Enhanced matrix removal (EMR) cartridge

Abstract

In some examples, a method comprises specifying a sorbent formulation for a targeted class of food contaminant analysis, and utilizing enhanced matrix removal (EMR) mixed-mode passthrough cleanup with the specified sorbent formulation. In other examples, an EMR cartridge may include a specified sorbent formulation for a targeted class of food contaminant analysis. The EMR cartridge may utilize EMR mixed-mode passthrough cleanup with the specified sorbent formulation.

Description

20240003-02 (AG20240003-02) ENHANCED MATRIX REMOVAL (EMR) CARTRIDGE PRIORITY

[0001] This application claims priority to commonly assigned and co-pending U.S. Provisional Patent Application Serial No. 63 / 599,481, filed November 15, 2023, titled “ENHANCED MATRIX REMOVAL (EMR) CARTRIDGE”, the disclosure of which is hereby incorporated by reference in its entirety.20240003-02 (AG20240003-02) BACKGROUND

[0002] Analysis of targeted chemical contaminants or ingredients in food and feed can be important to food safety. Contaminants introduced artificially or naturally, for example, during planting, growing, harvesting, production, transportation, and storage, can greatly impact the quality of food products, the safety of their consumption, public health, environmental control, and manufacturers’ financial profits. These contaminants include widely used pesticides and veterinary drugs, environmental or food processing contaminants such as per- and polyfluoroalkyl substances (PFASs), polycyclic aromatic hydrocarbons (PAHs), and naturally derived contaminants such as mycotoxins or contained food components such as food allergens. Therefore, food safety analysis continues to gain global attention, which has led to new regulations worldwide by many global or local regulation agencies.20240003-02 (AG20240003-02) BRIEF DESCRIPTION OF DRAWINGS

[0003] Features of the present disclosure are illustrated by way of example and not limited in the following figure(s), in which like numerals indicate like elements, in which:

[0004] Figure 1 illustrates a simplified EMR mixed-mode passthrough cleanup methodology using the new EMR cartridges disclosed herein for per- and polyfluoroalkyl substance (PFAS) and mycotoxin analysis, in accordance with an example of the present disclosure;

[0005] Figure 2 illustrates pigment removal provided by enhanced matrix removal (EMR) mixed-mode passthrough cleanup for fruits and vegetables matrices, using EMR PFAS Food I cartridges, in accordance with an example of the present disclosure;

[0006] Figure 3 illustrates matrix removal by EMR mixed-mode passthrough cleanup for representative animal-origin food matrices using EMR PFAS Food II cartridges, and evaluated by gas chromatography / mass spectrometry (GC / MS) full scan screening, in accordance with an example of the present disclosure;

[0007] Figure 4 illustrates matrix removal by EMR mixed-mode passthrough cleanup for representative dry and processed food / feed matrices using EMR mycotoxins cartridges, and evaluated by liquid chromatography / quadrupole time-of-flight (LC / QTOF) scan screening and sample dried residue, in accordance with an example of the present disclosure;

[0008] Figure 5 illustrates PFAS targets recovery in six representative food matrices using EMR mixed-mode cleanup by EMR PFAS food cartridges, and two conventional dispersive solid phase extraction (dSPE) cleanups, in accordance with an example of the20240003-02 (AG20240003-02) present disclosure;

[0009] Figure 6 illustrates recovery comparison for multiresidue mycotoxins in a corn matrix, using EMR mixed-mode passthrough cleanup versus another matrix cleanup method (e.g., SPE and dSPE), in accordance with an example of the present disclosure;

[0010] Figure 7 illustrates comparison of a conventional technique versus the method for PFAS disclosed herein in food analysis sample preparation, in accordance with an example of the present disclosure;

[0011] Figure 8 illustrates matrix effects on mycotoxin targets in representative food and feed samples prepared by different sample preparation methods, while the stable isotope dilution assay (SIDA) method is a conventional method being used, and Q-ext and EMR passthrough cleanup is the method disclosed herein using EMR mycotoxins cartridges, in accordance with an example of the present disclosure;

[0012] Figure 9 illustrates chromatograms of core PFAS targets in matrix blanks and validated LOQs from representative food matrix samples, where the workflow using new EMR PFAS food cartridges support the method validated at the required ultralow LOQ levels, in accordance with an example of the present disclosure;

[0013] Figure 10 illustrates a Certificate of Analysis (CoA) for EMR PFAS food cartridges per batch, in accordance with an example of the present disclosure;

[0014] Figure 11 illustrates an example of a method procedure using EMR PFAS I cartridges for fresh plant-origin food sample preparation, in accordance with an example of the present disclosure;

[0015] Figure 12 illustrates an example of a method procedure using EMR PFAS II20240003-02 (AG20240003-02) cartridges for animal-origin food sample preparation, in accordance with an example of the present disclosure; and

[0016] Figure 13 illustrates an example of a method procedure using EMR mycotoxins for dry feed / food sample preparation, in accordance with an example of the present disclosure.20240003-02 (AG20240003-02) DETAILED DESCRIPTION

[0017] For simplicity and illustrative purposes, the present disclosure is described by referring mainly to examples. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. It will be readily apparent however, that the present disclosure may be practiced without limitation to these specific details. In other instances, some methods and structures have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0018] Throughout the present disclosure, the terms "a" and "an" are intended to denote at least one of a particular element. As used herein, the term "includes" means includes but not limited to, the term "including" means including but not limited to. The term "based on" means based at least in part on.

[0019] Enhanced matrix removal (EMR) cartridges, and methods for EMR are disclosed herein.

[0020] As disclosed herein, the analysis of targeted chemical contaminants or ingredients in food and feed is important for food safety. Contaminants introduced artificially or naturally during planting, growing, harvesting, production, transportation, and storage, can greatly impact the quality of food products, the safety of their consumption, public health, environmental control, and manufacturers’ financial profits. These contaminants include widely used pesticides and veterinary drugs, environmental or food processing contaminants such as per- and polyfluoroalkyl substances (PFASs), polycyclic aromatic hydrocarbons (PAHs), and naturally derived contaminants such as mycotoxins or contained food components such as food allergens. Therefore, food safety analysis continues to gain global attention and is regulated worldwide by many global or local20240003-02 (AG20240003-02) regulation agencies.

[0021] Determination of chemical contaminants during food safety analysis is usually based on modern instrument detection, including liquid chromatography - tandem mass spectrometry (LC / MS / MS), gas chromatography – tandem mass spectrometry (GC / MS / MS) and other methods. Tandem mass spectrometry has become a well-known instrument detection method for the highly sensitive and selective determination of chemical contaminants in food. However, many food samples are unable to be run for analysis on an instrument directly due to the large variety, many different formats, and high complexity of food matrices involved. Food samples will thus often need suitable sample preparation prior to instrument detection.

[0022] For many food samples, sample preparation provides multiple functions. First, it converts the samples from a variety of formats into one that is suitable for instrument detection, such as converting a solid food to a liquid extract which can then be injected onto an instrument. Second, it provides extraction of the targets, which makes the compounds detectable by the instrument. Adjustment of the target compounds concentration can be introduced through appropriate sample dilution or concentration. Third, it provides food matrix cleanup. Matrix co-extractives can impact instrument detection significantly, either through various matrix effects that impact the targets’ MS detection, or matrix interferences that can hinder the compound’s chromatographic separation, or even accumulation of matrix contamination on the detection flow path that can deteriorate instrument performance over time. A final consideration of sample preparation concerns lab productivity. The use of simple, easy and robust sample preparation techniques is highly preferred, especially in high throughput labs, which is20240003-02 (AG20240003-02) needed for lab productivity.

[0023] Examples of sample preparation techniques used for food samples include liquid-liquid or liquid-solid extraction, QuEChERS extraction, which is a portmanteau word formed from "quick, easy, cheap, effective, rugged, and safe" , and solid phase extraction (SPE). Among these, QuEChERS is a popular technique used in food safety analysis due to its simple and easy procedure, applicability to many different targeted applications, suitability for large panel multiclass multiresidue targets, and good-enough matrix cleanup. QuEChERS extraction starts with liquid-solid or liquid-liquid extraction using acetonitrile, followed by dispersive salt partitioning using either buffered or non-buffered salts to separate the organic and aqueous / solid phases. After extraction, the organic layer on top is considered as the crude extract and used for subsequent dispersive SPE (dSPE) cleanup. dSPE cleanup makes use of various blended sorbents that may include primary secondary amine (PSA), MgSO4, or possibly graphitized carbon black (GCB) and C18.

[0024] The QuEChERS technique provides a suitable method for the simultaneous extraction of a broad panel of multiclass multiresidue organic compounds, regardless of their diverse physico-chemical properties, primarily in terms of polarity, solubility, volatility, acidity and alkalinity, and stability. The use of Acetonitrile (ACN) can also restrict the co- extraction of matrix interferences. Therefore, it is suited for food safety analysis, given the large variety and high complexity of food matrices. The follow-up dSPE cleanup technique is also a matrix targeted method, which primarily interacts with matrix co- extractives with limited impact on the desired target compounds. QuEChERS extraction has been used in sample preparation for food safety analysis, especially for pesticides,20240003-02 (AG20240003-02) PFAS, and mycotoxins.

[0025] However, conventional dSPE techniques can include a variety of limitations. First, with certain foods, dSPE can lead to insufficient matrix removal. dSPE cleanup works well for relatively simple food matrices such as fruit and vegetables, but for more complex animal-based foods, in some cases, the cleanup by dSPE is not sufficient. Inadequate matrix removal can cause various problems for the reliable analysis of target compounds, such as matrix effects on MS detection, insufficient LC or GC chromatographic separation for accurate target peak identification and integration, and poor method sensitivity or selectivity to meet analytical requirements. Secondly, use of a dispersive SPE format can make the procedure more time consuming, labor intensive, and difficult to automate. The method can involve multiple steps of sample transferring, repeatedly opening and closing dSPE tubes, vortexing and centrifugation. In addition, the withdrawal of supernatant after the cleanup can be challenging, especially for some food matrix where the fiber residue is difficult to fully centrifuge down. Third, there are currently many variations of dSPE kits designed for different official methods, various food matrices, and different formats. This multitude of options allows for flexibility, but can also make the proper selection technically challenging and confusing. Fourth, sorbents used in dSPE can display a lack of selectivity, causing unwanted interactions with some sensitive compounds, thus resulting in loss of target compounds. Lastly, loss of sample volume can make some post sample treatments difficult, such as post concentration by drying and reconstitution. In some cases, the dSPE cleanup recovery on sample volume can be around 50%. This can be due to the challenges of separation of sorbents from sample extract with centrifugation, especially with 15 mL dSPE tubes, which are difficult20240003-02 (AG20240003-02) to use with higher speed centrifugation.

[0026] An Enhanced Matrix Removal (EMR) mixed-mode passthrough cleanup methodology was previously introduced with introduction of the EMR-Lipid sorbent, and further developed with launch of the Carbon S sorbent. The EMR method is based on the use of appropriate EMR cartridges disclosed herein, offering high selectivity and efficiency on comprehensive matrix removal, making it a convenient, rapid and reliable sample matrix cleanup technique. The method provides better matrix removal and higher recovery for sensitive targets. The sorbents used in the EMR cartridges may include more efficient and selective materials such as EMR-Lipid, Carbon S sorbent, blended in optimized formulations based on the evaluation of both target recovery and matrix removal. Since EMR mixed-mode passthrough cleanup is compatible with traditional food sample extraction techniques including QuEChERS extraction and solvent extraction, the method can be readily applied after food sample extraction. The cartridge-based cleanup utilizes a simplified method with fewer transferring steps and the obsoletion of manipulations for dSPE tubes, thus saving time and effort. The cartridge-based cleanup also significantly improves the sample volume recovery, from 50% or less recovery in dSPE cleanup to > 90% by EMR passthrough cleanup. Cartridge format and sample flow through features also make it highly applicable for automation. The method has been applied for multiclass multiresidue large panel target analysis, such as pesticides and vet drugs. It also shows high potential for the specific class of food contaminants such as PFAS, mycotoxins etc.

[0027] With respect to PFAS analysis in food, sample preparation plays an important role in the entire method, providing the efficient PFAS extraction and removal of matrix20240003-02 (AG20240003-02) co-extractives. The large variety and high complexity of food matrices can challenge the sample preparation method, not only in terms of sample extraction and matrix cleanup efficiency, but also the overall method simplicity, sample processing efficiency, and accommodation of different matrices. Weak anion exchange (WAX) sorbent-based solid phase extraction (SPE) methods have been used widely for PFAS analysis in environmental samples such as water and soil, as well as other matrices. However, the SPE method is challenging for sample preparation of complex solid food matrices, as food samples need to be extracted and converted into an appropriate solvent media before loading into the cartridge. Also, the typical SPE procedure involving conditioning, equilibrium, loading, washing, and eluting requires a substantial amount of time and solvent.

[0028] QuEChERS extraction followed with typical dispersive SPE (dSPE) cleanup has been reported for PFAS in food sample preparation. However, dSPE cleanup does not provide efficient matrix removal for many food matrices, which cannot support the lower limits of quantitation (LOQ) requirement in food. Thus, additional weak anion- exchange solid phase extraction (WAX SPE) may be added after dSPE cleanup. However, this can cause the process to be time consuming and labor intensive, which can impact sample process productivity. This dSPE sample cleanup also results in loss of PFAS targets.

[0029] With respect to mycotoxin analysis in dry plant-origin and processed food and feed, mycotoxins are toxic compounds generated by various fungal species that can grow on many agricultural commodities and processed food and feed, either in the field or during storage. Consumption of foods or feeds contaminated with mycotoxins can cause20240003-02 (AG20240003-02) serious public health concerns. Many regulatory agencies have established maximum residue limits (MRLs) for mycotoxins to closely monitor and control dietary exposure from contaminated foods and feeds.

[0030] Current analytical techniques for mycotoxins are mostly based on LC / MS / MS detection, due to the high sensitivity and selectivity provided by this technique. Mycotoxins include many sensitive compounds that tend to be lost during typical sample preparation methods. Therefore, for multiclass multiresidue mycotoxins analysis in various dry sample matrices, the sample preparation method mainly relies on direct solvent / water mixture extraction with the use of a large panel of isotopically labelled internal standards (ISTD). This technique has been cross-validated in multiple labs and is widely used in many mycotoxin testing facilities. However, this technique relies on the significant use of large quantity of expensive isotopic ISTDs for sample matrix correction and instrument detection selectivity. The injection of sample crude extract to LC / MS / MS without further matrix cleanup can cause flow path carryover and MS source contamination and result in more frequent instrument downtime for cleaning and maintenance. Immunoaffinity columns are also used for sample matrix cleanup after sample extraction. However, this technique is limited either for single or a few major classes of mycotoxin analysis.

[0031] QuEChERS extraction followed by dispersive SPE (dSPE) cleanup has also been used in sample preparation for mycotoxin analysis. However, dSPE cleanup may not provide efficient matrix removal, and may also cause the loss of sensitive mycotoxins such as fumonisins and aflatoxins.

[0032] The apparatuses (e.g., an EMR cartridge, and / or a system utilizing an EMR20240003-02 (AG20240003-02) cartridge) and methods disclosed herein address the aforementioned technical challenges and drawbacks by providing for the use of EMR mixed-mode passthrough cleanup with specifically developed sorbent formulations for targeted classes of food contaminant analysis, particularly PFAS and mycotoxins analysis, and potentially including other food contaminants. The EMR mixed-mode passthrough cleanup method may be based on the sorbents interaction with matrix co-extractives. Thus, multiple interaction mechanisms may be applied for matrix interferences removal, including fats and lipids removal by the combination of size exclusion and hydrophobic interaction mechanism, organic acids, fatty acids and carbohydrates removal through the ionic and hydrophilic interaction mechanism, pigments removal through the selective planar interaction mechanism, and other hydrophobic interferences removal through the restricted hydrophobic interaction. The EMR cartridge disclosed herein may also be referred to as a Captiva EMR cartridge. Other aspects for the cartridge development may include the formula of the blended sorbents, and considerations on the cartridge frits and packing.

[0033] The development of the specific formulas for the blended sorbents may be based on the recovery of representative target compounds and sample matrix removal, followed by the determination of the optimized formula which provides an acceptable balance of these two parameters. An understanding of the target compounds physio- chemical properties, as well as the mechanism of interaction between the sorbents and matrix may be utilized for formula development and optimization. Achieving the ideal target recovery can be challenging when also attempting to combine this with the best matrix removal, especially for multiresidue analysis in complex food matrices.20240003-02 (AG20240003-02) Compromises may need to be taken with either the matrix removal efficiency or certain non-critical targets. Therefore, an important goal is to find the best “balance” for the maximal matrix removal, which also results in a minimal impact on target recovery. Another important consideration is the matrix masking effect, which involves the interaction of matrix co-extractives with sorbents which can be used to adjust the interaction of sorbents with some sensitive targets. In such a case, matrix co-extractives can function as protectants and prevent the targets retention on the sorbent and ultimately lead to the targets loss. Thus the EMR mixed-mode passthrough cleanup methodology may be utilized for matrix sample extract.

[0034] Understanding the sorbents function in matrix removal and interaction mechanism with matrix co-extractives is important for mixed-mode sorbent formula development. For animal-origin food matrices, lipids and fats are the major group of matrix co-extractives to be removed, and therefore, a sorbent such as EMR-Lipid is needed for the selective and efficient removal of lipids. For plant-based food matrices, many organic acids and pigments can be abundant in matrix crude extract, and therefore carbon materials and amine sorbents are needed to clean these types of interferences. Ionic interaction-based sorbents also help to remove other relatively polar interferences. Carbon S sorbent provides more selective pigment removal, thus reducing the potential impacts on sensitive planar compounds’ loss. For many other hydrophobic matrix co- extractives, C18 (e.g., endcapped (EC)-C18; available for sale from Agilent) sorbent can provide more general cleaning. However, this hydrophobic interaction is not very selective, attention is needed on the hydrophobic targets’ recovery when using EC-C18 sorbent and only allows the restricted general hydrophobic interaction. For specific20240003-02 (AG20240003-02) class(es) of contaminants analysis, these types of interactions need to be kept in mind for formula development and optimization.

[0035] For multiresidue PFAS targets, this class of compounds can contain acidic groups such as carboxylic and sulfonic acids. Therefore, it is recommended to be cautious with the use of a sorbent utilizing an ionic interaction mechanism for matrix removal. In addition, typical PFAS targets rarely contain planar structures, and are therefore more tolerant to the use of carbon-based sorbents containing graphitic regions. The higher selectivity provided by Carbon S therefore provides more flexibility to improve the overall matrix removal efficiency for multiresidue PFAS targets. EMR-Lipid sorbent with appropriate mix of hydrophobic and ionic based interactions provides high efficiency on various fatty food matrix cleaning. Therefore, the new EMR cartridges targeting PFAS analysis may include the use of blended sorbents incorporating a matrix-removal function without impact on PFAS targets recovery, such as at least a combination of two or more of EMR-Lipid sorbent, carbon-based sorbents, such as carbon S sorbent, a limited amount of ion-exchange sorbents or polar sorbents, such as amine sorbent, for example primary secondary amine (PSA) sorbent (available for sale from Agilent), or a limited amount of reverse-phase sorbents, such as alkane-bonded silica sorbent, for example EC-C18 sorbent (available for sale from Agilent). The formula development and optimization was also based on consideration of different types of food matrices, the ease of products selection and use, and optimally balanced matrix removal and PFAS targets recovery.

[0036] For multiclass multiresidue mycotoxins, several important targets are highly sensitive compounds, which greatly restricts the use of sorbents for matrix removal.20240003-02 (AG20240003-02) Given the sensitive targets, it may be necessary to be more cautious during formula development and optimization, and compromises may need to be taken on matrix removal to achieve the acceptable recoveries. The use of carbon material and ionic interaction-based amine sorbent may be used sparingly, and thus a relatively small quantity of these two sorbents were utilized.

[0037] Besides development of the blended sorbents and specific formulations, other considerations on the cartridge format may also be needed. The cartridge frits provide compacting force to the sorbents during assembly and appropriate filtration of sample particulates during sample flow through. The frits pore size impact the sample flow rate, and thus the overall cartridge ease of use for the bench scientist. For PFAS analysis, frit cleanliness may also prevent unwanted PFAS contamination from being introduced during cartridge use from the frit itself. The pre-qualification of PFAS cleanliness for the frits used on EMR PFAS food cartridges are thus relevant.

[0038] For food sample preparation, the use of EMR mixed-mode passthrough cleanup is normally followed with either QuEChERS extraction or direct solvent extraction. Figure 1 illustrates a simplified EMR mixed-mode passthrough cleanup methodology using the new EMR cartridges disclosed herein for per- and polyfluoroalkyl substance (PFAS) and mycotoxin analysis, in accordance with an example of the present disclosure.

[0039] According to examples disclosed herein, a method may include specifying a sorbent formulation for a targeted class of food contaminant analysis, and utilizing enhanced matrix removal (EMR) mixed-mode passthrough cleanup with the specified sorbent formulation.20240003-02 (AG20240003-02)

[0040] According to examples of the method disclosed herein, the food contaminant analysis may include a per- and polyfluoroalkyl substance (PFAS) analysis.

[0041] According to examples of the method disclosed herein, the food contaminant analysis may include a mycotoxins analysis.

[0042] According to examples of the method disclosed herein, for animal-origin food matrices, the specified sorbent formulation may include a matrix-removal sorbents, such as an EMR-Lipid sorbent.

[0043] According to examples of the method disclosed herein, for plant-based food matrices, the specified sorbent formulation may include one or more of a Carbon S sorbent, an amine sorbent, or an alkane-bonded silica sorbent.

[0044] According to examples of the method disclosed herein, the amine sorbent may be primary secondary amine (PSA) sorbent and the alkane-bonded silica sorbent may be EC-C18 sorbent.

[0045] According to examples of the method disclosed herein, the specified sorbent formulation may include ion-exchange sorbents or polar sorbents, such as amine sorbent, for example a primary secondary amine (PSA) sorbent.

[0046] According to examples of the method disclosed herein, the specified sorbent formulation may include reverse-phase sorbents, such as alkane-bonded silica sorbent, for example EC-C18 sorbent.

[0047] According to examples of the method disclosed herein, the specified sorbent formulation may include a blended sorbent incorporating an EMR-Lipid sorbent, a Carbon S sorbent, an amine sorbent, and an alkane-bonded silica sorbent.20240003-02 (AG20240003-02)

[0048] According to examples of the method disclosed herein, for fat / lipid containing food matrices, the specified sorbent formulation may include a blended sorbent incorporating an EMR-Lipid sorbent, a Carbon S sorbent, an amine sorbent, and an alkane-bonded silica sorbent.

[0049] According to examples of the method disclosed herein, for non-fat / lipid containing food matrices, the specified sorbent formulation may include a blended sorbent incorporating a Carbon S sorbent, an amine sorbent, and an alkane-bonded silica sorbent.

[0050] According to examples of the method disclosed herein, an EMR cartridge may include a specified sorbent formulation for a targeted class of food contaminant analysis. The EMR cartridge may utilize EMR mixed-mode passthrough cleanup with the specified sorbent formulation.

[0051] According to examples of the method disclosed herein, for animal-origin food matrices and dry or oily plant-origin food matrices, the specified sorbent formulation may include an EMR-Lipid sorbent in the range of about 30% to about 80%, and for fresh plant-based food matrices, the specified sorbent formulation may include the EMR-Lipid sorbent in the range of about 0%.

[0052] According to examples disclosed herein, a method may include utilizing EMR mixed-mode passthrough cleanup with a specified sorbent formulation for a targeted class of food contaminant analysis.

[0053] According to examples of the method disclosed herein, the method may further include performing a QuEChERS extraction or direct solvent extraction.20240003-02 (AG20240003-02)

[0054] According to examples disclosed herein, an enhanced matrix removal (EMR) cartridge may include a carbon S sorbent in an amount of from about 10 wt.% to about 70 wt.%, a primary secondary amine (PSA) sorbent in an amount of from about 10 wt.% to about 75, and an EC-C18 sorbent in an amount of from about 10 wt.% to about 35 wt.%.

[0055] According to examples disclosed herein, the EMR cartridge may further include an EMR lipid sorbent in an amount of from about 30 wt.% to about 80 wt.%.

[0056] According to examples disclosed herein, an enhanced matrix removal (EMR) cartridge may include a carbon base sorbent, an ion exchange or a polar sorbent, and a reverse-phase sorbent.

[0057] According to examples disclosed herein, the EMR cartridge may further include an EMR-lipid sorbent. The EMR lipid sorbent may be in an amount of from about 30% to about 80%.

[0058] According to examples disclosed herein, the carbon base sorbent may be a Carbon S sorbent. The Carbon S sorbent may be in an amount of from about 10 wt.% to about 70 wt.%.

[0059] According to examples disclosed herein, the ion exchange or the polar sorbent may be an amine sorbent. The amine sorbent may be a primary secondary amine sorbent. The primary secondary amine sorbent may be in an amount of from about 10 wt.% to about 75 wt.%.

[0060] According to examples disclosed herein, the reverse-phase sorbent may be an alkane-bonded silica sorbent. The alkane-bonded silica sorbent may be EC-C18 sorbent.20240003-02 (AG20240003-02) The EC-C18 sorbent may be in an amount of from about 10 wt.% to about 35 wt.%.

[0061] The workflow disclosed herein based on use of the EMR cartridges addresses at least the following aspects.

[0062] With respect to matrix removal, the new EMR mixed-mode passthrough cleanup method targets food matrix removal based on interactions between the blended sorbents with the matrix co-extractives using various mechanisms, including ionic andhydrophilic interactions, planar and - interactions, combinatory size exclusion andhydrophobic interaction, and general hydrophobic interactions. The method, using appropriate EMR cartridges, provides high matrix removal efficiency for both non-fat / lipid containing (e.g., fresh plant-origin) and fat / lipid containing (e.g., animal-origin) foods, fresh and dry foods, naturally grown and processed foods.

[0063] For plant-based food matrices, EMR mixed-mode passthrough cleanup provides highly efficient pigment removal, including chlorophyll, lutein, anthocyanidins, carotenoids and xanthophyll.

[0064] Figure 2 illustrates pigment removal provided by EMR mixed-mode passthrough cleanup for fruits and vegetables matrices, using EMR PFAS Food I cartridges, in accordance with an example of the present disclosure.

[0065] Referring to Figure 2, the images shown illustrate the appearance of various fruit and vegetable sample extracts before and after EMR PFAS Food I cleanup. For the different samples that display varying levels of natural pigmentation, all become colorless after EMR passthrough cleanup as shown, for example, at 200.

[0066] For fatty animal-origin food matrices, EMR mixed-mode passthrough cleanup20240003-02 (AG20240003-02) provides highly efficient removal of intermediate to non-polar matrix co-extractives, especially for the lipids such as triglycerides, phospholipids, fatty acids, cholesterol, sphingolipids etc. GC / MS full scan may be utilized to evaluate the matrix cleanup efficiency due to the low system background of GC chromatography, the sensitive detection of the majority of food matrix co-extractives, particularly for intermediate and nonpolar interferences, and its quick and relatively easy method of screening.

[0067] Figure 3 illustrates matrix removal by EMR mixed-mode passthrough cleanup for representative animal-origin food matrices using EMR PFAS Food II cartridges, and evaluated by gas chromatography / mass spectrometry (GC / MS) full scan screening, in accordance with an example of the present disclosure.

[0068] Referring to Figure 3, Figure 3 shows the GC / MS full scan chromatograms for representative animal-origin food matrix blanks without (top, for example, at 300) versus with (bottom, for example, at 302) the use of EMR mixed-mode passthrough cleanup. Results demonstrate that EMR mixed-mode passthrough cleanup provides highly efficient matrix removal for these fatty animal-origin food matrices.

[0069] For dry seed food / feed and complicated processed feed matrices, EMR mixed- mode passthrough cleanup provides comprehensive matrix removal for various matrix co-extractives. The sample extract dried residue weight may be utilized to evaluate the total matrix co-extractives. In addition, LC / QToF scan may be utilized to screen the complete matrix co-extractives.

[0070] Figure 4 illustrates matrix removal by EMR mixed-mode passthrough cleanup for representative dry and processed food / feed matrices using EMR mycotoxins cartridges, and evaluated by liquid chromatography / quadrupole time-of-flight (LC / QTOF)20240003-02 (AG20240003-02) scan screening and sample dried residue, in accordance with an example of the present disclosure.

[0071] Referring to Figure 4, Figure 4 shows the LC / QToF scan chromatograms and dried residue comparison for representative dry matrices evaluation for matrix removal efficiency. The QuEChERS extraction followed by EMR mixed-mode cleanup workflow was compared with the traditional SIDA method for corn and dog food sample preparation for multiresidue mycotoxins analysis. Results show that the QuEChERS extraction followed by the EMR mixed-mode cleanup workflow sample preparation method provides significantly cleaner matrix background.

[0072] With respect to targets recovery, maximization of the targets recovery is another goal for the EMR mixed-mode passthrough cleanup method and EMR cartridge development. In this regard, multiple strategies may be utilized to reduce the targets loss during sample matrix cleanup, including the use of highly selective sorbents such as EMR-Lipid or Carbon S (also referred to as Captiva EMR-Lipid or Carbon S), determination of the optimized formula to balance the targets recovery and matrix removal, the use of matrix mask methodology to prevent unwanted interactions, and use of a simplified workflow to reduce the opportunity for analyte loss.

[0073] Figure 5 illustrates PFAS targets recovery in six representative food matrices using EMR mixed-mode cleanup by EMR PFAS food cartridges, and two conventional dSPE cleanups, in accordance with an example of the present disclosure.

[0074] Referring to Figure 5, Figure 5 shows the recovery of 30 PFAS targets in six representative food matrices using the EMR PFAS Food I or II cartridges for passthrough cleanup, and its comparison with the results obtained using traditional dSPE cleanup.20240003-02 (AG20240003-02) Results demonstrate the consistently high PFAS recovery delivered when using the mixed-mode passthrough cleanup by EMR PFAS food cartridges. The results were based on highly efficient matrix removal demonstrated previously, indicating a good balance of target recovery with matrix removal provided by EMR mixed-mode passthrough cleanup. However, the traditional dSPE cleanup resulted in lower and inconsistent PFAS recovery, indicating the poor balance with matrix removal.

[0075] Figure 6 illustrates recovery comparison for multiresidue mycotoxins in a corn matrix, using EMR mixed-mode passthrough cleanup versus another matrix cleanup method, in accordance with an example of the present disclosure.

[0076] Referring to Figure 6, Figure 6 shows the recovery comparison of 21 typical mycotoxins during sample cleanup. The EMR mixed-mode passthrough cleanup using EMR mycotoxins cartridge at 600 demonstrates excellent recoveries from corn matrix extract. The other currently used matrix cleanup method (SPE and dSPE) at 602 shows a significantly low recovery for several critical mycotoxins including fumonisin (FB 1, 2 & 3), ochratoxin A (OTA) and Cyclopiazonic acid (CPA). While this competing method offers acceptable matrix removal efficiency, it nevertheless compromises significantly on some mycotoxins’ recovery, indicating the poor balance of the two.

[0077] With respect to advantages of the EMR cartridges disclosed herein, in addition to the problems resolved on matrix removal and target recovery, the workflow disclosed herein based on utilization of the EMR cartridges provides the following advantages.

[0078] First, the EMR cartridges disclosed herein provide a simplified workflow to thus save sample preparation time and effort.20240003-02 (AG20240003-02)

[0079] For example, Figure 7 illustrates comparison of a conventional technique versus the method for PFAS disclosed herein in food analysis sample preparation, in accordance with an example of the present disclosure.

[0080] Referring to Figure 7, compared to currently used methods, the workflow using QuEChERS extraction followed by EMR mixed-mode passthrough cleanup simplifies the sample preparation procedure, requiring less bench time and effort. In this regard, Figure 7 shows a side-by-side comparison of a traditional sample preparation method versus the workflow for PFAS in food analysis disclosed herein.

[0081] For the conventional method protocol shown at 700, the sample crude extract after QuEChERS is first cleaned by dSPE then filtered using a Nylon filter. An aliquot of the resulting filtrate (1mL) is then diluted with water tenfold (10x), or dried and reconstituted in water. In the meantime, the WAX SPE cartridge is pre-conditioned with MeOH, then equilibrated with water. The treated sample can then be loaded on the WAX cartridge. After washing, the sample then needs to be eluted with MeOH w / 1-2% NH4OH. The eluent is then collected, followed by the appropriate post-treatment prior to injection for final analysis.

[0082] For the workflow using QuEChERS extraction followed by EMR mixed-mode passthrough cleanup disclosed herein, as shown at 702, the sample crude extract after QuEChERS may be loaded either directly on the EMR PFAS Food I cartridge, or mixed with 10% water and then loaded on the EMR PFAS Food II cartridge. The sample typically flows through under gravity. The eluent is then collected, followed by the appropriate post-treatment before injection for final analysis. Thus, steps 704 of the conventional method protocol shown at 700 are performed by the step shown at 706.20240003-02 (AG20240003-02)

[0083] Considering the lengthy time needed for the usual dry and reconstitution steps for sample post-treatment, the workflow using QuEChERS extraction followed by EMR mixed-mode passthrough cleanup disclosed herein saves at least 30% of preparation time, and in many cases more than 50% of the time needed to prepare the same quantity of samples. Since this method is applicable for environmental tissue samples such as fish, the time saved can be even more significant when considering the Environmental Protection Agency (EPA) 1633 method for fish tissue sample preparation, with upwards to 50 – 75% of time saved.

[0084] With respect to advantages of the EMR cartridges disclosed herein, in addition to the problems resolved on matrix removal and target recovery, the workflow disclosed herein based on utilization of the EMR cartridges provides the further advantage of reduced matrix effect, accumulation of contamination on detection flow path and MS source.

[0085] For example, Figure 8 illustrates matrix effects on mycotoxin targets in representative food and feed samples prepared by different sample preparation methods, while the SIDA method is a conventional method being used, and Q-ext and EMR passthrough cleanup is the method disclosed herein using EMR mycotoxins cartridges, in accordance with an example of the present disclosure.

[0086] With respect to the advantage of reduced matrix effect, accumulation of contamination on detection flow path and MS source, this advantage can be attributed to less matrix co-extractives being injected on the instrument detection system, which can cause many problems with target analysis and instrument performance. When using MS detection, matrix interferences can cause suppression or enhancement of target20240003-02 (AG20240003-02) ionization in an MS source and make the detection of target compounds and their quantitation challenging and problematic. Figure 8 shows a matrix effect study for mycotoxin targets in representative feed / food matrices prepared by different sample preparation methods. The results show that the matrix effect on targets (suppression in this case) was much improved when using the Q-ext and EMR cleanup method to prepare the samples. In addition, a high concentration of matrix co-extractives introduced onto a detection system through sample injection can also have an impact on analytical instrument performance and robustness. These matrix co-extractives may contaminate the flow path, such as the LC injection port or column, accumulate in the LC column, and / or deposit onto the MS source. This can cause deteriorating instrument performance over time, and lead to poor quality chromatography, loss of detection sensitivity and selectivity, inconsistent quantitation results, and eventually failure.

[0087] With respect to advantages of the EMR cartridges disclosed herein, in addition to the problems resolved on matrix removal and target recovery, the workflow disclosed herein based on utilization of the EMR cartridges provides the further advantage of approaching ultralow method detection limits.

[0088] In this regard, Figure 9 illustrates chromatograms of core PFAS targets in matrix blanks and validated Limits of Quantitation (LOQs) from representative food matrix samples, where the workflow using new EMR PFAS Food cartridges support the method validated at the required ultralow LOQ levels, in accordance with an example of the present disclosure.

[0089] The improved target recovery and matrix removal through the use of EMR mixed-mode passthrough cleanup using appropriate EMR cartridges boosts method20240003-02 (AG20240003-02) sensitivity significantly, which allows the method disclosed herein to reach minimum detection limits (MDLs) and limits of quantitation (LOQs). This is especially relevant to the analysis of PFAS in food, as regulation requirements on method LOQs are currently down to 10 ppt or below for core PFAS targets in some food matrices. The new workflow for PFAS in food analysis was validated in multiple food matrices, meeting the specified ultralow LOQs. In this regard, Figure 9 shows chromatograms of core PFAS targets in matrix blanks and validated LOQs from representative food matrix samples.

[0090] With respect to advantages of the EMR cartridges disclosed herein, in addition to the problems resolved on matrix removal and target recovery, the workflow disclosed herein based on utilization of the EMR cartridges provides the further advantage of higher sample volume recovery.

[0091] In this regard, compared to the traditional dSPE cleanup used after QuEChERS extraction in many sample preparation methods used for food safety applications, EMR mixed-mode passthrough cleanup provides a higher overall sample volume recovery. For example, for conventional dSPE cleanup, the sample volume is typically around 50%, due to the nature of this technique causing inefficient separation of liquid with sorbent particles. Especially for large tube (15 ml) dSPE kits, the separation through centrifugation can be even more challenging, resulting in < 50% of the sample volume being recovered. The low volume recovered after dSPE cleanup results in difficulty in transferring sample supernatant, and can restrict sample post-treatment, especially when sample post-concentration steps through drying and reconstitution are needed.

[0092] The EMR mixed-mode passthrough cleanup is a cartridge-based filtration20240003-02 (AG20240003-02) format for sample extracts, where a sample flows through a compressed sorbent bed. The separation of the liquid sample from the sorbent bed is based on the filtration path. The tightly compressed sorbent particles and resulting filtration path allow for a better separation of liquid sample from the sorbent particles, and results in > 90% of sample volume being recovered. After cartridge cleanup, the sample eluent is already separated from the sorbent, which makes the need to transfer sample from off the top of lose sorbent powder obsoleted. The higher sample volume yields flexibility on sample post-treatment, especially when a large sample volume is needed for a high post sample concentration.

[0093] With respect to advantages of the EMR cartridges disclosed herein, in addition to the problems resolved on matrix removal and target recovery, the workflow disclosed herein based on utilization of the EMR cartridges provides the further advantage of qualified targeted PFAS cleanliness.

[0094] Figure 10 illustrates a CoA for EMR PFAS food cartridges per batch, in accordance with an example of the present disclosure.

[0095] Referring to Figure 10, the EMR PFAS food cartridges disclosed herein provide for the qualification for targeted PFAS cleanliness specifications, which is needed for the determination of targeted PFAS in food at ultralow parts per trillion (ppt) levels. The sorbents, cartridge tube and frits, and cartridge consolidation process may all be under strict monitoring and control to assure that the products do not introduce PFAS contamination at unacceptable levels. The targeted PFAS cleanliness is one of QC tests for each batch of products, with the CoA provided for each batch as shown in Figure 10.

[0096] The EMR cartridges and operation thereof are disclosed in further detail with reference to Figures 11-13.20240003-02 (AG20240003-02)

[0097] With respect to the EMR cartridges and operation thereof, individual sorbents that are or can be used in EMR cartridges may include EMR-Lipid sorbent, Carbon S sorbent or other synthetic carbon material, PSA or other amine sorbents, and an alkane- bonded silica sorbent such as EC-C18 sorbent.

[0098] The EMR-Lipid sorbent is composed of -cyclodextrin functionalized silica, which provides a highly efficient and selective interaction with molecules containing long aliphatic chains (typically lipid molecules) based on a combination of size exclusion and hydrophobic mechanisms. The silica-based sorbent also supports cartridge and plate formats, which is a key factor in developing simplified and automatable workflows. EMR- Lipid cartridges apply a simplified passthrough cleanup for lipid removal, which can be readily adopted with common food sample extraction techniques including QuEChERS and solvent extraction. This sorbent may be used in EMR cartridges that target animal- origin, dry or oily plant-origin, and complex food / feed matrices. The highly selective interaction mechanism allows large flexibility of this material used in the current blended sorbents, ranging from 30 – 80% in EMR cartridges targeting for fatty and complex food matrices. However, it may include less than 30% (for example, 0%) in EMR cartridges intended for use with non-fat / lipid containing food matrices due to the lack of interacting molecules in these samples.

[0099] With respect to the Carbon S sorbent or other synthetic carbon material, the Carbon S sorbent is an advanced hybrid carbon material with optimized carbon content and pore structure. The pigment removal provided by this carbon material is based onplanar or - interactions. The Carbon S sorbent retains typical pigment componentssuch as chlorophyll, lutein, anthocyanidins, carotenoids and xanthophylls. Compared to20240003-02 (AG20240003-02) traditional graphitized carbon black (GCB) sorbent, Carbon S sorbent provides equivalent or better pigment removal and can significantly improve the recovery of sensitive analytes. Carbon S sorbent provides a better balance between analyte recovery and matrix pigment removal efficiency over traditional GCB sorbent. Carbon S sorbent is used in various dSPE kits as an alternative to GCB and has demonstrated equivalent or improved performance. The Carbon S sorbent has also been used in EMR cartridges where a convenient passthrough cleanup is adopted for efficient and selective matrix removal with significant improvement in sensitive pesticide recoveries. However, even with the better balance of pigment removal and recovery of planar targets, the use of Carbon S sorbent still requires careful optimization, depending on whether the targets include any compounds with planar structures, and whether the food matrices are heavily pigmented. For molecular targets not including planar structures, such as PFAS, more Carbon S can be used in the blended sorbents, depending on how heavily pigmented the targeted food matrices are. For example, the amount of Carbon S can be from about 15 wt.% to about 60 wt.%, such as from about 20 wt.% to about 50 wt.%. However, when targets include compounds with highly planar structures, such as the mycotoxins, a small amount of Carbon S sorbent may be used. For example, the amount of Carbon S can be 10 wt.% or less, such as less than 5 wt.%.

[0100] With respect to PSA or other amine sorbents, PSA is a sorbent incorporating the primary secondary amine structure. This chemical group is primarily used to remove compounds with carboxylic groups such as fatty acids or other organic acids present in a sample matrix. However, it can also remove compounds incorporating carbonyl groups, such as many sugars. The removal of fatty acids by an amine sorbent, such as PSA20240003-02 (AG20240003-02) sorbent may serve as a complement to matrix-removal sorbents, such as EMR-Lipid for the complete lipid cleanup in a sample. However, a large amount of amine sorbent, such as PSA sorbent, or long contact time with it, may impact the analysis of acidic or basic targets, with lower recoveries for certain acidic targets or even degradation of base- sensitive analytes due to removal of acids from the extract. The matrix acidic co- extractives, using acidified solvent and water residue can provide a matrix masking effect by competing for the active sites on the amine sorbent, thus preventing the loss or degradation of sensitive targets. The use of amine sorbent requires the consideration of the target’s structure, as well as using various matrix masking strategies. The use of amine sorbent, such as PSA sorbent requires the consideration of the target’s structure, as well as using various matrix masking strategies. Since PFAS compounds include many acidic targets, in one example, the amine sorbent, such as PSA sorbent may be in an amount of from about 10 wt.% to about 60 wt.%, for example from about 15 wt.% to about 50 wt.%, depending on how much masking effect can be provided by the sample matrix. However, for mycotoxins that contain compounds with multiple carboxylic acid groups, causing a significant interaction with amine sorbent, such as PSA sorbent, in one example, the use of PSA in EMR mycotoxins cartridge sorbent blend may be in an amount less than 10 wt.%, such as less than 5 wt.%.

[0101] With respect to an alkane-bonded silica sorbent such as EC-C18 sorbent, the alkane-bonded silica sorbent may be added to the EMR cartridges as a complement to EMR-Lipid sorbent in order to remove highly lipophilic matrix components, such as sterols or waxes. However, the hydrophobic interaction-based mechanism of alkane-bonded silica sorbent may not be selective, and thus may cause loss of hydrophobic targets when20240003-02 (AG20240003-02) an excessive amount of alkane-bonded silica sorbent is used. For EMR cartridges intended for fat / lipid containing food matrices, in one example, the alkane-bonded silica sorbent percentage may be from about 15 wt.% to about 40 wt.% or more, such as from about 20 wt.% to about 35 wt.% in the blended sorbent. In EMR cartridges designed for non-fat / lipid containing food matrices, a small amount of alkane-bonded silica sorbent can still be useful for comprehensive matrix cleanup but may be kept at a smaller percentage of about 15 wt.% or less, for example about 10 wt.% or less.

[0102] The EMR cartridge format and specific bed mass may be determined based on consideration of the typical sample size used in food safety analysis, sample loading volume and sorbent capacity on matrix removal, total volume of the sorbent bed and headspace left in the cartridge tube, and any special requirements of sample post- treatment. The typical sample loading volume in food analysis is 2-6 mL, therefore, 3 mL and 6 mL format tubes may be used for all EMR cartridges. For PFAS in food analysis, relatively large sample loading volume may be utilized to allow for post sample drying and reconstitution with a large concentration factor, therefore, a 6 mL format may be applied for both EMR PFAS Food I and II cartridges. An additional format with more sorbent bed mass may be included in EMR PFAS Food I cartridges, to allow for larger loading volume. However, the 10 mL crude sample extract may need to be loaded separately. For mycotoxins in food and feed analysis, both 3 mL and 6 mL tubes may be used for flexible sample loading.

[0103] The general workflow for EMR mixed-mode passthrough cleanup was disclosed herein with respect to Figure 1. For specification, EMR PFAS Food I and II cartridges may be utilized for PFAS analysis in food, while EMR mycotoxins cartridges20240003-02 (AG20240003-02) may be utilized for mycotoxins analysis in dry food and feed. Both types of cartridges may be used after QuEChERS extraction and provide further matrix removal for the crude sample extract. The crude extract may be either mixed with water in an amount for from about 5 wt.% to about 20 wt.%, such as from about 10 wt.% prior to loading, for fat / lipid containing food matrices. For non-fat / lipid containing food matrices, the crude sample extract may be loaded directly.

[0104] Figure 11 illustrates an example of a method procedure using EMR PFAS I cartridges for non-fat / lipid containing food sample preparation. Figure 12 illustrates an example of a method procedure using EMR PFAS II cartridges for animal-origin food sample preparation.

[0105] For the EMR mycotoxins cartridge, the sample crude extract may need to be pre-mixed with about 10% water prior to loading on the cartridge. The recommended loading volume for the 3 mL cartridge may be from about 2 to about 2.5 mL, and for the 6 mL cartridge may be approximately from about 4 to about 5 mL.

[0106] Referring to the example of Figure 11, using EMR PFAS I cartridges for non- fat / lipid containing food sample preparation may include the following steps: Weigh about 10 g of ground sample into a 50 mL tube; Add about 10 mL of ACN with about 1% acetic acid. Vortex for about 20 seconds to mix; Add QuEChERS EN extraction salt and two ceramic homogenizers; Cap and shake the sample on a Geno / Grinder @ about 1500 rpm for about 5 minutes; Centrifuge tubes at about 5000 rpm for about 5 minutes;20240003-02 (AG20240003-02) Prewash the EMR PFAS I cartridges with about 5 mL of 1:1 ACN / MeOH with about 1% AA; Equilibrate cartridge with about 0.6 mL of corresponding sample; Elute by gravity and apply about 9-12 psi pressure at the end to dry the cartridge completely. Discard the eluent and place the pre-labelled collection tube; Transfer about 5 mL of supernatant into Captiva EMR PFAS Food I cartridges; Elute by gravity and apply about 10 psi for about 2 minutes at the end to completely dry the sorbent bed; Collect the eluent and dry at about 50 °C in the CentriVap; Reconstitute the dried sample with about 500 μL of about 80:20 MeOH / water; and Vortex for about 2 minutes, sonicate about 5 to 10 minutes, and centrifuge about 2 minutes.

[0107] Referring to the example of Figure 12, using EMR PFAS II cartridges for animal-origin food sample preparation may include the following steps: Weigh about 5 g homogenized sample into a 50 mL tube; Add about 10 mL of water. Vortex for about 10 to 15 minutes; Add about 10 mL of ACN with about 1% acetic acid (AA). Vortex for about 20 seconds to mix; Add QuEChERS EN extraction salt and two ceramic homogenizers;20240003-02 (AG20240003-02) Cap and shake the sample on a Geno / Grinder at 1500 rpm for about 5 minutes; Centrifuge tubes at about 5000 rpm for about 5 minutes; Transfer about 5.4 mL of supernatant to another about 15 mL tube and mix with about 0.6 mL of water; Optional: Prewash the Captiva EMR PFAS Food II cartridges with about 5 mL of 1:1 ACN / MeOH with about 1% AA; Equilibrate cartridge with about 0.8 mL of corresponding sample; Elute on gravity and apply about 9- 12 psi pressure at the end to completely dry the cartridge. Discard the eluent and replace with pre- labelled collection tubes; Transfer about 5 mL of supernatant mixture into EMR-PFAS Food II cartridges; Elute by gravity and apply about 10 psi for about 2 minutes at the end to completely dry the sorbent bed; Collect the eluent and dry at about 50 °C in the CentriVap (or TurboVap); Reconstitute the dried sample with about 450 μL of about 80:20 MeOH / water; and Vortex for about 2 minutes, sonicate about 5 to 10 minutes and centrifuge for about 2 minutes.

[0108] Figure 13 shows an example of a method procedure using EMR mycotoxins for dry feed / food sample preparation.

[0109] Referring to the example of Figure 13, using EMR mycotoxins for dry feed / food20240003-02 (AG20240003-02) sample preparation may include the following steps: Weigh about 2 g of sample powder into an about 50 mL tube; Spike standard to all prespiked QC samples, then vortex for about 10 to 15 seconds; Add about 7.5 mL of water with about 1% formic acid. Vortex for about 10 minutes; Add about 10 mL of ACN with about 2% formic acid; Add QuEChERS EN extraction salt and two ceramic homogenizers; Cap and shake the sample on a Geno / Grinder at about 1500 rpm for about 5 minutes; Centrifuge tubes at about 5000 rpm for about 5 minutes; Transfer about 2.7 mL of supernatant to another 15 mL tube and mix with about 0.3 mL water; Equilibrate Captiva EMR Mycotoxins 3 mL cartridge with about 0.5 mL of corresponding sample; Elute and dry the cartridge with about 9 to 12 psi pressure, discard the eluent, and replace with prelabelled collection tube; Transfer about 2 mL of sample mixture into cartridges; Elute by gravity or apply about 1 to 2 psi pressure, then increase to about 10 psi for at the end about 2 minutes to completely dry the sorbent bed; Collect the eluent and gently mix; and20240003-02 (AG20240003-02) Transfer about 555 μL of eluent into a 2 mL vial. Mix with about 425 μL water, and about 20 μL ISTD spiking solution. Vortex for about 10 to 15 seconds.

[0110] What has been described and illustrated herein is an example along with some of its variations. The terms, descriptions and figures used herein are set forth by way of illustration only and are not meant as limitations. Many variations are possible within the spirit and scope of the subject matter, which is intended to be defined by the following claims -- and their equivalents -- in which all terms are meant in their broadest reasonable sense unless otherwise indicated.

Claims

20240003-02 (AG20240003-02) What is claimed is:

1. A method comprising: specifying a sorbent formulation for a targeted class of food contaminant analysis; and utilizing enhanced matrix removal (EMR) mixed-mode passthrough cleanup with the specified sorbent formulation.

2. The method according to claim 1, wherein the food contaminant analysis includes a per- and polyfluoroalkyl substance (PFAS) analysis.

3. The method according to claim 1, wherein the food contaminant analysis for dry food includes a mycotoxins analysis.

4. The method according to claim 1, wherein, for animal-origin food matrices, the specified sorbent formulation comprises an EMR-Lipid sorbent.

5. The method according to claim 1, wherein, for plant-based food matrices, the specified sorbent formulation comprises one or more of a Carbon S sorbent, an amine sorbent, or an alkane-bonded silica sorbent.20240003-02 (AG20240003-02) 6. The method according to claim 5, wherein the amine sorbent is primary secondary amine (PSA) sorbent and the alkane-bonded silica sorbent is EC-C18 sorbent.

7. The method according to claim 1, wherein the specified sorbent formulation includes a blended sorbent incorporating an EMR-Lipid sorbent, a Carbon S sorbent, an amine sorbent, and an alkane-bonded silica sorbent.

8. An enhanced matrix removal (EMR) cartridge comprising: a carbon S sorbent in an amount of from about 10 wt.% to about 70 wt.%; a primary secondary amine (PSA) sorbent in an amount of from about 10 wt.% to about 75 wt.%; and an EC-C18 sorbent in an amount of from about 10 wt.% to about 35 wt.%.

9. The EMR cartridge of claim 8, further comprising an EMR lipid sorbent in an amount of from about 30 wt.% to about 80 wt.% 10. An enhanced matrix removal (EMR) cartridge comprising: a carbon base sorbent; an ion exchange or a polar sorbent; and a reverse-phase sorbent.20240003-02 (AG20240003-02) 11. The EMR cartridge of claim 10, further comprising an EMR-lipid sorbent.

12. The EMR cartridge of claim 11, wherein the EMR lipid sorbent is in an amount of from about 30% to about 80%.

13. The EMR cartridge of claim 10, wherein the carbon base sorbent is a Carbon S sorbent.

14. The EMR cartridge of claim 13, wherein the Carbon S sorbent is in an amount of from about 10 wt.% to about 70 wt.%.

15. The EMR cartridge of claim 10, wherein the ion exchange or the polar sorbent is an amine sorbent.

16. The EMR cartridge of claim 15, wherein the amine sorbent is a primary secondary amine sorbent.

17. The EMR cartridge of claim 16, wherein the primary secondary amine sorbent is in an amount of from about 10 wt.% to about 75 wt.%.20240003-02 (AG20240003-02) 18. The EMR cartridge of claim 10, wherein the reverse-phase sorbent is an alkane- bonded silica sorbent.

19. The EMR cartridge of claim 18, wherein the alkane-bonded silica sorbent is EC-C18 sorbent.

20. The EMR cartridge of claim 18, wherein the EC-C18 sorbent is in an amount of from about 10 wt.% to about 35 wt.%.

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