Extractant compositions

Abstract

Extractant compositions and, e.g., extractant compositions adapted for soil analysis, are disclosed herein. In accordance with an aspect of the disclosure, provided is an extractant composition including one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent comprising hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylene glycol-bis(β-aminoethyl ether)- N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, a salt thereof, or a combination of two or more thereof; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 6 or less.

Description

EXTRACTANT COMPOSITIONSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application Nos. 63 / 586978, filed 29 September 2023; 63 / 586984, filed 29 September 2023; 63 / 586990, filed 29 September 2023; 63 / 551120, filed 08 February 2024, all of which are incorporated herein by reference in their entireties.BACKGROUND

[0002] Periodic soil testing is an important aspect of the agricultural arts. Test results provide valuable information on the chemical makeup of the soil such as plant-available nutrients and other important properties (e.g. levels of nitrogen, magnesium, phosphorous, potassium, pH, etc.) so that various amendments may be added to the soil to maximize the quality and quantity of crop production.

[0003] In some existing soil sampling processes, collected samples are dried, ground, water is added, and then filtered to obtain a soil slurry suitable for analysis. Extractant is added to the slurry to pull out various plant available nutrients (analytes). The slurry is then analyzed to ascertain the levels of the various plant available nutrients so that soil amendments may be made where necessary to replenish depleted nutrients in certain regions of the agricultural planting field.BRIEF SUMMARY

[0004] This summary is intended merely to introduce a simplified summary of some aspects of one or more implementations of the present disclosure. Further areas of applicability of the present disclosure will become apparent from the detailed description provided hereinafter. This summary is not an extensive overview, nor is it intended to identify key or critical elements of the present teachings, nor to delineate the scope of the disclosure. Rather, its purpose is merely to present one or more concepts in simplified form as a prelude to the detailed description and brief description of the drawings provided below.

[0005] Aspects of the disclosure are generally directed to extractant compositions and, e.g., extractant compositions adapted for soil analysis. In accordance with an aspect of the disclosure,provided is an extractant composition including one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent comprising hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylene glycol-bis(P-aminoethyl ether)- N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, a salt thereof, or a combination of two or more thereof; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 6 or less. The acid may, in some embodiments, be in the form of a salt.

[0006] According to another aspect of the disclosure, provided is an extractant composition including about 0.03 M or more of a strong acid; about 0.001 M or more of a chelating agent; about 5 ppm or more of a metal; an exchangeable salt extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCb, SrCb, LiCl, and a combination of two or more thereof; and optionally, a fluoride source, wherein the extractant composition has a pH of about 6 or less.

[0007] In accordance with an additional aspect of the disclosure, provided is an extractant composition including one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 2 or less and the chelating agent is stable over a period of at least 3 months.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The present invention may become more fully understood from the detailed description and the accompanying drawings, wherein like elements are labeled similarly and in which:

[0009] FIG. 1 is a graph showing the correlation between ICP analysis and colorimetric analysis for phosphorous content using a comparative extractant composition;

[0010] FIG. 2 is a graph showing the correlation between ICP analysis and colorimetric analysis for phosphorous content using a non-limiting, example extractant composition in accordance with aspects of the disclosure; and

[0011] FIG. 3 is a graph showing a non-limiting, example extractant composition to a comparative extractant composition for phosphorous analysis using ICP according to aspects of the invention.

[0012] It should be understood that the various aspects are not limited to the arrangements and instrumentality shown in the drawings.DETAILED DESCRIPTION

[0013] For illustrative purposes, the principles of the present invention are described by referencing various exemplary embodiments thereof. Although certain embodiments of the invention are specifically described herein, one of ordinary skill in the art will readily recognize that the same principles are equally applicable to, and can be employed in other compositions and methods. Before explaining the disclosed embodiments of the present invention in detail, it is to be understood that the invention is not limited in its application to the details of any particular embodiment disclosed herein. The terminology used herein is for the purpose of description and not of limitation.

[0014] As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context dictates otherwise. The singular form of any class of the ingredients refers not only to one chemical species within that class, but also to a mixture of those chemical species. The terms “a” (or “an”), “one or more” and “at least one” may be used interchangeably herein. The terms “comprising”, “including”, and “having” may be used interchangeably. The term “include” should be interpreted as “include, but are not limited to”. The term “including” should be interpreted as “including, but are not limited to”.

[0015] As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. Thus, a range from 1-5, includes specifically 1, 2, 3, 4 and 5, as well as subranges such as 2-5, 3-5, 2-3, 2-4, 1-4, etc.

[0016] The term “about” when referring to a number means any number within a range of 10% of the number. For example, the phrase “about 2 wt.%” refers to a number between and including 1.8 wt.% and 2.2 wt.%.

[0017] All references cited herein are hereby incorporated by reference in their entireties. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.

[0018] The abbreviations and symbols as used herein, unless indicated otherwise, take their ordinary meaning. The abbreviation “wt.%” means percent by weight with respect to the extractant composition. The abbreviation ppm can either be based on mass (mg / kg) or volume (mL / L). The symbol “°” refers to a degree, such as a temperature degree or a degree of an angle. The symbols “h”, “min”, “mL”, “nm”, and “pm” refer to hour, minute, milliliter, nanometer, and micrometer,respectively. The abbreviation “UV-VIS” as referring to a spectrometer or spectroscopy, means Ultraviolet- Visible. The abbreviation “rpm” means revolutions per minute.

[0019] When referring to chemical structures, and names, the symbols “C”, “H”, and “O” mean carbon, hydrogen, and oxygen, respectively. The symbols“=” and “=” mean single bond, double bond, and triple bond, respectively.

[0020] ‘ ‘Volatile”, as used herein, means having a flash point of less than about 100° C. “Nonvolatile”, as used herein, means having a flash point of greater than about 100° C.

[0021] Any member in a list of species that are used to exemplify or define a genus, may be mutually different from, or overlapping with, or a subset of, or equivalent to, or nearly the same as, or identical to, any other member of the list of species. Further, unless explicitly stated, such as when reciting a Markush group, the list of species that define or exemplify the genus is open, and it is given that other species may exist that define or exemplify the genus just as well as, or better than, any other species listed.

[0022] The phrases, “a mixture thereof,” “a combination thereof,” or a combination of two or more thereof’ do not require that the mixture include all of A, B, C, D, E, and F (although all of A, B,C, D, E, and F may be included). Rather, it indicates that a mixture of any two or more of A, B, C,D, E, and F can be included. In other words, it is equivalent to the phrase “one or more elements selected from the group consisting of A, B, C, D, E, F, and a mixture of any two or more of A, B, C, D, E, and F.” Likewise, the term “a salt thereof’ also relates to “salts thereof.” Thus, where the disclosure refers to “an element selected from the group consisting of A, B, C, D, E, F, a salt thereof, and a mixture thereof,” it indicates that that one or more of A, B, C, D, and F may be included, one or more of a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included, or a mixture of any two of A, B, C, D, E, F, a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included.

[0023] All components and elements positively set forth in this disclosure can be negatively excluded from the claims. In other words, the extractant compositions of the instant disclosure can be free or essentially free of all components and elements positively recited throughout the instant disclosure. In some instances, the extractant compositions of the present disclosure may be substantially free of non-incidental amounts of the ingredient(s) or compound(s) described herein. A non-incidental amount of an ingredient or compound is the amount of that ingredient or compound that is added into the extractant composition by itself. For example, an extractantcomposition may be substantially free of a non-incidental amount of an ingredient or compound, although such ingredient(s) or compound(s) may be present as part of a raw material that is included as a blend of two or more compounds.

[0024] Some of the various categories of components identified may overlap. In such cases where overlap may exist and the extractant composition includes both components (or the composition includes more than two components that overlap), an overlapping compound does not represent more than one component. For example, certain compounds may be characterized as both an acid and a chelating agent. If a particular extractant composition includes both an acid and a chelating agent, such a compound will serve only as either an acid or a chelating agent — not both. ‘

[0025] For readability purposes, the chemical functional groups are in their adjective form; for each of the adjectives, the word “group” is assumed. For example, the adjective “alkyl” without a noun thereafter, should be read as “an alkyl group.”

[0026] Aspects of the disclosure are generally directed to extractant compositions and, e.g., extractant compositions adapted for soil analysis. For example, the extractant compositions may be adapted for combination and / or mixing with a soil slurry comprising at least one soil particle and water. The extractant compositions may be adapted to extract one or more analytes and / or nutrients from the soil in the soil slurry. For instance, the extractant compositions may be adapted to extract phosphorus, calcium, magnesium, potassium, boron, copper, manganese, iron, zinc, sulfur, and / or sodium from soil and / or a soil slurry. In some embodiments, the extractant composition is adapted to extract phosphorus, calcium, magnesium, and / or potassium from soil and / or a soil slurry.

[0027] In certain embodiments, the extractant compositions may be specifically adapted for soil analysis using UV / Vis, FUR, flame photometry, and / or inductively coupled plasma. The extractant compositions disclosed herein may, in certain embodiments, have a pH of about 6 or less, about 4 or less, or even about 2 or less while surprisingly maintaining stability of components therein, such as the chelating agent(s) for at least 3 months, at least 4 months, or even at least 6 months.

[0028] In accordance with an aspect of the disclosure, provided is an extractant composition including one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent comprising hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid,di ethylenetriaminepentaacetic acid, a salt thereof, or a combination of two or more thereof; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 6 or less.

[0029] According to another aspect of the disclosure, provided is an extractant composition including about 0.03 M or more of a strong acid; about 0.001 M or more of a chelating agent; about 5 ppm or more of a metal; optionally, an exchangeable salt extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCh, SrCb, LiCl, and a combination of two or more thereof; and optionally, a fluoride source, wherein the extractant composition has a pH of about 6 or less. In some embodiments, the extractant composition is a concentrated extractant composition.

[0030] In accordance with an additional aspect of the disclosure, provided is an extractant composition including one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 2 or less and the chelating agent is stable over a period of at least 3 months.

[0031] The extractant composition disclosed herein may have a pH of about 6 or less. In certain embodiments, the pH of the extractant composition is about 5 or less, about 4 or less, about 3 or less, about 2.75 or less, about 2.5 or less, about 2.25 or less, about 2 or less, about 1.75 or less, about 1.5 or less, about 1.25 or less, or about 1 or less. For instance, the extractant composition may have a pH from about 1 to about 4, about 1 to about 3, about 1 to about 2.75, about 1 to about 2.5, about 1 to about 2.25, about 1 to about 2, about 1 to about 1.75, about 1 to about 1.5; from about 1.25 to about 4, about 1.25 to about 3, about 1.25 to about 2.75, about 1.25 to about 2.5, about 1.25 to about 2.25, about 1.25 to about 2, about 1.25 to about 1.75; from about 1.5 to about 4, about 1.5 to about 3, about 1.5 to about 2.75, about 1.5 to about 2.5, about 1.5 to about 2.25, about 1.5 to about 2, about 1.5 to about 1.75; from about 1.75 to about 4, about 1.75 to about 3, about 1.75 to about 2.75, about 1.75 to about 2.5, about 1.75 to about 2.25, or any range or subrange thereof.

[0032] Preferably, the extractant composition is stable for a period of time of at least 3 months. For instance, the extractant composition may be stable for a period of at least 2 months, at least 3 months, at least 4 months, at least 5 months, at least 6 months, at least 8 months, at least 10 months, and / or at least 12 months. In some embodiments, the stability of the extractant composition isbased on chelating agent not precipitating over the period of time if the composition is maintained at a temperature of about 20°C (e.g., without mixing, shaking, and / or stirring the extractant composition). In further embodiments, the stability of the extractant composition is based on none of the dissolved compounds and / or suspended compounds precipitating over the period of time if the composition is maintained at a temperature of about 20°C (e.g., without mixing, shaking, and / or stirring the extractant composition). As mentioned above, in certain preferred embodiments, the extractant composition has any of the foregoing pH values while maintaining stability for any of the above listed periods of time.

[0033] Suitable components, such as those listed below, may be included or excluded from the formulations for the extractant compositions depending on the specific combination of other ingredients and the concentration or ratio of other ingredients. While the extractant composition is typically in the form of a single component composition, the extractant composition may have two phases in some embodiments.

[0034] The extractant compositions typically comprise one or more acid. Preferably, the one or more acid is a strong acid, such as a strong Lewis acid and / or Bronsted-Lowry acid. Examples of strong acids include chloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, hydrochloric acid, nitric acid, and sulfuric acid. In some embodiments, the one or more acid comprises hydrochloric acid, nitric acid, or a combination of two or more thereof. In another embodiment, the acid(s) comprises nitric acid, or a combination thereof. In yet a further embodiment, the acid(s) comprises nitric acid. The one or more acid may be in the form, or added to the extractant in the form, of a salt. For instance, the extractant composition may include or have any of the aforementioned acids disclosed herein (e.g., chloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, hydrochloric acid, nitric acid, and / or citric acid) incorporated into the extractant composition in the form of a salt.

[0035] The extractant composition may, preferably, include at least one strong Bronsted-Lowry acid. In some embodiments, the acid(s) may consist of strong Lewis acids and / or strong Bronsted- Lowry acids. For example, the one or more acids consist of strong acids, such as those selected from chloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, hydrochloric acid, nitric acid, and a combination of two or more thereof. In some instances, the acid(s) consists of an acid selected from hydrochloric acid, nitric acid, citric acid, a salt thereof, and a combination of two or more thereof.

[0036] The one or more acid (e.g., strong acid(s), such as strong Lewis acids and / or strong Bronsted-Lowry acids) may be present in the extractant composition in an amount of about 0.03 M or more. For example, the one or more acid may be present in a molar concentration from about 0.03 to about 0.6 M, about 0.03 to about 0.5 M, about 0.03 to about 0.4 M, about 0.03 to about 0.3 M, about 0.03 to about 0.2 M, about 0.03 to about 0.1 M; from about 0.05 to about 0.6 M, about 0.05 to about 0.5 M, about 0.05 to about 0.4 M, about 0.05 to about 0.3 M, about 0.05 to about 0.2 M, about 0.05 to about 0.1 M; from about 0.07 to about 0.6 M, about 0.07 to about 0.5 M, about 0.07 to about 0.4 M, about 0.07 to about 0.3 M, about 0.07 to about 0.2 M, about 0.07 to about 0.1 M; from about 0.1 to about 0.6 M, about 0.1 to about 0.5 M, about 0.1 to about 0.4 M, about 0.1 to about 0.3 M, about 0.1 to about 0.2 M; from about 0.15 to about 0.6 M, about 0.15 to about 0.5 M, about 0.15 to about 0.4 M, about 0.15 to about 0.3 M; from about 0.2 to about 0.6 M, about 0.2 to about 0.5 M, about 0.2 to about 0.4 M, about 0.2 to about 0.3 M; from about 0.3 to about 0.6 M, about 0.3 to about 0.5 M, about 0.3 to about 0.4 M; from about 0.4 to about 0.6 M, about 0.4 to about 0.5 M, about 0.5 to about 0.6 M, or any range or subrange thereof.

[0037] Without being limited to any particular theory, the inventors discovered that certain acids unexpectedly provided superior effects. Additionally, it was discovered that reducing and / or excluding other acids may enhance the benefits and / or properties of the extractant composition. For instance, in certain embodiments, the extractant composition may have a reduced amount, be substantially free of, or free of sulfuric. For example, the extractant composition may have a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of sulfuric acid. In at least one embodiment, the extractant composition may have about 0 M or 0 M of sulfuric acid.

[0038] Additionally or alternatively, the extractant composition may have a reduced amount, be substantially free of, or free of weak acids (other than chelating agents), such as weak Lewis acids and / or weak Bronsted-Lowry acid. For example, the extractant composition may have a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of weak acids and / or salts thereof, such as weak Lewis acids and / or weak Bronsted-Lowry acids. In at least one embodiment, the extractant composition may have about 0 M or 0 M of weak acids, including, e.g., weak Lewis acids and / or weak Bronsted-Lowry acids.

[0039] In certain embodiments, the extractant composition may have a reduced amount, be substantially free of, or free of acetic acid and / or a salt thereof. For example, the extractant composition may have a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of acetic acid and / or salts thereof. In at least one embodiment, the extractant composition may have about 0 M or 0 M of acetic acid and / or a salt thereof.

[0040] In certain embodiments, however, it was unexpectedly discovered that citric acid may be suitably utilized in certain embodiments of the extractant composition. Without being limited to any particular theory, citric acid in combination with the other components and / or ingredients of the extractant composition achieves enhanced extraction properties / characteristics.

[0041] The extractant composition typically includes one or more chelating agent(s). Non-limiting examples of chelating agent(s) include hydroxyethylethylenediaminetriacetic acid (HEDTA), trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, ethylenediaminetetraacetic acid (ED TA), monosodium EDTA, EDTA disodiumsalt, tetrasodium EDTA, or a combination of two or more thereof. For instance, the chelating agent(s) may be selected from hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylene glycol-bis(P-aminoethyl ether)- N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, a salt thereof, and a combination of two or more thereof.

[0042] The chelating agent(s) disclosed herein may be in the form of a salt. In some embodiments, the chelating agent(s) comprises trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA Monohydrate, disodium HEDTA, a salt of ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'- tetraacetic acid, a salt of diethylenetriaminepentaacetic acid, or a combination of two or more thereof. Additionally or alternatively, the chelating agent may be selected from hydroxyethylethylenediaminetriacetic acid, trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'- tetraacetic acid and / or a salt thereof, diethylenetriaminepentaacetic acid and / or a salt thereof, and a combination of two or more thereof.

[0043] The extractant composition may include the chelating agent(s) in an amount of about 0.001 M or more. For example, the chelating agent(s) may be present in a molar concentration from about 0.001 to about 0.03 M, about 0.001 to about 0.025 M, about 0.001 to about 0.02 M, about 0.001 to about 0.015 M, about 0.001 to about 0.01 M, about 0.001 to about 0.0075 M, about 0.001 to about 0.006 M, about 0.001 to about 0.005 M; from about 0.003 to about 0.03 M, about 0.003 to about 0.025 M, about 0.003 to about 0.02 M, about 0.003 to about 0.015 M, about 0.003 to about 0.01 M, about 0.003 to about 0.0075 M, about 0.003 to about 0.006 M; from about 0.005 to about 0.03 M, about 0.005 to about 0.025 M, about 0.005 to about 0.02 M, about 0.005 to about 0.015 M, about 0.005 to about 0.01 M, about 0.005 to about 0.0075 M; from about 0.007 to about 0.03 M, about 0.007 to about 0.025 M, about 0.007 to about 0.02 M, about 0.007 to about 0.015 M, about 0.007 to about 0.01 M; from about 0.01 to about 0.03 M, about 0.01 to about 0.025 M, about 0.01 to about 0.02 M, about 0.01 to about 0.015 M; from about 0.015 to about 0.03 M, about 0.015 to about 0.025 M, about 0.015 to about 0.02 M, about 0.02 to about 0.03 M, or any range or subrange thereof.

[0044] In some embodiments, however, the extractant composition has a reduced amount, is substantially free of, or is free of diethylenetriamene pentaacetate (DTPA) and / or a salt thereof. For example, the extractant composition may have a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of DTPA and / or salts thereof. In at least one embodiment, the extractant composition may have about 0 M or 0 M of DTPA and / or a salt thereof.

[0045] Additionally or alternatively, the extractant composition may have a reduced amount, be substantially free of, or be free of ethylenediaminetetraacetic acid (ED TA) and / or a salt thereof. For example, the extractant composition may have a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of ED TA and / or salts thereof. In at least one embodiment, the extractant composition may have about 0 M or 0 M of ED TA and / or a salt thereof.

[0046] The extractant composition typically comprises a metal. The metal may be in the form of elemental metal, an ion thereof, a salt thereof, and / or an oxide thereof. For example, the metal may be added into the extractant composition in the form of elemental metal, in a salt form, or as anion in a solution. When the metal is added into the extractant composition as a salt, in some embodiments the metal dissociates in the extractant composition to be a metal ion. The metal may be selected from lithium, rhodium, thallium, indium, an ion thereof, a salt thereof, an oxide thereof, and a combination of two or more thereof. In at least one embodiment, the metal comprises lithium, rhodium, an ion thereof, a salt thereof, or a combination of two or more thereof. In further embodiments, the metal comprises rhodium, indium, an ion thereof, a salt thereof, or a combination of two or more thereof. The extractant composition preferably is formulated such that the metal (e.g., elemental metal, metal ion, and / or metal salt) is not absorbed and / or adsorbed into the soil matrix of the soil sample and / or soil particles thereof. The metal may be a metal cation that is adapted for use as an internal reference standard for emission spectroscopy analysis in some instances.

[0047] In certain embodiments, extractant composition comprises lithium, an ion thereof, and / or a salt thereof. The lithium may be in the form of a salt and / or added in the form of a salt. Suitable examples of salt forms of lithium include lithium nitrate, lithium chloride, lithium acetate, lithium sulfate, lithium fluoride, lithium bromide, and lithium iodide.

[0048] The metal may be present in the extractant composition, such that the molar concentration of metal ions present in the extractant composition is about 5 ppm or more. For example, the metal may be present in an amount such that the molar concentration of metal ions present in the extractant may be from about 5 to about 3500 ppm, about 5 to about 3000 ppm, about 5 to about 2500 ppm, about 5 to about 2000 ppm, about 5 to about 1500 ppm, about 5 to about 1000 ppm, about 5 to about 700 ppm, about 5 to about 400 ppm, about 5 to about 200 ppm, about 5 to about 150 ppm, about 5 to about 125 ppm, about 5 to about 100 ppm, about 5 to about 75 ppm, about 5 to about 50 ppm; from about 25 to about 3500 ppm, about 25 to about 3000 ppm, about 25 to about 2500 ppm, about 25 to about 2000 ppm, about 25 to about 1500 ppm, about 25 to about 1000 ppm, about 25 to about 700 ppm, about 25 to about 400 ppm, about 25 to about 300 ppm, about 25 to about 200 ppm, about 25 to about 150 ppm, about 25 to about 125 ppm, about 25 to about 100 ppm, about 25 to about 75 ppm; from about 50 to about 3500 ppm, about 50 to about 3000 ppm, about 50 to about 2500 ppm, about 50 to about 2000 ppm, about 50 to about 1500 ppm, about 50 to about 1000 ppm, about 50 to about 700 ppm, about 50 to about 600 ppm, about 50 to about 500 ppm, about 50 to about 400 ppm, about 50 to about 300 ppm, about 50 to about 200 ppm, about 50 to about 150 ppm, about 50 to about 125 ppm, about 50 to about 100 ppm; from about 150 toabout 3500 ppm, about 150 to about 3000 ppm, about 150 to about 2500 ppm, about 150 to about 2000 ppm, about 150 to about 1500 ppm, about 150 to about 1000 ppm, about 150 to about 700 ppm, about 150 to about 600 ppm, about 150 to about 500 ppm, about 150 to about 400 ppm, about 150 to about 300 ppm, about 150 to about 200 ppm; from about 250 to about 3500 ppm, about 250 to about 3000 ppm, about 250 to about 2500 ppm, about 250 to about 2000 ppm, about 250 to about 1500 ppm, about 250 to about 1000 ppm, about 250 to about 700 ppm, about 250 to about 600 ppm, about 250 to about 500 ppm, about 250 to about 400 ppm; from about 350 to about 3500 ppm, about 350 to about 3000 ppm, about 350 to about 2500 ppm, about 350 to about 2000 ppm, about 350 to about 1500 ppm, about 350 to about 1000 ppm, about 350 to about 700 ppm, about 350 to about 600 ppm, about 350 to about 500 ppm; from about 550 to about 3500 ppm, about 550 to about 3000 ppm, about 550 to about 2500 ppm, about 550 to about 2000 ppm, about 550 to about 1500 ppm, about 550 to about 1000 ppm, about 550 to about 700 ppm; from about 800 to about 3500 ppm, about 800 to about 3000 ppm, about 800 to about 2500 ppm, about 800 to about 2000 ppm, about 800 to about 1500 ppm; from about 1200 to about 3500 ppm, about 1200 to about 3000 ppm, about 1200 to about 2500 ppm, about 1200 to about 2000 ppm, about 1200 to about 1500 ppm; from about 1600 to about 3500 ppm, about 1600 to about 3000 ppm, about 1600 to about 2500 ppm, about 1600 to about 2000 ppm, from about 2000 to about 3500 ppm, about 2000 to about 3000 ppm, about 2000 to about 2500 ppm; from about 2500 to about 3500 ppm, about 2500 to about 3000 ppm, or any range or subrange thereof.

[0049] In some embodiments, the total molar concentration of metal in the extractant composition is about 5 ppm or more. For instance, the total molar concentration of metal (e.g., elemental metal, a salt thereof, or a compound thereof) may be from about 5 to about 3500 ppm, about 5 to about 3000 ppm, about 5 to about 2500 ppm, about 5 to about 2000 ppm, about 5 to about 1500 ppm, about 5 to about 1000 ppm, about 5 to about 700 ppm, about 5 to about 400 ppm, about 5 to about 200 ppm, about 5 to about 150 ppm, about 5 to about 125 ppm, about 5 to about 100 ppm, about 5 to about 75 ppm, about 5 to about 50 ppm; from about 25 to about 3500 ppm, about 25 to about 3000 ppm, about 25 to about 2500 ppm, about 25 to about 2000 ppm, about 25 to about 1500 ppm, about 25 to about 1000 ppm, about 25 to about 700 ppm, about 25 to about 400 ppm, about 25 to about 300 ppm, about 25 to about 200 ppm, about 25 to about 150 ppm, about 25 to about 125 ppm, about 25 to about 100 ppm, about 25 to about 75 ppm; from about 50 to about 3500 ppm, about 50 to about 3000 ppm, about 50 to about 2500 ppm, about 50 to about 2000 ppm, about 50to about 1500 ppm, about 50 to about 1000 ppm, about 50 to about 700 ppm, about 50 to about 600 ppm, about 50 to about 500 ppm, about 50 to about 400 ppm, about 50 to about 300 ppm, about 50 to about 200 ppm, about 50 to about 150 ppm, about 50 to about 125 ppm, about 50 to about 100 ppm; from about 150 to about 3500 ppm, about 150 to about 3000 ppm, about 150 to about 2500 ppm, about 150 to about 2000 ppm, about 150 to about 1500 ppm, about 150 to about 1000 ppm, about 150 to about 700 ppm, about 150 to about 600 ppm, about 150 to about 500 ppm, about 150 to about 400 ppm, about 150 to about 300 ppm, about 150 to about 200 ppm; from about 250 to about 3500 ppm, about 250 to about 3000 ppm, about 250 to about 2500 ppm, about 250 to about 2000 ppm, about 250 to about 1500 ppm, about 250 to about 1000 ppm, about 250 to about 700 ppm, about 250 to about 600 ppm, about 250 to about 500 ppm, about 250 to about 400 ppm; from about 350 to about 3500 ppm, about 350 to about 3000 ppm, about 350 to about 2500 ppm, about 350 to about 2000 ppm, about 350 to about 1500 ppm, about 350 to about 1000 ppm, about 350 to about 700 ppm, about 350 to about 600 ppm, about 350 to about 500 ppm; from about 550 to about 3500 ppm, about 550 to about 3000 ppm, about 550 to about 2500 ppm, about 550 to about 2000 ppm, about 550 to about 1500 ppm, about 550 to about 1000 ppm, about 550 to about 700 ppm; from about 800 to about 3500 ppm, about 800 to about 3000 ppm, about 800 to about 2500 ppm, about 800 to about 2000 ppm, about 800 to about 1500 ppm; from about 1200 to about 3500 ppm, about 1200 to about 3000 ppm, about 1200 to about 2500 ppm, about 1200 to about 2000 ppm, about 1200 to about 1500 ppm; from about 1600 to about 3500 ppm, about 1600 to about 3000 ppm, about 1600 to about 2500 ppm, about 1600 to about 2000 ppm, from about 2000 to about 3500 ppm, about 2000 to about 3000 ppm, about 2000 to about 2500 ppm; from about 2500 to about 3500 ppm, about 2500 to about 3000 ppm, or any range or subrange thereof.

[0050] The extractant composition may comprise one or more extracting agents. The extracting agents may, preferably, be exchangeable salt extractants. The exchangeable salt extractant may include an ion that may exchange with an ion from a soil particle to promote releasing of nutrients from the soil particle. Non-limiting examples of exchangeable salt extractants include ammonium nitrate, ammonium fluoride, nitric acid, calcium chloride, Sikora buffer, BaCb, SrCh, HNO3, LiCl, calcium-acetate-lactate, oxalate, citrate-bicarbonate-dithionite, Mehlich 1, Mehlich 2, Mehlich 3, sodium chloride, Morgan extractant, and modified Morgan extractant. For instance, the extractant(s) may comprise ammonium nitrate, ammonium fluoride, nitric acid, or a combination of two or more thereof.

[0051] In certain embodiments, the extractant composition comprises a plurality of exchangeable salt extractants, such as 2, 3, 4, 5, or 6 exchangeable salt extractants, or any range or subrange formed therefrom. In some cases, the extractant composition may include a plurality of exchangeable salt extractants, wherein at least one of the plurality of exchangeable salt extractants is ammonium nitrate. In at least one preferred embodiment, the extractant composition comprises ammonium nitrate and ammonium fluoride.

[0052] The exchangeable salt extractant(s) may be present in the extractant composition in an amount from about 0.1 to about 3.6 M. For instance, the total molar concentration of exchangeable salt extractant(s) in the extractant composition may be from about 0.1 to about 3.6 M, about 0.1 to about 3 M, about 0.1 to about 2.4 M, about 0.1 to about 2 M, about 0.1 to about 1.6 M, about 0.1 to about 1.3 M, about 0.1 to about 1 M, about 0.1 to about 0.8 M; from about 0.15 to about 3.6 M, about 0.15 to about 3 M, about 0.15 to about 2.4 M, about 0.15 to about 2 M, about 0.15 to about 1.6 M, about 0.15 to about 1.3 M, about 0.15 to about 1 M, about 0.15 to about 0.8 M; from about 0.2 to about 3.6 M, about 0.2 to about 3 M, about 0.2 to about 2.4 M, about 0.2 to about 2 M, about 0.2 to about 1.6 M, about 0.2 to about 1.3 M, about 0.2 to about 1 M, about 0.2 to about 0.8 M; from about 0.5 to about 3.6 M, about 0.5 to about 3 M, about 0.5 to about 2.4 M, about 0.5 to about 2 M, about 0.5 to about 1.6 M, about 0.5 to about 1.3 M, about 0.5 to about 1 M; from about 0.8 to about 3.6 M, about 0.8 to about 3 M, about 0.8 to about 2.4 M, about 0.8 to about 2 M, about 0.8 to about 1.6 M, about 0.8 to about 1.3 M; from about 1.1 to about 3.6 M, about 1.1 to about 3 M, about 1.1 to about 2.4 M, about 1.1 to about 2 M, about 1.1 to about 1.6 M; from about 1.4 to about 3.6 M, about 1.4 to about 3 M, about 1.4 to about 2.4 M, about 1.4 to about 2 M, about 1.4 to about 1.6 M; from about 2 to about 3.6 M, about 2 to about 3 M, about 2 to about 2.4 M; from about 2.5 to about 3.6 M, about 2.5 to about 3 M, or any range or subrange thereof.

[0053] The extractant composition may include a reduced amount, be substantially free of, or free of ammonium acetate. For example, the extractant composition may have a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of ammonium acetate. In at least one embodiment, the extractant composition may have about 0 M or 0 M of ammonium acetate.

[0054] Additionally or alternatively, the extractant composition may include a reduced amount, be substantially free of, or free of ammonium oxalate. For example, the extractant composition mayhave a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of ammonium oxalate. In at least one embodiment, the extractant composition may have about 0 M or 0 M of ammonium oxalate.

[0055] Additionally or alternatively, the extractant composition may include a reduced amount, be substantially free of, or free of oxalate compounds. For example, the extractant composition may have a molar concentration of about 0.6 M or less, about 0.4 M or less, about 0.2 M or less, about 0.1 M or less, about 0.05 M or less, about 0.01 M or less, about 0.005 M or less, about 0.001 M or less, or about 0.0001 M or less of oxalate compounds. In at least one embodiment, the extractant composition may have about 0 M or 0 M of oxalate compounds.

[0056] The extractant composition may comprise a fluoride source. Non-limiting examples of a fluoride source include, but are not limited to, ammonium fluoride, sodium fluoride, potassium fluoride, hydrogen fluoride, zinc fluoride, and lithium fluoride. For example, the fluoride source may comprise ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride, or a combination thereof. The extractant composition may include a fluoride source selected from ammonium fluoride, sodium fluoride, lithium fluoride, or a combination thereof. In at least one embodiment, the extractant composition includes ammonium fluoride.

[0057] The fluoride source may be present in the extractant composition in an amount up to about 0.1 M. For example, the fluoride source may be present in the extractant composition in a molar concentration up to about 0.1 M, up to about 0.08 M, up to about 0.06 M, up to about 0.04 M, up to about 0.02 M, up to about 0.015 M, up to about 0.01 M; from about 0.001 to about 0.1 M, about 0.001 to about 0.08 M, about 0.001 to about 0.06 M, about 0.001 to about 0.04 M, about 0.001 to about 0.02 M, about 0.001 to about 0.015 M, about 0.001 to about 0.01 M; from about 0.005 to about 0.1 M, about 0.005 to about 0.08 M, about 0.005 to about 0.06 M, about 0.005 to about 0.04 M, about 0.005 to about 0.02 M, about 0.005 to about 0.015 M, about 0.005 to about 0.01 M; from about 0.01 to about 0.1 M, about 0.01 to about 0.08 M, about 0.01 to about 0.06 M, about 0.01 to about 0.04 M, about 0.01 to about 0.02 M, about 0.01 to about 0.015 M; from about 0.015 to about 0.1 M, about 0.015 to about 0.08 M, about 0.015 to about 0.06 M, about 0.015 to about 0.04 M, about 0.015 to about 0.02 M; from about 0.02 to about 0.1 M, about 0.02 to about 0.08 M, about 0.02 to about 0.06 M, about 0.02 to about 0.04 M; from about 0.05 to about 0.1 M, about 0.05 toabout 0.08 M, about 0.05 to about 0.06 M, about 0.08 to about 0.1 M, or any range or subrange thereof.

[0058] The extractant composition may include one or more flocculating agent(s). Examples of flocculating agent include, but are not limited to, polyacrylamide, cationic polyacrylamide, anionic polyacrylamide, polydiallyldimethyl ammonium chloride (PDADMAC), epichlorohydin / dimethylamine copolymer (ECH / DMA), chitosan, and polyaluminum chlorides. Calcium chloride is a flocculating agent that may be included or excluded from certain embodiments of the extractant composition. In at least one embodiment, the flocculating agent is a combination of polyacrylamide and calcium chloride. In further embodiments, the flocculating agent is polyacrylamide. The polyacrylamide may have a weight average molecular weight of 5,000,000 to 6,000,000. In one embodiment, a O.Ol M CaCh' IEO solution is used. Alternatively, the anhydride or other hydrates of calcium chloride can be used.

[0059] The molar concentration for the flocculating agent in the extractant composition may be about 0.005 M to about 0.7 M. For example, the extractant composition may have the flocculating agent in a molar concentration of about 0.005 to about 0.7 M, about 0.005 to about 0.5 M, about 0.005 to about 0.3 M, about 0.005 to about 0.1 M, about 0.005 to about 0.07 M, about 0.005 to about 0.04 M, about 0.005 to about 0.01 M; from about 0.01 to about 0.7 M, about 0.01 to about 0.5 M, about 0.01 to about 0.3 M, about 0.01 to about 0.1 M, about 0.01 to about 0.07 M, about 0.01 to about 0.04 M; from about 0.05 to about 0.7 M, about 0.05 to about 0.5 M, about 0.05 to about 0.3 M, about 0.05 to about 0.1 M; from about 0.1 to about 0.7 M, about 0.1 to about 0.5 M, about 0.1 to about 0.3 M; from about 0.2 to about 0.7 M, about 0.2 to about 0.5 M, about 0.2 to about 0.3 M; from about 0.4 to about 0.7 M, about 0.4 to about 0.5 M, about 0.05 to about 0.7 M, or any range or subrange thereof.

[0060] Additionally or alternatively, the flocculating agent(s) may be present in the extractant composition in an amount from about 0.005 to about 0.2 wt.%, based on the total weight of the extractant composition. For instance, the flocculating agent(s) may be present in an amount from about 0.005 to about 0.1 wt.%, about 0.005 to about 0.07 wt.%, about 0.005 to about 0.05 wt.%, about 0.005 to about 0.03 wt.%, about 0.005 to about 0.01 wt.%; from about 0.01 to about 0.2 wt.%, about 0.01 to about 0.15 wt.%, about 0.01 to about 0.1 wt.%, about 0.01 to about 0.07 wt.%, about 0.01 to about 0.05 wt.%, about 0.01 to about 0.03 wt.%; from about 0.03 to about 0.2 wt.%, about 0.03 to about 0.15 wt.%, about 0.03 to about 0.1 wt.%, about 0.03 to about 0.07 wt.%, about0.03 to about 0.05 wt.%; from about 0.06 to about 0.2 wt.%, about 0.06 to about 0.15 wt.%, about0.06 to about 0.1 wt.%, about 0.06 to about 0.08 wt.%; from about 0.08 to about 0.2 wt.%, about0.08 to about 0.15 wt.%, about 0.08 to about 0.1 wt.%; from about 0.1 to about 0.2 wt.%, about0.1 to about 0.15 wt.%; from about 0.13 to about 0.2 wt.%, about 0.13 to about 0.18 wt.%, about0.16 to about 0.2 wt.%, or any range or subrange thereof, based on the total weight of the extractant composition.

[0061] The system for analyzing an agricultural sample disclosed herein is usable with and may form part of an overall agricultural sampling and analysis systems, such as but not limited to those described in U.S. Patent Application Publication Nos. 2018 / 0124992A1, US20210123836A1,US20210123936A1, US20210131917A1, US20210131929A1, US20210208035A1US20210208036A1, US20210208037A1, US20210208123A1, US20210268456A1US20210285869A1, US20210341442A1, US20210341452A1, US20220196628A1US20230133335A1, US20230144670A1, US20230151810A1, US20230173415A1US20230243792A1, US20230243801A1, US20230243802A1, US20230243804A1US20230266289A1, US20230266290A1, US20230273130A1, US20230273171A1US20230273172A1, US20230273173A1, US20230304987A1, US20230417363A1US20230417635A1, US20240189743 Al, US20240189744A1, US20240192112A1US20240192708A1 , US20240198331 Al , US20240200547A1, PCT Publication Nos.W02021 / 171120, WO2021 / 171121, WO2022 / 243792, WO2022 / 243797, WO2022 / 243806.WO2022 / 243807, WO2022 / 243809, WO2022 / 259071, WO2022 / 259073, WO2022 / 259074.WO2023 / 031725, WO2023 / 031726, WO2023 / 031727, W02023 / 042032, W02023 / 042033.W02023 / 042035, W02023 / 042036, W02023 / 042037, W02023 / 042038, W02023 / 042039.WO2023 / 161727, WO2023 / 161728, WO2023 / 170480, WO2023 / 170482, WO2023 / 227959.WO2023 / 227960, WO2023 / 248015, WO2023 / 248016, WO2024 / 023728, WO2024 / 023729.W02024 / 023730, and WO2024 / 023731, PCT Application Nos. PCT / IB2024 / 051283, filed 12- Feb-2024 and PCT / IB2024 / 051820, filed 26-Feb-2024, U.S. Application Nos. 63 / 551120, filed 08-Feb-2024, 63 / 552730, filed 13-Feb-2024, 63 / 552739, filed 13-Feb-2024, 63 / 559305, filed 29- Feb-2024, 63 / 559308, filed 29-Feb-2024, 63 / 559312, filed 29-Feb-2024, 63 / 559316, filed 29-Feb- 2024, 63 / 586486, filed 29-Sep-2023, 63 / 586489, filed 29-Sep-2023, 63 / 586497, filed 29-Sep-2023, 63 / 586500, filed 29-Sep-2023, 63 / 586504, filed 29-Sep-2023, 63 / 586510, filed 29-Sep-2023, 63 / 586514, filed 29-Sep-2023, 63 / 586524, filed ll-Oct-2023, 63 / 586529, filed 29-Sep-2023, 63 / 586545, filed 29-Sep-2023, 63 / 586551, filed 29-Sep-2023, 63 / 586555, filed 29-Sep-2023, 63 / 586562, filed 29-Sep-2023, 63 / 586608, filed 29-Sep-2023, 63 / 586619, filed 29-Sep-2023, 63 / 586630, filed 29-Sep-2023, 63 / 586638, filed 29-Sep-2023, 63 / 586656, filed 29-Sep-2023, 63 / 586672, filed 29-Sep-2023, 63 / 586702, filed 29-Sep-2023, 63 / 586726, filed 29-Sep-2023, 63 / 586955, filed 29-Sep-2023, 63 / 586966, filed 29-Sep-2023, 63 / 586978, filed 29-Sep-2023, 63 / 586984, filed 29-Sep-2023, 63 / 586990, filed 29-Sep-2023, and 63 / 646070, filed 13-May-2024.EXAMPLESExample A

[0062] Three non-limiting example extractant compositions (Example Compositions A, B, and C) were prepared in accordance with aspects of the disclosure. The formulations of Example Compositions A, B, and C as well as a comparative composition (Comparative Composition 1) are shown in the below table.Example B

[0063] Soil samples were prepared for analysis using either ground up dry soils, homogenized moist soils, or a prepared soil slurry solution. Dry and moist soils were extracted by using a mass to volume ratio (w:v) of the soil to water (soil : water) of about 1: 10.

[0064] A soil slurry was then produced by mixing soil and water in a soil to water ratio (w:v) of 1:3. The soil slurry samples were then pulled into the extraction portion of the system and an extractant composition was added in a weight ratio of soil slurry sample to extractant composition (namely, Example Composition A) of 1:3. The analytes (e.g., nutrients) in the soil were thenextracted. After extraction, the sample was filtered. Although not occurring in this experiment, the extracted soil solution may, optionally, be allowed to settle before analysis for the liquid supernatant as an alternative to or in addition to the filtration.

[0065] The liquid extractant was then analyzed by established laboratory techniques. This may include but is not limited to the use of UV / Vis, FTIR, flame photometry, and inductively coupled plasma. When analyzed by flame photometry or molecular emission spectroscopy, such as Inductively Coupled Plasma (ICP) or Solution Cathode Glow Discharge (SCGD), lithium ions and / or indium ions may be used as an internal standard for the analysis. By monitoring variations in the intensity of lithium and / or indium emission spectra, analysts can automatically adjustments were made for variations in the ion excitation source and / or errors in pipetting and preparation of liquid extractant for analysis.Example C

[0066] Soil samples were prepared in accordance with procedures described in Example 2. The soil samples were analyzed for phosphorus using both ICP and the colorimetric analysis. The correlation between the two analysis techniques using Comparative Composition 1 was 0.9337 for dry soils and 0.8994 for moist soils (see FIG. 1). Interestingly, when the same comparison of ICP to colorimetric results was determined for Example Composition A, the resulting R-squared value was 0.9805 with a slope of 0.9608 (see FIG. 2), indicating a much better correlation with Example Composition A. FIG. 3 is a graph of Example Composition A to Comparative Composition 1 for phosphorous analysis using ICP.

[0067] The following are nonlimiting examples

[0068] Example 1 - an extractant composition comprising: one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent comprising hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylene glycol-bis(0- aminoethyl ether)-N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, a salt thereof, or a combination of two or more thereof; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 6 or less.

[0069] Example 2 - the extractant composition according to Example 1 comprising an exchangeable salt extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCh, SrCh, LiCl, and a combination of two or more thereof.

[0070] Example 3 - the extractant composition according to Example 2, wherein the exchangeable salt extractant comprises ammonium nitrate.

[0071] Example 4 - the extractant composition according to Example 2 or Example 3, wherein the molar concentration of the exchangeable salt extractant is from about 0.2 to about 3.6 M.

[0072] Example 5 - the extractant composition according to any foregoing Example, wherein the chelating agent comprises Trisodium HEDTA, Tripotassium HEDTA, Trisodium HEDTA Monohydrate, Disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, diethylenetriaminepentaacetic acid and / or a salt thereof, or a combination of two or more thereof.

[0073] Example 6 - the extractant composition according to any foregoing Example, wherein the chelating agent is present in a molar concentration from about 0.001 to about 0.03 M.

[0074] Example 7 - the extractant composition according to any foregoing Example, wherein the one or more acid comprises nitric acid, hydrochloric acid, citric acid, or a combination thereof.

[0075] Example 8 - the extractant composition according to any foregoing Example, wherein the one or more acid consists of strong Lewis acids.

[0076] Example 9 - the extractant composition according to any foregoing Example wherein the one or more acid is present in a molar concentration from about 0.03 to about 0.4 M.

[0077] Example 10 - the extractant composition according to any foregoing Example, wherein the metal is selected from an elemental metal, a metal ion, and a combination of two or more thereof.

[0078] Example 11 - the extractant composition according to any foregoing Example, wherein the metal is selected from lithium, rhodium, thallium, indium, and a combination of two or more thereof.

[0079] Example 12 - the extractant composition according to any foregoing Example, wherein the metal comprises lithium, indium, or a combination of thereof.

[0080] Example 13 - the extractant composition according to any foregoing Example, wherein the metal is present in a molar concentration from about 5 ppm to about 2500 ppm.

[0081] Example 14 - the extractant composition according to any foregoing Example, wherein the chelating agent is stable over a period of at least 3 months, optionally at least 4 months, at least 5 months, or at least 6 months.

[0082] Example 15 - the extractant composition according to any foregoing Example, wherein the extraction composition is substantially free of or free of DTPA.

[0083] Example 16 - the extractant composition according to any foregoing Example, wherein the extraction composition is substantially free of or free of EDTA.

[0084] Example 17 - the extractant composition according to any foregoing Example, wherein the extraction composition is substantially free of or free of acetic acid and / or a salt thereof.

[0085] Example 18 - the extractant composition according to any foregoing Example, wherein the extraction composition is substantially free of or free of weak Bronsted-Lowry acids.

[0086] Example 19 - the extractant composition according to any foregoing Example, the pH of the extractant composition is about 4 or less, optionally about 3 or less, about 2.5 or less, or about 2 or less.

[0087] Example 20 - the extractant composition according to any foregoing Example comprising a fluoride source is selected from ammonium fluoride, sodium fluoride, potassium fluoride, hydrogen fluoride, zinc fluoride, lithium fluoride, and a combination of two or more thereof.

[0088] Example 21 - the extractant composition according to Example 20, wherein the fluoride source comprises ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride, or a combination of two or more thereof.

[0089] Example 22 - the extractant composition according to Example 1 comprising ammonium nitrate, hydroxy ethylethylenediaminetriacetic acid (HEDTA), nitric acid, lithim, and indium.

[0090] Example 23 - the extractant composition according to Example 22, wherein the composition is free of ammonium fluoride.

[0091] Example 24 - an extractant composition comprising: about 0.03 M or more of a strong acid; about 0.001 M or more of a chelating agent; about 5 ppm or more of a metal; optionally, an extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCh, SrCh, LiCl, and a combination of two or more thereof; and optionally, an amount up to 0.1 M of a fluoride source, wherein the extractant composition has a pH of about 6 or less.

[0092] Example 25 - the extractant composition according to Example 22, wherein the strong acid is present in a molar concentration from about 0.03 to about 0.4 M.

[0093] Example 26 - the extractant composition according to Example 22 or Example 23, wherein the chelating agent is present in a molar concentration from about 0.001 to about 0.03 M.

[0094] Example 27 - the extractant composition according to one of Example 24 to Example 26, wherein the metal is present in a molar concentration from about 5 ppm to about 2500 ppm.

[0095] Example 28 - the extractant composition according to one of Example 24 to Example 27, wherein the chelating agent comprises hydroxyethylethylenediaminetriacetic acid (HEDTA), trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, ethylenediaminetetraacetic acid (EDTA), monosodium EDTA, EDTA disodiumsalt, tetrasodium EDTA, or a combination of two or more thereof.

[0096] Example 29 - the extractant composition according to one of Example 24 to Example 28, wherein the chelating agent is selected from hydroxy ethylethylenediaminetriacetic acid, trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, and a combination of two or more thereof.

[0097] Example 30 - the extractant composition according to one of Example 24 to Example 29, wherein the pH of the extractant composition is about 4 or less, optionally about 3 or less, about 2.5 or less, or about 2 or less, and wherein the chelating agent is stable over a period of at least 3 months.

[0098] Example 31 - the extractant composition according to one of Example 24 to Example 30, wherein the strong acid comprises nitric acid, hydrochloric acid, or a combination thereof.

[0099] Example 32 - the extractant composition according to one of Example 24 to Example 31, wherein extractant composition is substantially free or free of a weak Bronsted-Lowry and / or a salt thereof.

[0100] Example 33 - the extractant composition according to one of Example 24 to Example 32, wherein the metal is selected from an elemental metal, a metal ion, and a combination of two or more thereof.

[0101] Example 34 - the extractant composition according to one of Example 24 to Example 33, wherein the metal is selected from lithium, rhodium, thallium, indium, and a combination of two or more thereof.

[0102] Example 35 - the extractant composition according to one of Example 24 to Example 34, wherein the metal comprises lithium, indium, or a combination of two or more thereof.

[0103] Example 36 - the extractant composition according to one of Example 24 to Example 35, wherein the chelating agent is stable over a period of at least 3 months.

[0104] Example 37 - the extractant composition according to one of Example 24 to Example 36, wherein the chelating agent is stable over a period of at least 6 months.

[0105] Example 38 - the extractant composition according to one of Example 24 to Example 37, wherein the extraction composition is substantially free of or free of DTPA.

[0106] Example 39 - the extractant composition according to one of Example 24 to Example 38, wherein the extraction composition is substantially free of or free of EDTA.

[0107] Example 40 - the extractant composition according to one of Example 24 to Example 39, wherein the extraction composition is substantially free of or free of acetic acid and / or a salt thereof.

[0108] Example 41 - the extractant composition according to one of Example 24 to Example 40 comprising a fluoride source is selected from ammonium fluoride, sodium fluoride, potassium fluoride, hydrogen fluoride, zinc fluoride, lithium fluoride, and a combination of two or more thereof.

[0109] Example 42 - the extractant composition according to Example 41, wherein the fluoride source comprises ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride, or a combination of two or more thereof.

[0110] Example 43 - an extractant composition comprising: one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 2 or less and the chelating agent is stable over a period of at least 3 months.

[0111] Example 44 - the extractant composition according to Example 43 comprising an exchangeable salt extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCh, SrCh, LiCl, and a combination of two or more thereof.

[0112] Example 45 - the extractant composition according to Example 44, wherein the exchangeable salt extractant comprises ammonium nitrate.

[0113] Example 46 - the extractant composition according to Example 44 or Example 45, wherein the molar concentration of exchangeable salt extractant is from about 0.2 to about 3.6 M.

[0114] Example 47 - the extractant composition according to one of Example 43 to Example 46, wherein the one or more acid comprises nitric acid, citric acid, or a combination of two or more thereof.

[0115] Example 48 - the extractant composition according to one of Example 43 to Example 47, wherein the one or more acid is present in a molar concentration from about 0.03 to about 0.4 M.

[0116] Example 49 - the extractant composition according to one of Example 43 to Example 48, wherein the extractant composition is substantially free or free of weak Bronsted-Lowry acids.

[0117] Example 50 - the extractant composition according to one of Example 43 to Example 48, wherein the one or more acid consists of strong Bronsted-Lowry acids.

[0118] Example 51 - the extractant composition according to one of Example 43 to Example 50, wherein the metal is selected from an elemental metal, a metal ion, and a combination of two or more thereof.

[0119] Example 52 - the extractant composition according to one of Example 43 to Example 51, wherein the metal is selected from lithium, rhodium, thallium, indium, and a combination of two or more thereof.

[0120] Example 53 - the extractant composition according to one of Example 43 to Example 52, wherein the metal comprises lithium, indium, or a combination of two or more thereof.

[0121] Example 54 - the extractant composition according to one of Example 43 to Example 53, wherein the metal is present in a molar concentration from about 5 ppm to about 2500 ppm.

[0122] Example 55 - the extractant composition according to one of Example 43 to Example 54, wherein the chelating agent is stable over a period of at least 3 months.

[0123] Example 56 - the extractant composition according to one of Example 43 to Example 55, wherein the chelating agent is stable over a period of at least 6 months.

[0124] Example 57 - the extractant composition according to one of Example 43 to Example 56, wherein the chelating agent comprises hydroxyethylethylenediaminetriacetic acid (HEDTA), trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, ethylenediaminetetraacetic acid(EDTA), monosodium EDTA, EDTA disodiumsalt, tetrasodium EDTA, or a combination of two or more thereof.

[0125] Example 58 - the extractant composition according to one of Example 43 to Example 57, wherein the chelating agent is selected from hydroxy ethylethylenediaminetriacetic acid, trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, and a combination of two or more thereof.

[0126] Example 59 - the extractant composition according to one of Example 43 to Example 59, wherein the chelating agent is present in a molar concentration from about 0.001 to about 0.03 M.

[0127] Example 60 - the extractant composition according to one of Example 43 to Example 59, wherein the extraction composition is substantially free of or free of DTPA.

[0128] Example 61 - the extractant composition according to one of Example 43 to Example 60, wherein the extraction composition is substantially free of or free of EDTA.

[0129] Example 62 - the extractant composition according to one of Example 43 to Example 61, wherein the extraction composition is substantially free of or free of acetic acid and / or a salt thereof.

[0130] Example 63 - the extractant composition according to one of Example 43 to Example 62 comprising a fluoride source is selected from ammonium fluoride, sodium fluoride, potassium fluoride, hydrogen fluoride, zinc fluoride, lithium fluoride, and a combination of two or more thereof.

[0131] Example 64 - the extractant composition according to Example 63, wherein the fluoride source comprises ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride, or a combination of two or more thereof.

[0132] Example 65 - the extractant composition according to any one of Examples 43 to 64 further comprising a flocculating agent.

[0133] Example 66 - the extractant composition according to Example 65, wherein the flocculating agent comprising polyacrylamide in an amount from about 0.005 to about 0.2 wt.%.

Claims

CLAIMSWhat is Claimed is:

1. An extractant composition comprising: one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent comprising hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, a salt thereof, or a combination of two or more thereof; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 6 or less.

2. The extractant composition according to claim 1 comprising an exchangeable salt extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCh, SrCh, LiCl, and a combination of two or more thereof.

3. The extractant composition according to claim 2, wherein the exchangeable salt extractant comprises ammonium nitrate.

4. The extractant composition according to claim 2 or claim 3, wherein the molar concentration of the exchangeable salt extractant is from about 0.2 to about 3.6 M.

5. The extractant composition according to any foregoing claim, wherein the chelating agent comprises Trisodium HEDTA, Tripotassium HEDTA, Trisodium HEDTA Monohydrate, Disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, diethylenetriaminepentaacetic acid and / or a salt thereof, or a combination of two or more thereof.

6. The extractant composition according to any foregoing claim, wherein the chelating agent is present in a molar concentration from about 0.001 to about 0.03 M.

7. The extractant composition according to any foregoing claim, wherein the one or more acid comprises nitric acid, hydrochloric acid, citric acid, or a combination thereof.

8. The extractant composition according to any foregoing claim, wherein the one or more acid consists of strong Lewis acids.

9. The extractant composition according to any foregoing claim wherein the one or more acid is present in a molar concentration from about 0.03 to about 0.4 M.

10. The extractant composition according to any foregoing claim, wherein the metal is selected from an elemental metal, a metal ion, and a combination of two or more thereof.

11. The extractant composition according to any foregoing claim, wherein the metal is selected from lithium, rhodium, thallium, indium, and a combination of two or more thereof.

12. The extractant composition according to any foregoing claim, wherein the metal comprises lithium, indium, or a combination of thereof.

13. The extractant composition according to any foregoing claim, wherein the metal is present in a molar concentration from about 5 ppm to about 2500 ppm.

14. The extractant composition according to any foregoing claim, wherein the chelating agent is stable over a period of at least 3 months, optionally at least 4 months, at least 5 months, or at least 6 months.

15. The extractant composition according to any foregoing claim, wherein the extraction composition is substantially free of or free of DTPA.

16. The extractant composition according to any foregoing claim, wherein the extraction composition is substantially free of or free of EDTA.

17. The extractant composition according to any foregoing claim, wherein the extraction composition is substantially free of or free of acetic acid and / or a salt thereof.

18. The extractant composition according to any foregoing claim, wherein the extraction composition is substantially free of or free of weak Bronsted-Lowry acids.

19. The extractant composition according to any foregoing claim, the pH of the extractant composition is about 4 or less, optionally about 3 or less, about 2.5 or less, or about 2 or less.

20. The extractant composition according to any foregoing claim comprising a fluoride source is selected from ammonium fluoride, sodium fluoride, potassium fluoride, hydrogen fluoride, zinc fluoride, lithium fluoride, and a combination of two or more thereof.

21. The extractant composition according to claim 20, wherein the fluoride source comprises ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride, or a combination of two or more thereof.22 - the extractant composition according to claim 1 comprising ammonium nitrate, hydroxy ethylethylenediaminetriacetic acid (HEDTA), nitric acid, lithim, and indium.23 - the extractant composition according to claim 22, wherein the composition is free of ammonium fluoride.

24. an extractant composition comprising: about 0.03 M or more of a strong acid; about 0.001 M or more of a chelating agent; about 5 ppm or more of a metal; optionally, an extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCh, SrCb, LiCl, and a combination of two or more thereof; and optionally, an amount up to 0.1 M of a fluoride source, wherein the extractant composition has a pH of about 6 or less.

25. The extractant composition according to claim 22, wherein the strong acid is present in a molar concentration from about 0.03 to about 0.4 M.

26. The extractant composition according to claim 22 or claim 23, wherein the chelating agent is present in a molar concentration from about 0.001 to about 0.03 M.

27. The extractant composition according to one of claim 24 to claim 26, wherein the metal is present in a molar concentration from about 5 ppm to about 2500 ppm.

28. The extractant composition according to one of claim 24 to claim 27, wherein the chelating agent comprises hydroxy ethylethylenediaminetriacetic acid (HEDTA), trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, ethylenediaminetetraacetic acid (EDTA), monosodium EDTA, EDTA disodiumsalt, tetrasodium EDTA, or a combination of two or more thereof.

29. The extractant composition according to one of claim 24 to claim 28, wherein the chelating agent is selected from hydroxyethylethylenediaminetriacetic acid, trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol- bis(P-aminoethyl ether) -N,N,N',N' -tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, and a combination of two or more thereof.

30. The extractant composition according to one of claim 24 to claim 29, wherein the pH of the extractant composition is about 4 or less, optionally about 3 or less, about 2.5 or less, or about 2 or less, and wherein the chelating agent is stable over a period of at least 3 months.

31. The extractant composition according to one of claim 24 to claim 30, wherein the strong acid comprises nitric acid, hydrochloric acid, or a combination thereof.

32. The extractant composition according to one of claim 24 to claim 31, wherein extractant composition is substantially free or free of a weak Bronsted-Lowry and / or a salt thereof.

33. The extractant composition according to one of claim 24 to claim 32, wherein the metal is selected from an elemental metal, a metal ion, and a combination of two or more thereof.

34. The extractant composition according to one of claim 24 to claim 33, wherein the metal is selected from lithium, rhodium, thallium, indium, and a combination of two or more thereof.

35. The extractant composition according to one of claim 24 to claim 34, wherein the metal comprises lithium, indium, or a combination of two or more thereof.

36. The extractant composition according to one of claim 24 to claim 35, wherein the chelating agent is stable over a period of at least 3 months.

37. The extractant composition according to one of claim 24 to claim 36, wherein the chelating agent is stable over a period of at least 6 months.

38. The extractant composition according to one of claim 24 to claim 37, wherein the extraction composition is substantially free of or free of DTPA.

39. The extractant composition according to one of claim 24 to claim 38, wherein the extraction composition is substantially free of or free of EDTA.

40. The extractant composition according to one of claim 24 to claim 39, wherein the extraction composition is substantially free of or free of acetic acid and / or a salt thereof.

41. The extractant composition according to one of claim 24 to claim 40 comprising a fluoride source is selected from ammonium fluoride, sodium fluoride, potassium fluoride, hydrogen fluoride, zinc fluoride, lithium fluoride, and a combination of two or more thereof.

42. The extractant composition according to claim 41 , wherein the fluoride source comprises ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride, or a combination of two or more thereof.

43. an extractant composition comprising: one or more acid comprising hydrochloric acid, nitric acid, citric acid, or a combination of two or more thereof; a chelating agent; a metal; optionally, an exchangeable salt extractant; and optionally, a fluoride source, wherein the extractant composition has a pH of about 2 or less and the chelating agent is stable over a period of at least 3 months.

44. The extractant composition according to claim 43 comprising an exchangeable salt extractant selected from ammonium nitrate, ammonium fluoride, calcium chloride, Sikora buffer, BaCb, SrCh, LiCl, and a combination of two or more thereof.

45. The extractant composition according to claim 44, wherein the exchangeable salt extractant comprises ammonium nitrate.

46. The extractant composition according to claim 44 or claim 45, wherein the molar concentration of exchangeable salt extractant is from about 0.2 to about 3.6 M.

47. The extractant composition according to one of claim 43 to claim 46, wherein the one or more acid comprises nitric acid, citric acid, or a combination of two or more thereof.

48. The extractant composition according to one of claim 43 to claim 47, wherein the one or more acid is present in a molar concentration from about 0.03 to about 0.4 M.

49. The extractant composition according to one of claim 43 to claim 48, wherein the extractant composition is substantially free or free of weak Bronsted-Lowry acids.

50. The extractant composition according to one of claim 43 to claim 48, wherein the one or more acid consists of strong Bronsted-Lowry acids.

51. The extractant composition according to one of claim 43 to claim 50, wherein the metal is selected from an elemental metal, a metal ion, and a combination of two or more thereof.

52. The extractant composition according to one of claim 43 to claim 51, wherein the metal is selected from lithium, rhodium, thallium, indium, and a combination of two or more thereof.

53. The extractant composition according to one of claim 43 to claim 52, wherein the metal comprises lithium, indium, or a combination of two or more thereof.

54. The extractant composition according to one of claim 43 to claim 53, wherein the metal is present in a molar concentration from about 5 ppm to about 2500 ppm.

55. The extractant composition according to one of claim 43 to claim 54, wherein the chelating agent is stable over a period of at least 3 months.

56. The extractant composition according to one of claim 43 to claim 55, wherein the chelating agent is stable over a period of at least 6 months.

57. The extractant composition according to one of claim 43 to claim 56, wherein the chelating agent comprises hydroxy ethylethylenediaminetriacetic acid (HEDTA), trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol-bis(P-aminoethyl ether)-N,N,N',N'-tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, ethylenediaminetetraacetic acid (EDTA), monosodium EDTA, EDTA disodiumsalt, tetrasodium EDTA, or a combination of two or more thereof.

58. The extractant composition according to one of claim 43 to claim 57, wherein the chelating agent is selected from hydroxyethylethylenediaminetriacetic acid, trisodium HEDTA, tripotassium HEDTA, trisodium HEDTA monohydrate, disodium HEDTA, ethylene glycol- bis(P-aminoethyl ether) -N,N,N',N' -tetraacetic acid and / or a salt thereof, di ethylenetriaminepentaacetic acid and / or a salt thereof, and a combination of two or more thereof.

59. The extractant composition according to one of claim 43 to claim 59, wherein the chelating agent is present in a molar concentration from about 0.001 to about 0.03 M.

60. The extractant composition according to one of claim 43 to claim 59, wherein the extraction composition is substantially free of or free of DTPA.

61. The extractant composition according to one of claim 43 to claim 60, wherein the extraction composition is substantially free of or free of EDTA.

62. The extractant composition according to one of claim 43 to claim 61, wherein the extraction composition is substantially free of or free of acetic acid and / or a salt thereof.

63. The extractant composition according to one of claim 43 to claim 62 comprising a fluoride source is selected from ammonium fluoride, sodium fluoride, potassium fluoride, hydrogen fluoride, zinc fluoride, lithium fluoride, and a combination of two or more thereof.

64. The extractant composition according to claim 63, wherein the fluoride source comprises ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride, or a combination of two or more thereof.

65. The extractant composition according to any one of claims 43 to 64 further comprising a flocculating agent.

66. The extractant composition according to claim 65, wherein the flocculating agent comprising polyacrylamide in an amount from about 0.005 to about 0.2 wt.%.

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