Monoterpenoid and diterpenoid-based herbicidal composition

Abstract

An herbicidal composition can include about 40 wt. % to about 90 wt. % monocyclic monoterpenoids; about 0.1 wt. % to about 6.0 wt. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate and a remainder of the aqueous solution being water; and a remainder of the herbicidal composition including diterpenoids, wherein the herbicidal composition is a gel.

Description

MONOTERPENOID AND DITERPENOID-BASED HERBICIDAL COMPOSITIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims the benefit of and priority to United States Provisional Application No. 63 / 521,799, filed on June 19, 2023, the contents of which are hereby incorporated by reference in their entirety.BACKGROUND

[0002] Terpenes are major biosynthetic building blocks. Terpenes and terpenoids are also the primary constituents of the essential oils of many types of plants and flowers and play a role in plant defense against herbivory as disease resistance.

[0003] For example, US Patent 6,759,370 to Innes may disclose an herbicidal combination of monoterpene alcohols and fatty acid soaps, where the fatty acid soap may be derived from the reaction of a tall oil fatty acid (TOFA) with an alkali. Initially, Innes may have believed that the added fatty acid soap enhanced the effect of the primary active components and / or acted as an active component to disrupt plant function. However, in use, the soap bubbles may slide off the plant leaves and / or evaporate quickly.

[0004] Published PCT Application W02008 / 120095 to Innes and Johnson may disclose an herbicide mixture comprising a-terpineol and TOFA and a method for applying the herbicide over the soil for more than 10 minutes, which has the effect of disrupting plant function to a greater degree than the formulation of the earlier Innes patent. Specifically, Innes & Johnson discovered that the herbicidal activity of the pine oil may be due to the a-terpineol fraction only. The TOFA may act as a surfactant and is applied at 20% concentration in 80% water.

[0005] In the case of both Innes and the later Innes & Johnson references, the pine oil used was derived from sulfate wood turpentine that was obtained by condensation of the vapors during the cook in the Kraft (Sulphate) Pulping Process for producing paper.

[0006] Published PCT Application WO2020 / 257858 to Frith discusses the presence of impurities in pine oil derived via the Kraft process and the belief that these impurities could be minimized, thereby producing an improved end product. What was not understood at the time was that theTOFA used in the mix was also derived via the Kraft process, and this caused various impurities in the final product.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The foregoing and other objects, features, and advantages of the disclosure will be apparent from the following description of particular implementations of the disclosure, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the disclosure.

[0008] FIG. 1 is a gas chromatograph results of a sample of gum rosin lights;

[0009] FIG. 2 is graph of germination test results for various dilutions of the disclosed herbicidal composition;

[0010] FIG. 3 is a gray-scale photograph of a weed test site prior to application of the disclosed herbicidal composition; and

[0011] FIG. 4 is a gray-scale photograph of the weed test site of FIG. 3 after application of the disclosed herbicidal composition.DETAILED DESCRIPTION

[0012] According to an aspect of the disclosure, an herbicidal composition can include: about 40 wt. % to about 90 wt. % monocyclic monoterpenoids; and about 0.1 wt. % to about 6.0 wt. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with a remainder of the aqueous solution being water; and a remainder of the herbicidal composition being diterpenoids, so that the herbicidal composition is a gel.

[0013] In an implementation, the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate of the herbicidal composition can be included in the herbicidal composition in anamount of about 0.1 wt. % to about 6.0 wt. %, or about 0.1 wt. % to about 5.0 wt. %, or about 0.1 wt. % to about 4.0 wt. %, or about 0.1 wt. % to about 3.0 wt. %, or about 0.1 wt. % to about 2.0 wt. %, or about 0.1 wt. % to about 1.8 wt. %, or about 0.3 wt. % to about 6.0 wt. %, or about 0.5 wt. % to about 6.0 wt. %, or about 0.7 wt. % to about 6.0 wt. %, or about 0.9 wt. % to about 6.0 wt. %, or about 1.1 wt. % to about 6.0 wt. %, or about 1.3 wt. % to about 6.0 wt. %, or about 1.5 wt. % to about 6.0 wt. %, or about 0.3 wt. % to about 5.0 wt. %, or about 0.5 wt. % to about 4.5 wt. %, or about 0.7 wt. % to about 4.0 wt. %, or about 0.9 wt. % to about 3.5 wt. %, or about 1.1 wt. % to about 3.0 wt. %, or about 1.3 wt. % to about 2.5 wt. %, or about 1.5 wt. % to about 2.0 wt. %.

[0014] In an implementation, the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate can include greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with the remainder being water.

[0015] In an implementation, the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate can include about 10 vol. % water and about 90 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate (e.g., about 1 part water to about 9 parts of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume) to about 60 vol. % water and about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate (e.g., about 3 parts water to about 2 parts of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume).

[0016] In an implementation, the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate can include about 20 vol. % water and about 80 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate(e.g., 1 part water to 4 parts of the at least one of the alkali metalhydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume) to about 60 vol. % water and about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate(e.g., about 3 parts water to about 2 parts of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume).

[0017] In an implementation, the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate can include about 30 vol. % water and about 70 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate(e.g., 3 parts water to 7 parts of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume) to about 60 vol. % water and about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate(e.g., about 3 parts water to about 2 parts of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume).

[0018] In an implementation, the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate can include about 40 vol. % water and about 60 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate(e.g., 2 parts water to 3 parts of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume) to about 60 vol. % water and about 40 vol. % sodium hydroxide (e.g., about 3 parts water to about 2 parts of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate by volume).

[0019] In an implementation, the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate can include about 40 vol. %, or about 45 vol. %, or about 50 vol. %, or about 55 vol. %, or about 60 vol. % of the at least one of the alkali metal hydroxide, the alkaline earthmetal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with the remainder being water.

[0020] As disclosed herein, the at least one of the alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal acetate, and alkaline earth metal acetate can include, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (CaOH), magnesium hydroxide (MgOH), sodium acetate (NaCzHaOz), potassium acetate (KC2H3O2), calcium acetate (CaC2H3O2), and magnesium acetate (MgC2H3O2).

[0021] In an implementation, the at least one of the alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal acetate, and alkaline earth metal acetate can be an alkali metal hydroxide (e.g., Group 1 metal hydroxide) such as at least one of NaOH and KOH.

[0022] In an implementation, the alkali metal hydroxide can be NaOH which may be a beneficial option for plants.

[0023] In an implementation, the at least one of the alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal acetate, and alkaline earth metal acetate can be an alkali earth metal hydroxide (e.g., Group 2 metal hydroxide) such as at least one of CaOH and MgOH.

[0024] In an implementation, the at least one of the alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal acetate, and alkaline earth metal acetate can be an alkali metal acetate (e.g., Group 1 metal acetate) such as at least one of NaC2H3O2 and KC2H3O2.

[0025] In an implementation, the at least one of the alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal acetate, and alkaline earth metal acetate can be an alkali earth metal acetate (e.g., Group 2 metal acetate) such as at least one of CaC2H3O2 and MgC2H3O2.

[0026] According to an aspect of the disclosure, an herbicidal composition can include: about 0.1 wt. % to about 20 wt. % of a surfactant; and a remainder being at least one of a monocyclic monoterpenoid and a diterpenoid, wherein the herbicidal composition is a liquid.

[0027] In an implementation, the herbicidal composition can include: about 0.1 wt. % to about 10 wt. % of a polysorbate; about 0.1 wt. % to about 10 wt % decyl -glucoside; anda remainder being at least one of a monocyclic monoterpenoid and a diterpenoid, wherein the herbicidal composition is a liquid.

[0028] In an implementation, the herbicidal composition can include: about 10 wt. % of at least one of a polysorbate and decyl -glucoside; about 70 wt. % monocyclic monoterpenoids; and about 20 wt. % of a diterpenoid, wherein the herbicidal composition is a liquid.

[0029] In an implementation, the herbicidal composition can include: about 6.5 wt. % of the a polysorbate; about 3.5 wt. % decyl-glucoside; about 70 wt. % monocyclic monoterpenoids; and about 20 wt. % of a diterpenoid, wherein the herbicidal composition is a liquid.

[0030] In an implementation, the herbicidal composition can include: about 0.1 wt. % to about 20 wt. % of a surfactant; about 0.1 wt. % to about 10 wt % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with a remainder of the aqueous solution being water; and a remainder being at least one of a monocyclic monoterpenoid and a diterpenoid, wherein the herbicidal composition is a liquid.

[0031] According to an aspect of the disclosure, an herbicidal composition can include: greater than or equal to about 60 wt % a-terpineol; and a remainder including at least one of a surfactant and gum rosin lights.

[0032] In an implementation, the remainder can further include about 0.1 wt. % to about 10 wt. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition ofgreater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with a remainder of the aqueous solution being water.

[0033] In an implementation, the a-terpineol can be included in at least one of monocyclic monoterpenoids and diterpenoids.

[0034] In an implementation, the diterpenoids as referred to herein, can be gum rosin lights.

[0035] In an implementation, the diterpenoids can include dehydroabietic acid, abietic acid, and / or isomers thereof. For example, the diterpenoids can include abietic acid (e.g., having molecular formula C20H30O2, corresponding molecular mass of about 302 grams / mole (g / mol), International Union of Pure and Applied Chemistry (IUPAC) name abieta-7,13-dien-l 8-oic acid, and Chemical Abstracts Services (CAS) No. 514-10-3).

[0036] In an implementation, the monocyclic monoterpenoids can be oxygenated terpenes.

[0037] In an implementation, oxygenated terpenes can include isomers of terpineol, for example, a-terpineol, P-terpineol, y-terpineol, and / or 4-terpineol.

[0038] In an implementation, the monocyclic mono terpenoids can include pine oil including 15 wt. % terpene hydrocarbons and 85 wt. % terpenoids of which 70% can be monocyclic terpenoids, e.g., monocyclic monoterpenoids such as terpineol and / or isomers thereof (e.g., including a-terpineol, P-terpineol, y-terpineol, and / or 4-terpineol).

[0039] In an implementation, the monocyclic monoterpenoids can be EL Pinol 85 (e.g., a product of T&R Chemicals Inc.).

[0040] In an implementation, the monocyclic monoterpenoids can include pine oil containing greater than or equal to about 55 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

[0041] In an implementation, the pine oil can be formulated with a high purity terpineol composition, such as a composition that contains over 95 wt. % or even over 98 wt. % terpineol. It was surprisingly found that high purity terpineol (e.g., containing over 95 wt. % a-terpineol) had surprising activity as a herbicide. In comparison to pine oil alone, the activity of herbicides having high purity terpineol was found to be up to about 10 times more active.

[0042] In an implementation, the monocyclic monoterpenoids can include a-terpineol (e.g., having molecular formula CioHisO, corresponding molecular mass of about 154 g / mol, IUPAC name p-menth-l-en-8-ol, and CAS No. 98-55-5).

[0043] The surfactant can include a non-ionic surfactant such as a polysorbate. The polysorbate can include at least one of polysorbate 20, polysorbate 40, polysorbate 60, and polysorbate 80 where the number indicates the type of major fatty acid associated with the molecule (e.g., monolaurate is indicated by 20, monopalmitate is indicated by 40, monostearate by 60, and monooleate by 80).

[0044] In an implementation, the surfactant can include polysorbate 20 (e.g., having chemical formula C58H114O26 and corresponding molecular mass of about 1228 g / mol, IUPAC name polyoxyethylene (20) sorbitan monolaurate, and CAS No. 9005-64-5).

[0045] In an implementation, the surfactant can include polysorbate 40 (e.g., having chemical formula C62H122O26 and corresponding molecular mass of about 1284 g / mol, IUPAC name polyoxyethylene (20) sorbitan monopalmitate, and CAS No. 9005-66-7).

[0046] In an implementation, the surfactant can include polysorbate 60 (e.g., having chemical formula C64H126O26 and corresponding molecular mass of about 1312 g / mol, IUPAC name Polyoxyethylene (20) sorbitan monostearate, and CAS No. 9005-67-8).

[0047] In an implementation, the surfactant can include polysorbate 80 (e.g., having chemical formula C64H124O26 and corresponding molecular mass of about 1310 g / mol, IUPAC name Polyoxyethylene (80) sorbitan monooleate, and CAS No. 9005-65-6).

[0048] In an implementation, the herbicidal composition can include about 70 wt. % pine oil, about 20 wt. % gum rosin lights, about 10 wt. % polysorbate 80 and can be a liquid.

[0049] In an implementation, the herbicidal composition can include about 60 wt. % pine oil, about 37 wt. % gum rosin lights, about 3 wt. % polysorbate 80 and can be liquid.

[0050] In an implementation, the herbicidal composition can include about 37 wt. % gum rosin light, about 70 wt. % pine oil, and about 3 wt. % polysorbate 80 and can have a density of about 9,556 grams per cubic centimeter (g / cm3).

[0051] In an implementation, the herbicidal composition can include about 70 wt. % pine oil, about 20 wt. % gum rosin lights, about 6.5 wt. % polysorbate 80, about 3.5 wt. % decylglucoside, and can be a liquid.

[0052] In an implementation, the herbicidal composition can include about 90 wt. % pine oil, about 10 wt. % polysorbate 80, and can be a liquid.

[0053] In an implementation, the herbicidal composition can include about 90 wt. % pine oil, about 5 wt. % gum rosin lights, about 5 wt. % of at least one of polysorbate 80 and decylglucoside, and can be a liquid.

[0054] In an implementation, the herbicidal composition can include about 90 wt. % pine oil, about 5 wt. % gum rosin lights, about 3 wt. % polysorbate 80, about 2 wt. % decyl-glucoside and can be a liquid.

[0055] The herein described liquid herbicidal compositions can be homogeneous liquids which may be miscible in water up to a composition of about 10 vol. % of the herbicidal composition and about 90 vol. % water.

[0056] It has further been found that the liquid herbicidal compositions described herein can have insecticidal activity. Specifically, for use as an insecticide, the described herbicidal compositions can be diluted from about 60 vol % of the herbicidal composition and about 40 vol. % water, to about 1 vol. % herbicidal composition and about 99 vol. % water.

[0057] Additionally, it has been found that the portion of monocyclic monoterpenoids can be reduced to between about 2 wt. % and about 50 wt. %, or between about 2 wt. % and about 40 wt. %, or between about 3 wt. % and about 40 wt. %, without negatively affecting the insecticidal activity of the composition. For example, a reduced monocyclic monoterpenoid composition having insecticidal activity can include about 2 wt. % to about 40 wt. % monocyclic monoterpenoids, up to about 20 wt. % surfactant (e.g., a polysorbate as described herein), and a remainder being water.

[0058] More specifically, the insecticidal composition can include 2 wt. % to about 40 wt. % monocyclic mono terpenoids, up to about 20 wt. % surfactant (e.g., a polysorbate as described herein), between about 2 wt. % to about 10 wt. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkalineearth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with a remainder of the aqueous solution being water, and a remainder being water. In an implementation, in the insecticidal composition, the aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate can be an aqueous solution of potassium hydroxide.

[0059] The monocyclic monoterpenoids can include any source of monocyclic monoterpenoids having sufficiently high monocyclic terpenoid concentration. For example, pine oil may be used when the monocyclic terpenoid concentration is greater than or equal to about 70 wt. %. A source of pine oil can include crude sulfate turpentine (CST), derived from crude tall oil (CTO). However, CST and CTO include cellulose, hemicellulose, lignin, and / or sulfonated products. Another source of pine oil can include wood turpentine. Wood turpentine is derived from wood resin which is extracted from pine stumps using a solvent. The solvent residue in wood turpentine is removed using a steam distillation process. Alternatively, pine oil can be derived from gum turpentine. In this case, the obtained pine oil can be free of cellulose, hemicellulose, lignin, and sulfonated products. Gum turpentine is obtained from distilling the oleoresin collected by hand-tapping pine trees. Gum turpentine differs from CST in that the later comes from pulping mills utilizing the Kraft process to convert pulverized plant material into pulp for paper products and consequently can include aforementioned cellulose, hemicellulose, lignin, and / or sulfonated products (due at least in part to the use of sodium sulfide (NazS) in the Kraft process to break down the pulverized plant material). Hydrolysis of a-pinene can produce the monocyclic mono terpenoid a- terpineol.

[0060] CTO is typically recovered as a crude distillate and then separated into different fractions through tower distillation. Unfractionated CTO or even its derivative CST are not suitable sources of a-terpineol for the herbicidal composition disclosed herein because they include sulphonated products from the Kraft process which can reduce the efficacy of the herbicidal composition by their interaction with other components of the herbicidal composition and / or the herbicidal target.

[0061] The diterpenoids can include gum rosin lights (e.g., CAS No. 8050-09-7). Gum rosin lights are a colophony pine resin, that is, one of the residues left after the distillation of turpentine oil from liquid resin.

[0062] Three different streams can be obtained from such a distillation a heavy stream at the bottom (commonly referred to as “pitch” or “heavies”), a medium stream which is the distilled rosin, and the lighter stream (taken from the top of the distillation column), which is gum rosin lights. As a result, the gum rosin lights can include lighter molecules (e.g., having lower boiling point temperatures than molecules concentrated in the lower portions of the distillation column). Gum rosin lights can include abietic acid isomers and / or tautomers thereof. For example, gum rosin lights can include about 68 wt. % to about 70 wt. % abietic acid isomers and / or tautomers and about 30 wt. % to about 32 wt. % pinenes and / or isomers thereof (e.g., (lR)-(+)-a-pinene, (lS)-(-)-a-pinene, (lR)-(+)-P-pinene, and / or (IS)-(-)-P-pinene). Gum rosin lights, being a derivative of a pine tree oleoresin can contain numerous compounds. The main constituents of gum rosin lights are further described in the following.

[0063] In this way, the diterpenoids such as gum rosin lights derived from gum rosin can have no lignin, no cellulose, no hemicellulose, no sulfonated products, an average molecular mass of about 145 grams / mole to about 148 grams / mole, molecules having a molecular mass range of about 136 grams / mole to about 155 grams / mole, and / or molecules having boiling points that range of about 170 °C to about 217 °C, or a combination including at least one of the foregoing.

[0064] For example, the diterpenoids such as gum rosin lights derived from gum rosin can consist of no lignin, no cellulose, no hemicellulose, no sulfonated products, an average molecular mass of about 145 grams / mole to about 148 grams / mole, molecules having a molecular mass range of about 136 grams / mole to about 155 grams / mole, and / or molecules having boiling points that range of about 170 °C to about 217 °C, or a combination including at least one of the foregoing.

[0065] For example, based on analysis using gas chromatography as shown in gas chromatography results of FIG. 1, gum rosin lights can include: about 1.5 vol. % a-pinene (e.g., having a boiling point of about 155 °C, chemical formula CioHie, IUPAC name (lS,5S)-2,6,6-Trimethylbicyclo[3.1.1]hept-2-ene ((-)-a-Pinene), and CAS Nos. 80-56-8, 7785-70-8 ((+)-enantiomer), 7785-26-4 ((-)-enantiomer));about 0.2 vol. % camphene and / or isomers thereof (e.g., having a boiling point of about 159 °C, chemical formula C10H16, IUPAC name 2,2-Dimethyl-3- methylidenebicyclo[2.2.1]heptane, and CAS Nos. 79-92-5, 5794-03-6 ((+)-enantiomer), 5794- 04-7 ((-)-enantiomer); about 0.8 vol. % carene and / or isomers thereof (e.g., 3-carene having a boiling point of about 170 °C to about 172 °C, chemical formula C10H16, IUPAC name 3,7,7- Trimethylbicyclo[4.1.0]hept-3-ene, and CAS No. 13466-78-9); about 1.2 vol. % limonene and / or isomers thereof (e.g., having a boiling point of about 176 °C, chemical formula C10H16, IUPAC name l-Methyl-4-(prop-l-en-2-yl)cyclohex-l-ene, and CAS Nos. 138-86-3, 5989-27-5 ((+)-limonene), and / or 5989-54-8 (S -limonene)); about 6 vol. % terpineol and / or isomers thereof (e.g., having a boiling point of about 214 °C to about 217 °C, chemical formula CioHisO, IUPAC names p-Menth-l-en-8-ol (a-terpineol), p-Menth-8-en-l-ol (P-terpineol), p-Menth-4(8)-en-l-ol (y-terpineol), p-Menth-l-en-4-ol (4- terpineol), and CAS Nos. 98-55-5 (a-terpineol), 138-87-4 (P-terpineol), 586-81-2 (y-terpineol), 562-74-3 (4-terpineol)); about 87 vol. % rosin acids (e.g., which can include about 1.7 vol. % pimaric acid, about 4.5 vol. % isopimaric acid, about 3.7 vol. % palustric acid, about 2.1 vol. % dehydroabietic acid, about 9.5 vol. % abietic acid, about 1.5 vol. % neoabietic acid); and about 3.3 vol. % of unidentified organic compounds.

[0066] TABLE 1 - Gas Chromatography Results of FIG. 1

[0067] It is noted that unidentified components in the gas chromatograph results of FIG. 1 and TABLE 1 are components having no standard available at the time of the gas analysis.

[0068] In contrast, CST and TOFA, derivatives of CTO, are derived from the Kraft process. The Kraft process involves conversion of pulverized plant material (e.g., such as wood chips from stumps, bark, and the like) into wood pulp. In the Kraft process, the pulverized plant material is combined with a mixture of hot water, sodium hydroxide, and sodium sulfide, known as white liquor, to break the bonds that link lignin, hemicellulose, and cellulose. The combined material is cooked in digesters where a byproduct known as black liquor is further refined to produce CTO, which in itself through additional distillation and processes derives CST, TOFA, and tail-oil rosin (TOR), all of which contain at least residual quantities of lignin, hemicellulose, cellulose, and / or sulphonated products.

[0069] The monocyclic monoterpenoids can include pine oil having a high-purity terpineol composition, for example, a pine oil that has a composition that is greater than or equal to about 85 wt. %, or greater than or equal to about 95 wt. %, or greater than or equal to 98 wt. %, terpineol and / or isomers thereof including a-terpineol, P-terpineol, y-terpineol, and / or 4- terpineol. For example, the monocyclic monoterpenoids can include El Pinol 85 a product of T&R Chemicals Inc. (e.g., having a boiling point of about 153 °C to about 175 °C and CAS No. 8002-09-3) containing greater than or equal to about 85 wt. % terpineol and / or isomers thereof and related terpene alcohols. This formulation can induce a rapid and exponential wilting effect on plants.

[0070] For example, based on analysis using gas chromatography, monocyclic monoterpenoids (e.g., such as pine oil) can include: about 1 vol. % to about 2 vol. % a-pinene; about 0.01 vol. % to about 0.5 vol. % camphene and / or isomers thereof (e.g., having a boiling point of about 159 °C, chemical formula CioHie, IUPAC name 2,2-Dimethyl-3- methylidenebicyclo[2.2.1]heptane, and CAS Nos. 79-92-5, 5794-03-6 ((+)-enantiomer), 5794- 04-7 ((-)-enantiomer);about 0.01 vol. % to about 0.5 vol. % P-pinene (e.g., having a boiling point of about 165 °C to about 167 °C, chemical formula CioHie, IUPAC name 6,6-Dimethyl-2- methylidenebicyclo[3.1.1]heptane, and CAS Nos. 127-91-3); about 2.0 vol. % to about 4.0 vol. % carene and / or isomers thereof (e.g., 3-carene having a boiling point of about 170 °C to about 172 °C, chemical formula CioHie, IUPAC name 3,7,7- Trimethylbicyclo[4.1.0]hept-3-ene, and CAS No. 13466-78-9); about 3.0 vol. % to about 6.0 vol. % limonene and / or isomers thereof (e.g., having a boiling point of about 176 °C, chemical formula CioHie, IUPAC name l-Methyl-4-(prop-l-en-2- yl)cyclohex-l-ene, and CAS Nos. 138-86-3, 5989-27-5 ((+)-limonene), and / or 5989-54-8 (S- limonene)); about 6.0 vol. % to about 8.5 vol. % terpinene and / or isomers thereof (e.g., having a boiling point of about 173 °C to about 183 °C, chemical formula CioHie, IUPAC names 4- Methyl- 1 -( 1 -methylethyl)- 1 ,3 -cyclohexadiene (a-terpinene), 4-Methylene- 1 -( 1 - methylethyl)cyclohexene (P- terpinene), 4-Methyl-l-(l -methylethyl)- 1 ,4-cyclohexadiene (y- terpinene), l-Methyl-4-(propan-2-ylidene)cyclohex-l-ene (8-terpinene), and CAS Nos. 99-86-5 (a-terpinene), 99-84-3 (P-terpinene), 99-85-4 (y- terpinene), 586-62-9 (8-terpinene)); about 15 vol. % to about 20 vol. % CioHie alcohols (e.g., myrtenol, pinocarveol, and the like); and about 60 vol. % to about 75 vol. % terpineol and / or isomers thereof (e.g., having a boiling point of about 214 °C to about 217 °C, chemical formula CioHisO, IUPAC names p- Menth-l-en-8-ol (a-terpineol), p-Menth-8-en-l-ol (P-terpineol), p-Menth-4(8)-en-l-ol (y- terpineol), p-Menth-l-en-4-ol (4-terpineol), and CAS Nos. 98-55-5 (a-terpineol), 138-87-4 (P- terpineol), 586-81-2 (y- terpineol), 562-74-3 (4-terpineol)).

[0071] Based on additional analysis using gas chromatography, other components of monocyclic monoterpenoids (e.g., such as pine oil) can include: up to about 0.6 vol. % para-cymene (e.g., having IUPAC name: 1 -Methyl -4-(propan-2- yl)benzene); andup to about 2.0 vol. % isoborneol and / or isomers thereof (e.g., having IUPAC names (lS,2S,4S)-l,7,7-trimethylbicyclo[2.2.1]heptane-2-ol, and (1R,2R,4R)-1,7,7- trimethylbicyclo[2.2.1 ]heptane-2-ol).

[0072] It was surprisingly found that the gum rosin lights produce improved herbicidal activity when combined with the pine oil in the herbicidal composition. Specifically, while the gum rosin lights were initially selected as a potential adhesive agent for the herbicide composition, that is, to effectively “adhere (e.g., a surfactant function) the pine oil to the herbicidal target (e.g., the target plant (e.g., leaf and / or stem of the plant), target seed, or target soil), the improved surfactant qualities of gum rosin lights reduced application dilution rates of the herbicidal composition (e.g., less herbicidal composition could be used in diluted herbicidal compositions before application of the diluted herbicidal composition to plants, soil, and / or seeds) compared to pine oil formulations derived from CST without impacting the effectiveness of the herbicidal composition as an herbicide. This can be a result of the amount of time that the herbicidal composition remains on the plant.

[0073] The gum rosin lights may be more soluble in water (e.g., than TOFA) so that a relatively small amount of an alkali metal hydroxide (e.g., sodium hydroxide) in the herbicidal composition may produce a liquid formulation in comparison to formulations using TOFA. For example, the herbicidal composition containing less than or equal to about 6 vol. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate (e.g., an aqueous solution of sodium hydroxide) having a composition of about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate and the remainder of the aqueous solution being water (e.g., an aqueous solution of sodium hydroxide having a composition of about 40 vol. % sodium hydroxide and a remainder of the aqueous solution being water) can result in a liquid phase (e.g., a single homogenous liquid phase). Whereas, similar amounts of aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate in herbicidal compositions based on CST and TOFA fractions can result in liquid / solid separation (e.g., such as formation of an immiscible soap layer on the top of the liquid).

[0074] It was further discovered that a higher concentration of sodium hydroxide in the aqueous solution of sodium hydroxide resulted in the herbicidal composition becoming a gel or gel -like substance. For example, with an aqueous solution of sodium hydroxide having a sodium hydroxide composition of greater than or equal to about 40 vol. %, or about 45 vol. %, or about 50 vol. %, or about 55 vol. %, or about 60 vol. %, or about 65 vol. %, or about 70 vol. %, or about 75 vol. %, or about 80 vol. %, or about 85 vol. %, or about 90 vol. %, or about 95 vol. %, with the remainder being water, the herbicidal composition can take on gel (or gel-like) physical properties.

[0075] While not wishing to be bound to a particular theory or hypothesis, it is believed that terpenoid compounds containing oxygen moieties, such as alcohols, ketones, and carboxylic acids, provide herbicidal activity.

[0076] While not wishing to be bound to a particular theory or hypothesis, it is believed that the monocyclic monoterpene alcohols may penetrate the lipid bilayers of plant cells and interfere with or inhibit proton pump activity. Similarly, it is believed that the diterpenoids may penetrate the plant cell in a similar way.

[0077] Furthermore, it was found that the disclosed amount of the alkali metal hydroxide (e.g., such as sodium hydroxide) was sufficient to activate surfactant properties of the gum rosin lights. In this way, the herbicidal composition can be free of additional surfactants. Accordingly, the herbicidal composition may be almost entirely pine chemical derived (e.g., composed almost entirely of pine chemical derivatives).

[0078] Experiments with the disclosed herbicidal composition showed that the time it took for a plant to wilt after the application of a 20 vol. % herbicide and 80 vol. % water solution was significantly decreased when a high-purity terpineol solution was used as the source of monocyclic monoterpenoids in comparison to when an El Pinol 85% pine oil solution was used. Specifically, the wilting of leaves and discoloration of the plant occurred almost immediately after application with the high-purity terpineol solution, whereas it took hours for the same effect to be observed with the El Pinol 85% pine oil solution.

[0079] Based on this observation, the percentage increase in the relative concentration of monoterpenoids may be responsible for the accelerated herbicidal activity. In other words, higher concentration of monocyclic monoterpenoids, which was achieved with the high-purity terpineolsolution, resulted in a faster and more pronounced herbicidal effect on the plants compared to pine oil solutions having lower terpineol compositions. The results suggest that the purity and concentration of the terpineol solution used can have a significant impact on the effectiveness and speed of the herbicidal activity on plants. Accordingly, by knowing the veracity or vigor of a specific target plant, target seed, and / or soil formulations can be tailored to deliver sufficient activity to eradicate without delivering excess herbicide.EXPERIMENTAL RESULTS

[0080] Amaranthus palmeri weed seed germination was significantly (p<0.05) reduced by treatment with the herbicidal composition. In the experiment, twenty seeds of Amaranthus palmeri were placed onto petri dishes with the bottom covered with a double layer of muslin cloth moistened with 25 milliliters (mL) of sterile water. The seeds were then sprayed with a bottle sprayer with about 10 mL solution of one of water, glyphosate, or one of three different solutions of an herbicidal composition at dilutions in water as shown in Table 2. In this experiment, the herbicidal composition included about 20 wt. % gum rosin lights; about 70 wt. % El Pinol 85; and about 10 wt. % polysorbate 80. Germination of the seeds in each cloth was observed on the 4th, 6th, 8th, 10th, 12th, and 14thday after treatment application. The number of germinated seeds were counted during each observation and the percent germination was calculated based on the observations. The precent germination is presented in FIG. 2. It is noted that “DA-A” shown in FIG. 2 refers to days after application.

[0081] TABLE 2 - Seed Germination Study

[0082] As can be seen in FIG. 2, with all treatments of the diluted herbicidal composition the germination rates of the Amaranthus palmeri seeds was inhibited. Furthermore, less germination was observed for seeds treated with the disclosed herbicidal composition in comparison to seedstreated with glyphosate. Partial germination was captured with a decimal value to reflect the amount of germination that had occurred. At the 5% herbicidal dilution one of the twenty seeds partially germinated (about 30% germination) by the 10thday. At the 10% and 20% herbicidal dilution, none of the seeds germinated. In comparison, about 10 of the seeds germinated by the 10thday for the control sample (treated only with water). For the glyphosate treated seeds, one seed partially germinated (about 50% germination) by the 8thday.

[0083] FIG. 3 is a gray-scale photograph of a plot having numerous post emergent weeds growing before application of any treatment. The areas 100 show healthy, living weeds in various locations of the plot.

[0084] FIG. 4 is a gray-scale photograph of the plot of FIG. 10 twenty -four hours after treatment with a diluted herbicidal composition. In this experiment, the herbicidal composition included about 20 wt. % gum rosin lights; about 70 wt. % El Pinol 85; and about 10 wt. % polysorbate 80. The diluted herbicidal composition included 15 vol. % of the herbicidal composition and 85 vol. % water. The treatment was uniformly sprayed onto the plot with coverage of about 50 mL per square meter. As can be seen in FIG. 4, after application of the diluted herbicidal treatment, weeds in areas 110 are wilted and dying. The areas 110 correspond to the areas 100 in FIG. 3 and show that the weeds have yellowed (e.g., as indicated in the gray-scale by lightened tone) and have wilted and / or dried out (e.g., as indicated by curled leaves). As can be seen in the before (FIG. 3) and after (FIG. 4) photographs, the herbicidal treatment has had significant herbicidal effect within twenty-four hours of application.

[0085] TABLE 3 - Viscosity Observations

[0086] With reference to Table 3, it was found that by increasing the concentration of the sodium hydroxide, it was possible to produce a gel / gel-like product having a higher viscosity in comparison to a liquid formulation. For example, the viscosity of the herbicidal composition increased and no crystallization was observed when about 30 / 70 vol. % NaOH / water solution was used in the herbicidal composition. However, when the alkali metal hydroxide concentration was increased, for example, to about 50 / 50 vol. % NaOH / water solution to about 60 / 40 vol. % NaOH / water solution the herbicidal composition exhibited a gel / gel-like consistency.

[0087] The gel / gel-like herbicidal composition can be applied directly to plant leaves / stem and adhere to the surface of the leaves / stem, thus retaining the active ingredient(s) on the plant for a longer duration. The gel / gel-like product, due at least in part to their higher viscosity in comparison to liquid formulations, can remain on the plant for a longer period of time (e.g., 3 to 4 weeks) than liquid formulations (e.g., hours to days). Another method to achieve a gel-like consistency may include introducing air into the solution through a process called "whipping".

[0088] This finding suggests that the concentration of the aqueous solution of sodium hydroxide used in formulation of the herbicidal composition can impact the physical properties of the herbicide composition. Concentrations of NaOH in the aqueous solution of sodium hydroxide of greater than or equal to about 50 vol. % can lead to the formation of a gel-like product that has the ability to adhere to plant surfaces for an extended period of time. This can potentially result in a longer-lasting and more effective herbicidal effect on the target plants.

[0089] Unlike sodium hydroxide, when an aqueous solution of potassium hydroxide was used at concentrations above about 40 / 60 vol. % KOH / Water solution, crystal formation was not observed. Accordingly, whipping may be used with an alkali metal hydroxide such as KOH to achieve a gel / gel-like consistency of the herbicidal composition.

[0090] This unexpected result suggests that the physical properties of the herbicide formulation may not be solely dependent on the concentration of the alkali hydroxide used, but could also be influenced by other factors such as the chemical properties and interactions of the specific alkali hydroxide used. In this case, KOH may not exhibit the same behavior as NaOH in terms of gel formation, despite being another type of alkali hydroxide.

[0091] It was further found that a high viscosity formulation of the herbicide composition can be produced when a higher fraction of gum rosin lights was used along with higher fractions of theaqueous sodium hydroxide solution. For example, when the formulation includes about 30 wt. % or more gum rosin lights, about 65 wt. % pine oil and about 5 wt. % of an aqueous solution of sodium hydroxide having a composition of greater than or equal to about 55 vol. % sodium hydroxide, the viscosity of the high viscosity formulation can be greater than or equal to about 35 pascal- seconds (Pa-s) at 20 °C. The high viscosity formulation offers an alternative form of application that can have advantages in certain situations. For example, the high viscosity formulation can take on a form reminiscent of crystalized honey which can be applied directly to plants. When applied to plants in this form the plants can turn black and be effectively eradicated.

[0092] The surfactant can include a non-ionic surfactant. The non-ionic surfactant can include a polysorbate. For example, the polysorbate can include at least one of polysorbate 20, polysorbate 40, polysorbate 60, and polysorbate 80 where the number indicates the type of major fatty acid associated with the molecule (e.g., monolaurate is indicated by 20, monopalmitate is indicated by 40, monostearate by 60, and monooleate by 80). The non-ionic surfactant can include decylglucoside (e.g., having molecular mass of 320.426 g / mol, chemical formula CieffeOe, IUPAC name Decyl P-D-glucopyranoside, and CAS No. 58846-77-8). Decyl-glucoside can be a natural, plant-based biodegradable non-ionic surfactant. For example, decyl-glucoside can be synthesized from glucose (e.g., derived from corn starch) and fatty alcohol decanol (e.g., derived from coconut).

[0093] The surfactant can act as an emulsifier to homogenize the composition and increase the solubility of the herbicidal composition in water in comparison to an herbicidal composition that does not contain a surfactant. The surfactant can also promote even spreading of a liquid formulation of the herbicidal composition onto a target (such as on the surface of a leaf, seed or soil).

[0094] Stoloniferous plants propagate through stolons, which are stems that grow at or just below the soil surface, forming adventitious roots at the nodes and new plants from the buds. These plants can be difficult to eradicate due to their ability to spread even when injured but not killed.

[0095] The combination of pine oil and gum rosin lights in the herbicide composition was found to exhibit surprising activity. Specifically, the adhesive properties of gum rosin lights and thepresence of additional active terpineol in the composition contributed to increased effectiveness against stoloniferous plants, such as kikuyugrass in comparison to herbicidal compositions containing derivatives of CTO. Accordingly, the herbicide composition has unique properties that make it highly suitable for controlling these specific types of plants.

[0096] Furthermore, it has been found that herbicidal formulations including a surfactant (e.g., polysorbate 80) exhibited translocation activity through leaf laminar in diluted compositions of 5 vol. % of the herbicidal composition and 95 vol. % water. Translocation activity relates to transport processes within plants in which compounds (e.g., soluble organic compounds) are transported through plant tissue throughout the plant. For example, translocation can relate to the transport of compounds from leaf tissue to roots of the plant (e.g., through the plant phloem, an inner layer of the bark) and / or transport of compounds from roots to leaf tissue (e.g., through plant xylem, another inner layer of bark).

[0097] Furthermore, it has been found that pine oil / pine oil based herbicide contact with crops can provide growers with crop benefits including crop root growth, increased crop yield, repel pests, and strengthen the crop’s immune system to combat plant stress like diseases. Unlike conventional herbicides that often inflict “collateral damage” to crops. Pine oil can help keep plants sterile and can provide growth potential, for example, due to containing high levels of nitrogen. Pine oil can act as a bio-stimulant and a pest and disease deterrent. It can be highly water-soluble (e.g., so that it forms a single homogenous liquid phase that does not separate) and can be used as a foliar spray, as a root zone applicant, and / or soil treatment. Pine oil can be used with organic and / or mineral-based nutrient programs.

[0098] As a foliar spray bio-stimulant effects can be seen within days (e.g., 1-3 days after foliar application). Observations show plants treated with foliar spray containing pine-oil can perk up and show new growth within a few days. Due to the beneficial mechanisms of pine oil as a natural bio-stimulant and pest and disease deterrent, there can be very little risk of toxicity due to over use. Pine oil is 100% biodegradable thereby making it environmentally friendly. It can also work as a chelator to help facilitate take up of macro and micronutrients into the plants cells at a much faster rate, thus speeding up growth rates, and shortening the overall growth cycle.

[0099] Pine-oil can help kill algae, mold, and / or mildew and create a barrier to prevent these issues from returning to plants. For example, pine oil can prevent botrytis cinerea (also referredto as “gray mold”) as well as powdery mildew. Further, treatments with pine oil can have no noticeable phytotoxic effect on plants nor chemical residue on flowers or fruits.

[0100] Pine oil can also help to create a healthier root system, e.g., by promoting formation and / or growth of beneficial aerobic bacteria, and fungal colonies to grow and thrive, while preventing formation and / or growth of pathogen anaerobic colonies. For example, pine oil has been found to be effective in eliminating the growth of root-zone pathogenic fungal colonies (e.g., fusarium oxysporum and pythium aphenidermatum) . See Cindy Rea, Pine-ing for Organics, Maximum Yield, Volume 9, Number 4 - November, December 2006. Accordingly, pine oil can help create stronger roots which in turn provide for stronger plants with higher yields. Healthier plants can be less susceptible to attacks from predators and diseases and can be better suited to deal with stressors and adverse conditions.

[0101] Because there can be available nitrogen in pine oil products, they can be effective at boosting vegetative growth. These benefits of pine oil can be systemic and can be passed down to cuttings which can promote a more vigorous rooting and initial growth period for cuttings.

[0102] The herbicidal composition can be applied by any suitable method onto a target plant, seed, or soil. When in liquid phase, the herbicidal composition can be applied by spraying or pouring the liquid directly to a target plant, seed or soil. As such, the application can use any suitable spraying or pouring mechanisms, such as hand-held sprayers, distribution through irrigation systems, distribution though aerial spay applications, and the like.

[0103] The herbicidal composition can be in a liquid phase. Furthermore, the herbicidal composition can be dilutable with water to form a diluted herbicidal composition. For example, diluted herbicidal composition can be prepared by diluting the concentrated herbicidal composition with water. For example, the concentrated herbicidal composition can be diluted from about 1 vol. % herbicidal composition with about 99 vol. % water to about 50 vol. % herbicidal composition with about 50 vol. % water, or to about 40 vol. % herbicidal composition with about 60 vol. % water. Diluting the herbicidal composition can be accomplished by placing a first portion the water (or the concentrated herbicidal composition) in a container then adding a second portion of the concentrated herbicidal composition (or water) to the container to reduce the concentration of the herbicidal composition from the concentrated herbicidal composition to a diluted herbicidal composition.

[0104] The herbicidal composition can be applied by tilling target soil before applying the herbicidal composition then spraying, pouring or otherwise distributing the herbicidal composition on the tilled soil or onto the soil while it is being tilled (e.g., such as by sprayers configured to spray onto soil as, or just after, a tilling machine works soil). This application method can be performed during a planting phase while the soil is prepared for planting a crop. Soil can be wetted with water prior to, or after, applying the herbicidal composition to the soil. Wetting in this way can help to spread the herbicidal composition deeper into the soil and may help to prevent evaporation of the herbicidal composition (e.g., by forming a protective water barrier between the herbicidal composition and the sun). Applying the herbicidal composition to soil can kill seeds on the surface and / or prevent their germination.

[0105] Once the herbicidal composition is applied to the soil, compacting the soil can help retain the herbicidal composition in the soil (e.g., by reducing evaporative surface area of the soil in comparison to worked soil having a rougher surface).

[0106] In another technique, the liquid phase herbicidal composition can be sprayed onto waste discharged from a combine harvester. In this way, the herbicidal composition can help to prevent unwanted seeds (e.g., in the harvester waste) from germinating.

[0107] The herbicidal composition has shown activity against the fungal disease silver leaf (e.g., caused by the fungal pathogen chondrostereum purpureum) which attacks stone and pome fruits. This can be an important application of the herbicidal composition as traditional control methods require removing infected plants and / or burning them. Accordingly, the herbicidal composition can be diluted with water and applied directly to affected plants. In this case, dilution rates can range from about 1 vol. % of the concentrated herbicidal composition with about 99 vol. % water, to about 10 vol. % of the concentrated herbicidal composition with about 90 vol. % water. Or, more specifically, dilution rates can range from about 2 vol. % of the concentrated herbicidal composition with about 98 vol. % water to about 5 vol. % of the concentrated herbicidal composition with about 95 vol. % water.

[0108] Soil borne diseases can also be controlled with the use of the herbicidal composition. For example, pythium and other soil borne fungi can be controlled by application directly to soil as discussed herein. In this case, dilution rates can range from about 1 vol. % of the concentrated herbicidal composition with about 99 vol. % water, to about 15 vol. % of the concentratedherbicidal composition with about 85 vol. % water. Or, more specifically, dilution rates can range from about 2 vol. % of the concentrated herbicidal composition with about 98 vol. % water to about 10 vol. % of the concentrated herbicidal composition with about 90 vol. % water.

[0109] Insecticide activity has been shown with the use of the herbicidal composition. For example, thrips and other plant attacking insects can be controlled by application directly to the insect and / or onto plants that the insects attack. In this case, dilution rates can range from about 1 vol. % of the concentrated herbicidal composition with about 99 vol. % water, to about 10 vol. % of the concentrated herbicidal composition with about 90 vol. % water. Or, more specifically, dilution rates can range from about 2 vol. % of the concentrated herbicidal composition with about 98 vol. % water to about 8 vol. % of the concentrated herbicidal composition with about 92 vol. % water.

[0110] When in gel / gel-like form, the herbicidal composition can be applied by painting the gel / gel-like herbicidal composition directly onto a target plant, seed, or soil. For example, applying the gel / gel-like herbicidal composition can include using an applicator (e.g., brush, rod, roller, or the like) to transfer the gel / gel-like herbicidal composition from a container to the target plant, seed, or soil. A user can apply the gel / gel-like herbicidal composition by dipping the applicator into the gel / gel-like herbicidal composition then smearing, spreading, or painting the gel / gel-like herbicidal composition onto the target plant, seed or soil. Applying the gel / gel-like herbicidal composition in this way can provide greater adhesion to the plant surface in comparison to liquid formulations. This method of application may be more effective in targeting woody weeds or unwanted tree vegetation, and stolons (also referred to as “runners”) which include horizontally extending connections between parts of the plant and can be hard to kill, such as blackberries (e.g., found in Australia and New Zealand).

[0111] The gel / gel-like herbicidal composition may also be applied by a spraying method (described above) depending on the viscosity of the gel / gel-like herbicidal composition and the driving pressure provided by the spraying device used. A high-pressure sprayer (e.g., having a driving pressure of greater than or equal to about 20 pounds per square inch (gauge)(psig), or greater than or equal to about 30 psig, or about 50 psig, or 100 psig) may be used to force the gel / gel-like herbicidal composition through a nozzle. The sizing of the nozzle and the drivingpressure provided by the sprayer can be related so that higher driving pressure can be used to force the gel / gel-like herbicidal composition through a smaller nozzle diameter and vice-versa.

[0112] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure. All publications mentioned hereunder are incorporated herein by reference in their entirety.

[0113] As used herein, the term “gel” or “gel-like” can refer to a substance having semi-solid characteristics, such as exhibiting physical characteristics of a solid material (e.g., including no net flow from an unbound side of the material during steady state conditions) while also having a liquid phase portion, and can include a substance having a three-dimensional cross-linked network within a liquid phase which can provide structure to the substance so that the substance maintains its form when unbound by another physical boundary. For example, the three- dimensional cross-linked network can span the volume of the liquid phase and capture the liquid (e.g., through surface tension effects).

[0114] The various implementations described herein serve as examples of aspects of the disclosure and should not be interpreted as to limit the scope of the disclosed invention.

[0115] While various inventive implementations have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other compositions, means and / or structures for performing the function(s) and / or obtaining the result(s) and / or one or more of the advantages described herein, and each of such variations and / or modifications is deemed to be within the scope of the implementations described herein. More generally, those skilled in the art will readily appreciate that all compositions, parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual compositions, parameters, dimensions, materials, and / or configurations will depend upon the specific application or applications for which the teachings is / are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific inventive implementations described herein. It is, therefore, to be understood that the foregoing implementations are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, implementations may be practiced otherwisethan as specifically described and claimed. Implementations of the present disclosure are directed to each individual composition, feature, system, article, material, and / or kit described herein. In addition, any combination of two or more such compositions, features, systems, articles, materials, and / or kits, if such compositions, features, systems, articles, materials, and / or kits, are not mutually inconsistent, is included within the inventive scope of the present disclosure. It is to be understood that a singular form of a noun corresponding to an item may include one or more of the items, unless the relevant context clearly indicates otherwise.

[0116] As used herein, the terms “about” and “approximately” can refer to values that are plus or minus ten percent of the base value. That is, reference to “about 100” or “approximately 100” can refer to “90-110” inclusive. In some embodiments, “about” can refer to plus or minus two percent of the base value.

[0117] As used herein, each of the terms “weight %”, “wt %”, and “w / w” can refer to the mass of the specified component divided by the total mass of the mixture in which the component is part.

[0118] As used herein, each of the terms “volume %” and “vol %” can refer to the volume of the specified component divided by the total volume of the mixture in which the component is part.

[0119] As used herein, the term “v / w” can refer to the volume of the specified component divided by the total mass of the mixture in which the component is part.

[0120] As used herein, each of the phrases “A or B,” “at least one of A and B,” “at least one of A or B,” “A, B or C,”, A, B, and C”, “at least one of A, B and C,” and “at least one of A, B, or C” may include any one of the listed items, or all possible combinations thereof. For example, use of “at least one of’ preceding a group of items should be interpreted in a disjunctive way with respect to the group of items, e.g., so that presence of one item of the group meets the meaning of the recitation.

[0121] The words “a,” “an” and “the” are intended to include plural forms of elements unless specifically referenced as a single element. The term “at least” preceding a listing of elements denotes any one or any combination of the elements in the listing. In other words, the expression “at least one of ...” when preceding a list of elements, modifies the entire list of elements and does not modify the individual elements of the list.

[0122] The term “and / or” includes a combination of a plurality of related listed components, or any component among the plurality of related listed components.

[0123] Terms such as “first,” “second,” or “first” or “second” may be used simply to distinguish one component from other components, and do not limit the components in other aspects (e.g., importance or order).

[0124] Further, terms such as “front”, “rear”, “top”, “bottom”, “side”, “left”, “right”, “upper”, and “lower” used in the present disclosure are defined based on the drawings, and the shape and location of each component are not limited by the terms.

[0125] The term “comprise(ing)”, “include(ing)” or “have(ing)” is intended to indicate the presence of a characteristic, number, step, operation, process, component, part, feature, function, and / or element, or any combination thereof described in the present document, and the possibility of the presence or addition of one or more other characteristics, numbers, steps, operations, processes, components, parts, features, functions, and / or elements, or any combination thereof is not precluded.

[0126] A term, such as “about” or “substantially,” can be used at a corresponding numerical value or can be used as a meaning close to the numerical value when manufacturing, measurement, and / or material tolerances, which can be inherent in the stated meaning, are presented.

Claims

CLAIMSWhat is claimed is:

1. An herbicidal composition comprising: about 40 wt. % to about 90 wt. % monocyclic monoterpenoids; about 0.1 wt. % to about 6.0 wt. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate and a remainder of the aqueous solution being water; and a remainder of the herbicidal composition including diterpenoids, wherein the herbicidal composition is a gel.

2. The herbicidal composition of claim 1, wherein the diterpenoids are gum rosin lights.

3. The herbicidal composition of claim 1, wherein the diterpenoids include at least one of dehydroabietic acid, abietic acid, and isomers thereof.

4. The herbicidal composition of claim 1 , wherein the monocyclic monoterpenoids include isomers of terpineol.

5. The herbicidal composition as in one of claims 1-4, wherein the monocyclic monoterpenoids include pine oil containing greater than or equal to about 55 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

6. The herbicidal composition of claim 5, wherein the monocyclic monoterpenoids include pine oil containing greater than or equal to about 95 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

7. The herbicidal composition of claim 2, wherein the gum rosin lights are derived from tree -tapped oleoresin and include at least one of no lignin, no cellulose, no hemicellulose, no sulphonated products, an average molecular mass of about 145 grams / mole to about 148grams / mole, molecules having a molecular mass range of about 136 grams / mole to about 155 grams / mole, molecules having boiling points that range of about 170 °C to about 217 °C, or a combination including at least one of the foregoing.

8. The herbicidal composition of claim 1, wherein the aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate is an aqueous solution of sodium hydroxide.

9. The herbicidal composition of claim 2, wherein the aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate is an aqueous solution of sodium hydroxide.

10. The herbicidal composition of claim 6, wherein the aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate is an aqueous solution of sodium hydroxide.

11. The herbicidal composition as in one of claims 8-9, wherein the composition of the aqueous solution of sodium hydroxide is between about 40 vol. % and about 60 vol. % sodium hydroxide with the remainder of the aqueous solution being water.

12. The herbicidal composition as in one of claims 10, wherein the composition of the aqueous solution of sodium hydroxide is between about 40 vol. % and about 60 vol. % sodium hydroxide with the remainder of the aqueous solution being water.

13. An herbicidal composition comprising: about 1 wt. % to about 20 wt. % of a surfactant; and a remainder including at least one of monocyclic monoterpenoids and diterpenoids, wherein the herbicidal composition is a liquid.

14. The herbicidal composition of claim 13, wherein the surfactant includes: about 0.1 wt. % to about 10 wt. % of a polysorbate, andabout 0.1 wt. % to about 10 wt. % of decyl-glucoside.

15. The herbicidal composition of claim 13, wherein the surfactant includes about 10 wt. % of at least one of a polysorbate and decylglucoside, and the remainder includes: about 70 wt. % monocyclic monoterpenoids, and about 20 wt. % diterpenoids.

16. The herbicidal composition of claim 13, wherein the surfactant includes: about 6.5 wt. % of a polysorbate, and about 3.5 wt. % decyl-glucoside, and the remainder includes: about 70 wt. % monocyclic monoterpenoids, and about 20 wt. % diterpenoids.

17. The herbicidal composition as in one of claims 13-16, wherein the diterpenoids are gum rosin lights.

18. The herbicidal composition of claim 17, wherein the monocyclic monoterpenoids include pine oil containing greater than or equal to about 55 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

19. The herbicidal composition of claim 18, wherein the pine oil contains greater than or equal to about 95 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

20. The herbicidal composition of claim 13, further comprising: about 0.1 wt. % to about 10 wt. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of thealkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with a remainder of the aqueous solution being water.

21. The herbicidal composition of claim 20, wherein the aqueous solution of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate includes at least one of an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide.

22. The herbicidal composition of claim 13, wherein the surfactant includes a non-ionic surfactant.

23. The herbicidal composition of claim 22, wherein the non-ionic surfactant includes at least one of a polysorbate and decyl-glucoside.

24. A herbicidal composition comprising: greater than or equal to about 60 wt % a-terpineol, and a remainder including at least one of a surfactant and gum rosin lights.

25. The herbicidal composition of claim 24, wherein the remainder further includes: about 0.1 wt. % to about 10 wt. % of an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with a remainder of the aqueous solution being water, wherein the herbicidal composition is a liquid.

26. The herbicidal composition as in one of claims 13-25, wherein the herbicidal composition is dilutable with water to form a diluted herbicidal mixture including: greater than or equal to about 10 vol. % of the herbicidal composition, and a remainder of the diluted herbicidal mixture is water.

27. A method comprising: mixing at least one of a surfactant and an aqueous solution of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal acetate, and an alkaline earth metal acetate, having a composition of greater than or equal to about 40 vol. % of the at least one of the alkali metal hydroxide, the alkaline earth metal hydroxide, the alkali metal acetate, and the alkaline earth metal acetate with a remainder of the aqueous solution being water, into di terpenoids to form a first mixture; and mixing monocyclic monoterpenoids into the first mixture to form an herbicidal composition.

28. The method of claim 27, wherein the diterpenoids are gum rosin lights.

29. The method as in one of claims 27-28, wherein the monocyclic monoterpenoids include pine oil containing greater than or equal to about 55 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

30. The method of claim 29, wherein the pine oil contains greater than or equal to about 95 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol31. The method of claim 27, wherein the herbicidal composition has about 1 vol. % to about 20 vol. % of the surfactant.

32. The method of claim 31, wherein the surfactant further includes: about 0.11 wt. % to about 10 wt. % of a polysorbate, and about 0.1 wt. % to about 10 wt. %decyl-glucoside.

33. The method of claim 31, wherein the surfactant includes about 10 wt. % of at least one of a polysorbate and decyl-glucoside, and the remainder includes: about 70 wt. % monocyclic monoterpenoids, and about 20 wt. % diterpenoids.

34. The method of claim 31 , wherein the surfactant includes: about 6.5 wt. % of a polysorbate, and about 3.5 wt. % decyl-glucoside, and the remainder includes: about 70 wt. % monocyclic monoterpenoids; and about 20 wt. % diterpenoids35. The method as in one of claims 27-34 wherein, the diterpenoids are gum rosin lights, and the monocyclic monoterpenoids include pine oil containing greater than or equal to about 55 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

36. The method of claim 35, wherein the herbicidal composition is dilutable with water to form a diluted herbicidal mixture having a composition of greater than or equal to about 10 vol. % of the herbicidal composition, and a remainder of the diluted herbicidal mixture being water.

37. The method as in one of claims 27-36, wherein the herbicidal composition is appliable onto the at least one of a target plant, a target seed, and target soil.

38. The method of claim 37, wherein the target soil is tillable before applying the herbicidal composition to the target soil; and the target soil is compactable after applying the herbicidal composition to the target soil.

39. The method as in one of claims 37-38, wherein the target soil is wettable with water before applying the herbicidal composition.

40. The method as in one of claims 27-36 wherein the herbicidal composition has about40 wt. % to about 90 wt. % monocyclic mono terpenoids, about 0.1 wt. % to about 6.0 wt. % of the aqueous solution, and the remainder of the herbicidal composition includes diterpenoids,wherein the herbicidal composition is a gel.

41. The method of claim 40, further comprising: transferring the herbicidal composition to an applicator before applying the transferred herbicidal composition to the at least one of a target plant, a target seed, and target soil with the applicator.

42. The method of claim 40, further comprising: decreasing a water content of the aqueous solution to less than or equal to about 45 vol. % water so that the herbicidal composition has a viscosity of greater than or equal to about 35 Pa-sec at 20 °C.

43. An insecticidal composition comprising the herbicidal composition as in any one of claims 1-25 inclusive, wherein the insecticidal composition includes from about 1 vol. % to about 60 vol. % of the herbicidal composition.

44. The insecticidal composition of claim 43, wherein a remainder of the herbicidal composition is water.

45. An insecticidal composition comprising: about 2 wt. % to about 50 wt. % monocyclic monoterpenoids; and about 0.1 to about 20 wt. % of a surfactant; wherein the insecticidal composition is a liquid.

46. The insecticidal composition of claim 45, wherein a remainder of the insecticidal composition is water.

47. The insecticidal composition as in one of claims 45-46, wherein the monocyclic monoterpenoids include pine oil containing greater than or equal to about 55 wt. % of at least one of a-terpineol, P-terpineol, y-terpineol, and 4-terpineol.

48. The insecticidal composition as in one of claims 45-47, wherein the surfactant includes at least one of a polysorbate and decyl-glucoside.

49. The insecticidal composition as in one of claims 45-48, wherein the insecticidal composition is dilutable with water to form a diluted insecticidal mixture including: greater than or equal to about 1 vol. % of the insecticidal composition, and a remainder of the diluted insecticidal mixture is water.

Images