Reusable peas adsorbent

Abstract

An exemplary embodiment of the present disclosure provides a composition for treatment of a PFAS containing substance. The composition can comprise a plurality of magnetic nanoparticles having fluorinated functional groups on surfaces of the magnetic nanoparticles.

Description

Attorney Docket No: 011529.114821REUSABLE PFAS ADSORBENTCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This Application claims the benefit of US Provisional Application Serial No. 63 / 680,106 filed 07 August 2024, the entire contents and substance of which are incorporated herein by reference in their entirety as if fully set forth below.FIELD OF THE INVENTION

[0002] The various embodiments of the present disclosure relate generally to adsorbents and more particularly to reusable PFAS adsorbents.BACKGROUND

[0003] Per- and polyfluoroalkyl substances (PFAS) comprise a group of over 10,000 synthetic chemicals recognized for their exceptional durability, dielectric properties, and resistance to water and heat. Extensively used in various industrial and household applications, PFAS are often referred to as “forever chemicals” due to their persistence and stability, which lead to significant environmental and human accumulation.

[0004] Adsorption-based techniques for removing PFAS from aqueous environments are effective, straightforward, cost-efficient, eco-friendly, and simple in design. Several sorbents have proven effective in PFAS removal and are commercially available, such as granulated activated carbon (GAC) filters and ion exchange resins (fERs). These remediation methods rely on hydrophobic and electrostatic interactions, respectively.

[0005] Granular activated carbon, a well-established PFAS sorbent, has shown commendable performance. However, its efficiency is often compromised by the presence of other soluble cocontaminants. These non-fluorinated impurities can cause the sorbent to reach its capacity before fully capturing PFAS. Additionally, there is no effective regeneration strategy for carbon-based sorbents, reducing their cost-efficiency. Moreover, these methods may have limited removal efficiency for less hydrophobic and short-chain PFAS, leaving residual contaminants in the treated water. Co-contaminants can clog ion exchange sorbents and saturate activated carbons,1317627178v4Attorney Docket No: 011529.114821 significantly reducing their PFAS sorption capacity and lifespan. Therefore, developing novel sorbents with high selectivity for PFAS removal is essential.

[0006] Activated carbon and ion-exchange resins are common sorbents used for removing long- chain PFAS from water. Granular activated carbon can achieve a sorption capacity of 1.1 mg / g for PFOA. However, they are not as effective for the removal of short-chain PFASs and GenX, a specific type of PFAS used as a processing aid in the production of fluoropolymers; and they can be costly to operate and regenerate. An alternative approach involves enhancing hydrophobic interactions between sorbents and PFAS fluorous microgel star polymers that can capture PFOA / PFOS using hydrophobic interaction. These polymers have a backbone structure composed of poly(ethylene glycol) (PEG) for hydrophilicity and a core constructed by fluoride for hydrophobic interaction. However, they cannot be easily reused due to structural instability and existing in an unstable liquid phase.

[0007] Therefore, there is an urgent need to develop new sorbents with short equilibrium times, high sorption capacities, easy regeneration, and reusability for PFAS removal, addressing the limitations of current sorbents.SUMMARY OF THE INVENTION

[0008] According to a first aspect of the present disclosure, a composition for treatment of a PFAS containing substance is provided. The composition can comprise a plurality of magnetic nanoparticles (MNPs) having fluorinated functional groups on the surface of the MNPs.

[0009] According to a second aspect of the present disclosure, a method of forming a composition for treatment of a PFAS containing substance is provided. The method can comprise: forming a plurality of magnetic nanoparticles (MNPs); and surface-modifying the plurality of MNPs with fluorinated functional groups.

[0010] According to a third aspect of the present disclosure, a method of treating a PFAS mixture is provided. The method can comprise: providing a substance comprising a first concentration of at least one PFAS; mixing the substance with a composition for treatment of a PFAS containing substance, and removing at least a portion of the MNPs from the substance to form a first treated substance having a second concentration of at least one PFAS less than the first concentration.

[0011] These and other aspects of the present disclosure are described in the Detailed Description below and the accompanying drawings. Other aspects and features of embodiments will become apparent to those of ordinary skill in the art upon reviewing the following description2317627178v4Attorney Docket No: 011529.114821 of specific, exemplary embodiments in concert with the drawings. While features of the present disclosure may be discussed relative to certain embodiments and figures (FIGs.), all embodiments of the present disclosure can include one or more of the features discussed herein. Further, while one or more embodiments may be discussed as having certain advantageous features, one or more of such features may also be used with the various embodiments discussed herein. In similar fashion, while exemplary embodiments may be discussed below as device, system, or method embodiments, it is to be understood that such exemplary embodiments can be implemented in various devices, systems, and methods of the present disclosure.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0013] FIG. 1 depicts SEM micrograph of MNPs, in accordance with some embodiments of the present disclosure.

[0014] FIG. 2 shows X-ray diffraction patterns of an exemplary MNP (curve) compared to magnetite (vertical lines under the curve).

[0015] FIG. 3 shows magnetic moment measurements for a MNP, in accordance with some embodiments of the present disclosure.

[0016] FIG. 4 depicts a typical molecule used for surface modification, in accordance with some embodiments of the present disclosure.

[0017] FIGs. 5A-5B shows calibration curves for PFOA and PFOS.

[0018] FIG. 6 depicts adsorption isotherm data fitted with Langmuir model to extract the adsorption capacity and Langmuir constant.

[0019] FIGs. 7A-7B depicts the use of a pseudo second order model for determination of the rate constants for PFOA and PFOS.

[0020] FIG. 8 depicts the regeneration of an exemplary MNP for 1-5 cycles of use, where no loss of removal efficiency was observed.

[0021] FIG. 9 depicts MNP surface modification, in accordance with some embodiments of the present disclosure.3317627178v4Attorney Docket No: 011529.114821

[0022] FIGs. 10A-10B depicts a PFAS binding mechanism through fluorine-fluorine (F-F) interactions and MNP regeneration by solvent rinse, in accordance with some embodiments of the present disclosure.DETAILED DESCRIPTION

[0023] Although preferred exemplary embodiments of the disclosure are explained in detail, it is to be understood that other exemplary embodiments are contemplated. Accordingly, it is not intended that the disclosure is limited in its scope to the details of construction and arrangement of components set forth in the following description or illustrated in the drawings. The disclosure is capable of other exemplary embodiments and of being practiced or carried out in various ways. Also, in describing the preferred exemplary embodiments, specific terminology will be resorted to for the sake of clarity.

[0024] To facilitate an understanding of the principles and features of the present disclosure, various illustrative embodiments are explained below. The components, steps, and materials described hereinafter as making up various elements of the embodiments disclosed herein are intended to be illustrative and not restrictive. Many suitable components, steps, and materials that would perform the same or similar functions as the components, steps, and materials described herein are intended to be embraced within the scope of the disclosure. Such other components, steps, and materials not described herein can include, but are not limited to, similar components or steps that are developed after development of the embodiments disclosed herein.

[0025] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise.

[0026] Also, in describing the preferred exemplary embodiments, terminology will be resorted to for the sake of clarity. It is intended that each term contemplates its broadest meaning as understood by those skilled in the art and includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.

[0027] Ranges can be expressed herein as from “about” or “approximately” one particular value and / or to “about” or “approximately” another particular value. When such a range is expressed, another exemplary embodiment includes from the one particular value and / or to the other particular value.

[0028] By “comprising” or “containing” or “including” is meant that at least the named compound, member, particle, or method step is present in the composition or article or method,4317627178v4Attorney Docket No: 011529.114821 but does not exclude the presence of other compounds, materials, particles, method steps, even if the other such compounds, material, particles, method steps have the same function as what is named.

[0029] Mention of one or more method steps does not preclude the presence of additional method steps or intervening method steps between those steps expressly identified. Similarly, it is also to be understood that the mention of one or more components in a device or system does not preclude the presence of additional components or intervening components between those components expressly identified.

[0030] The materials described as making up the various members of the invention are intended to be illustrative and not restrictive. Many suitable materials that would perform the same or a similar function as the materials described herein are intended to be embraced within the scope of the invention. Such other materials not described herein can include, but are not limited to, for example, materials that are developed after the time of the development of the invention.

[0031] Reference will now be made in detail to exemplary embodiments of the disclosed technology, examples of which are illustrated in the accompanying drawings and disclosed herein. Wherever convenient, the same references numbers will be used throughout the drawings to refer to the same or like parts.

[0032] Certain embodiments of the present disclosure focus on improving selectivity to minimize competition from co-contaminants, creating regenerable sorbents for better cost efficiency and sustainability, and enhancing removal efficiency for a broader range of PFAS, including less hydrophobic and short-chain variants. Advancements in these areas are vital to overcoming current limitations, leading to more effective, sustainable, and cost-efficient PFAS remediation solutions in water treatment.

[0033] For example, magnetite (FesO^-based magnetic nanoparticle (MNP) sorbents can be used due to their high surface area and facile solid-liquid separation under an applied magnetic field. Co-precipitation can be employed to produce large quantity of adsorbent materials for water treatment due to its simplicity, scalability, and ability to produce nanoparticles with controlled size and composition. Additionally, fluorine-fluorine (F-F) interactions can also be used for PFAS adsorbent design. Fluorine atoms are highly electronegative and tend to form strong bonds with other fluorine atoms. This property is known as fluorophilicity and can be utilized to selectively attract and adsorb PFAS, which contain multiple fluorine atoms in their structures.5317627178v4Attorney Docket No: 011529.114821

[0034] Embodiments of the present disclosure provide low-cost functional MNPs to provide reusable binding towards PFAS. The low-cost MNPs can be prepared via co-precipitation. Subsequently, the purified MNPs can be surface-functionalized with a silane to create PFAS binding sites through fluorophilic interactions. The surface-functionalized MNPs can then be added to a PFAS-containing substance where the MNPs then bind to the PFAS. The PFAS-bound MNPs can then be removed from the substance. The adsorbed PFAS then can be easily detached through a simple solvent wash, and the adsorbent material can be reused for PFAS attachment. This method can offer an affordable approach to remove PFAS from substances such as water matrices.

[0035] An exemplary embodiment of the present disclosure provides a composition for treatment of a PFAS containing substance. The composition can comprise a plurality of MNPs having perfluoro functional groups on surfaces of the magnetic nanoparticles.

[0036] In any embodiments disclosed herein, the plurality of MNPs can comprise many different MNPs, including, but not limited to, ferrite nanoparticles e.g., oxides) and the like. In some embodiments, the plurality of MNPs can comprise FesO4 (FeO / Fe2O3).

[0037] The MNPs can have many different particle sizes in accordance with various embodiments of the present disclosure. For example, in some embodiments, the MNPs can have an average diameter of no more than 500 nm, no more than 400 nm, no more than 300 nm, no more than 200 nm, no more than 100 nm, or no more than 50 nm. In some embodiments, the MNPs can have an average diameter of at least 1 nm, at least 5 nm, at least 10 nm, at least 25 nm, at least 50 nm, or at least 100 nm. As those skilled in the art would understand, in some embodiments, the MNPs can have a range of diameters with any of the upper and lower limits disclosed above, e.g., l-500nm, 5-300nm, 10-200 nm, and the like.

[0038] In any of the embodiments disclosed herein, the plurality of MNPs can be surface- modified to display fluorinated functional groups. The fluorinated functional groups can comprise many different functional groups including, but not limited to, fluoroalkyls, fluorosilanes, polyfluoro or perfluoro functional groups, etc. Moreover, the fluoroalkyl and fluorosilane groups used to surface-modify the MNPs can be further substituted with a variety of different functional groups including, but not limited to, groups that can participate in electrostatic interactions with the PFAS-based fluorines within PFAS-containing substances. Non-limiting examples of functional groups that can electrostatically interact with PFAS-based fluorines include primary6317627178v4Attorney Docket No: 011529.114821 and secondary amines, alcohols, thiols, carboxylic acids, amides, esters, saturated alkyl groups, other halogens, and charged groups (anions and cation species).

[0039] The surface modified MNPs of the present disclosure can have many different binding capacities for PFAS materials, including PFOA and PFOS. For example, in some embodiments, the MNPs can have a binding capacity for PFOA of at least 2.5 mg / g, at least 25 mg / g, at least 50 mg / g, at least 75 mg / g, at least 100 mg / g, at least 200mg / g, or at least lOOOmg / g. In some embodiments, the MNPs can have a binding capacity for PFOA of no more than 200mg / g, or no more than 3000mg / g. As those skilled in the art would understand, in some embodiments, the MNPs can have a range of binding capacities with any of the upper and lower limits disclosed above, e.g., 2.5-25mg / g, 25-50mg / g, 50-75mg / g, 75-100mg / g, 100-200mg / g, 200-1000mg / g, 80- 110 mg / g, and the like.

[0040] In any of the embodiments disclosed herein, the MNPs can have a binding capacity for PFOS of at least 2.5 mg / g, at least 25 mg / g, at least 50 mg / g, at least 100 mg / g, at least 200mg / g, at least 300mg / g, at least 400mg / g, at least 500mg / g, or of at least lOOOmg / g. In some embodiments, the MNPs can have a binding capacity for PFOS of no more than 200mg / g, no more than 560 mg / g, or no more than 3000mg / g. As those skilled in the art would understand, in some embodiments, the MNPs can have a range of binding capacities with any of the upper and lower limits disclosed above, e.g., 2.5-25mg / g, 25-50mg / g, 50-75mg / g, 75-100mg / g, 100-200mg / g, 200- lOOOmg / g, 500-560 mg / g, and the like.

[0041] Another exemplary embodiment of the present disclosure provides a method of forming a composition for treatment of a PFAS containing substance. The method can comprise forming a plurality of MNPs. In some embodiments, forming a plurality of MNPs can comprise obtaining a plurality of MNPs. In some embodiments, forming the plurality of magnetic nanoparticles can comprise one of a coprecipitate or hydrothermal method.

[0042] In some embodiments the method can further comprise surface modifying the MNPs with many different functional groups including, but not limited to, fluoroalkyls, fluorosilanes, polyfluoro or perfluoro functional groups, etc. In some embodiments, the fluorosilanes can be many fluorosilanes known in the art, including, but not limited to, those having the following structure:7317627178v4Attorney Docket No: 011529.114821, wherein n is equal to 1-25 repeating units; R1 is selected from hydrogen(H), fluorine, CF3, amines, amides, esters, hydroxyls, halogens, etc.; R2 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.; R3 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.; and R4 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc. For example, in some embodiments, the fluorosilanes can have the following structure:In some embodiments, surface modifying the plurality of MNPs with fluorosilanes can produce polyfluoro or perfluoro (short- and / or long-chain) functional groups on surfaces of the MNPs. In some embodiments, the fluorosilanes can bond to the surfaces of the MNPs via a condensation reaction with hydroxyl groups on the surfaces of the MNPs forming a siloxane linkage.

[0043] Once the MNPs have been surface-modified, the method can further comprise placing the fluoro-fimctionalized MNPs in contact with a PFAS containing substance. The PFAS- containing substance can be any substance from which removal of PFAS is desired (e.g. , water, soil, air, etc.). While in the PFAS containing substance, the fluoro-fimctionalized MNPs can bind, e.g., absorb, with PFAS in the substance. After PFAS absorption, the method can further comprise removing at least a portion of the PFAS -absorbed MNPs from the substance to decrease the PFAS concentration in the substance.

[0044] Another embodiment of the present disclosure provides a method of treating a PFAS mixture, comprising: providing a substance comprising a first concentration of at least one PFAS; mixing the solution with any of the surface-modified MNP-containing compositions disclosed herein, such that at least a portion of the PFAS is absorbed by the MNPs; and removing at least a portion of the PFAS-absorbed MNPs from the solution, thus reducing the first concentration by at least one PFAS in the substance.8317627178v4Attorney Docket No: 011529.114821

[0045] The removed PFAS-absorbed MNPs can then be regenerated. In some embodiments, regenerating the removed PFAS-absorbed MNPs can comprise placing the removed MNPs in a substance comprising alcohol (e.g., methanol, ethanol, ethyl alcohol, acetone, etc.) to functionally desorb the attached PFAS, enabling the regenerated MNPs to be used again for PFAS removal.

[0046] Once the removed MNPs have been regenerated, the method can further comprise: replacing the regenerated MNPs into the PFAS-containing substance; allowing the regenerated MNPs to absorb more PFAS in the substance; and removing at least a portion of the replaced, PFAS-absorbed MNPs to further reduce the PFAS concentration in the substance. As those skilled in the art would understand, this process can be repeated iteratively until the substance has a desired concentration of the PFAS.EXAMPLES

[0047] The following examples are provided to further describe some of the embodiments disclosed herein. The examples are intended to illustrate, not to limit, the disclosed embodiments.Example 1. Adsorbent preparation

[0048] Either a coprecipitate method (Xu, J.; Luu, L.; Tang, Y., Phosphate removal using aluminum-doped magnetic nanoparticles. Desalination and Water Treatment 2017, 58, 238-249.) or hydrothermal method (Mansur, S.; Rai, A.; Holler, R. A.; Mewes, T.; Bao, Y., Synthesis and characterization of iron oxide superparticles with various polymers. Journal of Magnetism and Magnetic Materials 2020, 575, 167265.) can be employed to make MNPs with the adjustable size in the range of 10 to 200 nm as shown in FIG.l. The prepared MNPs were characterized to determine the crystal structure (FIG. 2) and magnetic properties (FIG. 3) of the particles. The peaks position, in the x-ray diffraction data (FIG. 2), centered at 20 = 31°, 36°, 44°, 58° and 63° can be indexed as the (220), (311), (400), (511) and (440) planes of magnetite, in agreement with the standard magnetite JCPDS card (card no. 19-0629). The magnetic moments of prepared MNPs (FIG. 3) show superparamagnetism without hysteresis and remnant magnetization at room temperature.

[0049] The prepared MNPs were thoroughly rinsed, and their surfaces were then modified with fluorosilanes, as shown in FIG. 4, to produce the perfluoro functional groups on the surfaces. Fluorosilanes can bond to the surface of the MNPs through a condensation reaction with hydroxyl groups present on the nanoparticle surface, forming a siloxane linkage (FIG. 9).9317627178v4Attorney Docket No: 011529.114821Example 2. PFAS quantification

[0050] The analysis of trace per- and polyfluoroalkyl substances (PFAS) was performed using a modified procedure based on established methodologies, including EPA Methods 537 & 1633 and an FDA Laboratory Information Bulletin (LIB). PFAS quantification was performed using liquid chromatography with tandem mass spectrometry (LC-MS-MS). First, a precise 150 mL water sample was passed through a weak anion exchange (WAX) solid-phase extraction (SPE) cartridge to concentrate the target compounds. The sample was then cleaned up with a graphitized carbon black (GCB) SPE cartridge to remove matrix interferences before being evaporated to dryness under a gentle stream of nitrogen. The residue was reconstituted in 1 mL of high-purity methanol. A 5 pL aliquot of the final extract was injected and analyzed on an Agilent 6475 Triple Quadrupole Liquid Chromatograph-tandem Mass Spectrometer (LC-MS / MS), which was chosen for its exceptional sensitivity. Chromatographic separation was achieved using an Agilent AZORBAX RRHD Eclipse Plus Cl 8 column with the column oven maintained at 55 °C (for both PFOA and PFOS compounds). A binary solvent gradient was employed with a mobile phase flow rate of 0.4 mL / min over a 12-minute run. The gradient started with 98% of an aqueous phase (0.5% acetonitrile in water with 2 mM ammonium acetate) and 2% acetonitrile, and was gradually ramped to a final composition of 5% aqueous phase and 95% acetonitrile before returning to initial conditions. All the water samples for LC / MS were filtered with a 30 kDa MWCO centrifugal filter to prevent column clogging. A gradient of diluted ammonium acetate and methanol was used as the mobile phase. A typical calibration curve for PFOS can be found in FIGs. 5A-5B.Example 3. PFAS adsorption isotherm study

[0051] As proof-of-principle, surface-functionalized MNPs were added to PFAS-containing substances to facilitate PFAS adsorption (FIG. 10A), followed by removal of the PFAS-bound MNPs. Specifically, a series of PFOA and PFOS solutions with concentrations ranging from 0.5 parts per million (ppm) to 40 ppm were prepared in deionized (DI) water. A small amount of MNP were added into 30 ml of PFAS solution. The mixtures were shaken overnight and the MNPs were removed from the treated water under a magnet. The amount of PFAS adsorbed on the adsorbent was calculated using Equation 1 : _ _ .Equation 110317627178v4Attorney Docket No: 011529.114821 where Co and Ceare the starting concentration and equilibrium concentration respectively, V is the volume of PFAS solution being treated and w is the weight of adsorbent being used. The removal data can be found in Table 1.

[0052] The plot of Ce / qeverse Ce(FIG. 6) was produced to calculate maximum adsorption capacity qm) and Langmuir constant ( T), as shown in Equation 2.Ce1 1— — — CeH - Equation 2 e m ^LQm

[0053] An excellent fit to the Langmuir model indicates that the developed adsorbent is highly effective, reliable, and efficient in capturing PFAS from contaminated water, following a well- defined adsorption process. The adsorbent's binding capacities, as shown in Table 2, are exceptionally high, exceeding 100 mg / g for PFOA and 500 mg / g for PFOS, which is a substantial improvement compared to the traditional activated carbon-based adsorbents that typically exhibit a binding capacity ranging from 0.5 to 2.5 mg / g.Example 4. PFAS adsorption kinetic study

[0054] PFAS solutions containing 1 ppm of PFOA and 1 ppm of PFOS were prepared in 50 ml of DI water and tap water respectively. 2.8 mg of MNP were added into the PFAS solution. The mixture was shaken for 24 hours, and samples of the solution are taken to measure the concentration of the adsorbate at predetermined time intervals. Amount adsorbed at time t, qt(mg / g), was calculated using Equation 1. The ratio of t / qt was plotted with T to obtain the rate constant, as shown in FIGs. 7A-7B.Example 5. PFAS regeneration study1.4 mg of MNP were added into 10 ml of PFAS mixture containing about 6 ppm PFOA and 6 ppm of PFOS. The MNP / PFAS mixture was shaken for 10 minutes. The treated solution was isolated from the MNPs under a magnetic field for PFAS measurement. The spent MNPs were regenerated with a simple solvent wash using 10 ml of ethanol for 10 minutes (FIG. 10B). After separating the regenerated MNPs from the ethanol using a magnet, they are ready for the next round of PFAS removal. Complete extraction of adsorbed PFOA and PFOS was achieved by washing the material with 10 ml of ethanol for 10 minutes. This process was repeated 5 times without loss of efficiency in adsorption or reuse, as shown in FIG. 8.11317627178v4Attorney Docket No: 011529.114821Table 1. Removal results from the PFOA isotherm studies.Table 2. Extracted adsorption capacities and Langmuir constants from the isotherm studies.

[0055] The disclosed technology can be further understood according to the following clauses:

[0056] Clause 1 : A composition for treatment of a PFAS containing substance, the composition comprising: a plurality of magnetic nanoparticles (MNPs) having fluorinated functional groups on the surface of the MNPs.

[0057] Clause 2: The composition of Clause 1 , wherein each of the plurality of MNPs comprises one or more poly fluoro or perfluoro functional groups on the surface of the MNPs.

[0058] Clause 3: The composition of Clause 2, wherein the polyfluoro or perfluoro functional groups comprise fluorosilanes.

[0059] Clause 4: The composition of any of Clauses 1-3, wherein the plurality of MNPs comprise FesCL (FeO / Fe2O3).

[0060] Clause 5: The composition of any of Clauses 1-4, wherein the plurality of MNPs have a particle size of from 10-200 nm.12317627178v4Attorney Docket No: 011529.114821

[0061] Clause 6: The composition of any of Clauses 1-5, wherein the composition has a binding capacity for PFOA greater than 50 mg / g.

[0062] Clause 7: The composition of Clause 6, wherein the binding capacity for PFOA is between 80 and 110 mg / g.

[0063] Clause 8: The composition of any of Clauses 1-5, wherein the composition has a binding capacity for PFOS of at least at least 200 mg / g.

[0064] Clause 9: The composition of Clause 8, wherein the binding capacity for PFOS is between 500 and 560 mg / g.

[0065] Clause 10: A method of forming a composition for treatment of a PFAS containing substance, comprising: forming a plurality of magnetic nanoparticles (MNPs); and surface-modifying the plurality of MNPs with fluorinated functional groups.

[0066] Clause 11 : The method of Clause 10, wherein the fluorinated functional groups comprise fluorosilanes.

[0067] Clause 12: The method of any of Clauses 10-11, wherein the plurality of MNPs comprise FesC (FeO / Fe2O3).

[0068] Clause 13: The method of any of Clauses 10-12, wherein the plurality of MNPs have a particle size of from 10-200 nm.

[0069] Clause 14: The method of any of Clauses 10-13, wherein surface modifying the plurality of MNPs with fluorosilanes produces polyfluoro or perfluoro functional groups on the surfaces of the MNPs.

[0070] Clause 15 : The method of any of Clauses 10-14, wherein the fluorosilanes bond to the surfaces of the MNPs via a condensation reaction with hydroxyl groups on the surfaces of the MNPs forming a siloxane linkage.

[0071] Clause 16: The method of Clause 15, wherein the fluorosilanes have the following structure:, wherein: n is equal to 1-25 repeating units;13317627178v4Attorney Docket No: 011529.114821R1 is selected from H, fluorine, CF3, amines, amides, esters, hydroxyls, halogens, etc.;R2 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.;R3 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.; andR4 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.

[0072] Clause 17: The method of Clause 15, wherein the fluorosilanes have the following structure:

[0073] Clause 18: A method of treating a PFAS mixture: providing a substance comprising a first concentration of at least one PFAS, mixing the substance with the composition of claim 2, and removing at least a portion of the MNPs from the substance to form a first treated substance having a second concentration of at least one PFAS less than the first concentration.

[0074] Clause 19: The method of Clause 18, further comprising regenerating the removed MNPs from the substance.

[0075] Clause 20: The method of Clause 19, wherein regenerating the removed MNPs comprises placing the removed MNPs in an alcohol.

[0076] Clause 21: The method of Clause 20, wherein the alcohol is ethanol.

[0077] Clause 22: The method of Clause 18, further comprising: replacing the removed MNPs with the regenerated MNPs within the first treated substance; and removing at least a portion of the replaced MNPs from the first treated substance to form a second treated substance having a third concentration of at least one PFAS less than the second concentration.

[0078] It is to be understood that the embodiments and claims disclosed herein are not limited in their application to the details of construction and arrangement of the components set forth in the description and illustrated in the drawings. Rather, the description and the drawings provide examples of the embodiments envisioned. The embodiments and claims disclosed herein are14317627178v4Attorney Docket No: 011529.114821 further capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purposes of description and should not be regarded as limiting the claims.

[0079] Accordingly, those skilled in the art will appreciate that the conception upon which the application and claims are based may be readily utilized as a basis for the design of other structures, methods, and systems for carrying out the several purposes of the embodiments and claims presented in this application. It is important, therefore, that the claims be regarded as including such equivalent constructions.

[0080] Furthermore, the purpose of the foregoing Abstract is to enable the United States Patent and Trademark Office and the public generally, and especially including the practitioners in the art who are not familiar with patent and legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The Abstract is neither intended to define the claims of the application, nor is it intended to be limiting to the scope of the claims in any way.

[0081] The present invention is not to be limited in scope by the specific embodiments described herein. Indeed, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are intended to fall within the scope of the appended claims.

[0082] All patents, applications, publications, test methods, literature, and other materials cited herein are hereby incorporated by reference in their entirety as if physically present in this specification.15317627178v4

Claims

Attorney Docket No: 011529.114821Claims1. A composition for treatment of a PFAS containing substance, the composition comprising: a plurality of magnetic nanoparticles (MNPs) having fluorinated functional groups on the surface of the MNPs.

2. The composition of claim 1 , wherein each of the plurality of MNPs comprises one or more polyfluoro or perfluoro functional groups on the surface of the MNPs.

3. The composition of claim 2, wherein the polyfluoro or perfluoro functional groups comprise fluorosilanes.

4. The composition of claim 2, wherein the plurality of MNPs comprise FesO4 (FeO / Fe2O3).

5. The composition of claim 2, wherein the plurality of MNPs have a particle size of from 10- 200 nm.

6. The composition of claim 2, wherein the composition has a binding capacity for PFOA greater than 50 mg / g.

7. The composition of claim 6, wherein the binding capacity for PFOA is between 80 and 110 mg / g.

8. The composition of claim 2, wherein the composition has a binding capacity for PFOS of at least at least 200 mg / g.

9. The composition of claim 8, wherein the binding capacity for PFOS is between 500 and 560 mg / g.

10. A method of forming a composition for treatment of a PFAS containing substance, comprising: forming a plurality of magnetic nanoparticles (MNPs); and surface-modifying the plurality of MNPs with fluorinated functional groups.

11. The method of claim 10, wherein the fluorinated functional groups comprise fluorosilanes.

12. The method of claim 10, wherein the plurality of MNPs comprise FesC (FeO / Fe2O3).

13. The method of claim 10, wherein the plurality of MNPs have a particle size of from 10- 200 nm.

14. The method of claim 11, wherein surface modifying the plurality of MNPs with fluorosilanes produces polyfluoro or perfluoro functional groups on the surfaces of the MNPs.16317627178v4Attorney Docket No: 011529.11482115. The method of claim 11, wherein the fluorosilanes bond to the surfaces of the MNPs via a condensation reaction with hydroxyl groups on the surfaces of the MNPs forming a siloxane linkage.

16. The method of claim 14, wherein the fluorosilanes have the following structure:n is equal to 1-25 repeating units;R1 is selected from H, fluorine, CF3, amines, amides, esters, hydroxyls, halogens, etc.;R2 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.;R3 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.; andR4 is selected from OCH3, OH3, OCH2CH3, H, Cl, etc.

17. The method of claim 14, wherein the fluorosilanes have the following structure:

18. A method of treating a PFAS mixture: providing a substance comprising a first concentration of at least one PFAS, mixing the substance with the composition of claim 1 , and removing at least a portion of the MNPs from the substance to form a first treated substance having a second concentration of at least one PFAS less than the first concentration.

19. The method of claim 18, further comprising regenerating the removed MNPs from the substance.

20. The method of claim 19, wherein regenerating the removed MNPs comprises placing the removed MNPs in an alcohol.

21. The method of claim 20, wherein the alcohol is ethanol.

22. The method of claim 18, further comprising:17317627178v4Attorney Docket No: 011529.114821 replacing the removed MNPs with the regenerated MNPs within the first treated substance; and removing at least a portion of the replaced MNPs from the first treated substance to form a second treated substance having a third concentration of at least one PFAS less than the second concentration.18317627178v4

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