JP4275633B2 - Pesticide residue extraction method and extraction kit - Google Patents

Pesticide residue extraction method and extraction kit Download PDF

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JP4275633B2
JP4275633B2 JP2005060563A JP2005060563A JP4275633B2 JP 4275633 B2 JP4275633 B2 JP 4275633B2 JP 2005060563 A JP2005060563 A JP 2005060563A JP 2005060563 A JP2005060563 A JP 2005060563A JP 4275633 B2 JP4275633 B2 JP 4275633B2
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solvent
extraction
logpow
hydrophobic
agricultural
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JP2006242825A (en
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雅彦 北山
正樹 小園
丘 大森
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Nippon Meat Packers Inc
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Priority to PCT/JP2006/304682 priority patent/WO2006093359A1/en
Priority to BRPI0608051-0A priority patent/BRPI0608051A2/en
Priority to CN200680013965.8A priority patent/CN101166965B/en
Priority to US11/885,515 priority patent/US20090214734A1/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G01N2001/4061—Solvent extraction

Description

本発明は残留農薬の抽出方法及び抽出キットに関する。より詳細には、農産物が含有する残留農薬を簡便にして且つ効率的に抽出する方法及びそれに使用する抽出キットに関する。   The present invention relates to a method for extracting residual agricultural chemicals and an extraction kit. More specifically, the present invention relates to a method for easily and efficiently extracting residual agricultural chemicals contained in agricultural products and an extraction kit used therefor.

従来より、農産物の生産性を高めるために種々の農薬が使用されてきた。近年、食物中の残留物質への関心が高まり、残留物質の測定が重視されてきている。これに対応する形で、国の方でも、農産物中に残存する残留物質に関する基準を設定しようとしている（非特許文献１参照）。
しかし、従来法は、少数の残留物質の測定を目標にしており、多くの残留物質の測定には適していなかった。農薬としては極めて多種多様の薬剤が使用されており、測定の簡便化及び迅速化を図るためには、多種類の農薬を一度に測定する方法の重要性が高まっている（非特許文献２参照）。
具体的には、従来の残留農薬の測定法は、測定ステップが煩雑で、時間（約６Ｈ）、費用、手間（約３０工程）がかかり、より簡便な手法及びキットが必要とされていた。また、水分の多い野菜・果実の測定では、親水性の高いアセトニトリルやアセトンなどの溶媒を使用しているため、色素など測定対象以外の成分も抽出され、これら夾雑物の除去に手間がかかること、更に、係る手間をかけても残存する夾雑物が、測定時のノイズとなることが問題となっていた。
一方、農薬の多くは低極性であり親水性の高い溶媒による抽出が適当でないものが多かった。また、従来法では、タマネギやキャベツなどのようにイオウ成分を含む場合、産生した硫酸イオンで酸性となり、酸性条件下では破壊される農薬成分もあったためｐＨ調整が必要であった。さらに、大豆など脂肪含量の高いものについては脱脂のために工程を増やすかあるいはGPCなどの高価な機器が必要とされていた。
食安発第0124001号厚生労働省医薬食品局食品安全部長通知 別添 「食品に残留する農薬、飼料添加物又は動物用医薬品の成分である物質の試験法」 食衛誌44.(5).234-245(2003),「農作物中の104種農薬残留スクリーニング分析に関わる試験技能評価の試み」 Conventionally, various agricultural chemicals have been used to increase the productivity of agricultural products. In recent years, interest in residual substances in food has increased, and the measurement of residual substances has been emphasized. Corresponding to this, the national government is also trying to set a standard for residual substances remaining in agricultural products (see Non-Patent Document 1).
However, the conventional method is aimed at measuring a small number of residual substances, and is not suitable for the measurement of many residual substances. A wide variety of drugs are used as pesticides, and in order to simplify and speed up the measurement, the importance of a method for measuring many types of pesticides at once is increasing (see Non-Patent Document 2). ).
Specifically, in the conventional method for measuring residual agricultural chemicals, the measurement steps are complicated, and it takes time (about 6H), cost, and labor (about 30 steps), and a simpler method and kit are required. In addition, in the measurement of vegetables and fruits with a lot of moisture, since solvents such as acetonitrile and acetone with high hydrophilicity are used, components other than the measurement target such as pigment are extracted, and it takes time to remove these impurities. Furthermore, it has been a problem that the impurities that remain even after such time and effort become noise during measurement.
On the other hand, many of the agricultural chemicals have low polarity and many are not suitable for extraction with a highly hydrophilic solvent. Further, in the conventional method, when a sulfur component such as onion or cabbage is included, pH adjustment is necessary because some agrochemical components become acidic with the produced sulfate ions and are destroyed under acidic conditions. Furthermore, for those with a high fat content such as soybeans, the number of processes was increased for degreasing, or expensive equipment such as GPC was required.
Notification of Food Safety No. 0124001, General Manager of Food Safety Department, Ministry of Health, Labor and Welfare, Ministry of Health, Labor and Welfare Attachment “Method for testing substances remaining in foods as ingredients of agricultural chemicals, feed additives or veterinary drugs” Food Safety Journal 44. (5) .234-245 (2003), "Trial of skill evaluation for screening analysis of 104 pesticide residues in crops"

上述のように、従来の残留農薬の測定法においては、農産物から残留農薬を抽出する工程（前処理工程）が非常に長く且つ煩雑であって、時間を要し、測定上の問題となっていた。
そこで、本発明者らは、簡易な前処理法（残留農薬の抽出方法）を検討したところ、従来の抽出溶媒と全く異なる抽出溶媒を使用すること及び農産物を前処理剤で処理することにより、簡便且つ効率的に残留農薬を抽出し得ることを見出した。
より具体的には、本発明者らは１）目的とする農薬を効率良く抽出でき、その一方で夾雑物質を抽出することのない抽出溶媒と２）前処理剤との組み合わせを検討した。
まず、上記１）を検討するに当たっては、農薬の化学的性質に着目して検討を行った。具体的には、化合物の極性の指標としてオクタノール／水分配係数（本明細書では、logPowと表記する）に着目した（logPowについては、国立医薬品食品衛生研究所ＨＰ 医薬品情報検索のデータベースなど参照）。
農薬の多くはlogPowが２〜７の間である。これらの農薬を幅広く効率的に溶解するにはlogPowが３〜４程度の極性を示す溶媒が適当である。一方、ジクロルボスの様にlogPow が１程度のものや、アセフェート、メタミドホスのようにマイナスの値を示す農薬もある。これらの農薬をも溶解するためにはより高い極性の溶媒が必要となる。
そこで、logPowを0から4程度の極性の疎水性溶媒を使用するか、又は疎水性溶媒と親水性溶媒の混合溶媒を使用して、脱水処理を施した試料を材料に農薬の抽出を行ったところ、色素やその他の夾雑物の抽出量が著しく低くなることを見出した。上記の混合溶媒としては、疎水性溶媒、好ましくは、ｎ−ヘキサン（logPow, 3.9)を主体として、そこにlogPowが-1.0〜0程度の親水性溶媒、好ましくは、アセトン（logPow, -0.24)を適量添加した溶媒が例示される。 As described above, in the conventional method for measuring residual agricultural chemicals, the process of extracting residual agricultural chemicals from agricultural products (pretreatment process) is very long and cumbersome, takes time, and is a measurement problem. It was.
Therefore, the present inventors examined a simple pretreatment method (extracting method of residual agricultural chemicals), and by using an extraction solvent completely different from the conventional extraction solvent and treating the agricultural products with the pretreatment agent, It was found that residual agricultural chemicals can be extracted easily and efficiently.
More specifically, the present inventors examined 1) a combination of an extraction solvent that can efficiently extract the target pesticide while not extracting impurities and 2) a pretreatment agent.
First, in examining the above 1), the investigation was conducted focusing on the chemical properties of agricultural chemicals. Specifically, we focused on the octanol / water partition coefficient (referred to as logPow in this specification) as an indicator of the polarity of the compound (for information on logPow, refer to the National Institute of Health Sciences HP database for drug information search, etc.) .
Most pesticides have a logPow between 2 and 7. In order to dissolve these agricultural chemicals widely and efficiently, a solvent having a polarity of logPow of about 3 to 4 is suitable. On the other hand, some pesticides have a logPow of about 1, such as dichlorvos, and negative pesticides, such as acephate and methamidophos. In order to dissolve these pesticides, a higher polarity solvent is required.
Therefore, pesticides were extracted from the dehydrated sample using logPow with a hydrophobic solvent with a polarity of 0 to 4 or a mixed solvent of hydrophobic and hydrophilic solvents. However, it has been found that the extraction amount of pigments and other impurities is significantly reduced. As the above mixed solvent, a hydrophobic solvent, preferably a n-hexane (logPow, 3.9) as a main component, and a logPow of about -1.0 to 0 is a hydrophilic solvent, preferably acetone (logPow, -0.24). A solvent to which an appropriate amount is added is exemplified.

次に、前記の２）に関し、上記の溶媒は疎水性溶媒を主体とするため水分の多い野菜などへの浸透性に問題がある。そこで、農産物試料を脱水剤、好ましくは珪藻土を使用する脱水工程に、予め付すことにより問題点を改善した。本方法により従来は使用できなかったｎ−ヘキサンのような低極性の疎水性溶媒を用いた抽出が可能になった。
本発明は係る知見に基づくもので、農産物から簡便且つ効率的に残留農薬を抽出する方法及びそれに使用する抽出キットを提供するものである。 Next, with respect to the above 2), since the above-mentioned solvent is mainly composed of a hydrophobic solvent, there is a problem in permeability to vegetables with a lot of moisture. Therefore, the problem was improved by subjecting the agricultural product sample to a dehydration step using a dehydrating agent, preferably diatomaceous earth, in advance. This method enabled extraction using a low-polarity hydrophobic solvent such as n-hexane, which could not be used conventionally.
The present invention is based on such knowledge, and provides a method for easily and efficiently extracting residual agricultural chemicals from agricultural products and an extraction kit used therefor.

上記の課題を解決するためになされた本願発明は、下記の工程からなる農産物中の残留農薬の抽出方法である。
(1)農産物を、残留農薬を抽出可能な形状に加工する工程；
(2)上記の処理がされた農産物を脱水剤で処理する工程；及び
(3)脱水処理された農産物から、logPowが０〜４である疎水性溶媒又は疎水性溶媒−親水性溶媒の混合溶媒を使用して残留農薬を抽出する工程。
上記の疎水性溶媒−親水性溶媒の混合溶媒としてはｎ−ヘキサン−アセトン混合溶媒を使用するのが好ましく、更に脱水剤で処理する工程と同時又はその後に、活性炭処理及び／又は逆相クロマトグラフィー用担体で処理するのがより好ましい。
本発明の抽出キットは、上記の方法に使用されるキットであり、脱水剤を主成分とする前処理剤、及びlogPowが０〜４である疎水性溶媒又は疎水性溶媒−親水性溶媒の混合溶媒からなる抽出剤で構成される。上記の疎水性溶媒−親水性溶媒の混合溶媒としてはｎ−ヘキサン−アセトン混合溶媒を使用するのが好ましく、また上記の前処理剤は脱水剤と共に、活性炭及び逆相クロマトグラフィー用担体の少なくとも一種を含むことが好ましい。 This invention made | formed in order to solve said subject is the extraction method of the residual pesticide in agricultural products which consists of the following processes.
(1) A process for processing agricultural products into a shape from which residual agricultural chemicals can be extracted;
(2) a step of treating the agricultural product subjected to the above treatment with a dehydrating agent; and
(3) A step of extracting residual agricultural chemicals from a dehydrated agricultural product using a hydrophobic solvent having a logPow of 0 to 4 or a mixed solvent of a hydrophobic solvent and a hydrophilic solvent.
As the mixed solvent of the above-mentioned hydrophobic solvent-hydrophilic solvent, it is preferable to use an n-hexane-acetone mixed solvent, and at the same time or after the step of treating with a dehydrating agent, activated carbon treatment and / or reverse phase chromatography. More preferably, it is treated with a carrier.
The extraction kit of the present invention is a kit used in the above method, a pretreatment agent mainly composed of a dehydrating agent, and a hydrophobic solvent having a logPow of 0 to 4 or a mixture of a hydrophobic solvent and a hydrophilic solvent. It consists of an extractant consisting of a solvent. As the mixed solvent of the above-mentioned hydrophobic solvent-hydrophilic solvent, it is preferable to use an n-hexane-acetone mixed solvent, and the above pretreatment agent is at least one of activated carbon and a carrier for reverse phase chromatography together with a dehydrating agent. It is preferable to contain.

本発明の方法及びキットによれば、抽出溶媒として疎水性溶媒を主体とする溶媒が使用されるので、色素などの夾雑物の抽出量が少なくなり、操作が簡便化されると共に測定精度の向上が図れる。更に、農産物を脱水剤で処理しているので、含硫農産物からの硫酸イオンの産生を抑制でき、酸性条件下で不安定な農薬成分の測定をも行うことができるという格別な効果を奏する。   According to the method and kit of the present invention, since a solvent mainly composed of a hydrophobic solvent is used as an extraction solvent, the extraction amount of impurities such as pigments is reduced, the operation is simplified and the measurement accuracy is improved. Can be planned. Furthermore, since the agricultural product is treated with the dehydrating agent, the production of sulfate ions from the sulfur-containing agricultural product can be suppressed, and the pesticide components that are unstable under acidic conditions can be measured.

本発明の方法は前記の工程よりなる残留農薬の抽出方法である。
本発明の方法においては、最初に農産物を残留農薬を抽出可能な形状に加工する。この工程は農産物の種類に応じて適宜な態様にて行われる。例えば、農産物が野菜類、果実類などのような場合には、裁断して小片化することにより行われ、豆類、穀類のような場合には粉砕して粉末化することにより行われる。何れにしても、農産物の形態に応じて、残留農薬の抽出効率が向上するような形状に加工する。 The method of the present invention is a method for extracting residual agricultural chemicals comprising the steps described above.
In the method of the present invention, an agricultural product is first processed into a shape from which residual agricultural chemicals can be extracted. This step is performed in an appropriate manner depending on the type of agricultural product. For example, when the agricultural products are vegetables, fruits and the like, the cutting is performed by cutting into small pieces, and when the agricultural products are beans and cereals, they are pulverized and powdered. In any case, it is processed into a shape that improves the extraction efficiency of residual agricultural chemicals according to the form of the agricultural product.

かくして加工された農産物（以下、農産物試料という）は次いで脱水工程に付される。前述のように、本発明の方法においては、抽出溶媒として疎水性溶媒を主体とする溶媒が使用されるので、農産物試料の含水量が多いと溶媒との親和性に欠けるので、脱水剤により水分含量を低減させる。
脱水剤としては慣用の脱水剤の何れも使用することができ、例えば珪藻土、モレキュラーシーブ、シリカゲル、無水硫酸ナトリウム、無水硫酸マグネシウムなどが例示できる。
係る脱水剤の使用量は、農産物試料中の水分含量、脱水剤の脱水能などに応じて適宜調整することができるが、通常、農産物試料に対して０．５〜３倍量（重量比）程度とされる。 The agricultural product thus processed (hereinafter referred to as agricultural product sample) is then subjected to a dehydration step. As described above, in the method of the present invention, a solvent mainly composed of a hydrophobic solvent is used as an extraction solvent. Therefore, if the water content of the agricultural product sample is high, the affinity with the solvent is insufficient. Reduce the content.
Any conventional dehydrating agent can be used as the dehydrating agent. Examples thereof include diatomaceous earth, molecular sieve, silica gel, anhydrous sodium sulfate, and anhydrous magnesium sulfate.
The amount of the dehydrating agent used can be adjusted as appropriate according to the water content in the agricultural product sample, the dehydrating ability of the dehydrating agent, etc., but usually 0.5 to 3 times the weight of the agricultural product sample (weight ratio). It is said to be about.

上記の工程で脱水された農産物試料は、logPowが０〜４である疎水性溶媒又は疎水性溶媒−親水性溶媒からなる混合溶媒による抽出工程に付される。
この工程で使用されるlogPowが０〜４である疎水性溶媒としては、logPowがこの範囲であれば慣用の溶媒を使用することができるが、例えばｎ−ヘキサン（logPow, 3.9）、酢酸エチル（logPow, 0.73）、ジクロロメタン（logPow, 1.25）、ベンゼン（logPow, 2.13）、トルエン（logPow, 2.69）、四塩化炭素（logPow, 2.64）などが例示され、これらの溶媒は２種以上を混合して使用してもよい。
また、抽出溶媒としては、疎水性溶媒と親水性溶媒の混合溶媒を使用してもよく、疎水性溶媒としては、上記記載の溶媒の他、オクタン（logPow, 5.0）などが例示できる。
親水性溶媒としては、例えばアセトン(logPow, -0.24)、メタノール(logPow, -0.82)、エタノール(logPow, -0.32)、アセトニトリル(logPow, -0.3)などの慣用の溶媒を使用することができる。
疎水性溶媒−親水性溶媒における混合比としては、疎水性溶媒：親水性溶媒＝９５〜３０：５〜７０（容量比、溶媒の混合比に関しては以下同様）、好ましくは８０〜４５：２０〜５５、より好ましくは５０：５０の比率の溶媒が使用される。親水性溶媒量がこの範囲より多くなると色素などの夾雑物の抽出量が増え、またこの範囲より少なくなると残留農薬の抽出量が低減するおそれがある。 The agricultural product sample dehydrated in the above process is subjected to an extraction process using a hydrophobic solvent having a logPow of 0 to 4 or a mixed solvent composed of a hydrophobic solvent and a hydrophilic solvent.
As the hydrophobic solvent having logPow of 0 to 4 used in this step, a conventional solvent can be used as long as logPow is within this range. For example, n-hexane (logPow, 3.9), ethyl acetate ( logPow, 0.73), dichloromethane (logPow, 1.25), benzene (logPow, 2.13), toluene (logPow, 2.69), carbon tetrachloride (logPow, 2.64), etc. These solvents are mixed in two or more. May be used.
Further, as the extraction solvent, a mixed solvent of a hydrophobic solvent and a hydrophilic solvent may be used, and examples of the hydrophobic solvent include octane (logPow, 5.0) in addition to the above-described solvents.
As the hydrophilic solvent, for example, a conventional solvent such as acetone (logPow, -0.24), methanol (logPow, -0.82), ethanol (logPow, -0.32), acetonitrile (logPow, -0.3) can be used.
The mixing ratio of the hydrophobic solvent to the hydrophilic solvent is as follows: hydrophobic solvent: hydrophilic solvent = 95 to 30: 5 to 70 (volume ratio, solvent mixing ratio is the same hereinafter), preferably 80 to 45:20 to 55, more preferably a 50:50 ratio of solvent is used. When the amount of the hydrophilic solvent is larger than this range, the amount of extracted impurities such as pigments increases, and when the amount of the hydrophilic solvent is smaller than this range, the amount of extracted residual agricultural chemicals may be reduced.

上述の疎水性溶媒及び親水性溶媒において、溶媒の毒性、沸点、融点、価格などを勘案すると、疎水性溶媒としてはｎ−ヘキサンを使用するのが好ましく、また親水性溶媒としてはアセトンを使用するのが好ましい。従って、疎水性溶媒−親水性溶媒の混合溶媒の好ましい例としては、ｎ−ヘキサン−アセトン混合溶媒が挙げられる。   Considering the toxicity, boiling point, melting point, price, etc. of the above-mentioned hydrophobic solvent and hydrophilic solvent, n-hexane is preferably used as the hydrophobic solvent, and acetone is used as the hydrophilic solvent. Is preferred. Therefore, a preferred example of the mixed solvent of hydrophobic solvent-hydrophilic solvent is an n-hexane-acetone mixed solvent.

抽出工程は、上記の抽出溶媒と農産物試料を適宜な方法で混合することに行われ、例えばホモジナイザーを使用した混合などが例示できる。この際、適当な脱水剤を共存させてもよい。
抽出時間は、農産物試料の種類、混合手段などに応じて適宜調整することができるが、ホモジナイザーを使用した場合には１〜１０分程度、通常２〜５分程度でホモジナイズすることにより行われる。 The extraction step is performed by mixing the extraction solvent and the agricultural product sample by an appropriate method, and examples thereof include mixing using a homogenizer. At this time, an appropriate dehydrating agent may be allowed to coexist.
The extraction time can be appropriately adjusted according to the type of agricultural product sample, mixing means, etc., but when a homogenizer is used, it is performed by homogenizing in about 1 to 10 minutes, usually about 2 to 5 minutes.

なお、本発明の方法においても、色素などの成分が抽出されて来る場合には活性炭処理を行ってもよい。また、大豆などのように脂肪分が多い農産物の場合には逆相クロマトグラフィー用担体（例えばＣ１８担体、Ｃ８担体等）を使用した脱脂処理をしてもよい。これらの操作により、抽出液中の色素などの夾雑物含量及び脂肪含量が著しく低減するので、機器分析に際してもサンプルの前処理工程の簡略化や測定時のノイズの低減に寄与することができる。
これらの活性炭処理及び脱脂処理は、前記の脱水工程及び／又は抽出工程において行うことができる。 In the method of the present invention, activated carbon treatment may be performed when components such as pigments are extracted. May also be a degreasing processing using reverse phase chromatography matrix in the case of fat is often agricultural products (e.g., C 18 carriers, C 8 carrier and the like), such as soybeans. By these operations, the contents of contaminants such as pigments in the extract and the fat content are remarkably reduced, so that it is possible to contribute to simplification of the sample pretreatment process and reduction of noise during measurement in instrumental analysis.
These activated carbon treatment and degreasing treatment can be performed in the dehydration step and / or the extraction step.

上記の抽出工程の後、濾過、遠心分離などの慣用の手段で抽出液を分離する。分離された抽出液は、必要に応じて、乾固、再溶解などの工程を経た後、ＧＣ／ＭＳなどの慣用の機器分析手段を用いて、残留農薬の分析・定量を行うことができる。   After the extraction step, the extract is separated by conventional means such as filtration and centrifugation. The separated extract can be subjected to steps such as drying and re-dissolution as needed, and then analysis and quantification of residual agricultural chemicals using conventional instrumental analysis means such as GC / MS.

本発明の方法によれば、色素やその他夾雑物の除去の手間を軽減でき、ノイズのない測定データを、時間（約６Ｈ→約１Ｈ）、費用、手間（約３０工程→約１０工程）をかけずに得ることが可能となった。また、水分が除去されているために硫酸イオンが生じることによるpH低下も起こらず、従来法で必要だったタマネギやキャベツなどのイオウ成分含有農産物の測定時のｐＨ調整も不必要となった。
このように、農産物中の残留農薬測定において、従来法より簡便に、短時間で、少ない有機溶媒の使用で、よりノイズの少ないデータを得ることが可能となった。 According to the method of the present invention, the trouble of removing pigments and other impurities can be reduced, and measurement data without noise can be saved in time (about 6H → about 1H), cost and effort (about 30 steps → about 10 steps). It became possible to get without spending. Moreover, since the water was removed, the pH was not lowered due to the generation of sulfate ions, and it was not necessary to adjust the pH when measuring agricultural products containing sulfur components such as onion and cabbage, which were necessary in the conventional method.
Thus, in the measurement of pesticide residues in agricultural products, it has become possible to obtain data with less noise by using a small amount of organic solvent in a shorter time and in a simpler manner than conventional methods.

本発明の残留農薬抽出キットは、上記の方法に使用されるキットであり、脱水剤を主成分とする前処理剤、及びlogPowが０〜４である疎水性溶媒又は疎水性溶媒−親水性溶媒の混合溶媒からなる抽出剤で構成される。
前処理剤に含まれる脱水剤としては前記の脱水剤が例示でき、また抽出剤であるlogPowが０〜４である疎水性溶媒又は疎水性溶媒−親水性溶媒の混合溶媒も前記の溶媒を例示することができる。
なお、前処理剤には、脱水剤と共に、前述した活性炭及び逆相クロマトグラフィー用担体の少なくとも一種を含んでいてもよく、活性炭及び逆相クロマトグラフィー用担体は前記のとおり、色素成分の除去と脱脂剤として作用する。
本発明のキットの使用方法としては、前記の本発明の抽出方法に準じて使用すればよい。 The residual agricultural chemical extraction kit of the present invention is a kit used in the above method, a pretreatment agent mainly composed of a dehydrating agent, and a hydrophobic solvent or a hydrophobic solvent-hydrophilic solvent having a logPow of 0 to 4. It is comprised with the extractant which consists of these mixed solvents.
Examples of the dehydrating agent contained in the pretreatment agent include the above-mentioned dehydrating agents, and examples of the solvent include hydrophobic solvents or hydrophobic solvent-hydrophilic solvent mixed solvents in which logPow as an extractant is 0 to 4. can do.
The pretreatment agent may contain at least one of the above-mentioned activated carbon and reverse phase chromatography carrier, together with the dehydrating agent. Acts as a degreasing agent.
What is necessary is just to use according to the extraction method of the said this invention as a usage method of the kit of this invention.

本発明の対象となる農産物としては残留農薬の測定を必要とする農産物であれば特に限定されず、例えば、野菜類（例えばホウレン草、玉ねぎ、白菜、キャベツ、きゅうり、なす、トマト等）、果実類（例えば柿、りんご、梨、みかん等）、豆類（例えば大豆、小豆、そらまめ、ささげ等）、種実類（例えばごま、栗、落花生等）、穀類（例えば米、小麦、大麦、蕎麦、とうもろこし等）、芋類（例えばじゃがいも、さつまいも、さといも、ながいも等）などが例示できる。
抽出対象とされる農薬は、農業の分野で使用されている農薬である限り限定されるものではない。 Agricultural products that are the subject of the present invention are not particularly limited as long as they require measurement of residual agricultural chemicals. For example, vegetables (for example, spinach, onions, Chinese cabbage, cabbage, cucumbers, eggplants, tomatoes, etc.), fruits (For example, strawberries, apples, pears, tangerines, etc.), beans (for example, soybeans, red beans, broad beans, sardines, etc.), seeds (for example, sesame, chestnuts, peanuts, etc.), cereals (for example, rice, wheat, barley, oats, corn, etc.) ), Moss (for example, potatoes, sweet potatoes, sweet potatoes, potatoes, etc.).
The pesticide to be extracted is not limited as long as it is a pesticide used in the field of agriculture.

以下、比較例及び実施例に基づいて、本発明をより詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、各例において、カッコ付の数字は工程のステップ数を表す。   EXAMPLES Hereinafter, although this invention is demonstrated in detail based on a comparative example and an Example, this invention is not limited to these Examples. In each example, the number in parentheses represents the number of steps in the process.

比較例１（従来法１）
ホウレン草全草からひげ根および変質葉を除去し(1)、フードプロッセッサーで細切・均質化した(2)。20ｇを秤量し (3)、アセトニトリル50ｍｌを加え(4)、10000回転で３分間ホモジナイズした(5)。吸引ろ過(6)の後、残留物にアセトニトリル２０mlを加え(7)再度ホモジナイズ(8)し、吸引ろ過した(9)。２つのろ液をあわせて(10)、アセトニトリルを添加し100ｍｌに定容した(11)。そのうち20ｍｌを分液ロートに分取(12)し、塩化ナトリウム10ｇ(13)と0.5Mリン酸緩衝液(pH7.0)20ｍｌを加え(14)、１０分間振盪(15)した。アセトニトリル層を分取し(16)、無水硫酸ナトリウムを加えて脱水(17)したものをろ過し(18)、35℃の温度条件下で減圧濃縮(19)をおこなった。乾固直前に減圧濃縮を中止し、窒素気流下で乾固(20)した後、残留物をトルエン・アセトニトリル混液(1:3)2ｍｌに溶解(21)し抽出液とした。ENVI-Carv/LC-NH2(6ml,500mg/5oomg)固相抽出カラムをトルエン・アセトニトリル混液(1:3)１０ｍｌでコンディショニングしておき(22)、抽出液を負荷(23)した。さらに20ｍｌのトルエン・アセトニトリル混液(1:3)20ｍｌを流し溶出液を分取 (24)後、35℃の温度条件下で減圧濃縮をおこない1ｍｌ以下に濃縮した(25)。アセトン１０mlを加え、再度1ｍｌ以下に濃縮(26)した後、アセトン５ｍｌを加えさらに濃縮を行った(27)。乾固直前に減圧濃縮を中止し、窒素気流下で乾固(28)した。残留物をアセトン・ｎ−ヘキサン混液(1:1)2ｍｌで溶解して(29)試験溶液とし、サンプルバイアルに移して(30)GC/MSによる分析(31)に供した。 Comparative example 1 (conventional method 1)
The roots and altered leaves were removed from the whole spinach (1), and then chopped and homogenized with a food processor (2). 20 g was weighed (3), 50 ml of acetonitrile was added (4), and homogenized for 3 minutes at 10,000 rpm (5). After suction filtration (6), 20 ml of acetonitrile was added to the residue (7), homogenized again (8), and suction filtered (9). The two filtrates were combined (10), and acetonitrile was added to bring the volume to 100 ml (11). Of this, 20 ml was dispensed into a separating funnel (12), 10 g (13) of sodium chloride and 20 ml of 0.5 M phosphate buffer (pH 7.0) were added (14), and the mixture was shaken (15) for 10 minutes. The acetonitrile layer was separated (16), dehydrated (17) by adding anhydrous sodium sulfate, filtered (18), and concentrated under reduced pressure (19) at 35 ° C. Concentration under reduced pressure was stopped immediately before drying, and after drying (20) under a nitrogen stream, the residue was dissolved (21) in 2 ml of a toluene / acetonitrile mixture (1: 3) to obtain an extract. The ENVI-Carv / LC-NH 2 (6 ml, 500 mg / 5oomg) solid phase extraction column was conditioned with 10 ml of a toluene / acetonitrile mixture (1: 3) (22), and the extract was loaded (23). Further, 20 ml of a 20 ml toluene / acetonitrile mixture (1: 3) was poured to separate the eluate (24), followed by concentration under reduced pressure at a temperature of 35 ° C. to concentrate to 1 ml or less (25). After adding 10 ml of acetone and concentrating again to 1 ml or less (26), the mixture was further concentrated by adding 5 ml of acetone (27). Concentration under reduced pressure was stopped immediately before drying, and drying (28) was performed under a nitrogen stream. The residue was dissolved in 2 ml of an acetone / n-hexane mixture (1: 1) to give (29) a test solution, which was transferred to a sample vial (30) for analysis by GC / MS (31).

比較例２（従来法２）
粉砕(1)した大豆10ｇを秤量し(2)、水２０ｍｌを添加し１５分間放置した(3)。アセトニトリル50ｍｌを加え(4)、10000回転で３分間ホモジナイズした(5)。吸引ろ過(6)の後、残留物にアセトニトリル２０mlを加え(7)再度ホモジナイズ(8)し、吸引ろ過した(9)。２つのろ液をあわせて(10)、アセトニトリルを添加し100ｍｌに定容した(11)。そのうち20ｍｌを分液ロートに分取(12)し、塩化ナトリウム10ｇ(13)と0.5Mリン酸緩衝液(pH7.0)20ｍｌを加え(14)、１０分間振盪(15)した後、アセトニトリル層を分取した(16)。Bond Elut C18(6ml, 1g)固相抽出カラムをアセトニトリル10ｍｌでコンディショニングしておき(17)、分取したアセトニトリル層を負荷(18)した。カラムに2ｍｌのアセトニトリルを加え溶出をおこなった(19)。溶出液に無水硫酸ナトリウムを加えて脱水(20)したしたものをろ過し(21)、35℃の温度条件下で減圧濃縮(22)をおこなった。乾固直前に減圧濃縮を中止し、窒素気流下で乾固(23)した後、残留物をトルエン・アセトニトリル混液(1:3)2ｍｌに溶解(24)し抽出液とした。ENVI-Carv/LC-NH2(6ml,500mg/5oomg)固相抽出カラムをトルエン・アセトニトリル混液(1:3)１０ｍｌでコンディショニングしておき(25)、抽出液を負荷(26)した。さらに20ｍｌのトルエン・アセトニトリル混液(1:3)20ｍｌを流し溶出液を分取 (27)後、35℃の温度条件下で減圧濃縮をおこない1ｍｌ以下に濃縮した(28)。アセトン１０mlを加え、再度1ｍｌ以下に濃縮(29)した後、アセトン５ｍｌを加えさらに濃縮を行った(30)。乾固直前に減圧濃縮を中止し、窒素気流下で乾固(31)した。残留物をアセトン・ｎ−ヘキサン混液(1:1)2ｍｌで溶解して(32)試験溶液とし、サンプルバイアルに移して(33)GC/MSによる分析(34)に供した。 Comparative example 2 (conventional method 2)
10 g of crushed soybean (1) was weighed (2), 20 ml of water was added and left for 15 minutes (3). 50 ml of acetonitrile was added (4) and homogenized for 3 minutes at 10,000 rpm (5). After suction filtration (6), 20 ml of acetonitrile was added to the residue (7), homogenized again (8), and suction filtered (9). The two filtrates were combined (10), and acetonitrile was added to bring the volume to 100 ml (11). 20 ml of that was dispensed into a separatory funnel (12), 10 g of sodium chloride (13) and 20 ml of 0.5 M phosphate buffer (pH 7.0) were added (14), shaken (15) for 10 minutes, and then the acetonitrile layer (16). A Bond Elut C 18 (6 ml, 1 g) solid phase extraction column was conditioned with 10 ml of acetonitrile (17), and the fractionated acetonitrile layer was loaded (18). The column was eluted with 2 ml of acetonitrile (19). The eluate was dehydrated (20) by adding anhydrous sodium sulfate, filtered (21), and concentrated under reduced pressure (22) under the temperature condition of 35 ° C. Concentration under reduced pressure was stopped immediately before drying, and after drying (23) under a nitrogen stream, the residue was dissolved (24) in 2 ml of a toluene / acetonitrile mixture (1: 3) to obtain an extract. The ENVI-Carv / LC-NH 2 (6 ml, 500 mg / 5oomg) solid phase extraction column was conditioned with 25 ml of a toluene / acetonitrile mixture (1: 3) (25), and the extract was loaded (26). Further, 20 ml of a 20 ml toluene / acetonitrile mixture (1: 3) was poured to separate the eluate (27), followed by concentration under reduced pressure at a temperature of 35 ° C. to concentrate to 1 ml or less (28). After adding 10 ml of acetone and concentrating again to 1 ml or less (29), the mixture was further concentrated by adding 5 ml of acetone (30). Concentration under reduced pressure was stopped immediately before drying, and drying (31) was performed under a nitrogen stream. The residue was dissolved in 2 ml of an acetone / n-hexane mixture (1: 1) to give (32) a test solution, which was transferred to a sample vial (33) for analysis by GC / MS (34).

実施例１（本発明方法１）
ホウレン草全草からひげ根および変質葉を除去し(1)、フードプロッセッサーで細切・均質化した(2)。2ｇを秤量し(3)、前処理剤（珪藻土2ｇ、活性炭0.3ｇ）とよく混ぜ合わせ(4)た後 、抽出液(ｎ−ヘキサン：アセトン＝１：１)25ｍｌ(5)と無水硫酸ナトリウム5ｇを加え(6)、10000回転で３分間ホモジナイズした(7)。5000回転で１０分の遠心により上清を得(8)、35℃で減圧乾固し(9)、アセトン２ｍｌに溶解した(10)。これをサンプルバイアルに移して(11)、GC/MSによる分析(12)に供した。 Example 1 (Method 1 of the present invention)
The roots and altered leaves were removed from the whole spinach (1), and then chopped and homogenized with a food processor (2). Weigh 2 g (3), mix well with pretreatment agent (diatomaceous earth 2 g, activated carbon 0.3 g) (4), then extract (n-hexane: acetone = 1: 1) 25 ml (5) and anhydrous sodium sulfate 5 g was added (6) and homogenized for 3 minutes at 10000 rpm (7). The supernatant was obtained by centrifugation at 5000 rpm for 10 minutes (8), dried under reduced pressure at 35 ° C. (9), and dissolved in 2 ml of acetone (10). This was transferred to a sample vial (11) and subjected to analysis by GC / MS (12).

実施例２（本発明方法2）
粉砕(1)した大豆2ｇを秤量し(2)、前処理剤（珪藻土2ｇ、C18逆相ビーズ2ｇ、活性炭0.3ｇ）とよく混ぜ合わせ(3)た後 、抽出液(ｎ−ヘキサン：アセトン＝１：１)25ｍｌ(4)と無水硫酸ナトリウム5ｇを加え(5)、10000回転で３分間ホモジナイズした(6)。5000回転で１０分の遠心により上清を得(7)、35℃で減圧乾固し(8)、アセトン２ｍｌに溶解した(9)。これをサンプルバイアルに移して(10)、GC/MSによる分析(11)に供した。 Example 2 (Method 2 of the present invention)
2g of ground soybean (2) was weighed (2), well mixed with pretreatment agent (2g of diatomaceous earth, 2g of C18 reverse phase beads, 0.3g of activated carbon), and then extracted (n-hexane: acetone). = 1: 1) 25 ml (4) and 5 g of anhydrous sodium sulfate were added (5), and homogenized for 3 minutes at 10,000 rpm (6). The supernatant was obtained by centrifugation at 5000 rpm for 10 minutes (7), dried under reduced pressure at 35 ° C. (8), and dissolved in 2 ml of acetone (9). This was transferred to a sample vial (10) and subjected to analysis by GC / MS (11).

上記従来法１及び２と本発明方法１及び２の工程数及びその方法を実施する際の所要時間（分）は以下のとおりである。
従来法１ ３１工程 ３１０分
従来法２ ３４工程 ３４０分
本発明方法１ １２工程 ６４分
本発明方法２ １１工程 ５９分 The number of steps of the conventional methods 1 and 2 and the methods 1 and 2 of the present invention and the required time (minutes) for carrying out the method are as follows.
Conventional method 1 31 steps 310 minutes Conventional method 2 34 steps 340 minutes Invention method 1 12 steps 64 minutes Invention method 2 11 steps 59 minutes

上記従来法１及び２と本発明方法１及び２において、対象農産物に各種農薬を１００ｐｐｂ添加した場合の回収試験を行った。その結果を、表１〜４に示す。なお、表１及び２は、それぞれ本発明方法１及び２の結果であり、表３及び４は、それぞれ従来法１及び２による結果（回収率：％、以下同様）である。   In the conventional methods 1 and 2 and the methods 1 and 2 of the present invention, a recovery test was conducted when 100 ppb of various agricultural chemicals were added to the target agricultural product. The results are shown in Tables 1-4. Tables 1 and 2 show the results of the inventive methods 1 and 2, respectively. Tables 3 and 4 show the results of the conventional methods 1 and 2 (recovery rate:%, the same applies hereinafter).

Figure 0004275633
Figure 0004275633

Figure 0004275633
Figure 0004275633

Figure 0004275633
Figure 0004275633

Figure 0004275633
Figure 0004275633

上記表１〜４を比較すると明らかなように、２、３の例外を除き、本発明の方法の方が高い回収率を示し、本発明の方法によれば、種々の残留農薬を効率的に抽出できることが判明した。   As is clear when Tables 1 to 4 are compared, with the exception of a few exceptions, the method of the present invention shows a higher recovery rate. It was found that it can be extracted.

次いで、抽出液のｎ−ヘキサン：アセトンの混合比率を変えて、各成分の抽出効率を調べた。
実施例３
前記本発明方法１において、抽出液としてｎ−ヘキサン：アセトン＝１０：０を使用し、対象農産物に各種農薬を１００ｐｐｂ添加した場合の回収試験を行った。その結果を表５に示す。 Subsequently, the extraction efficiency of each component was investigated by changing the mixing ratio of n-hexane: acetone in the extract.
Example 3
In the method 1 of the present invention, n-hexane: acetone = 10: 0 was used as an extract, and a recovery test was conducted when 100 ppb of various agricultural chemicals were added to the target agricultural product. The results are shown in Table 5.

実施例４
実施例３において、抽出液としてｎ−ヘキサン：アセトン＝７：３の混合比率の液を用いた以外は同様にして添加回収試験を行った。その結果を表５に併せて示す。 Example 4
In Example 3, an addition recovery test was conducted in the same manner except that a liquid having a mixing ratio of n-hexane: acetone = 7: 3 was used as the extraction liquid. The results are also shown in Table 5.

実施例５
実施例３において、抽出液としてｎ−ヘキサン：アセトン＝３：７の混合比率の液を用いた以外は同様にして添加回収試験を行った。その結果を表５に併せて示す。 Example 5
In Example 3, an addition recovery test was conducted in the same manner except that a liquid having a mixing ratio of n-hexane: acetone = 3: 7 was used as the extraction liquid. The results are also shown in Table 5.

比較例３
実施例３において、抽出液としてｎ−ヘキサン：アセトン＝０：１０の混合比率の液を用いた以外は同様にして添加回収試験を行った。その結果を表５に併せて示す。 Comparative Example 3
In Example 3, an addition recovery test was conducted in the same manner except that a liquid having a mixture ratio of n-hexane: acetone = 0: 10 was used as the extract. The results are also shown in Table 5.

Figure 0004275633
Figure 0004275633

表５に示されるように、抽出液としてアセトンのみを使用した場合には抽出結果が良くないが、アセトンにｎ−ヘキサンが混合してある抽出液、好ましくは少なくとも３０％程度以上のｎ−ヘキサンが混合された抽出液が好ましい抽出結果を示すことが確認された。   As shown in Table 5, when only acetone is used as the extract, the extraction result is not good. However, an extract obtained by mixing n-hexane with acetone, preferably at least about 30% or more n-hexane. It was confirmed that the extract mixed with a favorable extraction result.

更に、ｎ−ヘキサン−アセトン系以外の有機溶媒の抽出液での抽出結果を調べた。
実施例６
前記本発明方法１において、抽出液としてｎ−ヘキサンを使用し、対象農産物に各種農薬を１００ｐｐｂ添加した場合の回収試験を行った。その結果を表６に示す。 Furthermore, the extraction result with the extract of organic solvents other than n-hexane-acetone system was investigated.
Example 6
In the method 1 of the present invention, a recovery test was performed when n-hexane was used as an extract and 100 ppb of various agricultural chemicals were added to the target agricultural product. The results are shown in Table 6.

実施例７
実施例６において、抽出液としてベンゼン（logPow, 2.13）を用いた以外は、実施例6と同様に添加回収試験を行った。その結果を表６に併せて示す。 Example 7
In Example 6, an addition recovery test was conducted in the same manner as in Example 6 except that benzene (logPow, 2.13) was used as the extract. The results are also shown in Table 6.

比較例４
実施例６において、抽出液としてオクタン（logPow, 5.0）を用いた以外は、実施例6と同様に添加回収試験を行った。その結果を表６に併せて示す。 Comparative Example 4
In Example 6, an addition recovery test was performed in the same manner as in Example 6 except that octane (logPow, 5.0) was used as the extract. The results are also shown in Table 6.

比較例５
実施例６において、抽出液としてアセトニトリル（logPow, -0.3）を用いた以外は、実施例6と同様に添加回収試験を行った。その結果を表６に併せて示す。 Comparative Example 5
In Example 6, an addition recovery test was performed in the same manner as in Example 6 except that acetonitrile (logPow, -0.3) was used as the extract. The results are also shown in Table 6.

Figure 0004275633
Figure 0004275633

表６に示されるように、実施例６と７及び比較例４と５の対比によりlogPowが０〜４の範囲の外にあるオクタン（logPow, 5.0）やアセトニトリル（logPow, -0.3）を抽出液に用いた場合は良い結果を得られなかった。一方、logPowが０〜４の範囲内であるｎ−ヘキサン（logPow, 3.9）やベンゼン（logPow, 2.13）を用いた場合は、良好な抽出効率を得られることが確認された。   As shown in Table 6, as compared with Examples 6 and 7 and Comparative Examples 4 and 5, octane (logPow, 5.0) and acetonitrile (logPow, -0.3) whose logPow is outside the range of 0 to 4 are extracted. When used for, good results were not obtained. On the other hand, when n-hexane (logPow, 3.9) or benzene (logPow, 2.13) whose logPow is in the range of 0 to 4 was used, it was confirmed that good extraction efficiency could be obtained.

Claims (6)

下記の工程からなる農産物中の残留農薬の抽出方法。
(1)農産物を、残留農薬を抽出可能な形状に加工する工程；
(2)上記の処理がされた農産物を脱水剤で処理する工程；及び
(3)脱水処理された農産物から、オクタノール／水分配係数（logPow）が０〜４である疎水性溶媒又は疎水性溶媒−親水性溶媒の混合溶媒を使用して残留農薬を抽出する工程。 A method for extracting residual agricultural chemicals from agricultural products comprising the following steps.
(1) A process for processing agricultural products into a shape from which residual agricultural chemicals can be extracted;
(2) a step of treating the agricultural product subjected to the above treatment with a dehydrating agent; and
(3) A step of extracting residual agricultural chemicals from a dehydrated agricultural product using a hydrophobic solvent having a octanol / water partition coefficient (logPow) of 0 to 4 or a mixed solvent of a hydrophobic solvent and a hydrophilic solvent. 疎水性溶媒−親水性溶媒の混合溶媒がｎ−ヘキサン−アセトン混合溶媒である請求項１記載の抽出方法。   The extraction method according to claim 1, wherein the mixed solvent of the hydrophobic solvent and the hydrophilic solvent is an n-hexane-acetone mixed solvent. 脱水剤で処理する工程と同時又はその後に、活性炭処理及び／又は逆相クロマトグラフィー用担体で処理する請求項１又は２記載の抽出方法。   The extraction method according to claim 1 or 2, wherein the extraction is performed with a support for activated carbon treatment and / or reverse phase chromatography simultaneously with or after the step of treatment with a dehydrating agent. 脱水剤を主成分とする前処理剤、及びオクタノール／水分配係数（logPow）が０〜４である疎水性溶媒又は疎水性溶媒−親水性溶媒の混合溶媒からなる抽出剤で構成される農産物中の残留農薬の抽出キット。   In agricultural products composed of a pretreatment agent mainly composed of a dehydrating agent and an extractant composed of a hydrophobic solvent having a octanol / water partition coefficient (logPow) of 0 to 4 or a mixed solvent of a hydrophobic solvent and a hydrophilic solvent Pesticide residue extraction kit. 疎水性溶媒−親水性溶媒の混合溶媒がｎ−ヘキサン−アセトン混合溶媒である請求項４記載の抽出キット。   The extraction kit according to claim 4, wherein the mixed solvent of the hydrophobic solvent and the hydrophilic solvent is an n-hexane-acetone mixed solvent. 前処理剤が脱水剤と共に、活性炭及び逆相クロマトグラフィー用担体の少なくとも一種を含む請求項４又は５記載の抽出キット。   The extraction kit according to claim 4 or 5, wherein the pretreatment agent contains at least one of activated carbon and a carrier for reverse phase chromatography together with a dehydrating agent.
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