WO2020124203A1

WO2020124203A1 - Extraction cartridge and method for extracting pollutants

Info

Publication number: WO2020124203A1
Application number: PCT/CA2019/051743
Authority: WO
Inventors: Vincent Bedard; David CHABOT
Original assignee: Silicycle Inc.
Priority date: 2018-12-20
Filing date: 2019-12-04
Publication date: 2020-06-25
Also published as: TW202039045A

Abstract

The present disclosure relates to an extraction cartridge and a method for preparing a test liquid from an agricultural sample using said cartridge. The extraction cartridge comprises a first powder mixture layer comprising a molecular sieve and magnesium sulfate in an amount of less than 40% based on the weight of the first layer, and a second powder mixture layer comprising a mixture of 75-85% magnesium sulfate based on the weight of the second layer and one or more agents in powdered form for removing impurities.

Description

EXTRACTION CARTRIDGE AND METHOD FOR EXTRACTING POLLUTANTS

FIELD OF THE DISCLOSURE

[0001] The present disclosure relates to an extraction cartridge and a method for preparing a test liquid from an agricultural sample.

BACKGROUND OF THE DISCLOSURE

[0002] Pesticides are widely applied on crops to prevent or kill pests in agricultural production. Countries have standards on the presence of pesticide residues and establish the maximum amounts that can be found in agricultural products to ensure safety of their population.

[0003] The determination of pesticide contents in agricultural products such as fruits, vegetables, grains, dried beans, tea, spice and other herbaceous plants, can be accomplished by the QuEChERS method (Quick, Easy, Cheap, Effective, Rugged, Safe) to get a sample which can then be tested in appropriate equipment. However the QuEChERS method requires pretreatment of the samples and numerous steps of handling.

[0004] FPE (Fast Pesticide Extraction) is a cartridge used to extract pesticides contained in fruits and vegetables. FPE cartridges are a replacement for QuEChERS. A FPE cartridge extraction takes its main advantage in its simplicity and speed compared to a traditional QueChers extraction. The FPE cartridges allows for combining both the extraction and purification steps in one.

[0005] Currently existing or disclosed FPE mainly contain magnesium sulphate (MgS0 ). Magnesium sulfate is an excellent dehydrating agent, however in the presence of water, magnesium sulphate cements. This composition may result in a serious drawback when the extraction solvent is containing a significant amount of water and cause the MgS0 to cement in the cartridge. Once the MgS0 has cemented, the solvent front cannot evenly flow through the cartridge as preferential paths are created in the layer. This may cause a significant loss of efficiency and/or reliability of the results. SUMMARY OF THE DISCLOSURE

[0006] An aspect relates to an extraction cartridge comprising: a housing extending in an upright position along a longitudinal axis between an output port and an input port, the housing having an internal chamber defined therein; a first powder mixture layer filled in the internal chamber, wherein said first powder mixture layer is located below the input port; and a second powder mixture layer filled in the internal chamber, wherein said second powder mixture layer is located below the first powder mixture layer and above the output port.

[0007] A further aspect relates to a method for preparing a test liquid from an agricultural sample comprising : providing a sample solution by extracting a pesticide from said agricultural sample in a solvent; and circulating the sample solution through the first powder mixture layer and the second powder mixture layer as defined herein (e.g. as comprised in an extraction cartridge as defined herein); and recovering said test liquid.

DESCRIPTION OF THE DRAWINGS

[0008] Reference is now made to the accompanying figures in which:

[0009] Fig. 1 is a schematic cross sectional view of a cartridge in accordance with one embodiment;

[0010] Fig. 2 is a schematic cross-sectional view of the cartridge of Fig. 1 illustrating a layering of components contained therein; and

[0011] Fig. 3 is a schematic cross-sectional view of a housing of the cartridge of Fig. 1 in accordance with another embodiment.

DETAILED DISCLOSURE

[0012] Agricultural samples that may be used herein include fruits, vegetables, grains, dried beans, tea, spice and other herbaceous plants.

[0013] Referring to Fig. 1 , a cartridge in accordance with one embodiment is generally shown at 1. The cartridge 1 has a housing 10 and an adaptor 20. The housing 10 is configured to receive components therein and the adaptor 20 is used to fluidly connected the cartridge 1 with a source of the components. [0014] The housing 10 has an output port 11 via which the content of the cartridge 1 may exit an internal volume V defined by the housing 10. The housing 10 has an input port 12 for receiving the adaptor 20 and via which matter can be added to the internal volume V of the housing 1. In the embodiment shown, the cartridge 1 extends along a longitudinal axis L and a cross-sectional area of the internal volume V of the housing 10 taken on a plane normal to the longitudinal axis L is constant between the input port 12 and the output port 11.

[0015] In the embodiment shown, a thickness T of a peripheral wall 14 of the housing 10 taken in a radial direction relative to the longitudinal axis L is greater proximate the input port 12 than that at a remainder of the housing 10. This portion with an increased thickness may allow to provide a more secure connection with the adaptor 20 compared to configuration lacking this portion with the increased thickness.

[0016] In one embodiment, the housing 10 has a generally cylindrical shape. In a further embodiment, the housing is tapered (or has a narrowing cross-section area) along its length, or a portion of its length, toward the output port. The cross-section area proximate the input port 12 may be greater than the cross-section area proximate the output port 11. Other configurations are contemplated without departing from the scope of the present disclosure. The housing 10 may be made of any suitable material such as, for instance, polyethylene or medical grade polyethylene.

[0017] In one embodiment, the housing includes a locking mechanism M proximate the output port 11. The locking mechanism M may be used for connecting a luer to the housing 10. In the embodiment shown, the locking mechanism M includes a peripheral wall 10a circumferentially extending around the longitudinal axis L and being radially spaced apart from a wall 11a that a defines the output port 11 ; the wall 11a circumferentially extending around the longitudinal axis L. The wall 11a may define a constriction of the internal volume V. The wall 11a of the output port 11 may have a smaller diameter than that of the wall 14 of the housing 10. The peripheral wall 10a of the locking mechanism is disposed radially outwardly from the wall 10a of the housing 10. An annular cavity 10b is thereby defined radially between the peripheral wall 10a and the wall 11a relative to the axis L. The annular cavity 10b is configured for receiving a correspondingly sized portion of another element for securing the housing 10 to said element. The locking mechanism M may alternatively be a snap-fit connector, a tight fit connection, a threaded connector, a dog and slot connector. Any other suitable locking mechanism known in the art may be used without departing from the scope of the present disclosure. [0018] In the depicted embodiment, the adaptor 20 is received within the housing 10 via the input port 12 of the housing 10. The adaptor 20 may be threadingly received within the housing 10. The adaptor 20 may be a luer-lock. In the embodiment shown, the adaptor 20 is press-fitted in the housing 10. The adaptor 20 is matingly received within the housing 10 and defines a inner conduit 20a that is fluidly connected to the internal volume V of the housing 10. A connecting mechanism C is defined by the adaptor 20 at a distal end thereof. In the embodiment shown, the connecting mechanism C includes a male member 20b that is configured for mating with a correspondingly sized female member of another element.

[0019] In the depicted embodiment, the male member 20b defines threads 20c that are configured to threadingly engage corresponding threads of the female member. Any other suitable connecting mechanism known in the art may be used without departing from the scope of the present disclosure. For instance, the connecting mechanism may be a snap-fit connector, a tight fit connection, or a dog and slot connector.

[0020] Referring now to Fig. 3, another embodiment of the housing is generally shown at 100. For the sake of conciseness, only elements that differ from the housing 10 described herein above with reference to Figs. 1-2 are described herein below.

[0021] In the embodiment shown, the cartridge 100 is devoid of the peripheral wall 10a (Fig. 1) around the wall 111a of the output port 111 and devoid of the annular cavity 10b (Fig. 1). The locking mechanism M1 of the cartridge 100 may be defined by features located on an outer surface of the wall 111a of the output port 111. Such features may be, for instance, threads, grooves, and/or tabs. In the embodiment shown, the locking mechanism M1 is a threaded connector such as a luer-lock connector.

[0022] Referring now to Fig. 2, the layering inside the internal volume V of the housing 10 of the cartridge 1 is now described.

[0023] In one embodiment, the extraction cartridge further comprises one or more of a filter pad (40, 41 , 42), wherein said filter pads are in contact with said powder mixtures defined herein, wherein said filter pads are preferably fixed to the housing of the cartridge, on the top surface (40) of the first powder mixture layer 43. In one embodiment, the extraction cartridge further comprises a filter pad 42, preferably fixed to the housing of the cartridge, on the bottom surface of the second powder mixture layer 44. In one embodiment, the extraction cartridge further comprises two filter pads (40, 42), preferably fixed to the housing of the cartridge, one of which filter pad is on the top surface of the first powder mixture layer, and the other filter pad is on the bottom surface of the second powder mixture layer.

[0024] The first and second layers may directly contact with the filter pad(s). In one embodiment, in addition or alternative to the preceding embodiments, the extraction cartridge may further comprise a filter pad 41 , preferably fixed to the housing of the cartridge, between the first and second layer.

[0025] The first layer is capable of absorbing water from the sample solution, and most preferably said layer is not cementing upon circulating a sample solution through said first layer. The first layer is comprising molecular sieve or a mixture of molecular sieve and magnesium sulfate in an amount of less than 40% w/w based on the weight of the first layer (the magnesium sulfate amount therefore being non-nul (>0%)). Preferably the first layer is comprising from 100% to 70% molecular sieve and 0% to 30% magnesium sulfate w/w based on the weight of the first layer. In one embodiment the first layer is comprising 70-75% molecular sieve and about 25-30% magnesium sulfate, or is comprising about 70% molecular sieve and about 30% magnesium sulfate or is comprising about 75% molecular sieve and about 25% magnesium sulfate w/w based on the weight of the first layer.

[0026] As used herein, the expression“magnesium sulfate” is understood to be an anhydrous magnesium sulfate, preferably comprising no more than 2% wt/wt of water (assessed by LOD) or preferably less than 0.1 % (assessed by Karl fisher).

[0027] As used herein, the molecular sieve, such as 3A molecular sieve is understood to be anhydrous, preferably comprising less than 0.1% wt/wt of water (assessed by Karl fisher).

[0028] The second layer is capable of absorbing further water of the sample solution eluting from the first layer.

[0029] In one embodiment, the second layer is further comprising one or more agent, in powdered form, for removing (adsorbing) impurities, such as organic acid, sugars or pigments, which may interfere with the analysis of the test liquid obtained from the agricultural sample.

[0030] In one embodiment, the second layer is comprising magnesium sulfate and said one or more agent, in powdered form. In one embodiment, the second layer is comprising about 25% w/w or more of magnesium sulfate based on the weight of the second layer, and said one or more agent, in powdered form. In one embodiment, the second layer is comprising from about 60-90%, preferably about 70-90% or preferably about 75-85% w/w of magnesium sulfate and said one or more agent, in powdered form based on the weight of the second layer.

[0031] The second layer may therefore further comprise, in addition to the magnesium sulfate or mixture of molecular sieve and magnesium sulfate, one or more of a primary secondary amine (-(CH₂)3-NH-(CH₂)2-NH₂) phase grafted on silica which may for example remove sugars.

[0032] The second layer may comprise a C18 alkyl chain phase grafted onto silica to which may for example remove hydrophobic components.

[0033] The second layer may comprise graphitized carbon black which may for example remove pigments from the sample. Preferably the graphitized carbon black has a surface area less than 100 m²/g.

[0034] The second layer may comprise a zirconium-based component. The zirconium-based component may be zirconium grafted onto silica, C18 chain and zirconium grafted on silica or a mixture of C18 grafted onto silica in admixture with zirconium oxide powder.

[0035] In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising a mixture of molecular sieve and magnesium sulfate and the second layer is comprising magnesium sulfate.

[0036] In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising from about 70-75% molecular sieve and about 25-30% magnesium sulfate, or about 70% molecular sieve and about 30% magnesium sulfate or alternatively about 75% molecular sieve and about 25% magnesium sulfate w/w based on the weight of the first layer and the second layer is comprising a mixture of about 75-85% of magnesium sulfate based on the weight of the second layer, and one or more agent, in powdered form.

[0037] In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising a mixture of molecular sieve and magnesium sulfate and the second layer is comprising a diamine functionalized on silica and magnesium sulfate. In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising from about 70-75% molecular sieve and about 25-30% magnesium sulfate, or about 70% molecular sieve and about 30% magnesium sulfate or alternatively about 75% molecular sieve and about 25% magnesium sulfate w/w based on the weight of the first layer and the second layer is comprising a mixture of about 75-85% of magnesium sulfate based on the weight of the second layer, and a diamine functionalized on silica.

[0038] In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising a mixture of molecular sieve and magnesium sulfate and the second layer is comprising a diamine functionalized on silica, a C18 functionalized on silica and magnesium sulfate. In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising from about 70-75% molecular sieve and about 25-30% magnesium sulfate, or about 70% molecular sieve and about 30% magnesium sulfate or alternatively about 75% molecular sieve and about 25% magnesium sulfate w/w based on the weight of the first layer and the second layer is comprising a mixture of about 75-85% of magnesium sulfate based on the weight of the second layer, and a diamine functionalized on silica, and a C18 functionalized on silica.

[0039] In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising a mixture of molecular sieve and magnesium sulfate and the second layer is comprising a diamine functionalized on silica, a C18 functionalized on silica and magnesium sulfate.

[0040] In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising a mixture of molecular sieve and magnesium sulfate and the second layer is comprising a diamine functionalized on silica, a graphitized carbon black and magnesium sulfate. In one embodiment, the extraction cartridge is comprising/consisting of two layers, wherein the first layer is comprising from about 70-75% molecular sieve and about 25- 30% magnesium sulfate, or about 70% molecular sieve and about 30% magnesium sulfate or alternatively about 75% molecular sieve and about 25% magnesium sulfate w/w based on the weight of the first layer and the second layer is comprising a mixture of about 75-85% of magnesium sulfate based on the weight of the second layer, and a diamine functionalized on silica, and a graphitized carbon black.

[0041] In one embodiment, the filter pad is a fritted glass. The filter pad should be a filter pad which is not affecting the flow rate of solvent through the first and second layers.

[0042] In one embodiment, the method for preparing a test liquid from an agricultural sample is comprising : grounding to powder, the agricultural sample, preferably in a frozen state; adding an organic solvent into the grounded agricultural sample, and preferably shaking the two together, to provide a sample solution ; circulating the sample solution through the first powder mixture layer and the second powder mixture layer as defined herein (e.g. as comprised in an extraction cartridge as defined herein); and recovering said test liquid.

In one embodiment, the recovered test liquid from an agricultural sample obtained by the method herein is comprising

[0043] In one embodiment, the agricultural sample is grounded to powder while being in a frozen state, or in the presence of a cooling agent, such as dry ice (solid C0₂).

[0044] In one embodiment, the pH of the sample solution is from about 3 to 7.

[0045] In one embodiment, a first layer comprising a 70/30 mixture of 3A molecular sieve and magnesium sulfate has a density ranging from : 0.60 to 0.70 g/mL.

[0046] In one embodiment, a molecular sieve, such as a 3A molecular sieve may have the following features:

- Porosity : 3A

- Particle size : range: d10 > 2mhi

range: 10 mhi <d50<40 mhi

range: : 22 mhi <d90<80 mhi

- Moisture: Water content <0.1 %

- Density : 0.50 to 0.55 g/mL

[0047] In one embodiment, the magnesium sulfate may have the following features:

- Particle size : range: d10 > 2mhi

range: 10 mhi <d50<40 mhi

range: 22 mhi <d90<80 mhi

- Moisture: Water content <0.1 %

- Density : 0.85 to 0.95 g/mL.

[0048] In one embodiment, in said step of providing a sample solution by extracting a pesticide from said agricultural sample, said solvent is an organic or an aqueous-organic solvent. The organic solvent of said aqueous-organic solvent is water miscible. An aqueous-organic solvent may contain up to 25% (preferably 20-25%) v/v water in the organic solvent, Non-limiting examples of solvents include: acetonitrile, 1% of acetic acid in acetonitrile (v/v), ethyl acetate, hexanes, methyl-tert-butyl ether, and dichloromethane.

[0049] In one embodiment, sample solution is circulated through the first and second layer by gravity, in one embodiment, sample solution is circulated through the first and second layer by pressing the sample solution through the first and second layer, e.g. by applying a pressure at the input port. In one embodiment, sample solution is circulated through the first and second layer by pulling the sample solution , e.g. by applying a vacuum at the output port.

[0050] Throughout the specification, including in the examples, any reference to the water content (in %) after passing on a FPE is expressed on a wt / wt % basis.

Examples

[0051] Anhydrous MgS0 , reagent plus greater than 99.5% was bought from Sigma-Aldrich, HPLC grade solvents were bought from Fisher Chemical and ACS Reagent acetic acid > 99.7 was bought from Sigma-Aldrich). Primary secondary amine grafted on silica and C18 grafted on silica were obtained from SiliCycle inc, the graphitized carbon black was obtained from Agilent Technologies.

[0052] The primary secondary amine and C18 grafted on silica can be grafted on irregular silica gel or on spherical silica gel. Their respective characterizations are as follow:

Characterization of the Primary secondary amine grafted on silica

Characterization of the C18 grafted on silica

[0053] Both gave the same efficiency, however in the examples below, the spherical silica gel was used as it allowed to get a more homogenous mixture with the magnesium sulfate.

Example 1 : effectiveness of 3A molecular sieve powder as drying agent

[0054] Two grams of each of 3A molecular sieve powder and MgS0 were added in an empty cartridge (SiliaSep 4g - Dimension (ID X Length): 12 mm X 98 mm - Manufacturer: SiliCycle inc.). A green tea maceration solution was passed on each. The maceration solution used contained 0.5 g of powdered green Japanese tea macerated for 30 minutes in 5 mL of a 1% acetic acid solution diluted in acetonitrile (v / v) and 1 mL of water HPLC grade. The water content of this maceration was evaluated at 21 % in using a volumetric Karl Fisher titrator from Mettler Toledo (Model V20). The effectiveness of each desiccant was evaluated by measuring the water content after the maceration solution had passed over each of them at an elution rate of 1.5-2.0 ml_/ min.

[0055] The results demonstrated that the 3A molecular sieve powder was just as effective in drying the organic phase as MgS0 without cementing (See table 1)

Table 1A

[0056] In a manner similar to what is described above, the dehydration was also done with 13A molecular sieve with a maceration solution having an initial water content of 21 %. The results in Table 1 B show that is possible to dehydrate the maceration solution with 13A.

Table 1 B

Example 2: Composition of the first layer:

[0057] The following experiment demonstrated the possible variation in the first layer. The first powder layer may comprise molecular sieve alone or in admixture with MgS0 . Two grams of different mixtures of 3A molecular sieve powder and MgS0 were added in the same cartridges as described in example 1. The green tea maceration used was prepared as described in Example 1. Green tea maceration was passed through each cartridge at the same rate of elution as in Example 1.

[0058] The results demonstrated that molecular sieve alone or in admixture with MgS0 (3A/ MgS0 molecular sieve) (w/ w) will remove water from the organic phase (See Table 2). Cementation was observed for a mixture having an amount of magnesium sulfate of 40% or higher. At these higher amounts, the contact surface between the maceration solvent and the sorbent appears to be sub-optimal. It is believed that the extraction solvent does not flow efficiently through the layer and the diffusion in cartridges starts to be poor causing an increased water content. Table 2

Example 3: Composition of the second layer

[0059] The composition of the second layer was also varied while keeping the composition of the first layer constant at 70/30 and 75/25 (3A / MgS0 molecular sieve). The green tea maceration used was prepared as described in Example 1. The same amount of green tea maceration as described in Example 1 was passed through each cartridge at an elution rate of 1.5-2.0 rnU min. The results demonstrated that first layer coupled to a second layer of the same composition (70/30 and 75/25 (molecular sieve 3A / MgS0 )) made it possible to obtain an organic phase that is almost free of water (see Table 3).

[0060] It was observed that after the maceration solution had eluted through the first layer (70/30 and 75/25 molecular sieve 3A / MgS0 ) the maceration solution was sufficiently dried (See table 2) to avoid to cement the lower layer made with 100 % in magnesium sulfate. As show in table 3, it was possible to use 70/30 and 75/25 of a molecular sieve 3A / MgS0 mixture or only magnesium sulfate as desiccant in second layer. The water content in the test liquid was the same.

Table 3

Example 3 - Preparation of a general FPE

[0061] The upper layer of a FPE of general type is composed of 2.00 grams of 70/30 or and 75/25 (molecular sieve 3A / MgS0 ) (w/ w). The lower layer consists of 0.85 g of a diamine mixture functionalized on silica and anhydrous magnesium sulfate (14.3 / 85.7 w / w). The characteristics of the constituents of each of the layers of the general FPE are shown in Tables 4 and 5. Table 4

Table 5

[0062] Production of a first layer 5 Kg batch of a molecular sieve 3A / anhydrous magnesium sulphate mixture (70/30 w/ w and 75/25):

1. In a new 20L container, 3.5 kg of 3A molecular sielve 100 mesh and 1.5 kg of anhydrous magnesium sulphate were successively added;

2. The container was sealed and the content mixed on the rotating barrel overnight;

3. The mixture was transferred to the 5Kg powder mixer and mixed for 4 hours.

[0063] Production of a second layer 5 Kg batch of a Diamine / anhydrous magnesium sulphate mixture (14.3/ 85.7 w / w):

1. In a new 20L container, 4.285 Kg of anhydrous magnesium sulphate and 715g of diamine S49030B-A were successively added; 2. The container was sealed and the content mixed on the rotating barrel overnight;

3. The mixture was transferred to the 5Kg powder mixer and mixed for 4 hours.

Preparation of the FPE

[0064] The two layers were successively loaded in a 12 ml_ syringe and shaken in the vertical position for a 5 seconds to level the top of the second layer. A filter pad (fritted glass) was press fitted on the second layer at a pressure of about 7.5 psi. The syringe had a female luer-lock type lock fitted on the top side (i.e. input port) and a male luer-lock type lock fitted on the bottom side (i.e. output port) made of a medical grade polypropylene syringe having the following dimensions:

Example 4 - Preparation of a Rice and Cereal FPE

[0065] The first layer has the same compositions as in Example 3. The lower layer consists of 0.85 g of a mixture of diamine functionalized on silica, C18 functionalized on silica and anhydrous magnesium sulfate (12.9 / 9.68 / 77.42 w / w). The characteristics of the constituents of each layer of FPE cereal are shown in Tables 6 and 7. Table 6

Table 7

[0066] The first layer 5kg batches were prepared in the same manner as described in Example 3. The second layer 5kg batch was also prepared as described in Example 3, except that 3 871 g of anhydrous magnesium sulfate, 645g of diamine functionalized on silica (S49030B-A) and 484g de C18 functionalized on silica (S03230B-A) were used.

[0067] The two layers were successively loaded in the 12 mL syringe as described in Example 3. Example 5 - Preparation of a chlorophyl FPE

[0068] The first layer has the same compositions as in Example 3. The lower layer consists of 0.85 g of a mixture of diamine functionalized on silica, Graphitized carbon black and anhydrous magnesium sulfate (14.1 / 1.4 / 84.5 w / w). The characteristics of the constituents of each layer of the FPE chlorophyl are shown in Tables 8 and 9.

Table 8

Table 9

[0069] The first layer 5kg batches were prepared in a the same manner as described in Example 3. The second layer 5kg batch was also prepared as described in Example 3, except that 4225 g of anhydrous magnesium sulfate, 705g of diamine functionalized on silica (S49030B-A) and 70g of Graphitized carbon black were used.

Characterization of the graphitized carbon black

[0070] The container used was an aluminum container.

[0071] The two layers were successively loaded in the 12 ml_ syringe as described in Example 3. Example 6 - Preparation of a green tea FPE

[0072] The first layer has the same compositions as in Example 3. The lower layer consists of 0.85 g of a mixture of diamine functionalized on silica, Graphitized carbon black and anhydrous magnesium sulfate (13.7 / 4.1 / 82.2 w/ w). The characteristics of the constituents of each layer of the FPE chlorophyl are shown in Tables 10 and 1 1.

Table 10

Table 11

[0073] The first layer 5kg batches were prepared in a the same manner as described in Example 3. The second layer 5kg batch was also prepared as described in Example 3, except that 41 10 g of anhydrous magnesium sulfate, 685g of diamine functionalized on silica (S49030B-A) and 205 g of Graphitized carbon black were used. The container used was an aluminum container.

[0074] The two layers were successively loaded in the 12 ml_ syringe as described in Example 3.

Example 7 : Assessment of pesticide recovery and water content using general FPE

[0075] The agricultural sample was powder grounded with dry ice. 1 g of powder and the relevant pesticides were added to 5 ml_ of a solution comprising 1 % acetic acid in acetonitrile. The mixture was shaken on an horizontal shaker for 15 minutes (and optionally sonicated). The resulting mixture was then passed on the general FPE cartridge under an elution rate of about 1 drop/ sec. 5 ml_ of a solution comprising 1 % acetic acid in acetonitrile was further eluted in the cartridge and all the remaining solvent was flushed out of through the output port by pushing air. The filtrates were evaporated to dryness and reconstituted in acetonitrile to be analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) in accordance with the following analytical conditions: [0076] HPLC conditions:

Column : SiliaChrom dt C18, 50 X 3.0 m , 2.5 urn

Mobile phase A (MPA): 1 mM ammonium formate in 95/5 (Water HPLC grade/ Methanol

HPLC gradeO, 0.1% Formic acid (v/v).

Mobile phase B (MPB): 1 mM ammonium formate in 5/95 (Water HPLC grade/ Methanol

HPLC gradeO, 0.1% Formic acid (v/v).

Gradient :

[0077] Operating conditions:

Flow (ml/min) : 0.500 mL/min

Injection volume (uL) : 2.5

Column temperature (°C) : 35

Detection:

Instrument : Sciex API 3000

Ionisation : Electrospray ionisation (ESI)

Polarity : Positive

Acquisition mode : MRM Multiple reaction monitoring MRM Transition :

[0078] Extraction were conducted using apple as agricultural sample on the general FPE cartridges described above in Example 3. The samples were spiked with different pesticides at a concentration of 1 ppm and treated according to the protocol described above. The recovery results of each pesticide obtained with the FPE were compared with those of a commercially available cartridge (FaPEx General - Manufacturer: Great Engineering Technology Co.). (Fast Pesticide Extraction Kit-General sample, Getech company, product #: FaPEX-GEN50) The results below show that the FPE cartridges of this disclosure perform better (see Table 11). Also the water contents analysis, show that the cartridges according to this disclosure do not cement compared to the reference product (Table 12).

Table 11

*n=3

Table 12

Example 8: Assessment of pesticide recovery and water content using chlorophyl FPE The sample preparation and extraction was the same as described in Example 7, except that zucchini was used as agricultural sample. The results were compared with those of a commercially available cartridge (FaPEx Chlorophyll - Manufacturer: Great Engineering Technology Co.). (Fast Pesticide Extraction Kit- Chlorophyll sample, Getech company, product #: FaPEX-CHL50). The results presented in tables 13 and 14 showed that the FPE cartridges according to this disclosure are equally good as those of the reference product having regard to the extraction (see Table 13). However, as demonstrated by the water contents, the cartridges according to this disclosure did not cement compared to the reference cartridge (Table 14). Further the extracts obtained proved to be cleaner than that of the reference product. The extract obtained on the FPE cartridge of this disclosure (Example 5) was colorless while that of the reference product remained greenish.

Table 13

*n=3 Table 14

Example 9 : Assessment of pesticide recovery and water content using cereal FaPEx

[0079] The sample preparation and extraction was the same as described in Example 7, except that Rice from Rose Brand company was used as agricultural sample. A particle size distribution measurements provided the following distribution: 16% of particles had a size of between 2000 mhi-1000 mhi, 39% were between 1000 mhi-500 mhi, 24% were between 500 mhi-250 mhi and 21 % were smaller than 250 mhi. In summary, the ground powder was therefore smaller than about two millimeters. Further, before adding 5 ml_ of the acetonitrile comprising 1% acetic acid, 1 ml_ of distilled water was added and the resulting mixture shaken on a vortex spinner for 30 seconds and then left on standing for 10 minutes. The results were compared with those of a commercially available cartridge (FaPEx Cereal - Manufacturer: Great Engineering Technology Co.). (Fast Pesticide Extraction Kit- Cereal sample, Getech company, product #: FaPEX- CER50). The results presented in tables 15 and 16 showed that the FaPEx cartridges according to this disclosure (Example 4) are equally good as those of the reference product having regard to the extraction (see Table 15). However, as demonstrated by the water contents, the cartridges according to this disclosure did not cement compared to the reference cartridge (Table 16). Further the extracts obtained proved to be cleaner than that of the reference product. Table 15

*n=3

Table 16

Example 10 : Assessment of pesticide recovery and water content using green tea FaPEx

[0080] The sample preparation and extraction was the same as described in Example 9, except that green tea was used as agricultural sample. A particle size distribution measurements provided the following distribution: 1 % of particles had a size of between 2000 mhi-1000 mhi, 26% were between 1000 mhi-500 mhi, 37% were between 500 mhi-250 mhi and 36% were smaller than 250 mhi. The results were compared with those of a commercially available cartridge (FaPEx Tea - Manufacturer: Great Engineering Technology Co.). (Fast Pesticide Extraction Kit- Tea sample, Getech company, product #: FaPEX-TEA50). The results presented in tables 17 and 18 showed that the FPE cartridges according to this disclosure (example 6) are equally good or better than those of the reference product having regard to the extraction (see Table 17). However, as demonstrated by the water contents, the cartridges according to this disclosure did not cement compared to the reference cartridge (Table 18). Further the extracts obtained proved to be cleaner than that of the reference product.

Table 17

*n=3 Table 18

[0081] While specific embodiments of the present invention have been described in the examples, it is apparent that modifications and adaptations of the present invention will occur to those skilled in the art. The embodiments of the present invention are not intended to be restricted by the examples. It is to be expressly understood that such modifications and adaptations which will occur to those skilled in the art are within the scope of the present invention, as set forth in the following claims. For instance, features illustrated or described as part of one embodiment can be used in another embodiment, to yield a still further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the claims and their equivalents.

Claims

1. An extraction cartridge comprising: a housing (10) extending in an upright position along a longitudinal axis (L) between an output port (11) and an input port (12), the housing having an internal chamber defined therein; a first powder mixture layer (43) filled in the internal chamber, wherein said first powder mixture layer is located below the input port (12); and a second powder mixture layer (44) filled in the internal chamber, wherein said first powder mixture layer (43) is capable of absorbing water from a sample solution comprising one or more pesticides; wherein said second powder mixture layer (44) is located below the first powder mixture layer and above the output port (11).

2. The extraction cartridge as defined in claim 1 , wherein said first layer is comprising a mixture of i) molecular sieve and ii) magnesium sulfate in an amount of less than 40% w/w based on the weight of the first layer.

3. The extraction cartridge as defined in claim 1 or 2, wherein said second layer is capable of absorbing further water of the sample solution eluting from the first layer and wherein said second layer is comprising magnesium sulfate.

4. The extraction cartridge as defined in claim 3, wherein said second layer is further comprising one or more agent, in powdered form, for removing (adsorbing) impurities.

5. The extraction cartridge as defined in claim 4, wherein said second layer is comprising about 25% w/w or more of magnesium sulfate based on the weight of the second layer, and said one or more agent, in powdered form.

6. The extraction cartridge as defined in any one of claims 1 to 5, wherein the first layer is comprising from about 70-75% molecular sieve and about 25-30% magnesium sulfate, w/w based on the weight of the first layer, and the second layer is comprising a mixture of i) about 75-85% of magnesium sulfate based on the weight of the second layer, and ii) one or more agent, in powdered form.

7. The extraction cartridge as defined in any one of claims 1 to 5, wherein the first layer is comprising from about 70-75% molecular sieve and about 25-30% magnesium sulfate w/w based on the weight of the first layer and the second layer is comprising a mixture of i) about

75-85% of magnesium sulfate based on the weight of the second layer, and ii) a diamine functionalized on silica.

8. The extraction cartridge as defined in any one of claims 1 to 5, wherein the first layer is comprising from about 70-75% molecular sieve and about 25-30% magnesium sulfate w/w based on the weight of the first layer and the second layer is comprising a mixture of i) about

75-85% of magnesium sulfate based on the weight of the second layer, and ii) a diamine functionalized on silica, and iii) a C18 functionalized on silica.

9. The extraction cartridge as defined in any one of claims 1 to 5, wherein the first layer is comprising from about 70-75% molecular sieve and about 25-30% magnesium sulfate w/w based on the weight of the first layer and the second layer is comprising a mixture of i) about

75-85% of magnesium sulfate based on the weight of the second layer, and ii) a diamine functionalized on silica, and iii) a graphitized carbon black.

10. The extraction cartridge as defined in any one of claims 1 to 9, further comprising at least one of a filter pad (40) on the top surface of the first powder mixture layer (43), a filter pad (41) between said first and second layer (43,44) and a filter pad (42) on the bottom surface of the second powder mixture layer (44).

11. The extraction cartridge as defined in claim 10, wherein said at least one of a filter pad is fixed to the housing of the cartridge.

12. The extraction cartridge as defined in claim 10 or 11 , wherein said at least one of a filter pad is a fritted glass.

13. A method for preparing a test liquid from an agricultural sample comprising : providing a sample solution by extracting one or more pesticides from said agricultural sample in a solvent; and circulating the sample solution through a first powder mixture layer and a second powder mixture layer, preferably said layers being comprised in an extraction cartridge as defined in any one of claims 1 to12; and recovering said test liquid.

14. The method of claim 13, wherein said agricultural sample is a fruit, a vegetable, grains, a dried bean, tea, spice or other herbaceous plants.

15. The method of claim 14, wherein said step of providing a sample solution is comprising: grounding to powder, the agricultural sample; and adding said solvent into the grounded agricultural sample, to provide said sample solution.

16. The method of claim 15, wherein the agricultural sample is grounded to powder while being in a frozen state).

17. The method of any one of claims 13 to 16, wherein the pH of the sample solution is from about 3 to 7.

18. The method of any one of claims 13 to 17, wherein said solvent is an organic solvent or an aqueous-organic solvent mixture.

19. The method of claim 18, wherein said organic solvent is comprising acetonitrile, acetic acid in acetonitrile , ethyl acetate, hexanes, methyl-tert-butyl ether, and dichloromethane.