WO2006093359A1

WO2006093359A1 - Method of extracting residual pesticides and extraction kit

Info

Publication number: WO2006093359A1
Application number: PCT/JP2006/304682
Authority: WO
Inventors: Masahiko Kitayama; Masaki Kozono; Takashi Ohmori
Original assignee: Nippon Meat Packers, Inc.
Priority date: 2005-03-04
Filing date: 2006-03-03
Publication date: 2006-09-08
Also published as: BRPI0608051A2; CN101166965B; JP2006242825A; CN101166965A; JP4275633B2

Abstract

A method of extracting residual pesticides in an agricultural product and a kit to be used therein. Namely, a method of extracting residual pesticides which comprises: (1) the step of processing an agricultural product into a form allowing the extraction of the residual pesticides; (2) the step of treating the thus processed agricultural product with a dehydrating agent; and (3) the step of extracting the residual pesticides from the thus dehydrated agricultural product by using a hydrophobic solvent, which has an octanol/water competition coefficient (logPow) of from 0 to 4, or a solvent mixture of a hydrophobic solvent with a hydrophilic solvent. A kit to be used in the method as described above. By using the above method and kit, the procedure can be simplified and an effect of reducing the amount of extracted contaminants such as coloring matters can be established.

Description

Description Residual pesticide extraction method and extraction kit Technical Field

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. Background art

Conventionally, various pesticides 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 Japanese government is also trying to set standards for residual substances remaining in agricultural products (No. 0124001 from Japan, Food and Drug Administration, Ministry of Health, Labor and Welfare) (See “Methods for testing substances remaining in foods that are constituents of pesticides, feed additives or veterinary drugs”).

However, the conventional method is aimed at measuring a small number of residual substances and is not suitable for measuring many residual substances. A wide variety of chemicals are used as pesticides, and the importance of methods for measuring many types of pesticides at once has been increasing in order to simplify measurement and to make quick measurements. See 44. (5). 234-245 (2003), “Trial of skill evaluation for screening analysis of 104 pesticide residues in crops”.

Specifically, conventional methods for measuring residual pesticides require complicated steps, time (approximately 6 H), cost, and labor (approximately 30 steps), and simpler methods and kits are required. It was. In addition, in the measurement of high-moisture vegetables and fruits, a solvent such as acetonitrile, which has a high hydrophilicity, is used, so that components other than the measurement target such as pigment are also extracted, and these impurities can be removed. There is a problem that it takes time, and the impurities remaining even after such time and effort become noise during measurement.

On the other hand, many of the pesticides have low polarity and many are not suitable for extraction with highly hydrophilic solvents. In addition, in the conventional method, when onion contains cabbage and other ingredients such as cabbage, pesticide ingredients that become acidic with the sulfate ions produced and are destroyed under acidic conditions. Because of the heat, pH adjustment was necessary. 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. Disclosure of the invention

As described above, in the conventional method for measuring residual pesticides, the process of extracting residual pesticides from agricultural products (pretreatment process) is very long and cumbersome, requiring time and is a measurement problem. It was.

Therefore, the present inventors have studied 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 agricultural products with a pretreatment agent. It was found that residual agricultural chemicals can be extracted easily and efficiently. More specifically, the present inventors examined a combination of 1) an extraction pesticide capable of efficiently extracting the target pesticide, while not extracting impurities, and 2) a pretreatment agent. .

First, when examining 1) above, we focused on the chemical properties of pesticides. 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. logPow is widely used as an indicator of the degree of hydrophobicity of a substance (for information on logPow, see the National Institute of Health Sciences HP database for searching drug information).

Most pesticides have logPow between 2-7. In order to dissolve these pesticides 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 some pesticides have negative values such as facetate and methamidophos. In order to dissolve these pesticides, a more polar solvent is required.

Therefore, using a force of using a hydrophobic solvent with a logPow of about 0 to 4 or a mixed solvent of a hydrophobic solvent and a hydrophilic solvent, a pesticide is extracted from the dehydrated sample as a material. As a result, it was found that the amount of pigments and other impurities extracted was significantly reduced. The mixed solvent is a hydrophobic solvent, preferably a n-hexane (logPow, 3.9) as a main component, and a logPow of about -1.0 to 0 hydrophilic solvent, preferably acetone.

A solvent to which an appropriate amount of (logPow, -0.24) is added is exemplified. Next, with respect to the above 2), since the above solvent is mainly a hydrophobic solvent, there is a problem in permeability to vegetables with high water content. Therefore, the problem was improved by subjecting the agricultural product sample to a dehydration process using a dehydrating agent, preferably diatomaceous earth. This method enabled extraction using a hydrophobic solvent with low polarity 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 for the method.

The present invention made to solve the above problems is a method for extracting residual agricultural chemicals from agricultural products comprising the following steps.

(1) A process of 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 dehydrated agricultural products 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 hydrophobic solvent and the 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 photographic support. The extraction kit of the present invention is a kit used in the above method, comprising 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 consists of an extractant consisting of a mixed solvent. It is preferable to use a mixed solvent of n-hexane and acetone as the mixed solvent of the above-mentioned hydrophobic solvent and hydrophilic solvent, and the above pretreatment agent together with the dehydrating agent is a small amount of activated carbon and a carrier for reverse phase chromatography. It is preferable to include one kind. BEST MODE FOR CARRYING OUT THE INVENTION

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 agricultural products such as vegetables and fruits are cut, they are cut into small pieces, and when they are beans and cereals, they are ground and pulverized. In any case, it is processed into a shape that improves the extraction efficiency of residual pesticides according to the form of agricultural products. The processed agricultural products (hereinafter referred to as agricultural samples) are then subjected to a dehydration process. As described above, in the method of the present invention, a solvent mainly composed of a hydrophobic solvent is used as the extraction solvent. Therefore, if the water content of the agricultural product sample is large, the solvent is not compatible with the solvent. Reduce water 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 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.

The agricultural product sample dehydrated in the above process is subjected to an extraction process using a mixed solvent consisting of a hydrophobic solvent or a hydrophobic solvent having a logPow of 0 to 4 and a hydrophilic solvent.

As the hydrophobic solvent having a logPow of 0 to 4 used in this step, a conventional solvent can be used if the logPow is within this range. For example, n-hexane (logPow, 3.9), Examples include ethynole acetate (logPow, 0.73), dichloromethane (logPow, 1.25), benzene (logPow, 2.13), toluene (logPow, 2.69), carbon tetrachloride (logPow, 2.64), etc. These solvents may be used as a mixture of two or more.

Further, as the extraction solvent, a mixed solvent of a hydrophobic solvent and a hydrophilic solvent may be used. Examples of the hydrophobic solvent include octane (logPow, 5.0) in addition to the solvents described above. .

The hydrophilic solvents, such as acetone _{(lo g Pow, -0 24.} ), Methanol (logPow, - 0. 82), Etanoru (. LogPow, -0 32), Asetonitoriru (. LogPow, -0 3), such as Conventional solvents 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 below), preferably 80 to A solvent with a ratio of 45:20 to 55, more preferably 50:50 is used. If the amount of hydrophilic solvent exceeds this range, the amount of extracted pigments and other contaminants increases, and if the amount falls below this range, the amount of residual pesticides may decrease.

In consideration of the toxicity, boiling point, melting point, price, etc. of the above-mentioned hydrophobic solvent and hydrophilic solvent, it is preferable to use n-hexane as the hydrophobic solvent. Acetone is preferably used as the aqueous solvent. Therefore, a preferred example of a mixed solvent of a hydrophobic solvent and a hydrophilic solvent is a mixed solvent of _n- hexane monoaceton.

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 coexist.

The extraction time can be adjusted as appropriate depending on the type of agricultural product sample, mixing method, etc., but when a homogenizer is used, it can be adjusted to about 1 to 10 minutes, usually about 2 to 5 minutes. Done.

In the method of the present invention, activated charcoal treatment may be performed when components such as pigments are extracted. In the case of agricultural products with a high fat content such as soybeans, degreasing treatment using a carrier for reverse phase chromatography (eg, Ci ₈ carrier, C ₈ carrier, etc.) may be performed. By these operations, the contents of impurities such as pigments and the fat content in the extract are remarkably reduced, so that it is possible to contribute to simplification of the sample pretreatment process and reduction of noise during measurement in the instrumental analysis.

These activated carbon treatment and degreasing treatment can be performed in the dehydration step and Z or extraction step.

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 pesticides using conventional instrumental analysis means such as GC / MS. . According to the method of the present invention, it is possible to reduce the labor of removing pigments and other contaminants, and the measurement data without noise can be saved in time (approximately 6 H → approximately 1 H), cost, labor (approximately 30 steps → approximately 1 (0 step). In addition, pH is not lowered due to the formation of sulfate due to the removal of water, and pH adjustment is not necessary when measuring agricultural products containing onions such as cabbage and onion, which was necessary in the conventional method. became.

In this way, in the measurement of pesticide residues in agricultural products, it has become possible to obtain data with less noise by using organic solvents in a shorter time, in a shorter time, and using organic solvents. The residual pesticide 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 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 a hydrophobic solvent having a logPow of 0 to 4 or a mixed solvent of a hydrophobic solvent and a hydrophilic solvent. can do.

In addition, the pretreatment agent may contain at least one of the above-mentioned activated carbon and the carrier for reversed phase chromatography, together with the dehydrating agent. Acts as a degreasing agent.

As a method of using the kit of the present invention, it may be used according to the extraction method of the present invention.

Agricultural products subject to the present invention are not particularly limited as long as they require the measurement of residual agricultural chemicals. For example, vegetables (for example, spinach, onion, Chinese cabbage, cabbage, cucumber, eggplant, tomato, etc.), fruits (Eg, strawberries, apples, pears, tangerines, etc.), beans (eg, soybeans, red beans, broad beans, sardines, etc.), seeds (eg, sesame, chestnuts, peanuts, etc.), cereals (eg, rice, wheat, barley, oats) , Corn, etc.), moss (eg, sweet potato, sweet potato, sweet potato, long potato etc.).

The pesticides to be extracted are not limited as long as they are agricultural chemicals used in the agricultural field. Industrial use available

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 amount of extracted impurities such as pigments is reduced, the operation is simplified and the measurement accuracy is improved. Improvement can be achieved. Furthermore, since agricultural products are treated with a dehydrating agent, the production of sulfate ions from sulfur-containing agricultural products can be suppressed, and it is possible to measure pesticide components that are unstable under acidic conditions. Example

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 numbers with brackets indicate the number of steps in the process.

Comparative example 1 (conventional method 1)

Remove spine roots and altered leaves from whole spinach (1) and fine-tune with a food processor. Cutting · Homogenized (2). 20 g was weighed (3), 50 ml of acetonitrile was added (4), and homogenized at 10000 rpm for 3 minutes (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), added with acetonitrile, and adjusted to a volume of 100 ml (11). The 20 m l was separated (12) to a separating port Ichito them, and Shioi匕sodium 10 g (13) 0. 5M phosphate buffer _(P H7. 0) 20 m 1 was added (14), 1 0 Shake for 15 minutes (15). The acetonitrile layer was separated (16), dehydrated by adding anhydrous sodium sulfate (17), filtered (18), and concentrated under reduced pressure (35) at 35 ° C. Concentration under reduced pressure was stopped immediately before drying, followed by drying (20) under a nitrogen stream, and the residue was dissolved in toluene-acetonitrile mixture (l: 3) 2 ml (21) did. ENVI-Carv / LC-NH ₂ (6ml, 500mg / 5oomg) solid-phase extraction column was conditioned with 1Oml of toluene 'acetonitrile (1: 3) (22), and the extract was loaded (23) . Further, 20 ml of toluene-acetonitrile mixed solution (1: 3) was poured into 20 ml, and the eluate was separated (24), and then concentrated under reduced pressure at a temperature of 35 ° C. to concentrate to lm 1 or less (25). Aceton 1 O ral was added and concentrated again to lm 1 or less (26), and then acetone 5 ml was added and further concentrated (27). Concentration under reduced pressure was stopped immediately before drying, and drying (28) was performed under a nitrogen stream. Dissolve the residue in a mixture of acetone and n-hexane (l: l) 2 ml (29) to make the test solution, transfer to the sample vial (30), and use for analysis by GC / MS (31). did. Comparative Example 2 (Conventional method 2)

Powdered frame (1). 10 g of soybean was weighed (2), 20 ml of water was added and left for 15 minutes (3). Acetonitrile 50 ml 1 was added (4) and homogenized at 10,000 rpm for 3 minutes (5). After suction filtration (6), 2 O 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 adjust the volume to 100 ml (11). Dispense 20 ml of the solution into a separatory funnel (12), add 10 g (13) of sodium chloride salt and 20 ml of 0.5 M phosphate buffer (pH 7.0) (14), and shake for 10 minutes (15) After that, the acetonitrile layer was separated (16). A Bond Elut C ₁₈ (6 ml, lg) solid phase extraction column was conditioned with acetonitrile (10 ml) (17), and the fractionated acetonitrile layer was loaded (18). The column was eluted with 2 ml 1 acetonitrile (19). The eluate was dehydrated (20) by adding anhydrous sodium sulfate, filtered (21), and concentrated under reduced pressure (22) at 35 ° C. Concentration under reduced pressure was stopped immediately before drying, and drying (23) was performed under a nitrogen stream. Thereafter, the residue was dissolved (24) in a toluene / acetonitrile mixed solution (1: 3) 2 ml 1 to obtain an extract. ENVI-Carv / LC-NH ₂ (6ml, 500mg / 5oomg) solid phase extraction column was conditioned with toluene-acetonitrile (1: 3) 1 Om 1 (25), and the extract was loaded (26) . Further, 20 ml of toluene-acetonitrile mixed solution (1: 3) was flowed through 20 ml, and the eluate was separated (27), and then concentrated under reduced pressure at a temperature of 35 ° C. to concentrate to lm 1 or less (28). After adding 1 ml of acetone and concentrating again to lm 1 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 § seton _n - hexane mixture. (I: i) was dissolved in 2m 1 and (32) the test solution, subjected to a sample-by-transferred to § Le (33) Analysis by GC / MS (34) did. 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: l) 25m 1 (5) And 5 g of anhydrous sodium sulfate (6) were added, and homogenized for 3 minutes at 10,000 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). Example 2 (Method 2 of the present invention)

Powder frame (1) Weighed 2 g of soybean (2), mixed well with pretreatment agent (diatomaceous earth 2 g, C ₁₈ reverse phase beads 2 g, activated charcoal 0.3 g) (3), and then extracted liquid (n— Hexane: acetone = 1: 1) 25 m 1 (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). The number of steps of the conventional methods 1 and 2 and the inventive methods 1 and 2 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 Inventive method 1 1 2 step 6 4 min

Invention method 2 1 1 step 5 9 minutes

In the conventional methods 1 and 2 and the methods 1 and 2 of the present invention, a recovery test was conducted in the case where various agricultural chemicals were added to the target agricultural product at 100 ppp. The results are shown in Tables 1-4. Tables 1 and 2 show the results of the method 1 and 2 of the present invention, respectively. Tables 3 and 4 show the results of 988999099998099999999 9 according to the conventional methods 1 and 2, respectively (recovery rate:%, the same applies hereinafter). is there.

838888069808376 480211

Ό862023584042397 89111 Table 1 (Method 1 of the present invention) Recovery rate by 100 ppb addition recovery test

Pyrethroid recovery rate nitrogen-containing recovery rate organophosphorus

Acrinathrin Isoprocarp EPN 93.2 Cyhalothrin 01 Esplocalc facet 62.2 Cyhalothrin 02 Black mouth prophate Iifos 87.3 Cifluthrin 01 Shietofencarp ethoprophos 92.7 Ciflu Jun 02 Schiff mouth conasole 01 Chelyphos Phosphate 91 03 Cyproconazole 02 1 11 Kas' Sahos 95.3 Cyfluthrin 04 To the old 'N Calf' 09899888899999990089999999 999

373457553600875 ^^ 76535500 022771 Quinalhos 95.1 Sihelu'lemethrin Tenylchlor ^ ο30 ο 8420 ο ο 934689344090 Ο 80368. Chlorpyrifos 92.4 Lumetrin 02 Tef 'Kona' / 1 Le Chlorfenhinhos 01 96.9 Lumethrin 03 Tebufu Impirato 'Chlorfenhynhos 02 92.0 Sihelmetrine 04 Triash' Menol 01 Si 'Chlorho "49.2 Tefluthrin de Jashi' Menol 02 Si 'Methylvinfos 87.4 'Yashi' Non 95.3 Fenha's Relate Biliproxyfen Thiometon 82.9 Fenha 'Reele 02 Pirimicarb terbufos 92.7 Fulcitrin 01 Fenarimol Ha thion 94.6 Fulcitrin 02 Fennobalp halathion methyl 100.4 Fruha'linate 01 Pretilachlor 8.5 halaphos 'Linate 02 Probicona' No '-l 01 Pirimiphos methyl 93.7 Remetrin f Mouth Bicona' No '02 Huenitrothion 95.7 To' Lumetrin 02 ― Hendai Calf 'Fensulfostine 87.8

9'9 Organic Chlorine Recovery Microptanyl Fen'A 卜 97.5 One BHC 92 Mechi Talent Lubu 01 Frochihos 97.3 /? -BHC 4 Mechi Calp 02 Hosalon 82.4 r-BHc Metra Kroll Hostia 01 87.0

5 -BHC 03 Mefenacet Phostiase 2 87.8 ρ, ρ-DDD 98 Mepronil Malathion 93.8 ρ, ρ-DDE Lenacil methamidophos 49.3 ο, ρ -DD

ρ, ρ-DDT

Alt'lin 91

亍 'Ilt' Lynn 95

Endrin 9

Halfenphlox 03 Table 2 (Method 2 of the present invention) 回収 Recovery rate from 00 ppb addition recovery test

Organic phosphorus recovery

EPN 84.5 Acephate 60.1 Eifenphos 83.1 Etoprophos 85.1 Elyphos phos 82.1 Kas' Sahos 81.2 Kinalhos 87.1 Chlorhe'rifos 84.1 Chlorfenhi 01nhos 01 89.1 Chlorfenhienhos 02 90.5 Non 89.1 Chi-Met 80.1 亍 Rubufos 80.7 8-Lathion 89.6 Halathion Methyl 90.5 Hy-Lacrofos 83.8 Birimifosmethyl 86.4 Fennitrothion 84.9 Fensulfostin 80.6 Fento 94.3 Fento 94.3 F "Rothi Phos 81.5 Hosarone 79.5 Hostia" 01 81. 0 Hostiace "02 79.8 Malachi, 91.6 Metami" Hos 42.1

Table 3 (Conventional method 1) Recovery rate by 100 ppb addition recovery test

_899

046- 353

亍 'Ilt' Lynn

Yent 'Lin

Halfenprox

II Table 4 (Conventional method 2) Recovery rate by 100 ppb addition recovery test

Pyrethroid system ~ recovery rate Nitrogen-containing recovery rate Organophosphorus system

Acrinatrin Isofu "Locarfu" EPN

Cihalothrin 01 Espuro Calf's Face

Shi Λ Rotorin 02 Chloroph "Mouth Fam

Sifluthrin 01 Shi'etofencalf 'Ethos

Cyfluthrin 02 times Cyprokona 'no' one 01 Etrinphos

Cifludol 03 Ciproconaso 'One Le 02 Kassahos

Also 878887775777887776876676878776 99

Sifluthrin 04 3088 404 392 679 620 711 1

5 ^^ 8348253460925726233270214965611 61

Shihe Remethrin 亍 Nilchlor Chlorpyrifos

Sihe "lumetrin 02 亍 pconazole chlorfenvinphos 01

Sihe "Lumetrin 03 Tebufenpyrat 'Chlorfenvinphos 02

To Shi. Lumetrin 04 Triazi 'Menol 01 Si' Chlorho '

Tefluthrin Triazi 'Menol 02 Shi "Methylhinphos

亍 'Lutamethrin Ha' 'Kurobutoraso' 'Le Daisy' Non

Fenha "Relay 卜 Pyriproxyfen Thiometon

Fen / \ "Lelay Pass 02 Pirimicarb terbujos

Furcitrin 01 Fenarimole

Furcitrin 02 Huenobcalf '/ Lachi

Furuha 'Linet 01' Retilachlor Bilacrofos

Fulha 'linate 02 propiconazole 01 48777799778887786769577677 777 pyrimifosmethyl

'Lumetrin Probiconal 02 3285222238976233387966631171 1

What. Out of phosphorus 02-Hendai talent Lubu Fensulfostine

メタ 'Metallin' Fence

Organochlorine microbutanyl phentoate

Hi-BHG Mechical; 7'01: Loti

β -B C Mechiocarb 02 Hosalon

r -BHC Metolachlor Hostia '01

5-BHC Mehuenacet Phosphate '02

ρ, ρ-DDD Mepronil Malathion

ρ, ρ-DDE Lenacil methamidophos

ο, ρ-DDT

ρ, ρ-DDT 84878768888488796668666 857687 Alto "Rin π35004467 ^ 500597660 02050425911 *

-928444302855898506255357 61111 Theil "Rin

Endrin

ΛLuff I Inf ¾x

As is clear when Tables 1 to 4 are compared, with the exception of a few, the method of the present invention shows a higher recovery rate. According to the method of the present invention, various residual agricultural chemicals can be efficiently removed. It was found that it can be extracted. Next, the extraction efficiency of each component was examined 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: 0 is used as the extract. A recovery test was conducted when 100 ppb of various agricultural chemicals were added to the target agricultural products. The results are shown in Table 5.

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-xane: acetone = 7: 3 was used as the extract. The results are also shown in Table 5. 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-xane: acetone = 3: 7 was used as the extract. The results are also shown in Table 5. Comparative Example 3

In Example 3, an addition recovery test was conducted in the same manner except that a liquid having a mixing ratio of n-xane: acetone = 0: 10 was used as the extraction liquid. The results are also shown in Table 5.

Table 5 Recovery rate by 100 _PP b addition recovery test

n-hexane: acetone

Pesticide name

Example 3 Example 4 Example 5 Comparative Example 3

10: 0 7: 3 3: 7 0:10 pyrethroid

Acrinatrin 98.9 93.7 55.4

Λ Rotrin 01 00.1

87.5 80.2

Cyhalothrin 02 98.1 85.4 79.4

亍 Flutrin 77.1 75.3

Fenha "Lereto 00.3 92.4 85.1

Fenha'relate 02 94.1 90.1 84.1

-System

9 99 9

45 8

3 82 2

As shown, when only acetone is used as the extract, the extraction results Although it was not good, it was confirmed that an extract obtained by mixing Π-hexane with acetone, preferably an extract obtained by mixing at least about 30% of n-hexane, shows a preferable extraction result. . Furthermore, the extraction result with the extract of organic solvents other than n-hexane monoacetone was examined. Example 6

In the method 1 of the present invention, a recovery test was conducted when n-hexane was used as an extract and various agricultural chemicals were added to the target agricultural product at 100 ppb. The results are shown in Table 6. Example 7

In Example 6, an addition recovery test was performed 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.

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.

Comparative Example 5

In Example 6, an addition recovery test was conducted 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.

Recovery rate by 100ppb addition recovery test Example 6 Example 7 Comparative example 4 Comparative example 5

n-hexane hexane octane acetonitrile

3.9 2.13 5.0 -0.3

Pi b sroid

Acrinatrin 96.7 .2 X

Cyhalothrin 01 99.5 00.5 X

Cyhalothrin 02 01.1 97.9 X

9999

997 97 99.1 71.6

848

X; logPow is 0 by comparing Example 6 and 7 and Comparative Example 4 and 5, as indicated by the impossibility of measurement. When octane (logPow, 5.0) nitronitrile (logPow, -0.3) outside the range of ~ 4 was used in the extract, good results were not obtained. On the other hand, when n-hexane (logPow, 3.9) or benzene (logPow, 2.13) with logPow in the range of 0 to 4 was used, it was confirmed that good extraction efficiency could be obtained.

Claims

The scope of the claims

1. A method for extracting residual pesticides in agricultural products comprising the following steps.

(3) A process of extracting residual agricultural chemicals from dehydrated agricultural products using a hydrophobic solvent with a octanol / water partition coefficient (logPow) of 0 to 4 or a mixed solvent of a hydrophobic solvent and a hydrophilic solvent. .

2. The extraction method according to claim 1, wherein the mixed solvent of the hydrophobic solvent and the hydrophilic solvent is a η-hexaneasetone mixed solvent.

3. The extraction method according to claim 1 or 2, wherein treatment with activated carbon treatment and / or reverse phase chromatography support is carried out simultaneously with or after the treatment with the dehydrating agent.

4. Consists of a pretreatment agent composed mainly of a dehydrating agent and an extractant consisting 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. Extraction kit for residual pesticides in agricultural products.

5. The extraction kit according to claim 4, wherein the mixed solvent of the hydrophobic solvent and the hydrophilic solvent is an n-hexane-aceton mixed solvent.

6. The extraction kit according to claim 4 or 5, wherein the pretreatment agent contains at least one of activated carbon and a carrier for reversed phase chromatography together with a dehydrating agent.