−0.0080[Mg]+0.0136[P]+0.0304[Ca]−0.1550[V]−1.3612[Mn]+0.7862[As]+35.5875[Rb]+0.0055[Cd]+2.9792[Ba]−176.1382
中国 =0.0501[Mg]+0.0070[P]−0.0028[Ca]−0.6198[V]−3.5942[Mn]+4.9526[As]+168.9660[Rb]+0.0166[Cd]+18.0750[Ba]−603.5775
韓国 =0.0504[Mg]+0.0045[P]+0.0040[Ca]−0.5429[V]−5.6785[Mn]+6.7892[As]+141.0522[Rb]−0.0008[Cd]+9.3398[Ba]−498.8069
(3) Example of confirming the usefulness of the method of discriminating using the growing sea area discriminant 2 As an example, in addition to the elemental amounts of arsenic, cadmium and barium contained in dry seaweeds where the growing sea area of the original alga wakame is Sanriku, magnesium, phosphorus The calculation formula of the growth sea area discriminant 2 corresponding to dry seaweed using the elemental amounts of calcium, vanadium, manganese and rubidium is shown below.
Sanriku = -0.0018 [Mg] + 0.0168 [P] + 0.0291 [Ca]-0.2133 [V] -2.8511 [Mn] + 1.6303 [As] + 44.6330 [Rb] + 0.0148 [Cd] +3.3564 [Ba] -2155.8717
Setouchi = −0.0080 [Mg] +0.0136 [P] +0.0304 [Ca] −0.1550 [V] −1.3612 [Mn] +0.7862 [As] +35.5875 [Rb] +0.0055 [Cd] +2.9792 [Ba] -176.1382
China = 0.0501 [Mg] +0.0070 [P] -0.0028 [Ca] -0.6198 [V] -3.5942 [Mn] +4.9526 [As] +168.9660 [Rb] +0.0166 [Cd] +18.0750 [Ba] -603.5775
Korea = 0.0504 [Mg] + 0.0045 [P] + 0.0040 [Ca]-0.5429 [V]-5.6785 [Mn] + 6.7892 [As] + 141.0522 [Rb]-0.0008 [Cd] +9.3398 [Ba] -498.8069
上記式に、原藻ワカメの生育海域が三陸である乾燥ワカメ(表5)に示した、ヒ素、カドミウム、バリウムの元素量に加えマグネシウム、リン、カルシウム、バナジウム、マンガン、ルビジウムの元素量を代入したところ、三陸=207、瀬戸内=192、中国=−155、韓国=−18と、三陸の値が他の海域の数値より大きく、三陸で生育した原藻ワカメを用いた乾燥ワカメを用いた乾燥ワカメであると判別することができた。 Substitute the elemental amounts of magnesium, phosphorus, calcium, vanadium, manganese, and rubidium in addition to the elemental amounts of arsenic, cadmium, and barium shown in the dry wakame (Table 5), where the seaweed seaweed grows in Sanriku. As a result, Sanriku = 207, Setouchi = 192, China = -155, Korea = -18, the value of Sanriku is larger than the values of other sea areas, and drying using dried seaweed using raw algae wakame grown in Sanriku I was able to determine that it was a wakame.
≪各形態のワカメに共通した生育海域判別式による生育海域を判別する方法≫
構築したデータベースに含まれる元素の内、ストロンチウムを選択し、ストロンチウムの元素量で他の元素量をそれぞれ割り、次いで対数をとり、該数値を説明変数として判別分析することで4群を判別する分類関数3(ワカメの生育海域判別式3)を得た。
≪Method of discriminating the growing sea area using the growing sea area discriminant common to wakame of each form≫
Classification of 4 groups by selecting strontium from the elements contained in the constructed database, dividing the amount of other elements by the amount of strontium, then taking the logarithm, and discriminating and analyzing these numbers as explanatory variables Function 3 (Wakame's growing sea area discriminant 3) was obtained.
得られた4群を判別する分類関数3(ワカメの生育海域判別式3)は、下記にそれらを示すことができる。式中のA、B、C、D、E、F、G、H、I、K、Lは各元素の係数であり、Mは定数である。下記一般式に用いる係数および定数を表13に示す。
(ワカメの生育海域判別式3)
三陸 =A[log(Mg/Sr)]+B[log(P/Sr)]+C[log(Ca/Sr)]+D[log(V/Sr)]+E[log(Mn/Sr)]+F[log(Fe/Sr)]+G[log(Zn/Sr)]+H[log(As/Sr)]+I[log(Rb/Sr)]+K[log(Cd/Sr)]+L[log(Ba/Sr)]+M
三瀬戸内=A[log(Mg/Sr)]+B[log(P/Sr)]+C[log(Ca/Sr)]+D[log(V/Sr)]+E[log(Mn/Sr)]+F[log(Fe/Sr)]+G[log(Zn/Sr)]+H[log(As/Sr)]+I[log(Rb/Sr)]+K[log(Cd/Sr)]+L[log(Ba/Sr)]+M
中国 =A[log(Mg/Sr)]+B[log(P/Sr)]+C[log(Ca/Sr)]+D[log(V/Sr)]+E[log(Mn/Sr)]+F[log(Fe/Sr)]+G[log(Zn/Sr)]+H[log(As/Sr)]+I[log(Rb/Sr)]+K[log(Cd/Sr)]+L[log(Ba/Sr)]+M
韓国 =A[log(Mg/Sr)]+B[log(P/Sr)]+C[log(Ca/Sr)]+D[log(V/Sr)]+E[log(Mn/Sr)]+F[log(Fe/Sr)]+G[log(Zn/Sr)]+H[log(As/Sr)]+I[log(Rb/Sr)]+K[log(Cd/Sr)]+L[log(Ba/Sr)]+M
The classification function 3 for discriminating the four groups obtained (Wakame's growing sea area discriminant 3) can be shown below. In the formula, A, B, C, D, E, F, G, H, I, K, and L are coefficients of each element, and M is a constant. Table 13 shows coefficients and constants used in the following general formula.
(Wakame growth area discriminant 3)
Sanriku = A [log (Mg / Sr)] + B [log (P / Sr)] + C [log (Ca / Sr)] + D [log (V / Sr)] + E [log (Mn / Sr)] + F [log (Fe / Sr)] + G [log (Zn / Sr)] + H [log (As / Sr)] + I [log (Rb / Sr)] + K [log (Cd / Sr)] + L [log (Ba / Sr) ] + M
Mise Tonai = A [log (Mg / Sr)] + B [log (P / Sr)] + C [log (Ca / Sr)] + D [log (V / Sr)] + E [log (Mn / Sr)] + F [ log (Fe / Sr)] + G [log (Zn / Sr)] + H [log (As / Sr)] + I [log (Rb / Sr)] + K [log (Cd / Sr)] + L [log (Ba / Sr) ] + M
China = A [log (Mg / Sr)] + B [log (P / Sr)] + C [log (Ca / Sr)] + D [log (V / Sr)] + E [log (Mn / Sr)] + F [log (Fe / Sr)] + G [log (Zn / Sr)] + H [log (As / Sr)] + I [log (Rb / Sr)] + K [log (Cd / Sr)] + L [log (Ba / Sr) ] + M
Korea = A [log (Mg / Sr)] + B [log (P / Sr)] + C [log (Ca / Sr)] + D [log (V / Sr)] + E [log (Mn / Sr)] + F [log (Fe / Sr)] + G [log (Zn / Sr)] + H [log (As / Sr)] + I [log (Rb / Sr)] + K [log (Cd / Sr)] + L [log (Ba / Sr) ] + M
各形態のワカメに共通した生育海域判別式に、対象となるワカメに含まれる各元素量(濃度)をそれぞれ代入し、得られた値が最も大きい海域が生育した海域であると判別する。 The amount of each element (concentration) contained in the target seaweed is substituted into the growing sea area discriminant common to each form of seaweed, and it is determined that the sea area where the obtained value is the largest is the sea area where it grew.
≪わかめの生育海域を判別する方法の有用性確認3≫
「≪わかめの生育海域を判別する方法の有用性確認1≫」で得られた生育海域が明確な原藻ワカメの冷凍保管品、湯通し塩蔵ワカメおよび乾燥ワカメに含まれる12元素量(マグネシウム、リン、カルシウム、バナジウム、マンガン、鉄、亜鉛、ヒ素、ルビジウム、ストロンチウム、カドミウム、バリウム)を用いて、各形態のワカメに共通した生育海域判別式3に必要な元素量を代入した。結果として、全ての産地が正しく判別することができた。
≪Confirmation of usefulness 3 of the method to determine the sea area where seaweed grows≫
The amount of 12 elements (magnesium, phosphorus contained in frozen stored products of fresh seaweed wakame, boiled salted wakame, and dried wakame obtained in “<< Confirmation of usefulness of method for determining wakame's growing area 1”] , Calcium, vanadium, manganese, iron, zinc, arsenic, rubidium, strontium, cadmium, barium), and the necessary element amount was substituted into the growing sea area discriminant 3 common to each form of seaweed. As a result, all production areas were correctly identified.
各形態のワカメに共通した生育海域判別式の計算式を下記に示す。
三陸 =−47.4103[log(Mg/Sr)]+144.1830[log(P/Sr)]+649.9633[log(Ca/Sr)]−15.9965[log(V/Sr)]−110.8227[log(Mn/Sr)]+131.8724[log(Fe/Sr)]−159.1795[log(Zn/Sr)]−315.2929[log(As/Sr)]−77.4170[log(Rb/Sr)]+57.0174[log(Cd/Sr)]−815.1522[log(Ba/Sr)]−1631.7646
三瀬戸内=−50.7225[log(Mg/Sr)]+131.7277[log(P/Sr)]+653.6808[log(Ca/Sr)]−14.6226[log(V/Sr)]−106.7810[log(Mn/Sr)]+123.5824[log(Fe/Sr)]−137.5183[log(Zn/Sr)]−299.4739[log(As/Sr)]−67.4371[log(Rb/Sr)]+23.9402[log(Cd/Sr)]−785.2979[log(Ba/Sr)]−1493.0359
中国 =−29.0584[log(Mg/Sr)]+132.9428[log(P/Sr)]+625.5954[log(Ca/Sr)]−18.8345[log(V/Sr)]−97.3314[log(Mn/Sr)]+118.0612[log(Fe/Sr)]−154.8786[log(Zn/Sr)]−320.0668[log(As/Sr)]−63.5597[log(Rb/Sr)]+59.1816[log(Cd/Sr)]−660.2268[log(Ba/Sr)]−1309.6505
韓国 =−44.0012[log(Mg/Sr)]+137.6237[log(P/Sr)]+628.2615[log(Ca/Sr)]−16.2279[log(V/Sr)]−113.2484[log(Mn/Sr)]+135.6746[log(Fe/Sr)]−159.2027[log(Zn/Sr)]−294.5325[log(As/Sr)]−73.7673[log(Rb/Sr)]+50.7039[log(Cd/Sr)]−775.0606[log(Ba/Sr)]−1499.8765
The calculation formula of the discriminating sea area common to wakame of each form is shown below.
Sanriku = −47.4103 [log (Mg / Sr)] + 1448.1830 [log (P / Sr)] + 649.9633 [log (Ca / Sr)] − 15.9965 [log (V / Sr)] − 110 8227 [log (Mn / Sr)] + 131.8724 [log (Fe / Sr)]-159.1795 [log (Zn / Sr)]-3152929 [log (As / Sr)]-77.4170 [ log (Rb / Sr)] + 57.0174 [log (Cd / Sr)] − 815.1522 [log (Ba / Sr)] − 1631.7646
Mise Tonai = −50.7225 [log (Mg / Sr)] + 131.7277 [log (P / Sr)] + 6533.6808 [log (Ca / Sr)] − 14.6226 [log (V / Sr)] − 106.7810 [log (Mn / Sr)] + 123.5824 [log (Fe / Sr)]-137.5183 [log (Zn / Sr)]-299.4739 [log (As / Sr)]-67.4371 [Log (Rb / Sr)] + 23.9402 [log (Cd / Sr)]-785.2979 [log (Ba / Sr)]-1493.0359
China = -29.058 [log (Mg / Sr)] + 132.9428 [log (P / Sr)] + 6255.5594 [log (Ca / Sr)] − 18.8345 [log (V / Sr)] − 97 3314 [log (Mn / Sr)] + 118.0612 [log (Fe / Sr)]-154.8786 [log (Zn / Sr)]-320.0668 [log (As / Sr)]-63.5597 [ log (Rb / Sr)] + 59.816 [log (Cd / Sr)] − 660.2268 [log (Ba / Sr)] − 1309.6505
South Korea = −44.0012 [log (Mg / Sr)] + 177.6237 [log (P / Sr)] + 628.615 [log (Ca / Sr)] − 162.279 [log (V / Sr)] − 113 2484 [log (Mn / Sr)] + 135.6746 [log (Fe / Sr)]-159.2727 [log (Zn / Sr)]-294.5325 [log (As / Sr)]-73.7673 [ log (Rb / Sr)] + 50.7039 [log (Cd / Sr)] − 775.0606 [log (Ba / Sr)] − 14999.8765
上記式の各元素量に、原藻ワカメの生育海域が三陸である乾燥ワカメ(表5)に示した12元素量を代入したところ、三陸=1718、瀬戸内=1702、中国=1667、韓国=1709となり、三陸の値が他の海域の数値より大きくなり、三陸で生育した原藻ワカメを用いた乾燥ワカメであると判別することができた。 Substituting the elemental amounts of the above formulas for the 12 elements shown in dry seaweed (Table 5) where the seaweed seaweed is growing in Sanriku (Table 5), Sanriku = 1718, Setouchi = 1702, China = 1667, Korea = 1709 As a result, the value of Sanriku became larger than the value of other sea areas, and it was possible to discriminate it as a dry wakame using the original alga wakame grown in Sanriku.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014259686A JP6459495B2 (en) | 2014-12-24 | 2014-12-24 | How to determine the sea area of wakame |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014259686A JP6459495B2 (en) | 2014-12-24 | 2014-12-24 | How to determine the sea area of wakame |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016118516A JP2016118516A (en) | 2016-06-30 |
JP6459495B2 true JP6459495B2 (en) | 2019-01-30 |
Family
ID=56244076
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014259686A Active JP6459495B2 (en) | 2014-12-24 | 2014-12-24 | How to determine the sea area of wakame |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6459495B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6629782B2 (en) * | 2017-04-04 | 2020-01-15 | 株式会社レナテック | Age-related macular degeneration risk assessment method and system |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006141379A (en) * | 2004-11-18 | 2006-06-08 | Stems:Kk | Method for removing element toxic to human in seaweed and indication |
JP2011256153A (en) * | 2010-06-11 | 2011-12-22 | Yaizu Suisankagaku Industry Co Ltd | Method for producing fucoxanthin-containing brown algae extraction composition |
JP5558991B2 (en) * | 2010-09-22 | 2014-07-23 | 株式会社同位体研究所 | Wakame growing area identification method |
JP2014209096A (en) * | 2013-03-22 | 2014-11-06 | 不二製油株式会社 | Place of production determination method for soybean raw material and soybean processed product |
-
2014
- 2014-12-24 JP JP2014259686A patent/JP6459495B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2016118516A (en) | 2016-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Meng et al. | Accumulation of total mercury and methylmercury in rice plants collected from different mining areas in China | |
Zhu et al. | Application of hyperspectral technology in detection of agricultural products and food: A Review | |
JP6708829B1 (en) | Mixing tracking method and system for imported beef producing areas | |
Khan et al. | Determination of cadmium concentrations of vegetables grown in soil irrigated with wastewater: evaluation of health risk to the public | |
Shagal et al. | Bioaccumulation of trace metals concentration in some vegetables grown near refuse and effluent dumpsites along Rumude-Doubeli bye-pass in Yola North, Adamawa State | |
Kaunova et al. | Identification of wine provenance by ICP-AES multielement analysis | |
Derkowska et al. | Assessment of mycorrhizal frequency in the roots of fruit plants using different dyes | |
Rop et al. | Nutritional values of new Czech cultivars of Saskatoon berries (Amelanchier alnifolia Nutt.). | |
De Feudis et al. | Mid-term (30 years) changes of soil properties under chestnut stands due to organic residues management: An integrated study | |
Feng et al. | Discriminating batches of ‘Hayward’kiwifruit for storage potential | |
JP6459495B2 (en) | How to determine the sea area of wakame | |
Yu et al. | Spectroscopic properties of dissolved fulvic acids: an indicator for soil salinization in arid and semiarid regions in China | |
Debebe et al. | Metallic nutrients in enset (Ensete ventricosum) corm cultivated in Wolliso and Wolkite towns in Ethiopia | |
Vural et al. | Trace metal levels and some chemical parameters in herby cheese collected from south eastern Anatolia-Turkey | |
Khan et al. | Physicochemical characterization of the strawberry samples on regional basis using multivariate analysis | |
JP6455834B2 (en) | How to determine the sea area of wakame | |
Benincasa et al. | Quality and trace element profile of tunisian olive oils obtained from plants irrigated with treated wastewater | |
Schaefer et al. | Analytical and chemometric characterization of the Cruces River in South Chile | |
Flores et al. | Heavy metals accumulation in banana (musa spp.) leaves from industrial area in rio de Janeiro | |
Shaughnessy et al. | Reliability of the resorcinol method for identifying isomorphic phases in the Gigartinaceae (Rhodophyta) | |
Tufik | Productivity of potato seed submitted to different doses of potassium in hydroponic system | |
Al-Naimi et al. | Investigating chlorophyll and nitrogen levels of mangroves at Al-Khor, Qatar: an integrated chemical analysis and remote sensing approach | |
ZENG et al. | Rapid determination of cadmium residues in tomato leaves by Vis-NIR hyperspectral and Synergy interval PLS coupled Monte Carlo method | |
Anawar et al. | Effects of different drying processes on the concentrations of metals and metalloids in plant materials | |
Sivakumar et al. | Relating leaf nutrient status to fruit quality attributes in Litchi cv.‘Mauritius’ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170908 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20170908 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180516 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180605 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180702 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181211 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181217 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6459495 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |