# Patent

## Title
Limonene-containing herbicide compositions, herbicide concentrate formulations and methods for making and using same for organic production

## Abstract

Provided are methods, kits and compositions suitable for use in organic production for killing, controlling or suppressing a plant by administering to surfaces of the plant a herbicide composition comprising a herbicidally effective limonene component and an emulsifying agent in an aqueous emulsion, wherein the composition has a pH greater than 5. Also provided are methods, kits and compositions for killing, controlling or suppressing a plant, comprising administering to surfaces of the plant a herbicide composition comprising a herbicidally effective limonene component and an emulsifying agent in an aqueous emulsion, wherein the composition includes a wetting agent and an optional oil. Also provided are methods, kits and compositions for killing, controlling or suppressing a plant, comprising administering to surfaces of the plant a herbicide composition comprising a herbicidally effective limonene component, an emulsifying agent and optionally an added oil component in an aqueous emulsion, wherein the composition has a pH greater than 5 and includes a wetting agent. All components of the compositions suitable for use in organic production contain components which are either natural products obtained by non-chemical means and/or are included on the Environmental Protection Agency's List of Inert Ingredients (List 4A and 4B).

## Background
The present application is a continuation-in-part application which claims the benefit of PCT application No. PCT/US2006/07426, filed on Mar. 2, 2006, and published in English which is a continuation-in-part of U.S. application Ser. No. 11/071,398, filed on Mar. 2, 2005 now abandoned and also claims the benefit of U.S. application Ser. No. 11/071,398, filed on Mar. 2, 2005.


BACKGROUND
This invention relates to improvements in the field of herbicidal treatment of plants. The invention involves a method of herbicidal treatment of plants whereby unwanted plants and grasses are terminated using a formulation that can be used in organic production and that is highly effective to non-selectively kill plants it contacts. More particularly, the invention relates to “knock-down” herbicide formulations that comprise a herbicidally active limonene component The methods, formulations and kits according to the present invention further involve formulations which can be used for organic production according to the USDA's National Organic Program and can be labeled “For Organic Production” in accordance with rules promulgated by the USDA.
By way of background, limonene is a naturally occurring chemical found in high concentrations in citrus fruits and spices. Limonene, otherwise known as orange limonene or 1-methyl-4-(1-methylethenyl)cyclohexene or 4-isopropenyl-1-methyl cyclohexene, occurs naturally in various ethereal oils, particularly oils of lemon, orange, lime, grapefruit, caraway, dill and bergamot. It has a chemical formula of C10H16, a molecular weight of 136.2, and contains 88.1% Carbon and 11.8% Hydrogen by weight. The d-form of limonene is a liquid having a boiling point of 175.5-176 degrees centigrade.
Some limonene is prepared by extraction from plants of the mint family, a large quantity is obtained from citrus oils, which are typically 80-90% limonene, and some is obtained from pine oil. For example, d-limonene can be obtained from steam extraction of citrus peels of orange, lemon, lime, grapefruit and bergamot. Some of the extractions can contain as high as 90% d-limonene; however, to produce technical grades of d-limonene of higher purity, i.e., greater than about 95%, distillation of the oils is required. d-Limonene can also be synthesized chemically. d-Limonene has a pleasant citrus scent and it can be suitably used in any living environment.
In addition to uses as flavor additives in a wide variety of foods and beverages and uses in perfume materials, d-limonene has also been used in household and industrial cleaning products. It is readily available from commercial sources such as Florida Chemical Company, Inc., and is available in three different grades, named untreated/technical grade, food grade and lemon-lime grade. The food grade comprises about 97% d-limonene, the untreated/technical grade about 95%, and the lemon-lime grade about 70%, the balance in each case being other terpene hydrocarbons and oxygenated compounds.
Limonene has become a valuable industrial chemical. It finds use as a solvent and cleaning agent (in the manufacture of synthetic pine oil), as an expectorant, as a wetting and dispersing agent, as a monomer in the manufacture of various polymeric resins, as a flavorant in many food products and a precursor in the synthesis of the flavorant carvone, and as a polymerization inhibitor in storage of the tetrafluoroethylene monomer used in the manufacture of polytetrafluoroethylene (PTFE). It is also used in many soaps and perfumes for its lemon-like flavor and odor. In addition, limonene is a registered active ingredient in at least 15 pesticide products used as insecticides, insect repellents, and dog and cat repellents. For example, pesticide products containing limonene are used for flea and tick control on pets, as an insecticide spray, an outdoor dog and cat repellent, a fly repellent tablecloth, a mosquito larvicide, and an insect repellent for use on humans.
Limonene is of relatively low acute toxicity taken orally. The U.S. Food and Drug Administration considers limonene Generally Recognized as Safe (GRAS) as a food additive or flavoring, and as a fragrance additive. The U.S. Environmental Protection Agency has granted limonene an exemption from the requirement of a tolerance when it is used as an inert ingredient in pesticide formulations, and when used as an insect repellent tablecloth. For limonene to be used as an active ingredient in a formulation that can be used in organic production, the limonene needs to be from a natural source and obtained by non-chemical means. A more common way of obtaining this form of limonene is through physical separation from a natural source followed by distillation.
Turning now to consideration of herbicides, a wide range of chemicals are used to control weeds in the agricultural industry and to control unwanted vegetation in the landscaping industry. The aim of herbicides is to prevent weeds and unwanted plants from competing with a desired crop in the case of agricultural uses, or competing with preferred vegetation in landscaping applications.
At present, there are two main classes of herbicidal chemicals that are used in connection with terrestrial plants, which is the subject of the present invention. In particular, the herbicides are generally separated into those that have a “contact” action upon plants, and those that have a “systemic” action upon plants. Some herbicides have both a contact and systemic action on plants. Other types of herbicides act in other ways, such as, for example as soil sterilants.
Herbicides may either be selective or non-selective. Selective herbicides, for example “Treflan” (trifluralin), may be utilized for the selective destruction of certain types of grass. Non-selective herbicides such as “Roundup” (glyphosate) may be used as a general herbicide for destroying or controlling many different types of plants and grasses.
A large number of herbicides and plant hormones have been developed over the years. In the early days inorganic compounds such as sodium chlorate and sodium arsenite and various borate compounds were used. There were also developed other organic herbicides such as N-phenylcarbamate, “Randox”, and other chlorinated phenoxy compounds. In addition, industrial waste products were quite common. Later on, the hormone type weed killers 2,4-D (2,4-dichloro-phenoxyacetic acid) and 2,4,5-T (2,4,5-trichloro-phenoxyacetic acid) were developed, and have become quite common. More complicated organic weed killers and proprietary chemicals such as “Network” or “Roundup” (both glyphosates) have also been developed.
In many cases herbicides have deleterious effects. For example, they may poison beneficial crops, affect other plants or animals, and/or poison the soil. In addition, many herbicidal compositions presently on the market are highly toxic to humans and domestic animals. Most chemical herbicides are dangerous to mankind and are therefore dangerous when accidentally inhaled and/or absorbed into human and animal tissue. Because of the widespread concern of the deleterious side effects of currently available herbicides, and the problems associated with absorption and ingestion into other living matter, there is much concern as to the long-term use of complex and highly dangerous chemicals, especially when they enter into the food chain. Further, the use of such toxic chemicals in production of foods prevents such foods from being marketed as organic products in a majority of countries. In the United States consumer demand for organic products, particularly foods, has resulted in the development of rules regulating the production of organic food by the USDA. A herbicide having low or no toxicity that can be used in the production of organic products and for home use is desirable in view of the growing demand for organic products, the increased shift toward organic food production and the desire to protect our living environment from toxic materials.
There has been developed recently a relatively nontoxic herbicide which has fatty acids as its main constituents. This herbicide has a smothering effect on plants; however its efficacy is limited particularly in controlling perennial weeds. A further disadvantage is that the fatty acids are not readily carried or emulsified within an appropriate carrier fluid or solvent, which lessens its overall effectiveness due to the difficulties encountered in delivering the herbicide to plants.
It has been suggested recently that limonene can be used at a high concentration as a knock-down herbicide. In U.S. Pat. No. 5,998,335 to Selga et al., knock-down herbicidal compositions are described, one of which comprises about 95-96% by weight of d-limonene and about 4-5% of other components. The '335 patent reports that when this composition was applied to vegetation as a fine droplet spray (targeting 60-80% coverage of vegetation), most vegetation showed visible signs of stress (e.g., wilting or browning) within 2 to 24 hours of application of the herbicide. Selga et al. also reported in the '335 patent that an emulsified mixture of 60% d-limonene with water and commercial emulsifier was also tested. When this formulation was applied to vegetation as described above, most vegetation began showing visible signs of stress within 2 to 36 hours.
One disadvantage of the herbicides described by Selga et al. is that such high concentrations and volumes of limonene would be cost prohibitive and cumbersome for spraying large areas. These formulations also present practical challenges associated with effectively atomizing and spraying such oily or highly viscous compositions.
In light of the above, there is a continuing need for natural, safer, cost effective, and environmentally-friendly herbicides having increased efficiency and efficacy that can be formulated to provide a herbicide suitable for use in organic production in compliance with USDA regulations currently in effect. The present invention addresses this need and provides a wide variety of benefits and advantages.
SUMMARY
Embodiments of the methods, kits, and compositions disclosed herein involve herbicidal compositions containing components that allow the herbicidal compositions to qualify for use in organic production under the USDA's National Organic Program. In order for a herbicide to qualify for use in organic production, a herbicide's components must be a natural products obtained by non-chemical means or synthetic components defined under 7 CFR 205.601. A synthetic compound can comply with 7 CFR 205.601 by being included on the Environmental Protection Agency's lists 4A or 4B (Inerts of Minimal Concern).
A first aspect of the present disclosure provides for a method suitable for use in organic production for killing, controlling or suppressing a plant. The method involves providing a liquid herbicidal composition that includes water, a herbicidally active limonene component, and an emulsifying agent and spraying the herbicidal composition onto one or more leaves of a plant. In order to be suitable for use in organic production the limonene component must be obtained by non-chemical means and the emulsifying agent must either be a natural product obtained by non-chemical means or an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B. For the purposes of this document, the term “Environmental Protection Agency's List 4A or 4B” shall mean the U.S. Environmental Protection Agency List of Inert Pesticide Ingredients (including List A and List B) provided in Appendix A to this application.
A second aspect of the present disclosure provides for a method suitable for use in organic production for the non-selective burn down of plants. The method utilizes a liquid herbicide that includes water, a herbicidally active limonene component obtained from a natural source by non-chemical means, an emulsifying agent and a member selected from the group consisting of a wetting agent, a pH modifier effective to provide a pH greater than 5, an added oil component and a combination thereof. The emulsifying agent and any member selected from the group and included in the liquid herbicide are inert pesticide ingredients contained in the Environmental Protection Agency's List 4A or 4B. The method involves selecting an area having at least one plant growing within the area and spraying the liquid herbicide composition onto the area.
A third aspect of the present disclosure provides for a “ready to use” herbicidal composition for use in organic production that includes water, a herbicidally active limonene component and an emulsifying agent. The limonene utilized in the ready-to-use composition is a natural product obtained by non-chemical means. The emulsifying agent is a natural product obtained by non-chemical means and/or an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B provided in Appendix A. Such ready-to-use composition qualifies under the USDA's National Organic Program to be used in organic production and to be labeled “for organic production.” Preferred embodiments of the ready-to-use herbicide additionally include a member selected from the group consisting of a wetting agent, a pH modifier effective to provide a pH greater than 5, an added oil component and a combination thereof where the member selected and utilized is an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B.
A fourth aspect of the present disclosure provides for a herbicidal concentrate suitable for use in organic production that is adapted to be diluted with water. The concentrate includes a herbicidally active limonene component and an emulsifying agent. The limonene utilized in the concentrate is a natural product obtained by non-chemical means and the emulsifying agent is a natural products obtained by non-chemical means and/or an inert pesticide ingredients contained in the Environmental Protection Agency's List 4A or 4B provided in Appendix A. Such herbicidal concentrate qualifies under the USDA's National Organic Program to be used in organic production and to be labeled “for organic production.” Preferred herbicidal concentrates additionally contain and a member selected from the group consisting of a wetting agent, a pH modifier effective to provide a pH greater than 5, an added oil component and a combination thereof where the member selected and utilized is an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B.
A fifth aspect of the present disclosure provides for a method for making a herbicide composition suitable for use in organic production by providing the herbicidal concentrate described above and diluting and mixing the concentrate with water.
A sixth aspect of the present disclosure provides for a kit for providing a ready-to-use herbicide composition for indiscriminately killing, controlling or suppressing plants growing in the area and suitable for use in organic production. The kit includes a container having therein a ready-to-use liquid herbicide and instructions, recorded in a medium, for applying the herbicide to a preselected area. The herbicide composition includes water, a herbicidally active limonene component obtained by non-chemical means, an emulsifying agent and a member selected from the group consisting of a pH modifier effective to provide a pH greater than 5, a wetting agent, an added oil component, and a combination thereof. The emulsifying agent, and the member selected are natural products obtained by non-chemical means and/or are inert pesticide ingredients contained in the Environmental Protection Agency's List 4A or 4B. Preferred kits have a label stating “for organic production.”
A seventh aspect of the present disclosure provides for a kit for providing a herbicide composition suitable for use in organic production. The kit includes a container having therein a liquid herbicide concentrate and instructions, recorded in a medium, for diluting the concentrate with water to provide a herbicide composition. The liquid herbicide concentrate includes a herbicidally active limonene component obtained by non-chemical means, an emulsifying agent and a member selected from the group consisting of a pH modifier effective to provide a pH greater than 5, a wetting agent, an added oil component, and a combination thereof. The emulsifying agent and the member selected are either natural products and/or are inert pesticide ingredients contained in the Environmental Protection Agency's List 4A or 4B. Preferred kits have a label stating “for organic production.”
An eighth aspect of the present disclosure provides for a kit for providing a herbicide composition suitable for use in organic production. The kit includes:
(a) a first container having therein a liquid herbicide concentrate that includes a herbicidally active limonene component obtained by non-chemical means, an emulsifying agent and a member selected from the group consisting of a pH modifier effective to provide a pH greater than 5, a wetting agent, an added oil, and a combination thereof;
(b) a second container having therein an additive formulation including a member selected from the group consisting of a pH modifier effective to provide a pH greater than 5, a wetting agent, and a combination thereof; and
(c) instructions, recorded in a medium, for combining and diluting the concentrate and additive formulation with water to provide a herbicide composition. The emulsifying agent, any member selected from the group consisting of a pH modifier effective to provide a pH greater than 5, a wetting agent, an added oil, and any combination thereof are natural products and/or are inert pesticide ingredients contained in the Environmental Protection Agency's List 4A or 4B. Preferred kits have a label stating “for organic production.”
A ninth aspect of the present disclosure provides for a kit for providing a herbicide composition suitable for use in organic production. The kit includes:
(a) a first container having therein a liquid herbicide concentrate that includes a herbicidally active limonene component obtained by non-chemical means and an emulsifying agent;
(b) a second container having therein an additive formulation that includes a member selected from the group consisting of a pH modifier effective to provide a pH greater than 5, a wetting agent, an added oil, and a combination thereof; and
(c) instructions, recorded in a medium, for combining and diluting the concentrate and additive formulation with water to provide a herbicide composition. The emulsifying agent and the member selected are a natural product obtained by non-chemical means and/or are an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B. Preferred kits have a label stating “for organic production.”
The compositions, methods and kits disclosed herein provide particular advantages to growers involved in organic production. Currently plastic sheeting, mulch and the like are the predominant methods of weed control allowed in organic production under the USDA's National Organic Program. In order for a herbicide to qualify for use in organic production, its components must be a natural product obtained by non-chemical means or a synthetic component defined under 7 CFR 205.601. A synthetic compound can comply with 7 CFR 205.601 by being included on the Environmental Protection Agency's lists 4A or 4B (Inerts of Minimal Concern). 7 CFR 205.601 and EPA's lists 4A and 4B as they exist on the filing date of this application are hereby incorporated by reference in their entirety to identify the inert ingredients which can be selected for use in products intended for organic production. A 2004 listing of inert pesticide ingredients contained in the EPA's latest published list 4A and 4B is included in Appendix A.
Further objects, features, aspects, forms, advantages and benefits shall become apparent from the description and drawings contained herein.
While the actual nature of the invention covered herein can only be determined with reference to the claims appended hereto, certain forms and features, which are characteristic of the preferred embodiments disclosed herein, are described briefly as follows.



BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a bar graph setting forth the wilting assessment results at 2 and 24 hours from a field study of common grasses and broadleaves in turf conducted in November of 2004. Statistical analysis is by Duncan's MRT (P<<0.05). Treatments with the same letter or letter combination are not significantly different.
FIG. 2 is a bar graph setting forth the wilting assessment results at 2 and 7 days from a field study of common grasses and broadleaves in turf conducted in November of 2004. Statistical analysis is by Duncan's MRT (P<0.05). Treatments with the same letter or letter combination are not significantly different.
FIG. 3 sets forth a plot of the data presented in FIGS. 1 and 2.
FIG. 4 is a bar graph setting forth the color assessment results at 2 and 24 hours from a field study of common grasses and broadleaves in turf conducted in November of 2004. Statistical analysis is by Duncan's MRT (P—<0.05) Treatments with the same letter or letter combination are not significantly different.
FIG. 5 is a bar graph setting forth the color assessment results at 2 and 7 days from a field study of common grasses and broadleaves in turf conducted in November of 2004. Statistical analysis is by Duncan's MRT (P-0.05). Treatments with the same letter or letter combination are not significantly different.
FIG. 6 sets forth a plot of the data presented in FIGS. 4 and 5.
FIG. 7 is a bar graph setting forth results from a field study on lambsquarters conducted in Florida in January of 2005. Ratings are based on 0 to 10 (no damage to dead). Statistical analysis is by Duncan's MRT (P<0.05). Treatments with the same letter or letter combination are not significantly different.
FIG. 8 is a bar graph setting forth results from a greenhouse study on lambsquarters conducted in Michigan in January of 2005. Ratings are based on 0 to 100% (no damage to dead). Statistical analysis is by Duncan's MRT (P—<0.05). Treatments with the same letter or letter combination are not significantly different.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
For the purposes of promoting an understanding of the principles of the invention, reference will now be made to the embodiments described herein and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Any alterations and further modifications in the described fluids, methods, devices or kits, and any further applications of the principles of the invention as described herein, are contemplated as would normally occur to one skilled in the art to which the invention relates.
It has been discovered that the effectiveness of limonene compositions as non-selective, “burn down” herbicides can be significantly improved by increasing the pH of the composition to a pH of greater than 5, by including a wetting agent in the composition, or both. Accordingly, this invention provides in one embodiment a method of killing, controlling or suppressing a plant by administering to surfaces of the plant a herbicide composition comprising a herbicidally effective limonene component and an emulsifying agent in an aqueous emulsion, wherein the composition has a pH greater than 5. In another embodiment, the invention provides a method of killing, controlling or suppressing a plant by administering to surfaces of the plant a herbicide composition comprising a herbicidally effective limonene component and an emulsifying agent in an aqueous emulsion, wherein the composition includes a wetting agent. In yet another embodiment of the invention, there is provided a method of killing, controlling or suppressing a plant by administering to surfaces of the plant a herbicide composition comprising a herbicidally effective limonene component and an emulsifying agent in an aqueous emulsion, wherein the composition has a pH greater than 5 and includes a wetting agent.
It has further been discovered that the methods, formulations and kits of this present invention can involve herbicide formulations that qualify for use in organic production under the USDA's National Organic Program and qualify to be so labeled.
Additionally, it has been discovered that the addition of increased amounts of an added oil component further enhances the performance of the herbicide. Preferred herbicidal concentrates contain from about 2 weight percent to about 20 weight percent of an added oil component that includes castor oil, cottonseed oil, soybean oil, sunflower oil, pine oil and coconut oil or a combination thereof. Suitable added oil components further include ethoxylated oil derivatives. More preferred embodiments of the herbicide concentrate contains from about 4 weight percent to about 12 weight percent of the added oil component. Provided the added oil component is included in the Environmental Protection Agency's List 4B, it can be incorporated into a herbicide used for organic production under the USDA's Organic Program (7 CFR 205.601) regardless of whether it is a natural product or obtained by chemical means and considered a synthetic material.
In this description of the invention, the term “herbicidal” or “herbicidally effective” refers to the quality of being effective to kill, control or suppress a plant when at least a minimum amount of the herbicide composition contacts the plant. The term “kill” as used herein in relation to a herbicide means to cause the above-ground portion of a plant to irreversibly cease normal function, typically resulting in wilting and browning and/or necrosis of the normally green tissues of the plant. It is, of course, possible that a plant, particularly a perennial plant, that is killed within this meaning, may “re-sprout” and produce new growth. The term control as used herein in relation to a herbicide means that, in a treated area, the plants experience at least about 90% mortality. The term “mortality” as used herein can refer to a percentage of individual plants in the treatment area that are killed, or a percentage of the total mass or total surface area of vegetation in the treatment area that experiences wilting, bleaching, browning or necrosis. The term “suppress” is used herein in relation to a herbicide to mean that, in a treatment area, the plants experience from about 40 to about 90% mortality. Application of an inventive herbicide composition to the plant causes the plant, where contacted, to wilt, bleach, or brown, which results in necrosis of the leaf (“burn down”) and oftentimes death of the plant.
Herbicide compositions in accordance with many preferred embodiments of the present invention are nonselective and non-systemic, and are effective against almost any vegetation, specifically against common crop and garden weeds, both annual and perennial. They are “contact herbicides” in that their action results from contact with plant surfaces rather than uptake by the plant. In addition, inventive formulations are “knockdown” (i.e. fast acting, typically within several hours) or “burn down” herbicides, which must be sprayed over a substantial portion of the above-ground part of the plant in order to have an optimal or desired effect. Conveniently, the herbicides are applied as a fine droplet spray. In addition, it is believed that inventive herbicides have optimal burn down effect in relatively warm temperatures and relatively dry conditions (relative to average temperatures and moisture for a given location). The active ingredient of the present herbicidal compositions has the advantage of being an environmentally friendly, natural product, which is unlikely to cause environmental pollution or create toxicity problems for humans or domestic animals. Because limonene-containing oils are natural oils, the non-toxic aqueous herbicide compositions of the invention are environmentally acceptable and have little, if any deleterious effect on humans, wildlife and non-target vegetation.
For purposes of clarity, the term “herbicide composition” is used herein to refer to a liquid that is actually contacted with a plant, such as from a sprayer, to achieve burn down in accordance with the invention. A herbicide composition of the invention can be made and provided to an end user as a pre-made (or “pre-mixed” or “ready to spray”) herbicide composition in some forms of the invention. In other forms of the invention, the herbicide composition can be mixed by the end user at or near the place where the herbicide composition will be used by diluting a herbicide concentrate formulation and optionally adding other ingredients. As used herein, the terms “herbicide formulation” and “herbicide concentrate” and “herbicide concentrate formulation” are used interchangeably to refer to a formulation of ingredients in accordance with the invention that can be diluted with water, with the optional addition of other ingredients, to provide a herbicide composition. This manner of providing a herbicide concentrate formulation may be desirable, for example, where vegetation covering a large area is to be sprayed, for example, using commercial spraying equipment, and thus a great volume of the herbicide composition is needed. In such a case, a herbicide formulation can be provided to an end user, optionally together in a kit, with instructions for mixing the formulation with water, and perhaps other ingredients in or near the sprayer to provide a herbicide composition. Such herbicide formulations and herbicide kits are described further herein, but attention is first given to herbicide compositions of the invention.
In accordance with the invention, a non-selective, burn down herbicide composition includes a herbicidally active limonene component, an emulsifying agent and a hydrophilic solvent, preferably water, and that includes a wetting agent, or has a pH greater than 5, or includes a wetting agent and has a pH greater than 5.
The herbicidally active limonene component includes limonene or a limonene derivative in sufficient amount that it is effective, when in a herbicide composition provided in accordance with the present invention, to kill, control or suppress plants that are contacted with a sufficient amount of the herbicide composition. A sufficient amount is considered to be an amount contacting a sufficient surface of the plants to achieve a desired result. The herbicidally active limonene component can be a pure or substantially pure limonene or limonene extract, or a multi-component composition that includes limonene. In this regard, the herbicidally active limonene component can comprise an essential oil that includes limonene, preferably at least about 8% limonene by weight. For example, the limonene can be provided in the form of a citrus oil, a pine oil, eucalyptus oil or a tea tree oil, any of which can be the herbicidally active limonene component in accordance with the invention.
Furthermore, the herbicidally active limonene component can comprise a modified limonene, as long as the modified limonene has herbicidal activity in accordance with the invention. For example, based upon work that has been reported by others, it appears that oxygenation of limonene to provide limonene oxide may improve water solubility characteristics while maintaining similar burn-down functionality compared to unmodified limonene. Such modified limonene compounds are contemplated by the present invention, and are expressly included within the meaning of the term “herbicidally active limonene component.”
In one preferred embodiment, the herbicidally active limonene component comprises a citrus oil, e.g. orange oil. In another preferred embodiment, the herbicidally active limonene component comprises d-limonene derived from a citrus oil. The fraction of the citrus oil comprising d-limonene can be separated off by vacuum distillation, or any other conventional separation process. d-Limonene is volatile, and is separated off in the distillate. The distillate is a highly concentrated composition of the d-limonene, comprising about 95-96% by weight of d-limonene and about 4-5% by weight of other components. This distillate may be utilized in a herbicidal composition of the present invention.
Although it is possible to use unrefined citrus oil, instead of the vacuum distillate, as discussed above, vacuum distillation (or other separation process, such as steam distillation (azeotroping), solvent extraction, supercritical extraction etc.) has the advantage of separating the herbicidally active ingredient from flavor components of the citrus oil. The flavor components then form a valuable by-product, which can be utilized in, for example, foodstuffs or pharmaceutical compositions.
Other terpenes, particularly monoterpenes, that have similar herbicidal properties to limonene in formulations as provided herein are considered equivalent to limonene for purposes of the present invention. Similarly, other natural oils having high terpene content and having similar herbicidal properties to the limonene-containing oils discussed above in formulations as provided herein are considered equivalent to the limonene-containing oils for purposes of the present invention. “High terpene content” as used herein means those natural oils having a terpene content of at least 50 per cent. It is preferable that the natural oil contains at least 90 per cent terpene. Such terpenes and terpene containing natural oils are expressly encompassed within the meaning of the term “herbicidally active limonene component” as used herein.
When pure or substantially pure limonene is used in an inventive herbicide concentrate suitable for organic use, the herbicide composition preferably includes from about 8 percent to about 100 percent by weight of the limonene, preferably from about 8 percent to about 90 percent by weight. It is understood by a person of ordinary skill in the art that a herbicide composition having a lower concentration of limonene can be used to achieve a similar response by spraying a higher volume of the herbicide composition on the plant (increasing the volume increases the amount of limonene to which the plant is exposed).
Certain preferred embodiments of the herbicide concentrates suitable for organic use generally contain from about 8% by weight to about 90% by weight limonene and more preferred embodiments generally contain from about 35% by weight to about 85% by weight limonene. Certain preferred embodiments of the ready-to-use formulations and/or the diluted concentrates suitable for organic use generally contain from about 2% by weight to about 25% by weight limonene and more preferred embodiments generally contain from about 10% by weight to about 20% by weight.
When a terpene containing natural oil is used, the amount of the natural oil in the herbicide will depend upon the amount of terpenes in the specific oil used. In one embodiment, the herbicide composition includes from about 8 percent to about 100 percent by weight of such a natural oil, preferably from about 12 percent to about 30 percent by weight and more preferably from about 15 percent to about 25 percent by weight. For a herbicide composition containing limonene to qualify for use in organic production under 37 CFR 205.601, the limonene must be a natural product produced by non-chemical means such as by distillation.
As discussed above, the remainder of the herbicide composition in this embodiment comprises water (or optionally another hydrophilic solvent), one or more emulsifying agents, and one or more of a wetting agent and a pH modifier.
The emulsifying agent is preferably a non-toxic emulsifying agent, and can be a surfactant or other emulsifying agent known in the art, or a mixture of one or more thereof. The emulsifying agents employed should be capable, when mixed with water and the herbicidally active limonene component, of forming an emulsion, preferably a homogeneous emulsion.
Useful emulsifying agents include lauryl dimethyl amine oxide, polyoxypropylene, octylphenol ethoxylates (5EO to 12EO), nonylphenol ethoxylates, polyoxyethylene block copolymers alcohol ethoxylate. Such alkylphenol ethoxylates are available commercially under the tradenames Surfonic® OP-100, Surfonic® OP-120, Surfonic® OP-70, Surfonic® OP-50, Triton X-405 and Triton X-45. Alternatively, the emulsifying agent can be a polyethoxylated castor oil (POE from 16-40). Such emulsifying agents are available commercially under the trade names of Alkamuls® EL620 and Alkamuls® EL-719 originally available from Rhone Poulenc Co, but now owned by Rhodia Inc. located at 259 Prospect Plains Road, Cranbury, N.J. 08512. It is non-toxic to humans and animals and will not cause skin or eye irritation. Surfonic® is a registered trademark of Huntsman Petrochemical Corporation, 500 Huntsman Way, Salt Lake City, Utah 84108. Triton® is a registered trademark of the Dow Chemical Company, Midland, Mich. Alkamuls® is a registered trademark of Rhodia Inc., 259 Prospect Plains Road, Cranbury, N.J. 08512.
Other commercially available emulsifying agents that are non-toxic, such as polyoxyethylenesorbitans supplied by ICI Americas or Sigma Chemical Company, may also be suitably used for the present invention. In a preferred embodiment a polyoxyethylenesorbitan monooleate such as Tween 80 may be used. Tween is a registered trademark of ICI Americas Inc.; 10 Finderne Avenue, Bridgewater, N.J. 088073300 and can be obtained from Sigma-Aldrich, 3050 Spruce St., St. Louis, Mo. 63103.
Surfactants such as anionic and nonionic surfactants are acceptable emulsifying agents for use in a herbicide composition of the present invention. Preferred anionic surfactants include salts of fatty acids, alkyl sulphates, alkyl ether sulphonates and alkyl aryl sulphonates. Preferred nonionic surfactants include nonylphenol ethoxylate surfactants. Examples of preferred surfactants include about 10 per cent sulfonic acid, about 6 per cent to about 7 per cent sodium laurel sulfate, from about 8 per cent to about 12 per cent alcohol ethoxylate and from about 1 per cent to about 2 per cent olefin sulfonate.
In general, the emulsifying agent should be present in an amount sufficient to render the herbicidally active limonene component miscible in the water or other hydrophilic solvent. Generally, the ready-to-use or diluted herbicide composition suitable for organic use will contain from about 0.05 percent to about 15 percent by weight of one or more emulsifying agent, preferably from about 0.5 percent to about 10 percent by weight and more preferably from about 2 percent to about 8 percent by weight. The herbicide concentrate will generally contain from about 1% to about 30% by weight emulsifying agent, more preferably from about 5% to about 20% by weight emulsifying agent.
Herbicides prepared according to embodiments of the present invention for use in organic production include emulsifying agents that are either natural products produced by non-chemical means or a synthetic compound defined by 7 CFR 205.601. As noted above, an inert material can comply with 7 CFR 205.601 by being included on either of the EPA's list 4A or 4B provided in Appendix A. Preferred emulsifiers from testing thus far include the surfactants, (nonylphenol polyoxyethylene 10), (alkylether mono & di-phosphate ester), (2,6,8-trimethyl-4-nonyl ether ethoxylate), ((poly(oxy-1,2-ethanediyl, alpha-(nonylphenyl-omega-hydroxy-), and (octylphenol ethoxylate).
While an inventive herbicide composition will typically comprise an emulsion of a herbicidally active limonene component with water, an inventive composition can include another non-toxic hydrophilic solvent instead of or in addition to water, such as, for example, ethanol, dilute acetic acid solutions, and the like.
As stated above, in one embodiment of the invention, the herbicide composition has a pH greater than 5. In another embodiment, the herbicide composition has a pH of from about 5 to about 10. The pH of the naturally acidic limonene can be raised by including a pH modifier in the herbicide composition. Examples of pH modifiers that can be selected for use in connection with the invention include, without limitation, potassium carbonate, sodium hydroxide and potassium hydroxide. In one preferred embodiment, the pH of the composition can range from about 6 to about 8. In another preferred embodiment, the pH range of the herbicidal composition is from about 8 to about 10.
For embodiments comprising organic formulations, preferred pH modifiers are selected from the group of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, and calcium carbonate. Other bases listed in EPA List 4A or 4B can also be used to provide formulations that can be used in organic production according to the present disclosure. Preferred embodiments of the formulations used for organic production typically range from about 6 to about 9.
Thus, in certain preferred embodiments of the invention, herbicide compositions, which are suitable for application as a spray in organic production, include about 8% to about 100% w/w %, preferably about 2% to about 25% w/w %, and more preferably from about 10% to about 20% by weight of a herbicidally active limonene component; from about 0.05% to about 15% w/w %, preferably about 0.5% to about 10% w/w %, and more preferably from about 2% to about 8% by weight of an emulsifying agent; a pH modifier in an amount effective to maintain a desired pH in the composition; and the balance of water or other selected hydrophilic solvent. In one preferred embodiment, there is provided a herbicide composition comprising a herbicidally active limonene component at a concentration of at least about 8% w/w %, an emulsifying agent effective to dissolve or disperse the herbicidally active limonene component in water, in an effective amount, a pH modifier effective to maintain a pH greater than 5, and a hydrophilic solvent, preferably water.
In another embodiment of the invention, the herbicide composition includes a wetting agent effective to improve the wetting properties, and possibly also the penetration properties, of the herbicide composition. When a wetting agent is included in a herbicide composition of the invention, the composition sprayed on the weeds or other vegetation can be applied at a lower rate (i.e., measured in gallons per acre) to achieve an equivalent result because the wetting agent causes each droplet of the composition to spread over a greater surface area of the plant. When a wetting agent is absent, the composition sprayed on a plant must cover a significantly greater surface area of the plant to achieve a similar result.
Many wetting agents suitable for use in herbicides are known to a person of ordinary skill in the art, and are available commercially. Examples of wetting agents that can be selected for use in connection with the invention, including formulations suited for organic production include, without limitation, nonylphenol ethoxylate, octylphenol ethoxylate, and anionic, cationic and nonionic (including silicone based) surfactants and methylated seed oil. In one preferred embodiment suited for organic production, the composition includes from about 0.05% to about 15% w/w % of a wetting agent. In another preferred embodiment suited for organic production, the herbicide composition includes from about 0.5% to about 10% w/w %, more preferably from about 2% to about 8% w/w %, of a wetting agent. For embodiments comprising organic formulations, suitable wetting agents include nonylphenol ethoxylate, octylphenol ethoxylate, dodecyl sulfate, sodium salt, caseins or other wetting agent listed in EPA List 4A or 4B reproduced in Appendix A.
Thus, in certain preferred embodiments of the inventive, herbicide compositions suitable for use in organic production, which are suitable for application as a spray, include about 8% to about 100% w/w %, more preferably about 8% to about 30% w/w %, and more preferably from about 10% to about 20% by weight of a herbicidally active limonene component; from about 0.05% to about 15% w/w %, more preferably about 0.5 to about 10% w/w %, and more preferably from about 2% to about 8% by weight of an emulsifying agent; from about 0.02% to about 1.0% w/w %, more preferably about 0.05% to about 0.5% w/w %, and the balance of water or other selected hydrophilic solvent. In one preferred embodiment, there are provided herbicide compositions comprising a herbicidally active limonene component at a concentration of at least about 8% w/w %, an emulsifying agent effective to dissolve or disperse the herbicidally active limonene component in water, a wetting agent at a concentration of at least about 0.05% w/w % and a hydrophilic solvent, preferably water.
In still another embodiment of the invention, the herbicide composition includes a wetting agent effective to improve the wetting and penetration properties of the composition and has a pH greater than 5. In another embodiment, the herbicide composition, including a wetting agent, has a pH from about 5 to about 10. In yet another embodiment, the pH is from about 6 to about 9. Examples of wetting agents and pH modifiers that can be selected for use in connection with the invention include those described above as non-limiting examples.
Thus, in certain preferred embodiments of the invention suitable for use in organic production, herbicide compositions, which are suitable for application as a spray, include about 8% to about 100% w/w %, more preferably about 8% to about 30% w/w %, and more preferably from about 10% to about 20% by weight of a herbicidally active limonene component; from about 0.05% to about 15% w/w %, more preferably about 0.5% to about 10% w/w %, and more preferably from about 2% to about 8% by weight of an emulsifying agent; a pH modifier in an amount effective to maintain a pH greater than 5; and the balance of water or other selected hydrophilic solvent. In one preferred embodiment, there are provided herbicide compositions comprising a herbicidally active limonene component at a concentration of at least about 8% w/w %, an emulsifying agent effective to dissolve or disperse the a herbicidally active limonene component in water, a wetting agent at a concentration of at least about 0.05% w/w %; a pH modifier effective to maintain a pH greater than 5, and a hydrophilic solvent, preferably water.
The addition of an added oil component to the herbicides discussed above can further increase the herbicide's efficacy, knock down, and long-term killing effect. In testing, so far, the formulations containing as little as 0.05% w/w % of an added oil component have demonstrated a beneficial effect resulting from the presence of the added oil component.
Thus, such further preferred embodiments discussed above, of the novel herbicide compositions suitable for use in organic production, taking into account the added oil component, include about 8% to about 100% w/w %, more preferably about 8% to about 30% w/w %, and more preferably from about 10% to about 20% by weight of a herbicidally active limonene component; from about 0.05% to about 10% w/w %, more preferably about 0.1% to about 8% w/w %, and more preferably from about 0.2% to about 5% by weight of an emulsifying agent; from about 0.02% to about 1.0% w/w %, more preferably about 0.05 to 0.5% and more preferably from about 0.1% to about 0.2% by weight of a wetting agent; a pH modifier in an amount effective to maintain a pH greater than 5; an amount of an added oil component sufficient to increase the herbicide's efficacy and lengthen the herbicide's period of efficacy; and the balance of water or other selected hydrophilic solvent. Based on initial studies, at least about 0.05% w/w % of an added oil component was preferred and from about 0.25% to about 0.5% w/w % of an added oil component was more preferred. However, more recent studies have shown that improved efficacy can be obtained with added oil components utilized in amounts up to about 35% by weight. For example preferred herbicidal concentrates containing from about 2% by weight to about 20% by weight have proven particularly efficacious. More preferred herbicidal concentrates contain from about 4% by weight to about 12% by weight added oil components. Preferred ready-to-use formulations and/or concentrates which have been diluted prior to use contain from about 0.5% to about 6% of the added oil component. The more preferred ready-to-use or diluted concentrates contain from about 1% to about 4% of the added oil component. While not to be bound by theory, it is believed from testing thus far that the added oil component contained in these preferred embodiments results in a better emulsion which retards the volatilization of limonene both before and after application to the plant and facilitates absorption onto leaf surfaces, thus increasing and extending the herbicide's efficacy and both its knockdown and long term ability. The added oil component also thickens the formulation resulting in better adhesion to the plant leaf surfaces.
The herbicide compositions of this invention suitable for use in organic production can be prepared by entirely conventional procedures known to those of ordinary skill in the art. For example, the compositions can be made by preparing an aqueous mixture of the water, the emulsifying agent and the herbicidally active limonene component. The resulting mixture can then be agitated until a dispersion or emulsion is formed. In one manner of making a herbicide composition according to the invention, each non-aqueous component can be added serially into a container, with stirring, preferably for at least about 1 minute after the addition of each component before adding the next component. After all of the non-aqueous components are mixed, the batch is agitated for another 10 minutes and the water can be mixed in to provide the herbicide composition. It can then be tested for quality control, filtered and filled into suitable containers for shipment, storage or immediate use.
The invention has been described thus far in terms of the final herbicide composition, and inventive herbicides can be made, sold and shipped as ready-to-use solutions. It is understood, however, that an excellent manner of providing a herbicide composition to an end user is by first preparing a concentrate formulation that is then diluted with water or other hydrophilic solvent by the end user to provide a herbicide composition for application to target weeds or other vegetation. Thus, herbicide compositions in accordance with the invention can be packaged as ready-to-use herbicides, or can be packaged as herbicide concentrate formulations. Where an inventive herbicide is to be used in a relatively small quantity, such as for home uses, the herbicide can be packaged in a conventional ready-to-use dispensing system. In contrast, when the end user is a farmer or professional applicator who intends to use the herbicide on a large area, it would be more desirable to provide a herbicide concentrate formulation that is ready for dilution. As used herein, the terms “formulation” and “herbicide formulation” are intended to refer to such a concentrate.
In one embodiment, the formulation includes a herbicidally active limonene component mixed with an emulsifying agent. In this embodiment, the formulation, along with a pH modifier, a wetting agent, or both (which can be obtained separately or provided with the formulation in a kit) are mixed with water or other hydrophilic solvent by the end user, for example, in a commercial sprayer. In another embodiment, the pH buffering agent, the wetting agent, or both, are premixed with the herbicidally active limonene component the emulsifying agent to provide a formulation that can be mixed directly with water or other hydrophilic solvent to provide a herbicide composition of course, it is also possible to provide all of the ingredients separately to an end user, with instructions regarding mixing the ingredients together to provide a herbicide composition or a herbicide formulation.
In a particularly preferred embodiment, the herbicide formulation includes a herbicidally active limonene component mixed with an emulsifying agent, and is provided separately from the pH modifier, the wetting agent, or both. A person of ordinary skill in the art will appreciate that the function of the emulsifying agent is to emulsify the herbicidally active limonene component with water, and the amount of emulsifying agent to include in a herbicide formulation or a herbicide composition is related to the amount of limonene in the formulation, irrespective of how diluted the limonene will be in the final herbicide, composition. Thus, whether the herbicide formulation is ultimately mixed with water in a water-to-formulation ratio of, for example, 1:1, 3:1 or higher, the amount of emulsifying agent per unit limonene can remain unchanged. In contrast, the amount of pH modifier that would desirably be included in a herbicide composition can depend upon the volume and the initial pH of water mixed with the formulation; and the amount of wetting agent that would desirably be included in a herbicide composition is dependent upon the total volume of the herbicide composition. Therefore, the emulsifying agent can advantageously be mixed with the herbicidally active limonene component in a herbicide formulation, while the pH modifier and the wetting agent are desirably added at the time the herbicide formulation is mixed with water to provide the final herbicide composition.
In certain preferred embodiments of the invention, there are provided herbicide formulations comprising a herbicidally active limonene component at a concentration of at least about 8% (w/w %), and an emulsifying agent at a concentration of from about 0.5% to about 10% (w/w %). In another embodiment, a herbicide formulation is provided that comprises a herbicidally active limonene component at a concentration of at least about 8% (w/w %), an emulsifying agent at a concentration of from about 0.5 to about 10% (w/w %), and a pH modifier in an amount effective to maintain the pH of the final herbicide composition above 5. In another embodiment, a herbicide formulation is provided that comprises a herbicidally active limonene component at a concentration of at least about 8% (w/w %), an emulsifying agent at a concentration of from about 0.5 to about 10% (w/w %), and a wetting agent at a concentration of from about 0.2% to about 10% (w/w %). In yet another embodiment, a herbicide formulation is provided that comprises a herbicidally active limonene component at a concentration of at least about 8% (w/w %), an emulsifying agent at a concentration of from about 0.5 to about 10% (w/w %), a wetting agent at a concentration of from about 0.2% to about 10 (w/w %); and a pH modifier in an amount effective to maintain the pH of the final herbicide composition above 5.
Said formulations can advantageously be mixed with water, and optionally one or more additional ingredients, at or near the location where the end user intends to apply the herbicide composition to plants. Thus, the invention provides in one aspect a method for making a herbicide composition that includes providing a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component and an emulsifying agent; diluting the formulation with water to provide a herbicide composition; and mixing into the herbicide composition a pH modifier effective to provide a pH greater than 5 in the composition. In another aspect, the invention provides a method for making a herbicide composition that includes providing a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component and an emulsifying agent; diluting the formulation with water to provide a herbicide composition; and mixing into the herbicide composition a wetting agent. In yet another aspect, there is provided a method for making a herbicide composition that includes providing a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component and an emulsifying agent; diluting the formulation with water to provide a herbicide composition; and mixing into the herbicide composition a wetting agent and a pH modifier effective to provide a pH greater than 5. The invention also provides a method for making a herbicide composition that includes providing a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component, an emulsifying agent and a pH modifier effective to provide a pH greater than 5 in the formulation; diluting the formulation with water to provide a herbicide composition; and mixing into the herbicide composition a wetting agent.
A herbicidal formulation made or selected in accordance with the present invention can also be packaged or otherwise provided together with additional components in a kit. In one embodiment of the invention, a kit for non-selective burn down of plants is provided that includes a container having therein a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component, an emulsifying agent and a pH modifier effective to provide a pH greater than 5; and instructions, recorded in a medium, for diluting the formulation to provide a herbicide composition. In another embodiment, also recorded in the medium are instructions for applying the herbicide composition to a pre-selected area for killing, controlling or suppressing plants growing in the area.
In another embodiment, a kit for non-selective burn down of plants is provided that includes a container having therein a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component and an emulsifying agent; and instructions, recorded in a medium, for diluting the formulation with water and adding a pH modifier effective to provide a pH greater than 5. In another embodiment, also recorded in the medium are instructions for applying the herbicide composition to a pre-selected area for indiscriminately killing, controlling or suppressing plants growing in the area.
In another form of the invention, there is provided a kit for non-selective burn down of plants that includes a container having therein a liquid herbicide, the herbicide including water, a herbicidally active limonene component, an emulsifying agent and a wetting agent; and instructions for applying the herbicide to a pre-selected area for killing, controlling or suppressing weeds or other plants in the area.
Also provided by the invention is a kit for nonselective burn down of plants that includes a container having therein a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component and an emulsifying agent; and instructions, recorded in a medium, for diluting the formulation and mixing in a wetting agent to provide a herbicide composition. In another embodiment, also recorded in the medium are instructions for applying the herbicide composition to a pre-selected area for killing, controlling or suppressing plants growing in the area.
In another form of the invention, a kit for nonselective burn down of plants is provided that includes a container having therein a liquid herbicide, the herbicide including water, a herbicidally active limonene component, an emulsifying agent, a wetting agent and a pH modifier effective to provide a pH greater than 5; and instructions for applying the herbicide to a pre-selected area for indiscriminately killing plants growing in the area. Another kit for non-selective burn down of plants is provided that includes a container having therein a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component, an emulsifying agent and a pH modifier effective to provide a pH greater than 5; and instructions, recorded in a medium, for diluting the formulation and adding a wetting agent to provide a herbicide composition. Still another embodiment of the invention is a kit for non-selective burn down of plants that includes a container having therein a liquid herbicide formulation, the herbicide formulation including a herbicidally active limonene component and an emulsifying agent; and instructions, recorded in a medium, for diluting the formulation with water and adding a wetting agent and a pH modifier effective to provide a pH greater than 5.
In addition to inclusion of herbicide formulations in a kit, as described above, the invention also contemplates providing a pre-made, complete herbicide composition with other components in a kit. Thus, in another, form of the invention, a kit for non-selective burn down of plants is provided that includes a container having therein a liquid herbicide, the herbicide including water, a herbicidally active limonene component, an emulsifying agent and one or more member selected from a wetting agent and a pH modifier effective to provide a pH greater than 5; and instructions, recorded in a medium, for applying the herbicide to a pre-selected area for indiscriminately killing plants growing in the area.
An inventive herbicide composition or herbicide concentrate formulation in accordance with the invention can be prepared to include a variety of other beneficial ingredients in addition to the ingredients discussed above. By “beneficial”, it is meant that the additional ingredient provides some additional functionality, efficacy, quality or other desirable attribute the herbicide or herbicide concentrate. For example, the herbicidally active limonene component may be blended with other, cheaper, and somewhat less volatile oils to form effective herbicides. Various natural oils (such as cottonseed oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, olive oil, coconut oil, coconut milk, corn oil, grape seed oil and peanut oil) have been reported by others to lack significant herbicidal activity; however, they can be blended with the herbicidally active limonene component of the present invention to form effective herbicidal compositions.
As discussed previously, it has also been discovered that the further addition of an added oil component, whether natural or processed, has proven beneficial to the preferred methods, kits and compositions described herein, increasing the herbicidal effectiveness of the embodiments as to immediate knockdown effect and to long term killing ability as well. For example, testing performed thus far has shown that the presence of such ethoxylated derivatives of castor oil have proven particularly useful as an added oil component as illustrated in Examples 4-7 below. As described above, based on testing performed thus far, this added oil component is preferred to be present in an amount of at least about 0.05% w/w % and in more preferred amounts of from about 0.25% to about 0.5% w/w %. For embodiments comprising organic formulations, preferred oils include oils that are either natural products obtained by non-chemical processes or oils listed in EPA List 4A or 4B, such as for example castor oil, cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and their ethoxylated derivatives.
One or more other ingredients may optionally be included in the compositions of the invention in order to provide aesthetic or other beneficial properties thereto. Such optional ingredients are, for example, antimicrobial agents, preservatives, deodorizers, coloring agents, fragrances, additional emulsifiers, additional solubilizers, corrosion inhibitors and additional solvents. The only requirement is that for any particular composition such optional ingredients be compatible with the other ingredients present in the composition or formulation.
By way of example, optional ingredients that can be incorporated include the following: an antimicrobial, such as, for example, phenolic compounds such as ophenylphenol and o-benzyl[p-chlorophenol]; quaternary ammonium compounds such as alkyldimethylbenzylammonium chloride, octyldecyldimethylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride and alkyldimethylbenzylammonium saccharinate; a deodorizer, such as, for example, N-alkyl-N-ethylmorpholinium ethyl sulfate; and a corrosion inhibitor, such as, for example, mono- and triethanolamine, ammonium hydroxide, sodium molybdate, sodium benzoate and tetra sodium ethylenediamine tetraacetate.
Other optional ingredients, as well as the amounts of the optional ingredients that can be employed, can readily be determined by one skilled in the art. For example, the phenolic and quaternary ammonium antimicrobial agents generally will not exceed a concentration of about 0.2 percent by weight in the final herbicide composition.
In order to provide a reasonable shelf-life to the herbicide compositions, it is preferable that a preservative be added to the composition. One such suitable preservative is sodium benzoate commercially supplied by Pfizer, Inc. Other commercially available preservatives used for preserving food, as would be known to those of ordinary skill in the art, may also be suitably used.
The beneficial agents described above, and many others, as would be contemplated by a person of ordinary skill in the art, are well known to those skilled in the art and are available commercially.
In a further aspect, the invention provides a method for killing, controlling or suppressing unwanted plant growth, wherein a herbicide composition provided in accordance with the present invention is applied to the unwanted plant or plants. The composition is then permitted to remain in contact with the plant, preferably the leaves of the plant, for a period of time sufficient to kill, control or suppress the plant. The time required for effective treatment of a given plant is dependent upon a variety of factors including, but not limited to concentration, spray coverage, pH of the herbicide solution, the species of the plant, the size/age/maturity of the plant, the availability of leaf surfaces or other green surfaces, and ambient conditions.
In an agricultural setting, spray applications with standard equipment typically use 20 to 35 gallons per acre for good coverage. Commercial electrostatic sprayers can bring the rates down significantly to less than 10 gal/acre and still achieve good coverage. In one manner of practicing the invention, the method includes spraying the herbicide on the area at a rate of from about 5 gal/acre to about 40 gal/acre. In another preferred manner of practicing the invention, the method includes spraying the herbicide on the area at a rate of from about 5 gal/acre to about 35 gal/acre.
In a homeowner or professional landscaping setting, spray applications on weeds are typically susceptible to runoff. Depending concentration of the herbicidally active limonene component in the herbicide composition as well as the density and maturity/size of the weeds, the equivalent spray volume per acre could be from a couple of quarts to 100 gallons per acre or more.
The invention will be further described with reference to the following specific Examples. It will be understood that these Examples are intended to be illustrative and not restrictive in nature.
EXAMPLE 1
Preparation of Herbicide Formulation
A herbicide formulation (MM-01) was prepared in accordance with the invention to include 94.0 w/w % limonene with the following emulsifiers: 1.3
w/w % TergitolTM NP-8 (nonylphenol ethoxylate surfactant), 2.0 w/w % TergitolTM NP-9 (nonoxynol 9.5 surfactant) and 2.7 w/w % Pluracol® P-425 (polypropylene glycol surfactant). The resulting formulation contains 88% limonene w/w %. For making a 100 gallon batch of this herbicide formulation, each component is added one by one and the mixture is stirred for 10 minutes after each addition and before adding the next component, to ensure complete and homogeneous blending of the components. After all the components are mixed, the batch is agitated for another 10 minutes, tested for quality control, filtered and filled into suitable containers.
Preparation of Herbicide Composition
The formulation was diluted with water to a 3:1 ratio by volume, represented as water:herbicide formulation ratio, to provide a herbicide composition (22% limonene w/w %). It is estimated that the pH of the 3:1 ratio composition was 4.5. The pH was lowered to 4 with lemon juice in a first test batch and raised to pH 9 with potassium carbonate in a second test batch. In addition, a herbicide composition with the 3:1 ratio was modified by adding 0.05% silicone based surfactant (Silwet) in a third test batch.
Protocol for Testing Herbicide Compositions
This field trial was conducted in Northern California during November, 2004. Each of the herbicide compositions described above was sprayed onto postemergent plants with backpack spray equipment to ensure good coverage without runoff. Primary weeds evaluated were Bermuda grass, fescue, and strawberry clover.
Color and wilting ratings were taken at 2 hours, 1 day, 2 days, and 7 days after treatment. Data collected for the test compositions were compared to an untreated control (UTC) and an area of vegetation treated with Paraquat (Gramoxone®). This trial contained 3 reps per treatment (except the Paraquat treatment which was a single strip). Treatments were randomly distributed within a rep. Color and wilting ratings were taken at 2 hours, 1 day, 2 days and 7 days after treatment. Results are set forth in FIGS. 1-6.
Discussion
In this trial, in which all treatment received 3:1 ratios (water:limonene formulation), the plants responded very rapidly. In broadleaf plants, discoloration followed by necrosis, and blackening of the leaf tissue occurred within 2 to 4 hours. In grasses, the response was more gradual, and leaves tended to gradually change from green to yellow to brown.
All MM-01 treatments resulted in a visual, burn down response within 2 hours. After Day 1, all MM-01 treatments were significantly different (P<0.05) from the untreated control (UTC).
The best MM-01 treatments were with 0.05% silicone surfactant and at pH 9. At days 2 and 7, both were significantly better than the other treatments. At days 2 and 7, the surfactant and pH 9 treatments were numerically equivalent to the Paraquat standard.
Wilting responses increased over time for all MM01 treatments. Color ratings for MM-01 did not change significantly over time.
The differences attributed to pH and surfactant are very apparent. In the 7 days after treatment, the impact of surfactant on wilting and color was tallied and the results are set forth in Table I below:












TABLE I







MMO1
MMO1





Effect
3:1 ratio
(3:1 ratio)





Measured
(pH 4.5)
+0.05%
Difference
Difference





















Wilting
2.67
3.33
0.6
24.7%



Color
3.67
5.00
1.33
36.2%












Average differences

1.00
30.5%









At 7 days after treatment, the impact of pH on wilting and color was also tallied, and the results are set forth in Table II below:













TABLE II






Effect
pH 4
pH 9
Difference
Difference








Wilting
3.00
3.67
0.67
22.3%



Color
3.33
4.67
1.34
40.2%












Average differences

1.01
31.3%









The use of a nonionic, silicon surfactant increased the wilting ratings by 24.7% and color by 36.2%.
The use of pH 9 increased the wilting ratings by 22.3% and color by 40.2%.
EXAMPLE 2
A field trial was conducted in Zellwood, Fla. The same formulation described in Example 1 was used in the Florida trial. All limonene treatments were made at a 3:1 ratio by volume, represented as water:herbicide formulation ratio, to provide a herbicide composition of 22% limonene (w/w %). Four reps per treatment were used; all treatments were randomly distributed within a rep. The weed species was common lambsquarters (1 to 2 feet in height). Treatments applied were pH 3, 7, 8 and 9 with and without a silicone surfactant, Silwet; each treatment was sprayed until runoff. The commercial burn down standard, Gramoxone (Paraquat) was included. Readings were taken at 1 and 2 hours, and 1, 3 and 7 days. An immediate wilting of the lambsquarters was observed with all limonene treatments starting at 1 hour. Effects with Gramoxone (Paraquat) were first observed on day 1 and improved by Day 3. After the first 2 hours limonene effects were stabilized. Results after 3 days are set forth in FIG. 7.
Large common lambsquarters are a difficult to control weed for limonene, making it a good candidate to evaluate difference caused by pH and surfactants. Evaluating the effect of pH, pH 7 gave the best response with and without surfactant. Without surfactant, it was significantly better than pH 3.
Side by side comparisons with the surfactant can also be made. Although not statistically significant, surfactant increased limonene activity with almost every pH with an average increase of 6.1% (see Table)












TABLE III






Treatment
pH
pH + Silwet
Difference
% Difference





















pH 3
3.7
4.3
0.6
16.2%



pH 7
4.7
5.0
0.3
6.4%



pH 8
4.3
4.7
0.4
9.3%



pH 9
4.3
4.0
−0.3
−7.5%












Average differences

0.25
6.1









EXAMPLE 3
A series of trials were conducted at Michigan State University (MSU) in East Lansing, Mich. to optimize the response with limonene on key weeds. Grasses responded strongly to limonene, which diminishes their suitability for pH and surfactant evaluations since all treatments gave an excellent herbicidal response. Mature common lambsquarters does not respond well to limonene making it a good candidate for these trials.
The same formulation described in Example 1 was used in the MSU greenhouse trials. Four reps per treatment were used. All limonene treatments were made at a 3:1 ratio by volume, represented as water:herbicide formulation ratio, to provide a herbicide composition of 22% limonene (w/w %). The herbicide composition was applied in spray chamber designed to mimic an agricultural application. Spray volume was 60 gallons per acre and the spray nozzle pressure was 40 psi. The weed species was common lambsquarters (1 to 2 feet in height). Treatments applied were pH 3, 5, 7, 8 and 9 without any surfactant. A single reading was taken at day 4. Results are set forth in FIG. 8.
There was a strong trend towards a pH response with pH 5 being the optimal pH. pH 7 and 8 had numerically better responses than pH 3 (11.4% and 7.5% respectively) or unadjusted limonene at pH 4.2 (14.7% and 10.6% respectively). pH 9 was significantly lower than the other treatments.
All surfactants improved the performance of the limonene formulation in water. The silicon based product, Sylgard, was significantly better by comparison.
A further series of greenhouse test treatments, as described below in Examples 4-7, were also conducted at Michigan State University (MSU). Weeds, typically in the 4-8 leaf stage, were contacted with control and test formulations. The spray volume used was 60 gallons per acre with a spray pressure of 40 psi. Plant conditions were determined and the percent control evaluated one day after treatment (Examples 4-5) and additionally five days after treatment (Examples 6-7). For all of these Examples, percentages (%) of components are always being given as weight percents (w/w %) of the total composition unless specifically indicated otherwise.
EXAMPLE 4
Common lambsquarter (Chenopodium album) was contacted with each of 6 different compositions, formulated as follows: 1) deionized water alone (control); 2) 21.6% d-limonene, 5% alcohol ethoxylate (BIO-SOFT® N25-7), 1.3% castor oil ethoxylate (TOXIMUL® 8242), and the balance water; 3) 21.6% d limonene alone in water; 4) 10% of an BIO-SOFT® N25-7 in water; 5) 5% TOXIMUL® 8242 and 3% hydrogen peroxide (to increase water solubility of the TOXIMUL® 8242) in water; and 6) 5% TOXIMUL® 8242 alone in water. BIO-SOFT® and TOXIMUL® 8242 are registered trademarks of The Stepan Company, 22 W Frontage Rd Northfield, Ill. 60093. The results of these tests and observations are provided in Table IV below.













TABLE IV











% control





BIO-SOFT ®


(1) day




TOXIMUL ®
N25-7

%
after


Treatment #
Limonene %
8242%
Surfactant %
Water %
H2O2
treatment






















1
0
0
0
100.00
0
0
c*


2
21.6
1.3
5
77.10
0
35
a*


3
21.6
0
0
78.40
0
0
c*


4
0
0
10
90.00
0
8
b*


5
0
5
0
92.00
3
0
c*


6
0
5
0
95.00
0
0
c*





*Treatments with the same letter are not statistically significant (P < 0.05).






As can be seen in Table IV, the formulations in Treatments 1, 3, 5 and 6 resulted in no practical effect on the treated plants. While the surfactant, BIO-SOFT® N25-7 (Treatment 4) had some effect, the preferred embodiment of the invention in Treatment 2 had substantially better herbicide performance controlling on the lambsquarter in only one day's time.
EXAMPLE 5
The study conducted in Example 4 was repeated with giant foxtail (Setaria faberi). The results are provided in Table V below.













TABLE V











% control





BIO-SOFT ®


(1) day




TOXIMUL ®
N25-7

%
after


Treatment #
Limonene %
8242%
Surfactant %
Water %
H2O2
treatment






















7
0
0
0
100.00
0
0
c*


8
21.6
1.3
5
77.10
0
46
a*


9
21.6
0
0
78.40
0
14
b*


10
0
0
10
90.00
0
13
b*


11
0
5
0
92.00
3
0
c*


12
0
5
0
95.00
0
0
a*





*Treatments with the same letter are not statistically significant (P < 0.05).






Once again, as can be seen in Table V, the formulations in Treatments 7, 11, and 12 resulted in no practical effect on the treated plants. While the surfactant, BIO-SOFT® N25-7 (Treatment 10) and limonene alone (Treatment 9) had some effect, the preferred embodiment of the invention in Treatment 8 had substantially better herbicide performance on the giant foxtail in only one day's time.
EXAMPLE 6
Common lambsquarter (Chenopodium album) was contacted here with nine different formulations illustrated in Table VI below. Both one day and five days after treatment, plant conditions were examined and the percent control evaluated through visual observation. The results are provided in Table VI below.












TABLE VI










BIO-SOFT ®

% Control



TOXIMUL ®
N25-7

(Days after Treatment)













Treatments #
Limonene %
8242%
Surfactant %
Water %
(1)
(5)


















13
0
0
0
100.00
0
e*
0
f*


14
21.6
0
0
78.40
30
d*
20
e*


15
21.6
0
2.5
75.90
40
c*
18
e*


16
21.6
0.25
2.5
75.65
50
b*
35
d*


17
21.6
0.38
2.5
75.52
46
bc*
34
d*


18
21.6
0.25
2.5
75.65
53
b*
39
cd*


19
21.6
0.25
3.75
74.40
69
a*
49
ab*


20
21.6
0.25
4.38
73.77
70
a*
45
bc*


21
21.6
0.25
5.0
73.15
73
a*
55
a*





*Treatments with the same letter are not statistically significant (P < 0.05).






As can be seen in Table VI, the formulations in Treatments 15-21 show an increased herbicidal effect with increasing quantities of TOXIMUL® 8242 and/or BIO-SOFT® N25-7 compared to Treatment 13 (the control) and Treatment 14 (aqueous Limonene alone). After one day, treatments 19-21 demonstrated substantially better herbicide performance on lambsquarter in only one day's time.
EXAMPLE 7
Velvetleaf (Abutilon theoprasti) was contacted here with nine more formulations composed as illustrated in Table VII below. Both one day and five days after treatment, plant conditions were examined and the percent control evaluated through visual observation. The results are provided in Table VII below.












TABLE VII










BIO-SOFT ®

% Control



TOXIMUL ®
N25-7

(Days after Treatment)













Treatments #
Limonene %
8242%
Surfactant %
Water %
(1)
(5)


















22
0
0
0
100.00
0
f*
0
f*


23
21.6
0
0
78.40
19
e*
48
e*


24
21.6
0
2.5
75.90
58
d*
65
cd*


25
21.6
0.25
2.5
75.65
71
abc*
68
bcd*


26
21.6
0.38
2.5
75.52
70
bc*
69
abc*


27
21.6
0.25
2.5
75.65
69
bc*
69
abc*


28
21.6
0.25
3.75
74.40
75
ab*
70
ab*


29
21.6
0.25
4.38
73.77
75
ab*
70
ab*


30
21.6
0.25
5.0
73.15
78
a*
73
a*





*Treatments with the same letter are not statistically significant (P < 0.05) . . .






As can be seen in Table VII, the formulations in Treatments 25-30 show an increased herbicidal effect with increasing quantities of TOXIMUL® 8242 and/or BIO-SOFT® N25-7 compared to Treatment 22 (the control), Treatment 23 (aqueous limonene alone) and Treatment 24 (aqueous BIO-SOFT® N25-7 alone). Treatments 25-30 had substantially better herbicide performance on velvetleaf in only one day's time.
EXAMPLE 8
The following ingredients were combined in sequence with stirring to provide a homogeneous blend:
76 parts by weight D-limonene
6 parts by weight pine oil
6 parts by weight castor oil, ethoxylated (POE40)
5 parts by weight nonylphenol ethoxylated (10 mole)
7 parts by weight octylphenol ethoxylate (5EO)
Three parts by weight water were slowly added to one part by weight of the blend with continued stirring and stirring continued for about 15 minutes following the addition of water. A ready-to-use (RTU) microemulsion of the herbicide suitable for organic production resulted.
EXAMPLE 9
The following ingredients were combined in sequence with stirring to provide a homogeneous blend:
70 parts by weight D-limonene,
10 parts by weight pine oil,
7 parts by weight castor oil, ethoxylated (POE40)
5.5 parts by weight nonylphenol ethoxylated (10 mole)
7.5 parts by weight octylphenol ethoxylate (5EO)
Three parts by weight water were slowly added to one part by weight of the blend with continued stirring and stirring continued for about 15 minutes following the addition of water. The resulting emulsion was suitable for use as a herbicide in an agricultural setting for organic production.
EXAMPLE 10
Lambsquarter (Chenopodium album) and Giant Foxtail (Setaria faberi) were contacted here with a control solution and the two emulsions described in Examples 8 and 9 above to provide the results illustrated in Table VIII below. Both one day and two days after treatment, plant conditions were examined and the percent control evaluated through visual observation.











TABLE VIII








%
%


Trial
Plant
Treatment
Control 1DAT
Control 2DAT







1
Common
CONTROL
 0b
 0b



Lambsquarters





2
Common
Example 8
92a
92a



Lambsquarters
Microemulsion











LSD (0.05)
 7
 7











3
Giant Foxtail
CONTROL
 0c
 0d


4
Giant Foxtail
Example 8
98a
99a




Microemulsion




5
Giant Foxtail
Example 9
90a
89a




Emulsion











LSD (0.05)
20
15





% Control refers to herbicidal activity, with 0% representing no effect and 100% representing plant death.


DAT is for Days After Treatment.


Treatments with the same letters are not statistically significant (P ≦ 0.05)






EXAMPLE 11
Barnyardgrass (Echinochloa crus-galli) and Velvetleaf (Abutilon theoprasti) were contacted here with a control solution and the two emulsions described in Examples 8 and 9 above to provide the results illustrated in Table IX below. At one hour, 18 hour and two days after treatment, plant conditions were examined and the percent control evaluated through visual observation.












TABLE IX








% Control
% Control






1 hr.
18 hr.
%





after
after
Control


Trial
Plant
Treatment
treatment
treatment
2 DAT




















6
Barnyardgrass
CONTROL
 0d
 0c
 0c


7
Barnyardgrass
Example 9
80b
95a
100a




Emulsion


8
Barnyardgrass
Example 8
90a
95a
100a




Microemulsion










LSD (0.05)
 2
 5
 6












9
Velvetleaf
CONTROL
 0c
 0c
 0c


10
Velvetleaf
Example 8
88a
95a
 98a




Microemulsion


11
Velvetleaf
Example 9
50b
73b
 76b




Emulsion










LSD (0.05)
 9
 3
 4





% Control refers to herbicidal activity, with 0% representing no effect and 100% representing plant death.


DAT is for Days After Treatment.


Treatments with the same letters are not statistically significant (P ≦ 0.05)






A comparison of the level of control achieved with the herbicide formulations suitable for use in organic production above (Examples 10 and 11) to the earlier control of Lambsquarters, Velvetleaf and Giant Foxtail demonstrates a higher level of control for the formulations tested. Additionally the formulations prepared in Examples 8 and 9 and tested above are suitable for use in organic production under the USDA's National Organic Program.
While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiments have been shown and described and that all changes and modifications that come within the spirit of the invention are desired to be protected.
While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiments have been shown and described and that all changes and modifications that come within the spirit of the invention are desired to be protected.







APPENDIX A







U.S. Environmental Protection Agency


List of Inert Pesticide Ingredients










CAS #
Name










List A










50-70-4
Sorbitol



50-81-7
L-Ascorbic acid



50-99-7
Dextrose



56-81-5
Glycerin



57-10-3
Hexadecanoic acid



57-11-4
Stearic acid



57-13-6
Urea



57-50-1
Sugar



62-54-4
Calcium acetate



63-42-3
D(+)-Lactose



68-04-2
Sodium citrate



77-92-9
Citric acid



97-64-3
Ethyl lactate



110-17-8
Fumaric acid



110-27-0
Isopropyl myristate



111-03-5
9-Octadeceneoic acid (Z)-,2,3-




dihydroxypropyl ester (9Cl)



112-80-1
Oleic acid



121-33-5
Vanillin



123-95-5
Butyl stearate



124-38-9
Carbon dioxide



127-08-2
Potassium acetate



127-09-3
Sodium acetate



137-66-6
Ascorbyl palmitate



138-22-7
Butyl lactate



142-18-7
Dodecanoic acid, 2,3-




dihydroxypropyl ester



143-07-7
Dodecanoic acid



143-18-0
9-Octandecenoic acid (Z)-,




potassium salt



143-19-1
9-Octandecenoic acid (Z)-,




sodium salt



144-33-2
Citric acid, disodium salt



144-55-8
Sodium bicarbonate



298-14-6
Potassium bicarbonate



471-34-1
Calcium carbonate



532-32-1
Benzoic acid, sodium salt



544-63-8
Myristic acid



546-93-0
Magnesium carbonate



553-70-8
Benzoic acid, magnesium salt



557-04-0
Octadecanoic acid, magnesium salt



557-05-1
Octadecanoic acid, zinc salt



582-25-2
Benzoic acid, potassium salt



589-68-4
Tetradecanoic acid, 2,3-




dihydroxypropyl ester



593-29-3
Octadecanoic acid, potassium salt



764-71-6
Potassium octoate



813-94-5
Citric acid, calcium salt (2:3)



822-16-2
Octadecanoic acid, sodium salt



557-05-1
Zinc stearate



813-94-5
Calcium citrate



866-83-1
Citric acid, monopotassium salt



866-84-2
Citric acid, tripotassium salt



994-36-5
Citric acid, sodium salt



1002-89-7
Ammonium stearate



1302-78-9
Bentonite



1309-37-1
Iron oxide (Fe2O3)



1309-48-4
Magnesium oxide



1314-13-2
Zinc oxide



1317-60-8
Hematite



1317-61-9
Iron oxide



1317-65-3
Limestone (no asbestos and less




than 1% crystalline silica)



1318-00-9
Vermiculite (no asbestos and less




than 1% crystalline silica)



1318-02-1
Zeolites (excluding erionite (CAS




Reg. No. 66733-21-9))



1318-93-0
Montmorillonite



1323-83-7
Octadecanoic acid, diester with




1,2,3-propanetriol (9Cl)



1327-36-2
Mullite



1327-43-1
Aluminum magnesium silicate



1327-44-2
Aluminum potassium silicate



1332-09-8
Pumice



1332-58-7
Kaolin (no asbestos and less than




1% crystalline silica)



1335-30-4
Aluminum silicate, hydrated



1343-88-0
Magnesium silicate



1343-90-4
Magnesium silicate, hydrate



1344-00-9
Silicic acid, aluminum sodium salt



1344-95-2
Calcium silicate



1345-25-1
Iron oxide (FeO)(Fe2O3), (Fe3O4)



1393-03-9
Soapbark (Quillaja saponin)



1406-18-4
Vitamin E



1592-23-0
Octadecanoic acid, calcium salt



1863-63-4
Benzoic acid, ammonium salt



1984-06-1
Octadecanoic acid, sodium salt



2090-05-3
Benzoic acid, calcium salt



3609-96-9
Citric acid, dipotassium salt



5323-95-5
9-Octadecenoic acid, 12-hydroxy-,




monosodium salt, (9Z,12R)



5743-26-0
Calcium acetate, monohydrate



5949-29-1
Citric acid, monohydrate



6100-05-6
Citric acid, tripotassium salt,




monohydrate



6107-56-8
Calcium octanoate



6132-04-3
Sodium citrate dihydrate



6858-44-2
Sodium citrate pentahydrate



6915-15-7
Malic acid



7440-44-0
Carbon



7447-40-7
Potassium chloride



7487-88-9
Sulfuric acid, magnesium salt (1:1)



7492-30-0
9-Octadecenoic acid, 12-hydroxy-,




monopotassium salt, (9Z,)



7631-86-9
Silicon dioxide (crystalline - free




forms only)



7646-93-7
Potassium bisulfate



7647-14-5
Sodium chloride



7693-13-2
Citric acid, calcium salt (2:3)



7699-41-4
Silica, amorphous, precipitated




and gel



7704-34-9
Sulfur



7727-37-9
Nitrogen



7727-73-3
Sulfuric acid, disodium salt,




decahydrate



7732-18-5
Water



7757-82-6
Sodium sulfate



7778-18-9
Calcium sulfate



7778-49-6
Citric acid, potassium salt



7778-80-5
Potassium sulfate



7782-42-5
Graphite (no asbestos and less than




1% crystalline silica)



8001-22-7
Soybean oil



8001-23-8
Safflower oil



8001-25-0
Olive oil



8001-26-1
Linseed oil (unboiled)



8001-29-4
Cottonseed oil



8001-30-7
Corn oil



8001-31-8
Coconut oil



8001-78-3
Castor oil, hydrogenated



8001-79-4
Castor oil



8002-03-7
Peanut oil



8002-24-2
Sperm oil



8002-31-1
Cocoa



8002-43-5
Lecithins



8002-48-0
Malt extract



8002-74-2
Paraffin wax



8002-75-3
Palm oil



8006-54-0
Lanolin



8006-95-9
Wheat germ oil



8007-69-0
Almond oil



8008-74-0
Sesame seed oil



8012-89-3
Beeswax



8013-17-0
Invert sugar



8015-86-9
Carnuba wax



8016-13-5
Fish oil



8016-70-4
Hydrogenated soybean oil



8028-66-8
Honey



8029-43-4
Corn syrup



8030-76-0
Lecithins, soya



8031-18-3
Fuller's earth



8042-47-5
White mineral oil (petroleum)



8052-35-5
Molasses



9000-07-1
Carrageenan



9000-11-7
Cellulose, carboxymethyl ether



9000-30-0
Guar gum



9000-40-2
Carob gum (locust bean gum)



9002-88-4
Polyethylene



9004-32-4
Cellulose carboxymethyl ether,




sodium salt



9004-34-6
Cellulose



9004-35-7
Cellulose acetate



9004-53-9
Dextrins



9004-62-0
Cellulose, 2-hydroxyethyl ether



9004-64-2
Cellulose, 2-hydroxypropyl ether



9004-65-3
Cellulose, 2-hydroxypropyl methyl




ester



9004-67-5
Cellulose, methyl ether



9005-25-8
Cornstarch



9005-38-3
Sodium alginate



9006-04-6
Rubber



9007-48-1
1,2,3-Propanetriol, homopolymer




(9Z)-9-octadecenoate



9009-32-9
1,2,3-Propanetriol, homopolymer,




octadecanoate



9050-36-6
Maltodextrin



994-36-5
Citric acid, sodium salt



10034-76-1
Calcium sulfate, hemihydrate



10034-99-8
Magnesium sulfate heptahydrate



10101-41-4
Calcium sulfate, dihydrate



10279-57-9
Silica, hydrate



11099-07-3
Octadecanoic acid, ester with 1,2,3-




propanetriol (9Cl)



11138-66-2
Xanthan gum



12001-26-2
Mica group minerals



12001-27-3
Lime (chemical) dolomitic



12003-38-2
Mica



12003-51-9
Silicic acid (H4SiO4), aluminum




sodium salt (1:1:1)



12063-19-3
Zinc iron oxide



12068-86-9
Iron magnesium oxide (Fe2MgO4)



12168-85-3
Calcium oxide silicate Ca3O(SiO4))



12207-97-5
Magnesium oxide silicate




(Mg3O(Si2O5)2), monohydrate



12259-21-1
Iron oxide (Fe2O3), hydrate



12694-22-3
9-Octadecanoic acid, monoester




with oxybis (propanediol)



12736-96-8
Silicic acid, aluminum potassium




sodium salt



13397-24-5
Gypsum



13397-26-7
Carbonic acid, calcium salt




(calcite)



13429-27-1
Tetradecanoic acid, potassium salt



13776-74-4
Silicic acid (H2SiO3), magnesium




salt (1:1)



13983-17-0
Wollastonite



14987-04-3
Magnesium silicon oxide




(Mg2Si3O8)



16389-88-1
Dolomite (CaMg(CO3)2)



18996-35-5
Citric acid, monosodium salt



24634-61-5
Potassium sorbate



25496-72-4
9-Octadecanoic acid (9Z)-,




monoester with 1,2,3-propanetriol



25637-84-7
9-Octadecenoic acid (9Z)-,diester




with 1,2,3-propanetriol



26402-22-2
Decanoic acid, monoester with




1,2,3-propanetriol



26402-26-6
Octanoic acid, monoester with




1,2,3-propanetriol



26499-65-0
Plaster of Paris



26657-95-4
Hexadecanoic acid, diester with




1,2,3-propanetriol (9Cl)



26657-96-5
Hexadecanoic acid, monoester with




1,2,3-propanetriol (9Cl)



27214-38-6
Tetradecanoic acid, monoester with




1,2,3-propanetriol (9Cl)



27215-38-9
Dodecanoic acid, monoester with




1,2,3-propanetriol (9Cl)



27638-00-2
Dodecanoic acid, diester with




1,2,3-propanetriol (9Cl)



31566-31-1
Octodecanoic acid, monoester with




1,2,3-propanetriol (9Cl)



36354-80-0
Octodecanoic acid, diester with




1,2,3-propanetriol (9Cl)



37244-96-5
Nepheline syenite



49553-76-6
9-Octodecanoic acid, ester with




1,2,3-propanetriol (9Cl)



51395-75-6
Cellulose, mixt. with cellulose




carboxymethyl ether sodium salt



53563-63-6
Tetradecanoic acid, diester with




1,2,3-propanetriol (9Cl)



53988-07-1
Decanoic acid, diester with 1,2,3-




propanetriol (9Cl)



60676-86-0
Silica, vitreous



61789-97-7
Tallow



61789-98-8
Cork



61789-99-9
Lard



61790-53-2
Diatomaceous earth (less than 1%




crystalline silica)



63231-67-4
Silica Gel (Ca3O(SiO4))(Ca(SiO3))



64044-51-5
Lactose, monohydrate



65996-61-4
Cellulose, pulp



68131-04-4
Humic acid, sodium salt



68131-12-4
Meat meal



68131-37-3
Corn syrup solids



68334-00-9
Hydrogenated cottonseed oil



68409-75-6
Bone meal



68424-10-2
Cottonseed meal



68442-85-3
Cellulose, regenerated



68476-25-5
Feldspar group minerals (no




asbestos and less




than 1% crystalline silica)



68476-37-9
Glue (as depolymerized animal




collagen)



68476-78-8
Cane syrup



68514-28-3
Humic acid, potassium salt



68514-74-9
Hydrogenated palm oils



68514-76-1
Citrus pulp, orange



68525-86-0
Corn flour



68553-81-1
Rice bran oil



68876-77-7
Yeast



68916-18-7
Coffee grounds



68916-91-6
Licorice extract



68917-73-7
Oils, wheat



68917-75-9
Wintergreen oil



68937-99-5
Sunflower seeds



68989-22-0
Zeolites, NaA



68991-42-4
Paprika



71010-52-1
Gellan gum (tolerance




pending approval)



71012-10-7
9-Octadecenoic acid, monoester




with tetraglycerol



84681-71-0
Hydrogenated rapeseed oil



85409-30-5
Bentonite, sodian



93763-70-3
Perlite, expanded



112926-00-8
Silica gel, pptd., cryst.-free



112945-52-5
Silica, amorphous, fumed, cryst.-




free



120962-03-0
Canola oil



130885-09-5
Perlite (no asbestos and less than




1% crystalline silica)



134134-87-5
Oat protein



—
Animal feed items conforming to




40 CFR 180.950(b)



—
Animal glue



—
Cardboard



—
Cat food



—
Clam shells



—
Commonly consumed food




commodities conforming to 40




CFR 180.950(a)



—
Cotton



—
Douglas fir bark



—
Edible fats and oils conforming to




40 CFR 180.950(c)



—
Egg shells



—
Oyster shells



—
Paper



—
Peat moss



—
Sawdust



—
Vinegar (maximum of 8% acetic




acid in solution)







List B










50-21-5
Lactic acid



57-48-7
D-Fructose



57-55-6
Propylene glycol



57-88-5
(3.beta.)-Cholest-5-en-3-ol



58-08-2
1H-Purine-2,6-dione, 3,7-dihydro-




1,3,7-trimethyl-



58-56-0
Thiamine mononitrate



58-86-6
D-Xylose



59-30-3
Folic acid



60-00-4
Ethylenediaminetetraacetic acid




(EDTA)



62-33-9
Ethylenediaminetetraacetic acid




(EDTA), calcium disodium



63-68-3
L-Methionine



64-02-8
Ethylenediaminetetraacetic acid




(EDTA), tetrasodium salt



64-17-5
Ethanol



64-19-7
Acetic acid



65-85-0
Benzoic acid



67-48-1
Choline chloride



67-63-0
Isopropyl alcohol



67-97-0
Vitamin D3



68-19-9
Vitamin B12



68-26-8
Vitamin A



71-23-8
n-Propanol



71-36-3
1-Butanol



73-22-3
L-Tryptophan



77-90-7
Acetyl tributyl citrate



78-23-9
Pentaerythritol monostearate



79-09-4
Propionic acid



80-56-8
alpha-Pinene



81-88-9
Rhodamine B (conforming to 40




CFR 180.2020)



91-53-2
Ethoxyquin



94-13-3
Propyl p-hydroxybenzoate



96-48-0
gamma-Butyrolactone



97-78-9
Glycine, N-methyl-N-(1-




oxododecyl)



98-86-2
Acetophenone



99-76-3
Methyl p-hydroxybenzoate



102-76-1
Glyceryl triacetate



103-26-4
Methyl cinnamate



106-65-0
Butanedioic acid, dimethyl ester



106-97-8
n-Butane



108-24-7
Acetic anhydride



110-15-6
Butanedioic acid



110-44-1
Sorbic acid



111-20-6
Decanedioic acid



111-27-3
1-Hexanol



111-70-6
1-Heptanol



112-30-1
1-Decanol



112-62-9
Methyl oleate



115-10-6
Dimethyl ether



115-83-3
Pentaerythritol tetrastearate



120-72-9
Indole, 1H-



124-07-2
Octanoic acid



124-10-7
Methyl tetradecanoate



126-96-5
Sodium diacetate



134-03-2
Sodium ascorbate



137-08-6
beta-Alanine,N-(2,4-dihydroxy-




3,3-dimethyl-1-oxobutyl)-, calcium




salt (2:1), (R)-(9CI) (CA IN



137-40-6
Sodium propionate



139-33-3
Ethylenediaminetetraacetic acid




(EDTA), disodium salt



139-44-6
Glyceryl tris(12-hydroxystearate)



141-78-6
Ethyl acetate



142-03-0
Aluminum acetate, basic



142-48-3
Glycine, N-methyl-N-(1-




oxooctadecyl)



143-28-2
Oleyl alcohol



147-14-8
Copper phthalocyanine blue



147-81-9
Arabinose (8CI, 9CI)



150-38-9
Ethylenediaminetetraacetic acid




(EDTA), trisodium salt



151-21-3
Dodecyl sulfate, sodium salt



334-48-5
Capric acid



497-19-8
Sodium carbonate



506-87-6
Carbonic acid, diammonium salt



515-98-0
Ammonium lactate



527-07-1
Gluconic acid, sodium salt



527-09-3
Cupric gluconate



533-96-0
Sodium sesquicarbonate



544-60-5
Ammonium oleate



563-71-3
Ferrous carbonate



577-11-7
Sodium bis(2-ethylhexyl)




sulfosuccinate



584-08-7
Carbonic acid, dipotassium salt



598-62-9
Carbonic acid, manganese(2+)




salt (1:1)



631-61-8
Ammonium acetate



637-12-7
Aluminum stearate



689-82-7
2-Butenedioic acid (Z)-,




monopotassium salt



811-97-2
1,1,1,2-Tetrafluoroethane



814-80-2
Calcium lactate



860-22-0
FD&C Blue No. 2



868-18-8
Sodium tartrate



928-96-1
3-Hexen-1-ol, (Z)-



1066-33-7
Ammonium bicarbonate



1302-42-7
Sodium aluminate



1305-62-0
Calcium hydroxide



1305-78-8
Calcium oxide



1309-42-8
Magnesium hydroxide



1310-58-3
Potassium hydroxide



1310-73-2
Sodium hydroxide



1312-76-1
Potassium silicate



1317-95-9
Tripoli



1318-23-6
Boehmite (Al(OH)O)



1328-53-6
C.I. Pigment Green 7



1336-21-6
Ammonium hydroxide



1338-41-6
Sorbitan monostearate



1343-98-2
Silicic acid



1344-09-8
Sodium silicate



1344-28-1
Aluminum oxide



1344-43-0
Manganous oxide



1639-66-3
Sodium dioctyl sulfosuccinate



2809-21-4
1-Hydroxyethylidene-1,1-




diphosphonic acid



3012-65-5
Ammonium citrate, dibasic



3624-77-9
Glycine, N-methyl-N-(1-oxo-9-




octadecenyl)-, sodium salt




(9CI) (CA INDEX NAME)



4075-81-4
Calcium propionate



4468-02-4
D-Gluconic acid, zinc complex



5136-55-0
Glycine, N-methyl-N-(1-




oxooctadecyl)-, sodium salt



5905-52-2
Ferrous lactate



5964-35-2
Ethylenediaminetetraacetic acid




(EDTA), tetrapotassium salt



5989-27-5
d-Limonene



6028-57-5
Aluminum octanoate



6381-92-6
Ethylenediaminetetraacetic acid




(EDTA), disodium salt dihy



6107-56-8
Calcium octanoate



6484-52-2
Ammonium nitrate



6834-92-0
Silicic acid (H2SiO3), disodium




salt



7320-34-5
Tetrapotassium pyrophosphate



7379-28-3
Ethylenediaminetetraacetic acid




(EDTA), potassium salt



7379-28-4
Ethylenediaminetetraacetic acid




(EDTA), sodium salt



7439-89-6
Iron (Fe)



7440-59-7
Helium



7440-66-6
Zinc (metallic)



7446-70-0
Aluminum chloride



7558-79-4
Disodium phosphate



7558-80-7
Sodium dihydrogen phosphate



7601-54-9
Trisodium phosphate



7631-99-4
Sodium nitrate



7632-05-5
Sodium phosphate



7647-01-0
Hydrogen chloride



7647-15-6
Sodium bromide



7664-38-2
Phosphoric acid



7664-93-9
Sulfuric acid



7681-38-1
Sodium bisulfate



7681-49-4
Sodium fluoride



7681-53-0
Sodium hypophosphite



7697-37-2
Nitric acid



7705-08-0
Ferric chloride



7720-78-7
Ferrous sulfate



7722-76-1
Ammonium phosphate (monobasic)



7722-88-5
Diphosphoric acid, tetrasodium salt



7727-43-7
Barium sulfate (1:1)



7722-88-5
Tetrasodium pyrophosphate



7757-86-0
Phosphoric acid, magnesium salt




(1:1)



7757-87-1
Phosphoric acid, magnesium salt




(2:3)



7757-93-9
Phosphoric acid, calcium salt (1:1)



7758-11-4
Potassium phosphate (dibasic)



7758-16-9
Sodium acid pyrophosphate



7758-23-8
Phosphoric acid, calcium salt (2:1)



7758-29-4
Sodium tripolyphosphate



7758-87-4
Tricalcium phosphate



7772-98-7
Sodium thiosulfate



7778-53-2
Phosphoric acid, tripotassium salt



7778-77-0
Potassium phosphate, monobasic



7779-88-6
Zinc nitrate



7779-90-0
Phosphoric acid, zinc salt (2:3)



7782-44-7
Oxygen



7782-63-0
Ferrous sulfate heptahydrate



7783-20-2
Ammonium sulfate



7783-28-0
Diammonium phosphate



7784-25-0
Ammonium alum



7785-87-7
Manganese sulfate



7785-88-8
Sodium aluminum phosphate



7786-30-3
Magnesium chloride



7803-63-6
Ammonium bisulfate



8000-25-7
Oils, rosemary



8000-46-2
Oils, geranium



8001-26-1
Linseed oil (boiled)



8001-69-2
Cod liver oil



8002-09-3
Pine oil



8002-33-3
Sulfated castor oil



8002-72-0
Onions, oil



8005-44-5
Fatty alcohols



8007-08-7
Oils, ginger



8008-57-9
Orange oil



8008-79-5
Spearmint oil



8009-03-8
Petrolatum



8014-19-5
Oils, palmarosa



8015-73-4
Oils, basil



8016-20-4
Oils, grapefruit



8016-85-1
Oils, tangerine



8016-96-4
Oils, vetiver



8021-28-1
Oils, Fir



8021-99-6
Charcoal, bone



8022-15-9
Oils, lavandin



8022-56-8
Oils, sage



8023-77-6
Resins, oleo-, capsicum



8023-84-5
Catnip



8028-48-6
Sweet orange peel tincture



8028-89-5
Caramel



8029-31-0
Beer



8030-12-4
Tallow,



8050-33-7
Polyoxyethylene ester of rosin



8052-48-0
Sodium tallow soap



8061-51-6
Lignosulfonic acid, sodium salt



8061-52-7
Lignosulfonic acid, calcium salt



9000-01-5
Gum Arabic



9000-50-4
Oils, oakmoss-resinoid (CA




INDEX NAME)



9000-69-5
Pectin



9000-70-8
Gelatin



9000-71-9
Casein



9002-86-2
Polyvinyl chloride resin



9002-89-5
Polyvinyl alcohol



9002-92-0
Polyoxyethylene dodecyl mono




ether



9003-01-4
Acrylic acid polymer



9003-04-7
Acrylic acid polymer, sodium salt



9003-05-8
Polyacrylamide



9003-06-9
Acrylamide - acrylic acid resin



9003-07-0
Polypropylene



9003-09-2
Ethene, methoxy-, homopolymer



9003-11-6
Polyoxyethylene-polyoxypropylene




copolymer



9003-18-3
Acrylonitrile—butadiene copolymer



9003-18-3
2-Propenenitrile, polymer with 1,3-




butadiene



9003-20-7
Polyvinyl acetate



9003-22-9
Vinyl chloride - vinyl acetate




copolymer



9003-39-8
Polyvinylpyrrolidone



9003-49-0
Polymerized butyl acrylate



9003-53-6
Polystyrene resin



9003-55-8
Butadiene-styrene copolymer



9003-56-9
2-Propenenitrile, polymer with 1,3-




butadiene and ethenylbenzene



9003-68-3
Polyethylene terephthalate



9003-70-7
Styrene-divinyl benzene copolymer




resin matrix



9004-81-3
Polyoxyethylene monolaurate



9004-82-4
Dodecanol, ethoxylated, monoether




with sulfuric acid, sodium salt



9004-95-9
Polyoxyethylene monohexadecyl




ether



9004-96-0
Polyoxyethylene monooleate



9004-98-2
Polyoxyethylene mono(cis-9-




octadecenyl) ether



9004-99-3
Polyoxyethylene monostearate



9005-00-9
Polyoxyethylene monooctadecyl




ether



9005-07-6
Polyoxyethylene dioleate



9005-08-7
Polyoxyethylene distearate



9005-37-2
Propylene glycol alginate



9005-42-9
Ammonium caseinate



9005-46-3
Sodium caseinate



9005-64-5
Polyoxyethylene sorbitan




monolaurate



9005-65-6
Polyoxyethylene sorbitan




monooleate



9005-66-7
Polyoxyethylene sorbitan




monopalmitate



9005-67-8
Polyoxyethylene sorbitan




monostearate



9005-70-3
Polyoxyethylene sorbitan trioleate



9005-71-4
Polyoxyethylene sorbitan tristearate



9006-50-2
Egg white



9011-05-6
Urea-formaldehyde resin



9011-13-6
Styrene - maleic anhydride resin



9011-14-7
Polymethyl methacrylate



9011-16-9
Maleic anhydride - methylvinyl




ether copolymer



9011-29-4
Polyoxyethylene sorbitol




hexastearate



9012-76-4
Chitosan



9014-85-1
Polyethylene glycol ether with 1,4-




diisobutyl-1,4-dimethylbutynediol




(2:1)



9014-90-8
Nonylphenol, ethoxylated,




monoether with sulfuric acid,




sodium salt



9014-92-0
Polyoxyethylene dodecylphenol



9014-93-1
Polyoxyethylene dinonylphenol



9016-45-9
Polyoxyethylene nonylphenol



9018-04-6
1,4-Butanediol, copolymer with




4,4′-diphenylmethane diisocyanate




and polytetramethylene glycol



9033-79-8
2-Propenoic acid, polymer with




sodium 2-propenoate



9036-19-5
Polyoxyethylene (1,1,3,3-




tetramethylbutyl)phenyl ether



9038-29-3
Oxirane, methyl-, polymer with




oxirane, decyl ether



9038-95-3
Polyethylene-polypropylene glycol,




monobutyl ether



9041-33-2
Oxirane, methyl-, polymer with




oxirane, mono-2-propenyl ether



9063-38-1
Starch, carboxymethyl ether,




sodium salt



9064-13-5
Poly[oxy(methyl-1,2-ethanediyl)],




alpha(methylphenyl)-omega-




hydroxy



9081-17-8
Nonylphenol, ethoxylated,




monoether with sulfuric acid



9084-06-4
Naphthalenesulfonic acid, polymer




with formaldehyde, sodium salt



10016-20-3
alpha—Cyclodextrin



10025-67-9
Sulfur chloride



10028-22-5
Ferric sulfate



10043-01-3
Aluminum sulfate



10043-52-4
Calcium chloride



10102-17-7
Sodium thiosulfate, pentahydrate



10103-46-5
Calcium phosphate



10124-56-8
Sodium hexametaphosphate



10191-41-0
2H-1-Benzopyran-6-ol,3,4-




dihydro-2,5,7,8-tetramethyl-




2-(4,8,12-trimethyltridecyl)-



10213-79-3
Silicic acid, disodium salt,




pentahydrate



10361-29-2
Carbonic acid, ammonium salt



10377-60-3
Magnesium nitrate



12001-76-2
Vitamin B complex



12124-97-9
Ammonium bromide



12125-02-9
Ammonium chloride



12173-47-6
Hectorite



12174-11-7
Attapulgite



12269-78-2
Pyrophyllite



12276-01-6
Ethylenediaminetetraacetic acid




(EDTA), copper (II) salt



13092-66-5
Phosphoric acid, magnesium salt




(2:1)



13463-67-7
Titanium dioxide



13870-28-5
Silicic acid (H2Si2O5), disodium




salt



14025-15-1
Ethylenediaminetetraacetic acid




(EDTA), disodium copper salt



14025-21-9
Ethylenediaminetetraacetic acid




(EDTA), disodium zinc salt



14464-46-1
Cristobalite



14729-89-6
Ethylenediaminetetraacetic acid




(EDTA) disodium iron (II) salt



14807-96-6
Talc (no asbestos and less than 1%




crystalline silica)



14977-37-8
Potassium magnesium sulfate




(Mg2K2(SO4)3)



15375-84-5
Ethylenediaminetetraacetic acid




(EDTA) disodium manganese



15468-32-3
Tridymite (SiO2)



15593-82-5
Silicic acid (H6Si2O7),




hexasodium salt



15708-41-5
Ethylenediaminetetraacetic acid




(EDTA) iron(III) sodium salt



15974-07-9
Calcium zinc phosphate




(CaZn2(PO4)2)



17099-81-9
Ethylenediaminetetraacetic acid




(EDTA), iron(III) salt



17217-76-4
1,2,3-Propanetricarboxylic acid, 2-




hydroxy-, iron (3+) salt (1:1),




trihydrate



17421-79-3
Ethylenediaminetetraacetic acid




(EDTA) monosodium salt



17572-97-3
Ethylenediaminetetraacetic acid




(EDTA), tripotassium salt



18917-93-6
Magnesium lactate



19019-43-3
Glycine, N-(carboxymethyl)-N-[2




[(carboxymethyl)amino]ethyl]-,




trisodium salt



21645-51-2
Aluminum hydroxide



20344-49-4
Iron hydroxide oxide (Fe(OH)O)



20427-59-2
Copper (II) hydroxide



20727-33-7
Dioctyl* sodium sulfosuccinate-




methylheptyl) (* octyl is




1-methylheptyl)



20824-56-0
Ethylenediaminetetraacetic acid




(EDTA), diammonium salt



21645-51-2
Aluminum hydroxide



21662-09-9
4-Decenal, (4Z)-



24937-78-8
Ethylene, polymer witrh vinyl




acetate



24937-78-8
Ethylene, polymer with vinyl




acetate



24938-04-3
Polyethylene terphthalate-




polyethylene isophthalate film




Propenoic acid, 2-methyl-butyl




ester, polyer with 2-




(dimethylamino)ethyl 2-methyl-2-




propenoate and methyl 2-



24938-16-7
2-methyl-2-propenoate



24968-79-4
Acrylic acid methyl ester, polymer




with acrylonitrile



25038-59-9
Poly(ethylene terephthalate)



25067-01-0
Vinyl acetate, polymer with n-butyl




acrylate



25085-02-3
Sodium acrylate, polymer with




acrylamide



25085-34-1
Styrene acrylic acid copolymer



25085-39-6
2-Propenoic acid, polymer with 1,3-




butadiene and ethenylbenzene



25085-41-0
Vinyl acetate-butyl acrylate-




acrylic acid terpolymer



25086-29-7
Vinylpyrrolidinone-styrene




polymer



25086-48-0
Vinyl chloride, vinyl acetate and




vinyl alcohol copolymer



25086-89-9
Polyvinylpyrrolidone-vinyl acetate




copolymer



25087-06-3
Maleic acid monoethyl ester-vinyl




methyl ether copolymer



25119-68-0
Maleic acid monobutyl ester-vinyl




methyl ether copolymer



25119-83-9
Acrylic acid, copolymer with butyl




acrylate



25135-39-1
Acrylic acid, polymer with ethyl




acrylate and methylmethacrylate



25153-40-6
Methyl vinyl ether-maleic acid




copolymer



25212-88-8
Ethyl acrylate-methacrylic acid




copolymer



25213-02-9
1-Hexene, polymer with ethene



25213-24-5
Vinyl alcohol-vinyl acetate




copolymer



25231-21-4
Polyoxypropylene monostearyl




ether



25266-02-8
Maleic anhydride-1-octadecene




copolymer



25322-68-3
Polyethylene glycol



25322-69-4
Polypropylene glycol



25608-12-2
2-Propenoic acid, homopolymer,




potassium salt



25719-52-2
Dodecyl 2-methylacrylate polymer



25719-60-2
beta-Pinene homopolymer



25750-06-5
Styrene-methyl methacrylate-2-




ethylhexyl acrylate copolymer



25750-84-9
Acrylic acid, butyl ester, polymer




with ethylene



25956-17-6
FD&C Red No. 40



25987-30-8
Acrylic acid, polymer with




acrylamide, sodium salt



25987-66-0
Acrylic acid butyl ester, polymer




with methacrylic acid, methyl




methacrylate and styrene



26027-38-3
p-Nonylphenol, ethoxylated



26099-09-2
Maleic acid homopolymer



26160-96-3
Butylated polyvinylpyrrolidone



26183-44-8
Dodecyl alcohol, ethoxylated,




monoether with sulfuric acid



26183-52-8
Polyoxyethylene monodecyl ether



26266-57-9
Sorbitan monohexadecanoate



26316-40-5
Ethylene oxide-propylene oxide




copolymer ethylenediamine ether



26337-35-9
Acetic acid ethenyl ester, polymer




with carbon monoxide and ethene



26604-01-3
Acrylic acid, polymer with




acrylonitrile, ethyl acrylate and N-




(hydroxymethyl)acrylamide



26635-76-7
Glycols, polyethylene,




mono(oleylamines)-ethyl ester



26636-39-5
Polyoxyethylene monoeicosyl ether



26636-40-8
Polyoxyethylene docosyl ether



26873-77-8
2-Propenoic acid, 2-methyl-,




polymer with ethenylbenzene, 2-




ethylhexyl 2-propenoate and




2-propene



26915-70-8
Tridecanol, ethoxylated, phospate




ester



27012-62-0
Acrylic acid methyl ester, polymer




with acrylonitrile and 1,3-butadiene



27252-80-8
Poly(oxy-1,2-ethanediyl), alpha-




methyl-omega(2-propenyloxy)-




(CA INDEX NAME)



27274-31-3
Poly(oxy-1,2-ethanediyl),.alpha.-2-




propenyl.-omega.-hydroxy-



27306-78-1
Poly(oxy-1,2-ethanediyl), alpha-




methyl-omega[3-[1,3,3,3-




tetramethyl-1-




[(trimethylsilyl)oxy]disiloxanyl]




propoxy]-(2-propenyloxy)



27306-79-2
Polyoxyethylene monotetradecyl




ether



27458-93-1
Isooctadecanol



27756-15-6
Acrylic acid-stearyl methacrylate




copolymer



27937-16-4
Poly[imino(1-oxo-1,12-




dodecanediyl)]



28062-44-4
Vinyl pyrrolidone-acrylic acid




copolymer



28211-18-9
2-Pyrrolidinone, 1-ethenyl-,




polymer with 1-eicosene



28430-58-2
Vinyl acetate, polymer with methyl




acrylate and methyl methacrylate



29437-34-1
2-Propenoic acid, butyl ester,




polymer with ethyl 2-propenoate




and 2-propenenitrile



29710-31-4
Cetyl octanoate



29781-80-4
(alpha-D-Glucopyranoside, octyl



29836-26-8
(beta-D-Glucoopyranoside, octyl



30364-51-3
Glycine, N-methyl-N-(1-




oxotetradecyl)-, sodium salt



30581-59-0
Vinyl pyrrolidone-




dimethylaminoethylmethacrylate




copolymer



30795-23-4
2-Propenoic acid, butyl ester,




polymer with ethenylbenzene and




2-ethylhexyl 2-propenoate



30938-41-1
Polymer of vinyl acetate, n-butyl




acrylate, vinyl chloride, and acrylic




acid



31307-92-3
Polyoxyethylene sorbitol



31307-95-6
Maleic acid monoisopropyl ester-




vinyl methyl ether copolymer



31394-71-5
Polypropylene glycol monooleate



31800-88-1
Octyloxypoly(ethyleneoxy)ethyl




phosphate



32649-30-2
2-Butenedioic acid (Z)-, polymer




with ethenol, sodium salt



36347-52-1
Ethanaminium, N,N,N-trimethyl-2-




[(2-methyl-1oxo-2-propenyl)oxy]-,




chloride, polymer with methyl 2-




methyl-2-propenoate



36653-82-4
Cetyl alcohol



37199-81-8
Maleic anhydride, polymer with




2,4,4-trimethylpentene, sodium salt



37280-82-3
Polyoxyethylene polyoxypropylene




phosphate



37286-64-9
Polyoxypropylene monomethyl




ether



37340-60-6
Nonylphenol, ethoxylated,




phosphate ester, sodium salt



37764-25-3
N,N-Diallyl-2,3-




dichloroacetamide



39362-51-1
Oxirane, methyl-, polymer with




oxirane, acetate



39464-64-7
Dinonylphenol, ethoxylated,




phosphated



41444-50-2
Octyl glucoside



41444-55-7
Decyl glucoside



41487-53-0
2-Propenoic acid, 2-methyl-,




polymer with ethyl 2-




propenoate, sodium salt



41928-09-0
Polyethylene glycol ether with 2,2′




methylenebis(4-(tert-octyl)phenol)




(2:1)



50769-39-6
Butylpolyethoxyethanol esters of




phosphoric acid 4B



51192-09-7
Polyoxyethylene glycerin




monooleate



51609-41-7
4-Nonylphenol, ethoxylated,




phosphate ester



51617-79-9
Polyoxyethylene octadecylphenol



51811-79-1
Nonylphenol, ethoxylated,




phosphate ester



52503-15-8
Polyethylene glycol nonylphenyl




ether phosphate potassium salt



52558-73-3
Glycine, N-methyl-N-(1-




oxotetradecyl)



52831-04-6
Acrylic acid-alpha-methylstyrene-




styrene copolymer



53504-41-9
Polyurethane



54116-08-4
Sodium tridecylpoly(oxyethylene)




sulfate



54549-23-4
D-Glucoside, octyl



55069-68-6
Polyethylene glycol hexaether with




sorbitol, diester with dodecanoic




and oleic acids



55989-05-4
2-Propenoic acid, 2-methyl-,




polymer with ethyl 2-




propenoate and methyl 2-methyl-2-




propenoate, ammonium salt



56090-69-8
Oxirane, methyl-, polymer with




oxirane, monoacetate, 2-propenyl




ether



56388-96-6
Poly(oxyethylene)tridecylacetic




acid



57171-56-9
Polyoxyethylene sorbitol




hexaoleate



57451-03-3
Nonylphenol, ethoxylated,




monoether with




sulfuric acid, triethanolamine salt



58128-22-6
Octadecanoic acid, 12-hydroxy-,




homopolymer, octadecanoate



58846-77-8
N-Decyl glucoside



59139-23-0
Polyethylene glycol nonylphenyl




ether phosphate ethanolamine salt



59766-31-3
Potassium titanium oxide




(K2Ti8O17)



59800-21-4
Poly(oxy-1,2-ethanediyl), alpha-




hydro-omegahydroxy-, ether with




D-glucitol (6:1),-9-octadecenoate



59947-99-8
beta-D-Glucoside, decyl



60092-15-1
Maleic anhydride-methylstyrene




copolymer, sodium salt



60828-78-6
Polyoxyethylene 2,6,8-trimethyl-4-




nonyl ether



60864-33-7
Benzyl ether of 1,1,3,3-




tetramethylbutylphenoxy




polyethoxy ethanol



60874-89-7
Polyethylene glycol ether with




methylenebis(diamylphenol)



61725-89-1
Oxirane methyl-, polymer with




oxirane, tridecyl ether



61788-60-1
Methyl esters of cottonseed oil



61789-14-8
Glycerides, tallow sesqui-,




hydrogenated



61789-30-8
Potassium coconut oil soap



61790-37-2
Fatty acids, tallow



61790-38-3
Fatty acids, tallow, hydrogenated



61790-90-7
Fatty acids, tall-oil, hexaester with




sorbitol, ethoxylated



61790-92-9
Fatty acids, tall-oil, pentaester with




sorbitol, ethoxylated



61791-12-6
Castor oil, ethoxylated



61791-23-9
Soybean oil, ethoxylated



61791-26-2
Amines, tallow alkyl, ethoxylated



61791-31-9
N,N-Bis(2-hydroxyethyl)(coconut




oil alkyl)amine



61824-34-8
Polyoxyethylene sorbitol




pentaoleate



61827-84-7
Oxirane, methyl-, polymer with




oxirane, octyl ether



61016-40-3
Ethylenediaminetetraacetic acid




(EDTA) disodium copper (II)



62386-95-2
Methyl vinyl ether-maleic acid




copolymer calcium sodium salt



63089-86-1
Polyoxyethylene sorbitol




tetraoleate



63148-62-9
Silicones and siloxanes, dimethyl



63150-03-8
2-Propenoic acid, 2-methyl-,




dodecyl ester, polymer with eicosyl




2-methyl-2-propenoate, hexadecyl




2-methyl-2-propenoate, octadecyl 2-




methyl-2-propenoate, pentadecyl 2-




methyl-2-propenoate, tetradecyl 2-




methyl-2-propenoate and tridecyl 2-




methyl-2-propenoate



63231-81-2
Poly(vinylpyrrolidone-1-




hexadecene)



63393-89-5
Coumarone-indene resin



63428-83-1
Polyamide resins



63705-03-3
Polyglycerol diisostearate



63744-68-3
Butyl acrylate-ethyl acrylate-




methacrylic acid-methyl




methacrylate-styrene copolymer



63798-35-6
Starch acetate adipate



64754-90-1
Chlorinated polyethylene



65405-40-5
Butyl acrylate-vinyl acetate-acrylic




acid copolymer



65996-63-6
Starch, acid-hydrolyzed



65997-15-1
Cement, portland, chemicals



66070-75-5
Fatty acids, tall-oil, polymers with




bisphenol A and epichlorohydrin



66070-87-9
Polyglyceryl phthalate ester of




coconut oil fatty acid



66071-03-2
Linseed oil, polymd.,oxidized



66071-16-7
Soybean oil, polymer with maleic




anhydride



66071-94-1
Corn, steep liquor



66402-68-4
Metakaolin



67401-50-7
Ethylenediaminetetraacetic acid




(EDTA), tetrasodium salt



67674-67-3
Poly(oxy-1,2-ethanediyl), .alpha.-




3-[1,3,3,3-tetramethyl-1




[(trimethylsilyl)oxy]disiloxanyl]




propyl]-omega.hydroxy-



67701-08-0
Fatty acids, C16-18 and C18-




unsatd



67701-09-1
Potassium salts of fatty acids (C8-18




and C18 unsatd.)



67701-10-4
Soap: (Fatty acids, C8-18 and C18-




unsatd., sodium salts)



67746-08-1
Linseed oil, polymd.



67761-98-2
Fatty acids, tall-oil, polymer with




ethylene glycol, pentaerythritol,




and phthalic anhydride



67762-09-8
Soybean oil, polymer with ethylene




glycol, glycerol, pentaerythritol and




phthalic anhydride



67762-38-3
Fatty acids, C16-18 & C18-unsatd.,




Me esters



67762-87-2
Siloxanes and silicones, di-Me, 3-




hydroxypropyl Me, ethers with




polyethylene-polypropylene glycol



67762-90-7
Dimethyl silicone polymer with




silica



67762-96-3
Siloxanes and silicones, di-




Me, hydroxyterminated, ethers with




polypropylene glycol mono-Bu




ether



67922-57-0
Polyethylene glycol nonylphenyl




ether phosphate magnesium salt



68002-20-0
1,3,5-Triazine-2,4,6-triamine,




polymer with formaldehyde,




methylated



68002-70-0
Glycerides, C16-22



68037-40-1
2,5-Furandione, polymer with




ethylbenzene, sulfonated, sodium




salt



68037-62-7
Siloxanes and silicones, di-Me, Me




hydrogen, reaction products with




polyethylene glycol monoacetate



68038-31-3
Fatty acids, tall-oil, polymers with




pentaerythritol, phthalic anhydride




and rosin



68071-54-5
Castor oil, dehydrated, polymer




with p-tertbutylbenzoic acid,




glycerol and phthalic anhydride




(CA INDEX NAME)



68130-47-2
Poly(oxy-1,2-ethanediyl), alpha-




hydro-omega-hydroxy-mono-




C8-10-alkyl ethers, phosphates



68131-29-3
Soybean oil, polymer with phthalic




anhydride, trimellitic anhydride and




trimethylolpropane



68131-40-8
Alcohols, C11-C15-secondary,




ethoxylated



68152-57-8
Rosin, fumarated, polymer with




ethylene glycol and pentaerythritol



68153-10-6
Oils, lard, sulfated, sodium salts,



68154-33-6
Fatty acids, coco, esters with




sorbitan, ethoxylated-



68187-71-3
Calcium salts of tall-oil fatty acids



68187-76-8
Castor oil, sulfated, sodium salt



68187-84-8
Castor oil, oxidized



68201-51-4
Oils, menhaden, oxidized



68308-36-1
Soybean meal



68309-49-9
Soybean oil, polymer with




isophthalic acid, linseed oil and




trimethylolpropane



68333-69-7
Rosin, maleated, polymer with




pentaerythritol



68333-79-9
Ammonium polyphosphate



68411-97-2
Glycine, N-methyl-, N-coco acyl




derivs. INDEX NAME)



68413-17-2
Fatty acids, tall-oil, polymers with




isophthalic acid, pentaerythritol and




walnut oil



68424-50-0
Fatty acids, tall-oil, C12-15-alkyl




esters, sulfated, sodium salts



68424-61-3
Glycerides, C16-18 and C18-




unsatd. mono- and di-



68425-44-5
Amides, coco, N-(hydroxyethyl),




ethoxylated



68440-66-4
Siloxanes and silicones, di-Me, 3-




hydroxypropyl Me, ethers with




polypropylene glycol mono-Bu




ether (CA INDEX NAME)




(Pending)



68441-17-8
Oxidized polyethylene



68458-49-1
Polyphosphoric acids, esters with




polyethylene glycol nonylphenyl




ether



68476-82-4
Peanut meal



68511-11-5
Hexanedioic acid, polymer with 1,4-




butanediol and 1,2-propanediol,




didodecanoate



68513-95-1
Soy flour



68514-61-4
Milk, hydrolyzed



68514-75-0
Oils, orange-juice



68525-90-6
Fatty acids, C8-18, esters with




sorbitol, ethoxylated



8526-94-3
Alcohols, C12-20



68527-08-2
Alkenes, C > 10 .alpha.-, polymd.



68551-13-3
Alcohols, C12-15, ethoxylated




propoxylated



68553-02-6
Fatty acids, coco, esters with




polyethylene glycol ether with




glycerol (3:1)



68554-64-3
Siloxanes and silicones, di-Me, 3-




hydroxypropyl Me, ethers with




polyethylene glycol mono-Me




ether



68585-15-9
Oxirane, methyl, polymer with




oxirane, mono C6-C10 alkyl ethers,




phosphates



68601-19-5
Poly(oxy-1,2-ethanediyl),




.alpha.,.alpha.′[[methyl[3-




(tridecyloxy)propyl]imino]di-2,1




ethanediyl



68605-57-2
Fatty acids, tall-oil, polymers with




bisphenol A, epichlorohydrin, rosin




and tung oil



68608-58-2
Whey



68611-44-9
Silane, dichlorodimethyl-, reaction




products with silica



68630-83-1
Styrene, polymer with methacrylic




acid and polyethoxylated (Z)-2-




butenedioic acid



68646-20-4
Sorbitol tall oil fatty acid




sesquiester, ethoxylated



68648-20-4
Fatty acids, tall-oil, sesquiesters




with sorbitol, ethoxylated



68648-89-5
Benzene, ethenyl-, polymer with 2-




methyl-1,3-butadiene, ydrogenated



68650-09-9
Fatty acids, tall-oil, mixed esters




with glycerol and polyethylene




glycol



68650-28-2
Polyethylene glycol-polyisobutenyl




anhydride-tall oil fatty acid




copolymer



68890-80-2
Benzene, ethenyl-, polymer with




2,5-furandione, 2-butoxyethyl




ester, ammonium salt



68891-29-2
Alcohols, C8-10, ethoxylated,




monoether with sulfuric acid,




ammonium salt



68908-64-5
Poly(oxy-1,2-ethanediyl),




-hydro-. omega.-hydroxy-, mono-




C10-12-alkyl ethers, phosphates



68909-20-6
Silanamine, 1,1,1-trimethyl-N-




(trimethylsilyl)-, hydrolysis




products with silica



68917-18-0
Cornmint oil



68919-53-9
Fatty acids, soya, Me esters



68919-54-0
Sunflower-oil fatty acids, Me ester



68920-66-1
Alcohols, C16-18 and C18-unsatd.,




ethoxylated



68920-69-4
Alcohols, C9-11, propoxylated



68937-55-3
Siloxanes and silicones, di-Me, 3-




hydroxypropyl Me, ethoxylated




propoxylated



68938-54-5
Siloxanes and silicones, di-Me, 3-




hydroxypropyl Me, ethers with




polyethylene glycol mono-Me




ether



69011-22-9
Benzene, diethenyl-, polymer with




etenylbenzene and




ethenylethylbenzene, sulfonated,




sodium salts



69227-21-0
Alcohols, C12-18, ethoxylated




propoxylated



69364-63-2
Poly(oxy-1,2-ethanediyl), alpha-




isohexadecylomega-hydroxy-



69669-25-6
Potassium salts of fatty acids-




C20)



70131-50-9
Clay



70142-34-6
12-Hydroxystearic acid-




polyethylene glycol




copolymer



70425-89-7
Isooctyl acrylate-stearyl




methacrylate-acrylic acid




copolymer



70549-17-6
Butyl acrylate-2-ethylhexyl




acrylate-2-hydroxyethyl acrylate-




styrene copolymer



70632-06-3
Alcohols, C12-15, ethoxylated,




carboxylated, sodium salts



71012-10-7
Oleic acid, 2-(2-(2-(2




hydroxyethoxy)ethoxy)




ethoxy)ethyl ester



71394-17-7
2-Propenoic acid, 2-methyl-,




polymer with butyl 2-methyl-2-




propenoate, ethenylbenzene, 2-




ethylhexyl 2-propenoate and




methyl 2--methyl-2-propenoate



71526-07-3
1-Oxa-4-azaspiro[4.5]decane, 4-




(dichloroacetyl)



71820-36-5
Castor oil, maleic anhydride, and




polyethylene glycol copolymer



72869-69-3
Oils, apricot



73038-25-2
Poly(oxy-1,2-ethanediyl), alpha-




isotridecylomega-hydroxy-,




phosphate



73050-07-4
Poly(oxy-1,2-ethanediyl),.alpha.




(butoxyhydroxyphosphinyl)-




.omega.-hydroxy,C13-15-alkyl




ethers, sodium salts



73050-08-5
Poly(oxy-1,2-ethanediyl),




.alpha.,.alpha.′phosphinicobis




[.omega.-hydroxy-, di-C13-15-




alkyl ethers, sodium salts



73050-09-6
Poly(oxy-1,2-ethanediyl),.alpha.-




phosphono.omega.-hydroxy-,C13-15-




alkyl ethers, disodium




salts



73513-47-0
Ethylenediaminetetraacetic acid




(EDTA) disodium zinc salt, dih



73637-19-1
Ethylenediaminetetraacetic acid




(EDTA) disodium copper(II) salt



73637-20-4
Ethylenediaminetetraacetic acid




(EDTA) disodium manganese



73891-99-3
Rape oil,



74504-64-6
1,2,3-Propanetriol, homopolymer,




dodecanoate



74775-06-7
Poly[oxy(methyl-1,2-




ethanediyl)],.alpha.-(1




oxopropyl)-.omega.-




(tetradecyloxy)-



74811-65-7
Croscarmellose sodium



78266-09-8
1-Propanesulfonic acid, 2-hydroxy-




3-(2-propenyloxy)-,monosodium




salt, polymer with 2-propenoic acid



78330-24-2
Poly(oxy-1,2-ethanediyl),.alpha.-




hydro-.omega.hydroxy-, mono-




C11-14-isoalkyl ethers, C13-rich,




phosphates



84775-78-0
Ascophyllum nodosum, ext



85637-75-8
Oxirane, methyl-, polymer with




oxirane, mono[2-(2-butoxyethoxy)




ethyl] ether



86864-96-2
2-Propenoic acid, polymer with 2-




hydroxypropyl 2-propenoate and




sodium 2-propenoate



87823-33-4
3,5-Bis(6-isocyanatohexyl)-2H-




1,3,5-oxadiazine-2,4,6-(3H,5H)-




trione, polymer with




diethylenetriamine



89511-79-5
2-Propenoic acid, 2-methyl-




.polymer with ethyl 2-propenoate




and methyl 2-methyl-2-propenoate,




sodium salt



89678-90-0
Acrylic acid, styrene, .alpha.-




methyl styrene copolymer,




ammonium salt



91994-94-4
Acetylated lanolin alcohol



97043-91-9
Alcohols, C9-16, ethoxylated



97675-81-5
Fish meal



97676-23-8
Licorice extract (licorice and




licorice derivates)



97765-70-3
Cheese



97766-30-8
Orange, sweet, valencia, ext.



97953-25-8
Acrylic acid-sodium acrylate-




sodium-2-methylpropanesulfonate




copolymer



99607-70-2
Acetic acid, [(5-chloro-8-




quinolinyl)oxy]-, 1-




methylhexyl ester (9CI)



99734-09-5
Polyethylene glycol




mono(tristyrylphenyl)ether



100403-38-1
Glycerides, animal, reaction




products with sucrose



100403-39-2
Glycerides, palm-oil, reaction




products with sucrose



100403-40-5
Glycerides, tallow, reaction




products with sucrose



100403-41-6
Glycerides, vegetable-oil, reaction




products with sucrose



100934-04-1
Methacrylic acid-methyl




methacrylate-polyethylene glycol




methyl ether methacrylate




copolymer



102900-02-7
Poly(oxyethylene/oxypropylene)




monoalkyl(C6-C10)ether sodium




fumarate adduct



104133-09-7
Tetraethoxysilane, polymer with




hexamethyldisiloxane



105362-40-1
Triethanolamine, compd. with




poly(oxyethylene)




tristyrylphenyl ether phosphate



108419-34-7
Acetic acid, C9-11-branched alkyl




esters, C10-rich



109961-42-4
2-Propenenitrile, polymer with




1,2,4-triethenylcyclohexane,




hydrolyzed



114033-68-0
2-Propenoic acid, polymer with 2-




propanol, reaction products with




sodium acrylate



114133-44-7
Hexanedioic acid, polymer with N-




(2-aminoethyl)1,3-propanediamine,




aziridine, (chloromethyl)oxirane,




1,2-ethanediamine, N,N′′-




1,2-ethanediylbis[1,3-




propanediamine], formic




acid and .alpha.-hydro.omega.-




hydroxypoly(oxy,2-ethanediyl)



117272-76-1
Siloxanes and silicones, 3-




hydroxypropyl Me, ethers with




polyethylene glycol mono-Me ether



119432-41-6
Poly(oxy-1,2-ethanediyl), .alpha.-




sulfo-.omega.[tris(1-




phenylethyl)phenoxy]-ammonium




salt



119724-54-8
Methyl methacrylate-methacrylic




acid monomethoxypolyethylene




glycol methacrylate copolymer



121776-33-8
3-(Dichloroacetyl)-5-(2-furanyl)-




2,2dimethyloxazolidine



125303-89-1
Castor oil, hydrogenated, polymer




with adipic acid, ethylenediamine




and 12-hydroxyoctadecanoic acid



125826-44-0
Hexanedioic acid, polymer with 2,2-




dimethyl-1,3-propanediol,-




hexanediol, hydrazine, 3-hydroxy-




2-(hydroxymethyl)-2-




methylpropanoic acid and 1,1′-




methylenebis[4-




isocyanatocyclohexane], compd.




with N,N-diethylethanamine



125997-17-3
Poly(oxy-1,2-ethandiyl),.alpha.-




acetyl-.omega.-[3-{1,3,3,3-




tetramethyl-1[(trimethylsilyl)




oxy]disiloxanyl]propoxy)-



127036-24-2
Poly(oxy-1,2-ethanediyl),.alpha.-




undecyl.omega.-hydroxy-,




branched and linear



128446-33-3
1-alpha-Cyclodextrin, 2-




hydroxypropyl ethers



128497-20-1
Oils, Macadamia



130353-60-5
Acrylic acid-divinyl benzene




copolymer



130498-22-5
Wheat flour



132175-04-3
Polyethylene glycol-polyisobutenyl




anhydride-tall oil fatty acid




copolymer



132538-94-4
Oils, orange-juice, citrus sinensis



132580-45-1
Alpha[2,4,6-Tris[1-




(phenyl)ethyl}phenyl]-omega




hydroxypoly(oxyethylene)




poly(oxypropylene) copolymer



134180-76-0
Oxirane, methyl-, polymer with




oxirane, mono[3-[1,3,3,3-




tetramethyl-1




[(trimethylsilyl)oxy]disiloxanyl]




propyl] ether



135590-91-9
Diethyl-1-(2,4-dichlorophenyl)-5-




methyl-2-pyrazolin-3,5-




dicarboxylate



137091-12-4
Acetic acid ethenyl ester, polymer




with ethanol and alpha-2-propenyl-




omega-hydroxypoly(oxy-




1,2-ethandiyl)



139871-83-3
2-Butenedioic acid (Z)_, polymer




with ethenol and ethenyl acetate,




sodium salt



143819-63-0
Poly(oxy-1,2-ethanediyl), .alpha.-




hydro-.omega.hydroxy-, monoether




with (hydroxymethyl)decane



151006-66-5
Acrylic acid terpolymer, partial




sodium salt



154518-36-2
Alcohols, C9-11-iso-, C10-rich,




ethoxylated propoxylated



162627-18-1
Fatty acids, C18-unsatd., trimers,




reaction products with




triethylenetetramine



163436-84-8
Polyoxyethylene tristyrylphenol




phosphate, potassium salt



163520-33-0
3-Isoxazolecarboxylic acid, 4,5-




dihydro-5,5-diphenyl-, ethyl ester



176022-82-5
Poly[oxy(methyl-1,2-




ethanediyl)],.alpha.-[2-[bis(2




hydroxyethyl)amino]propyl]-




.omega.-hydroxy-,




ether with.alpha.-hydro-.omega.




hydroxypoly(oxy-1,2-ethanediyl)




(1:2), mono-C12-16-alkyl ethers



188027-78-3
5H-1,3-Dioxolo[4,5-




f]benzimidazole, 6-chloro-5-[(3,5




dimethyl-4-isoxazolyl)sulfonyl]-2,2-




difluoro



374602-90-1
Ashes (residues), sunflower seed




hull



—
Crustacea (raw and processed




forms)



—
Dried crickets



—
Dried mealworms



—
Eggs (raw and processed forms)



—
Fish (raw and processed forms)



—
Ground grass seed



—
Leaves, apple



—
Milk (raw and processed forms)



—
Nitrogen fixing bacteria



—
Peanut shells



—
Peanuts (raw and processed forms)



—
Pecan shell flour



—
Polymer of n-butyl acrylate, methyl




methacryalate, methacrylic acid




and aminopropyl methacrylate



—
Sand



—
Seeds, lettuce



—
Silkworm pupae



—
Soybeans (raw and processed




forms)



—
Sulfur Coated Urea



—
Thumb tacks



—
Tree nuts (raw and processed




forms)



—
Wood flower



—
Wheat (raw and processed forms)

## Claims

1. A method suitable in organic production for killing, controlling or suppressing a plant, comprising:
providing a liquid herbicidal composition comprising a herbicidally active limonene component, polyoxyethoxylated castor oil, octyphenol ethoxylate, potassium carbonate, and castor oil and spraying said herbicidal composition onto one or more leaves of a plant.

2. The method according to claim 1, wherein said liquid herbicidal composition additionally comprises an added oil component, wherein said added oil component is a natural product obtained by non-chemical means and/or is an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B.

3. The method according to claim 1 wherein said spraying comprises spraying in a manner whereby the herbicidal composition contacts at least 60% of the surface area of the plant's leaf or leaves.

4. The method of according to claim 1, wherein said providing includes providing a liquid herbicidal composition having said herbicidal limonene component present in said composition at a concentration of from about 10% to about 20%.

5. The method according to claim 2, wherein said providing includes providing a liquid herbicidal composition having an added oil component present at a concentration of from about 0.5% to about 6%.

6. The method according to claim 5, wherein said liquid herbicidal composition includes an added oil component selected from the group consisting of cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and combinations thereof.

7. The method according to claim 6, wherein said liquid herbicidal composition includes an emulsifying agent, wherein said emulsifying agent is selected from the group consisting of ethoxylated nonylphenol, alkylether mono & di-phosphate ester, 2,6,8-trimethyl-4-nonyl ether ethoxylate, poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl-omega-hydroxy), and combinations thereof.

8. The method according to claim 5, wherein said providing includes providing a composition containing poly(oxy-1,2-ethanediyl), and alpha-(nonylphenyl-omega-hydroxy-).

9. A method for non-selective burn down of plants compatible with organic production, the method comprising:
(a) selecting an area having at least one plant growing therein; and
(b) spraying a liquid herbicide composition onto said area, said herbicide composition comprising a herbicidally active limonene component, polyoxyethoxylated castor oil, octyphenol ethoxylate, potassium carbonate, and castor oil.

10. The method according to claim 9, wherein said spraying includes spraying said liquid herbicide composition containing an added oil component.

11. The method according to claim 10, wherein said spraying includes spraying said liquid herbicide composition containing from about 0.5% to about 6% of said added oil component.

12. The method according to claim 11, wherein said spraying includes spraying said liquid herbicide composition containing an added oil component selected from the group consisting of cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and a combination thereof.

13. The method according to claim 12, wherein said spraying includes spraying said liquid herbicide composition containing emulsifying agents selected from the group consisting of nonylphenol polyoxyethylene 10 phosphate ester, alkylether mono & di-phosphate ester; 2,6,8-trimethyl-4-nonyl ether ethoxylate; poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl-omega-hydroxy); and combinations thereof.

14. The method according to claim 13, wherein said spraying includes spraying said liquid herbicide composition containing poly(oxy-1,2-ethanediyl), and alpha-(nonylphenyl-omega-hydroxy).

15. The method according to claim 9, wherein said spraying includes spraying said liquid herbicide composition containing a wetting agent.

16. The method according to claim 15, wherein said spraying includes spraying said liquid herbicide composition containing a wetting agent selected from the group consisting of nonylphenol ethoxylate, dodecyl sulfate, sodium salt, caseins and combinations thereof.

17. A herbicidal composition for use in organic production, comprising a herbicidally active limonene component, polyoxyethoxylated castor oil, octyphenol ethoxylate, potassium carbonate, and castor oil.

18. The herbicidal composition according to claim 17, and further comprising an added oil component, wherein said added oil component is a natural product obtained by non-chemical means and/or is an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B.

19. The herbicidal composition according to claim 18, wherein said limonene component is present at a concentration from about 2% to about 25%.

20. The herbicidal composition according to claim 18, containing from about 0.5% to about 6% of said added oil component.

21. The herbicidal composition according to claim 20, wherein said added oil component is selected from the group consisting of cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and combinations thereof.

22. The herbicidal composition according to claim 21, wherein said herbicidal composition includes an emulsifying agent selected from the group consisting of nonylphenol polyoxyethylene 10 phosphate ester; alkylether mono & di-phosphate ester; 2,6,8-trimethyl-4-nonyl ether ethoxylate; poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl-omega-hydroxy); and combinations thereof.

23. The herbicidal composition according to claim 22, wherein said emulsifying agent comprises at least one surfactant and said composition contains from about 0.5% to about 15% of said at least one surfactant.

24. The herbicidal composition according to claim 23, wherein said at least one surfactant includes poly(oxy-1,2-ethanediyl), and alpha-(nonylphenyl-omega-hydroxy).

25. A ready-to-use composition according to claim 17 wherein the composition further comprises an inert pesticide ingredient included in the Environmental Protection Agency's List 4A or 4B.

26. A herbicidal concentrate adapted to be diluted with water and used in organic production, the herbicidal concentrate comprising a herbicidally active limonene component, polyoxyethoxylated castor oil, octyphenol ethoxylate, potassium carbonate, and castor oil.

27. The herbicidal concentrate according to claim 26, and further comprising a member selected from the group consisting of a wetting agent, a pH modifier effective to provide a pH greater than 5, an added oil component, and combinations thereof, wherein said member selected is a natural product obtained by non-chemical means and/or is an inert pesticide ingredient contained in the Environmental Protection Agency's List 4A or 4B.

28. The herbicidal concentrate according to claim 27, having an added oil component selected from the group consisting of cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and combinations thereof.

29. The herbicidal concentrate according to claim 27, having an emulsifying agent comprising at least one surfactant selected from the group consisting of nonylphenol polyoxyethylene 10 phosphate ester, alkylether mono & di-phosphate ester; 2,6,8-trimethyl-4-nonyl ether ethoxylate; poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl-omega-hydroxy); and combinations thereof.

30. The herbicidal concentrate according to claim 29, having an added oil component at a concentration of from about 4% to about 12%.

31. The herbicidal concentrate according to claim 30, wherein said emulsifying agent comprises poly(oxy-1,2-ethanediyl), and alpha-(nonylphenyl-omega-hydroxy).

32. The herbicidal concentrate of claim 31, wherein said limonene comprises from about 8% to about 85% of said concentrate.

33. A concentrate according to claim 26 wherein the concentrate further comprises an inert pesticide ingredient included in the Environmental Protection Agency's List 4A or 4B.

34. A method for making a herbicide composition, comprising:
(a) providing a liquid herbicide formulation comprising a herbicidally active limonene component, polyoxyethoxylated castor oil, octyphenol ethoxylate, potassium carbonate, and castor oil, and
(b) diluting and mixing said formulation with water.

35. The method according to claim 34, wherein said liquid herbicide formulation includes an added oil component selected from the group consisting of cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and combinations thereof.

36. The method according to claim 35, wherein said liquid formulation includes an emulsifying agent which comprises at least one surfactant selected from the group consisting of nonylphenol polyoxyethylene 10 phosphate ester; alkylether mono & di-phosphate ester; 2,6,8-trimethyl-4-nonyl ether ethoxylate; poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl-omega-hydroxy); and combinations thereof.

37. The method according to claim 36, wherein said liquid herbicide formulation includes limonene at a concentration of from about 35% to about 85%.

38. The method according to claim 37, wherein said liquid herbicide formulation includes an added oil component at a concentration of from about 2% to about 20%.

39. The method according to claim 37, wherein said liquid herbicide formulation includes an emulsifying agent at a concentration of from about 5% to about 20%.

40. A kit for providing a ready-to-use herbicide composition suitable for organic production comprising:
a container having therein a ready-to-use liquid herbicide composition, the herbicide comprising a herbicidally active limonene component, polyoxyethoxylated castor oil, octyphenol ethoxylate, potassium carbonate, and castor oil; and
instructions, recorded in a medium, for applying the herbicide composition to a pre-selected area for indiscriminately killing, controlling or suppressing plants growing in the area.

41. The kit according to claim 40, wherein said liquid herbicide composition contains a limonene component at a concentration of from about 2% to about 25%, an emulsifying agent at a concentration of from about 0.05% to about 15%, and an added oil component at a concentration of from about 0.5% to about 6%.

42. The kit according to claim 41, wherein:
(a) said emulsifying agent comprises at least one surfactant selected from the group consisting of nonylphenol polyoxyethylene 10 phosphate ester; alkylether mono & di-phosphate ester; 2,6,8-trimethyl-4-nonyl ether ethoxylate; poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl-omega-hydroxy); and combinations thereof, and
(b) said added oil component is selected from the group consisting of cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and combinations thereof.

43. The kit according to claim 42, wherein said surfactants include poly(oxy-1,2-ethanediyl), and alpha-(nonylphenyl-omega-hydroxy).

44. The kit of claim 40, further including a label stating “for organic production.”

45. A kit for providing a herbicide composition suitable for use in organic production comprising:
a container having therein a liquid herbicide concentrate, the herbicide concentrate comprising a herbicidally active limonene component, polyoxyethoxylated castor oil, octyphenol ethoxylate, potassium carbonate, and castor oil; and
instructions, recorded in a medium, for diluting the concentrate with water to provide a herbicide composition.

46. The kit according to claim 45, wherein said liquid herbicide concentrate contains a limonene component at a concentration of from about 35% to about 85%, an emulsifying agent at a concentration of from about 1% to about 30%, and an added oil component at a concentration of from about 2% to about 20%.

47. The kit according to claim 46, wherein:
(a) said emulsifying agent comprises at least one surfactant selected from the group consisting of nonylphenol polyoxyethylene 10 phosphate ester; alkylether mono & di-phosphate ester; 2,6,8-trimethyl-4-nonyl ether ethoxylate; poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl-omega-hydroxy); and combinations thereof, and
(b) said added oil component is selected from the group consisting of cottonseed oil, soybean oil, sunflower oil, pine oil, coconut oil and combinations thereof.

48. The kit according to claim 47, wherein said surfactants include poly(oxy-1,2-ethanediyl), and alpha-(nonylphenyl-omega-hydroxy).

49. The kit of claim 43, further including a label stating “for organic production.”