# Patent

## Title
Method of cleaning residual pesticide from an agricultural vessel

## Abstract

The present invention generally relates to methods of cleaning residual pesticide from an agricultural vessel, and to kits and compositions useful for the practice of such methods.

## Background
REFERENCE TO RELATED APPLICATIONS
This application is the United States National Stage Application of International PCT Application No. PCT/US2013/038660, filed Apr. 29, 2013, and claims the benefit of U.S. Provisional Application Ser. No. 61/640,999, filed May 1, 2012, and U.S. Provisional Patent Application Ser. No. 61/724,054, filed Nov. 8, 2012, the entire disclosures of which are incorporated herein by reference.


FIELD OF THE INVENTION
The present invention generally relates to methods of cleaning residual pesticide from an agricultural vessel, and to kits and compositions useful for the practice of such methods.
BACKGROUND OF THE INVENTION
Auxin herbicides, such as 2,4-D and dicamba, are highly effective for the control of broadleaf weeds, particularly weeds that have become resistant to glyphosate. Dicamba, for example, causes significant damage to plants even at extremely low application levels.
When a pesticidal composition is sprayed, a residual amount of the active pesticidal agent typically remains in the tank. This pesticidal residue, if left untreated, can pose a significant problem for farmers by unintentionally damaging crops and desirable plants. As a result, special precautions must be taken to prepare spray tanks for subsequent use following the application of pesticides. This problem is particularly acute for auxin herbicides, such as dicamba, where even small amounts of herbicidal residue could result in significant damage to sensitive crop plants.
Due to the high potency of dicamba, three full rinses of the spray tank are traditionally required to ensure zero crop damage from the residue. Typical cleaning methods require the cleaning rinse to stand in the spray tank for at least four hours, and preferably should be allowed to soak overnight. This process, although effective, is both expensive and cumbersome. The rinses require additional water in the field, and the long soaking period reduces the time that the equipment is available for spraying crops.
An alternative method of degrading pesticidal residue in the field, which reduces the water use and time required for the farmer to switch to another pesticide, is therefore highly desirable.
SUMMARY OF THE INVENTION
Briefly, therefore, the present invention is directed to methods of preparing a tank for use in connection with a second pesticide following use of the tank in connection with a first pesticide. In various embodiments, the first pesticide is an herbicide. The first and second pesticides may be the same pesticide (e.g., dicamba). In various embodiments, the method comprises introducing a cleaning mixture into a tank containing a residual amount of a first pesticide; the cleaning mixture comprises (a) a source of transition metal ions, and (b) a source of hydrogen peroxide. Optionally, the cleaning solution may further comprise water. The method further comprises allowing the cleaning mixture to remain in the tank for a time sufficient to degrade at least a portion of the residual amount of the first pesticide, thereby forming a waste mixture comprising degradation products of the first pesticide; and removing the waste mixture from the tank.
The present invention is further directed to kits for use in cleaning a tank following the use of the tank in connection with a pesticide. Generally, the kits comprise a source of hydrogen peroxide and a source of transition metal ions.
In preferred embodiments of the present invention, the transition metal ions are polyvalent iron ions.
Other objects and features will be in part apparent and in part pointed out hereinafter.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is directed to the expected concentration of dicamba with respect to time on a logarithmic scale as described in Example 5.
FIG. 2 is directed to the reaction rate constant as a function of initial hydrogen peroxide concentration as described in Example 5.
FIG. 3 is directed to the reaction rate constant as a function of the molar ratio of iron ions to glyphosate in the reaction mixture as described in Example 5.



Corresponding reference characters indicate corresponding parts throughout the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention, it has been discovered that the Fenton reaction may be utilized to provide an economical and effective means of degrading residual pesticides (e.g., herbicides) in agricultural vessels (e.g., spray tanks).
In the Fenton reaction, in which a source of iron ions is utilized, ferrous iron ions are oxidized by hydrogen peroxide to produce hydroxyl radicals:

Fe2++H2O2→Fe3++OH−+OH.  (1)

A second reaction, in which the iron (III) product compound is reduced in the presence of hydrogen peroxide, makes the Fenton reaction catalytic with respect to iron:

Fe3++H2O2→Fe2++H++HOO.  (2)

In most environments, reaction (2) is several orders of magnitude slower than reaction (1), and thus becomes the rate-limiting step where an excess of H2O2 is present.
More generally, other transition metals have also been observed to catalyze reactions similar to the Fenton reaction, wherein transition metal ions react with hydrogen peroxide to produce hydroxyl radicals. For example, the transition metal may be selected from the group consisting of copper, vanadium, chromium, molybdenum, tungsten, manganese, cobalt, nickel, cerium, ruthenium, aluminum, antimony, zinc, titanium, tin, barium, and combinations thereof. Preferably, the transition metal ions are polyvalent. Cobalt is an example of a transition metal known to engage in a Fenton-like reaction with hydrogen peroxide. Accordingly, although the methods, compositions, and kits described herein are described primarily with respect to the traditional Fenton reaction, which involves polyvalent iron ions as the metal catalyst, one skilled in the art would understand that the present invention encompasses the use of other transition metals as described above.
When hydroxyl radicals are produced in the presence of a pesticide, the pesticide is degraded into reaction products that do not retain pesticidal activity. Surprisingly, it has been discovered that this reaction may be incorporated into an improved process for cleaning pesticidal residue from spray tanks that provides a high level of effectiveness and requires significantly less cleaning time than traditional rinses. The result is a convenient and inexpensive solution that is beneficial for both farmers and custom applicators. In particular, the methods of the present invention are suitable for in-field applications and also are more rapid than conventional tank cleaning methods. For example, as detailed elsewhere herein, the methods of the present invention are suitable for tank cleaning that occurs over a period of no more than 30 minutes and, in various preferred embodiments, methods that occur over a shorter period of time (e.g., less than about 10 minutes, or even less than about 5 minutes).
Generally, the method involves the preparation of an aqueous cleaning mixture comprising a source of transition metal ions (e.g., polyvalent iron ions) and a source of hydrogen peroxide. The cleaning mixture is introduced into a tank containing a residual amount of the pesticide, and is allowed to remain in the tank for a time sufficient to substantially degrade the pesticidal residue. As used herein, “degradation” refers to the process whereby the pesticide decomposes into reaction products that do not retain pesticidal activity.
Optionally, the present method may incorporate a pre-rinse step, wherein an amount of an aqueous medium (e.g., water) is introduced into the tank prior to the cleaning step. The pre-rinse step is useful to reduce any excessive pesticidal residue that may be present in the tank, thereby decreasing the total amount of pesticide that remains to be degraded by the cleaning solution. The waste product formed by the pre-rinse step, referred to herein as a diluted pesticidal residue mixture, comprises a portion of the residual first pesticide. Typically, at least a portion of the diluted pesticidal residue mixture is removed from the tank (e.g., by spraying) prior to introduction of the cleaning mixture into the tank.
Typically, the aqueous medium (e.g., rinse water) is introduced into the tank in a volumetric ratio, with respect to the pesticidal residue at a typical pesticidal concentration, of at least about 1:1, at least about 2:1, at least about 5:1, at least about 10:1, at least about 20:1, or at least about 50:1.
Generally, the amount of pesticide remaining in the tank and any appurtenant apparatus (e.g., spray lines, pumps, etc.) can be reliably estimated by one skilled in the art based on the size and shape of the tank, the spray apparatus, and the concentration of the first pesticide mixture. In most cases, the amount of dead volume present in a spray tank, and in any equipment connected thereto (e.g., a boom spray apparatus), will be known to the skilled worker and/or the equipment manufacturer, and may be used to obtain a reasonably accurate estimate of the amount of pesticidal residue remaining therein. Once the amount of pesticidal residue remaining in the tank is estimated, appropriate amounts of the sources of transition metal ions and hydrogen peroxide forming the cleaning mixture can be selected for introduction into the tank. More particularly, appropriate molar ratios of hydrogen peroxide to pesticidal residue and to the transition metal ions are disclosed below and can be used to determine appropriate quantities of the sources of hydrogen peroxide and transition metal ions to form the cleaning mixture.
Where the spray tank is a component of a larger system, for example a boom spray system, the cleaning mixture can also be used to clean the hoses, pumps, and spray nozzles incorporated therein. Typically, water may be added to the cleaning mixture in an amount sufficient to allow the cleaning mixture to recirculate through the system (e.g., the boom spray system). The volume of liquid necessary for effective recirculation is dependent on the particular equipment to be cleaned, and can be reliably determined by one skilled in the art.
Generally, the amount of water incorporated into the cleaning mixture will correspond to the amount necessary to effectively recirculate the mixture through the system, as described above. This water may be provided by the source of transition metal ions, source of hydrogen peroxide, and/or as additional water added along with the source of transition metal ions and source of hydrogen peroxide. Typically, water constitutes at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 98%, or at least about 99% by mass of the cleaning mixture.
After the pesticidal residue has been degraded, a waste mixture comprising degradation products of the first pesticide is formed, which should be removed from the tank. Typically, the waste mixture is removed from the tank by spraying. Generally, a final water rinse following the addition of the cleaning mixture is not required.
A significant advantage of the present invention, as compared to the prior art, is that the present methods may be performed in a relatively brief amount of time. More particularly, it has been surprisingly discovered that Fenton-type chemistry is effective for degradation of pesticidal residues over time scales such that tank cleaning methods incorporating Fenton chemistry are dramatically shorter than the tank cleaning methods typically employed in the prior art. For example, the duration between introduction of the cleaning mixture into the tank and removal of the waste mixture from the tank is typically less than about 2 hours. Depending on the concentration of iron ions and hydrogen peroxide in the cleaning mixture, and the amount of pesticidal residue in the tank, the duration may be less than about 1 hour, less than about 1 hour, less than about 30 minutes, less than about 25 minutes, less than about 20 minutes, less than about 15 minutes, less than about 10 minutes, or even less than about 5 minutes.
In most cases, at least about 50% by weight, at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95%, or at least about 99% by weight of the pesticidal residue is degraded prior to removal of the waste mixture from the tank.
In various embodiments, a pre-rinse step is not incorporated and the method proceeds over a duration of no more than about 30 minutes. That is, the waste mixture is removed from the tank (e.g., by spraying) within no more than about 30 minutes of introduction of the cleaning mixture into the tank (e.g., within no more than about 15 minutes or no more than about 5 minutes). Further in accordance with such embodiments, suitable degradation of the pesticidal residue (e.g., at least about 70% or at least about 80% by weight) is achieved during such methods.
The method may generally be used to degrade various pesticides known in the art. Typically, the first pesticide comprises one or more first herbicides. Non-limiting examples of water-soluble herbicides that may be degraded using the present methods include acifluorfen, acrolein, amitrole, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chlorambenc, chloroacetic acid, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, difenzoquat, endothall, fenac, fenoxaprop, flamprop, flumiclorac, flumioxazin, fluoroglycofen, flupropanate, fomesafen, fosamine, fluroxypyr, glufosinate, glyphosate, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, picloram, quinclorac, sulfamic acid, 2,3,6-TBA, TCA, triclopyr and water-soluble salts or esters thereof.
Non-limiting examples of water-insoluble herbicides that may be degraded using the present methods include acetochlor, aclonifen, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carfentrazone-ethyl, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, daimuron, desmedipham, desmetryn, dichlobenil, diclofop-methyl, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoterb, diphenamid, dithiopyr, diuron, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenuron, flamprop-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluazoate, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluorochloridone, flupoxam, flurenol, fluridone, fluroxypyr-I-methylheptyl, flurtamone, fluthiacet-methyl, graminicides, halosulfuron, haloxyfop, hexazinone, imazosulfuron, indanofan, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lenacil, linuron, mefenacet, metamitron, metazachlor, methabenzthiazuron, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, pebulate, pendimethalin, pentanochlor, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron, prodiamine, profluazol, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyri buticarb, pyridate, pyriminobac-methyl, quinclorac, quinmerac, quizalofop, quizalofop-P, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thidiazimin, thifensulfuron, thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, trietazine, trifluralin, triflusulfuron and vernolate.
Preferably, the present method is effective to degrade the residue of auxin herbicides. Exemplary auxin herbicides include 2,4-dichlorophenoxyacetic acid (2,4-D), 4-(2,4-dichlorophenoxy)butanoic acid (2,4-DB), dichloroprop, (4-chloro-2-methylphenoxy)acetic acid (MCPA), 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB), mecoprop, dicamba, picloram, quinclorac, agriculturally acceptable salts or esters of any of these herbicides, and mixtures thereof.
The present method is particularly effective for the degradation of dicamba and 2,4-D. Without being bound to any particular theory, it is believed that the dominant degradation pathway utilized by the present method involves an attack on the ether linkages present in the dicamba and 2,4-D molecules. High-performance liquid chromatography (HPLC) analysis involving dicamba as described in the working examples herein shows a decrease in the dicamba molecule concentration followed by a corresponding increase in the concentration of 2,4-dichlorosalicylate as a degradation product. In certain embodiments, in addition to dicamba or 2,4-D, the present method is also effective for the degradation of flumioxazin.
The polyvalent iron ions may be derived from any water-soluble compound comprising iron in a +2 or +3 oxidation state. Suitable compounds include ferric ammonium sulfate, ferric chloride, ferric oxide, ferric oxide hydrate, ferric sulfate, ferrous ammonium sulfate, ferrous oxide, ferrous chloride, ferrous sulfate and/or iron salts of di-, tri- or other polycarboxylic acids such as iron citrate. Ferrous sulfate, ferric chloride and iron citrate are preferred sources of iron ions for use with the present method.
Ferrous sulfate is a particularly preferred source of iron ions. Ferrous sulfate dissolves readily in water, and has been found to exhibit favorable reaction kinetics as compared to other sources of polyvalent iron. Additionally, ferrous sulfate does not cause damage to most plastics or stainless steel, materials which are commonly used in pesticidal tanks.
The concentration of transition metal ions in the source of transition metal ions is typically at least about 5 grams per liter (g/L), at least about 7.5 g/L, at least about 10 g/L, at least about 12.5 g/L, at least about 15 g/L, at least about 17.5 g/L, at least about 20 g/L, or at least about 25 g/L.
Aqueous hydrogen peroxide is readily available from commercial suppliers, and is a preferred reagent for use with the present method. Alternatively, the method may utilize one or more compounds that react or dissociate to produce hydrogen peroxide in an aqueous environment. Exemplary reagents of this type include sodium perborate, sodium percarbonate, and other sources of peroxides, such as adducts of urea and peroxide.
Typically, hydrogen peroxide is incorporated into the cleaning mixture in a concentration of at least about 100 grams per liter of cleaning mixture. To reduce cleaning time and increase the rate of pesticidal degradation, a higher concentration of hydrogen peroxide may be incorporated into the cleaning mixture. Typically, the concentration of hydrogen peroxide in the source of hydrogen peroxide is at least about 125 g/L, at least about 150 g/L, at least about 175 g/L, at least about 200 g/L, at least about 225 g/L, or at least about 250 g/L.
In cases where it is possible to accurately estimate the amount of pesticidal residue remaining in the tank, the amount of hydrogen peroxide added to the cleaning mixture may be adjusted accordingly. Typically, the molar ratio of hydrogen peroxide to residual pesticide is at least about 10:1, at least about 25:1, at least about 50:1, at least about 75:1, at least about 100:1, at least about 125:1, or at least about 150:1. Generally, higher hydrogen peroxide to pesticide ratios provide for faster degradation of the pesticidal residue.
In certain embodiments, the molar ratio of hydrogen peroxide to residual pesticide (e.g., first pesticide) is from about 10:1 to about 60:1, from about 10:1 to about 50:1, or from about 10:1 to about 40:1. In other embodiments, the molar ratio of hydrogen peroxide to residual pesticide (e.g., first pesticide) is from about 15:1 to about 35:1, from about 20:1 to about 35:1, or from about 25:1 to about 35:1. In still other embodiments, the molar ratio of hydrogen peroxide to residual pesticide (e.g., first pesticide) is from about 10:1 to about 30:1, or from about 10:1 to about 20:1.
Generally, the relative amounts of the hydrogen peroxide source and the transition metal source are incorporated into the cleaning mixture such that the initial molar ratio of hydrogen peroxide to transition metal ions is from about 500:1 to about 1:1. More typically, the initial molar ratio of hydrogen peroxide to transition metal ions is at least about 5:1, at least about 8:1, at least about 10:1, at least about 12:1, at least about 15:1, at least about 20:1, at least about 25:1, or at least about 50:1 with hydrogen peroxide being in molar excess. As used herein, the term “initial molar ratio” at least refers to the molar ratio of the hydrogen peroxide to transition metal ions at the outset of the cleaning operation (e.g., when the sources of hydrogen peroxide and transition metal ions are combined prior to initiation of the Fenton reaction). This does not, however, exclude the possibility that such molar ratios may persist during the cleaning operation. Typically, the source of hydrogen peroxide will be added to the cleaning mixture in a mass ratio of at least about 0.5:1, at least about 1:1, at least about 2:1, at least about 5:1, or at least about 10:1 as compared to the source of transition metal ions.
Additional considerations may apply when the pesticidal residue comprises a species that chelates or otherwise binds with free metal ions in solution. For example, many phosphate-containing herbicides (e.g., glufosinate) are known to be effective chelators. A particularly notable example of a species known to chelate free metal ions is N-(phosphonomethyl)glycine, commonly referred to as glyphosate.
Glyphosate is a highly effective and commercially important broad spectrum herbicide useful in controlling the growth of germinating seeds, emerging seedlings, maturing and established woody and herbaceous vegetation, and aquatic plants. Glyphosate is used as a post-emergent herbicide to control the growth of a wide variety of annual and perennial grass and broadleaf weed species in cultivated crop lands, including cotton production, and is the active ingredient in the ROUNDUP family of herbicides available from Monsanto Company (Saint Louis, Mo.).
In addition to its herbicidal properties, glyphosate, by virtue of the presence of carboxyl and a phosphonomethyl groups or ligands, can function as a strong complexing agent and can chelate or otherwise bind with free metal ions in solution. In particular, glyphosate has been observed to chelate or bind with polyvalent iron ions, which are preferred for use with the methods described herein. As a consequence, the present methods require more metal ions to be added to the cleaning mixture when glyphosate is present in the herbicidal residue to compensate for this effect.
Frequently, herbicidal glyphosate formulations also contain relatively low concentrations of N-(phosphonomethyl)iminodiacetic acid (PMIDA) and/or salts thereof which are intermediate compounds produced during the glyphosate manufacturing process. Like glyphosate, PMIDA also chelates or binds with metal ions, and therefore also contributes to the requirement of additional transition metal ions added to the cleaning mixture.
For example, it has been observed that when no metal chelation is present (i.e., in the absence of glyphosate), suitable degradation of dicamba residue may occur with very low amounts of metal catalyst in the cleaning mixture (e.g., <1 mM). In the presence of glyphosate, however, herbicidal degradation was only observed with cleaning mixtures having transition metal ion concentrations that provided at least a 1:1 molar ratio of polyvalent iron ions to glyphosate, acid equivalent (a.e.).
Accordingly, when glyphosate is present, the molar ratio of transition metal ions to glyphosate is preferably greater than 1:1. Typically, the ratio is at least about 2:1, at least about 3:1, or at least about 4:1. In certain embodiments, the molar ratio of transition metal ions to glyphosate is from about 1:1 to about 8:1, from about 1:1 to about 6:1, or from about 2:1 to about 4:1.
Generally, the methods of the present invention do not require the use of a pH adjusting agent. Aqueous solutions of iron (II), typically derived from a source such as ferrous sulfate, have been found to be effective without adjustment of pH.
The use of a pH adjusting agent may be desirable, however, when aqueous solutions of iron (III) are employed. At a pH of up to about 2, ferric iron has a strong tendency to hydrolyze to form a binuclear species, [Fe(H2O)4(OH)2Fe(H2O)4]4+ and at a pH above about 2 to 3 polynuclear Fe—OH species. The latter results in the precipitation of colloidal or hydrous ferric oxide.
The cleaning mixture preferably has a pH of from about 2 to about 4. Sodium hydroxide is typically used to raise the pH, if necessary, while a lower pH is typically achieved through addition of the acidic counterion corresponding to the iron source (e.g., H2SO4 when ferrous sulfate is used, or HCl when ferric chloride is used). Glyphosate salts, if present in the herbicidal residue, typically act to buffer the system to a pH of approximately 4.
As shown in Equation 1, reproduced below, the Fenton reaction involves the oxidation of ferrous iron ions by hydrogen peroxide to produce hydroxyl radicals:

Fe2++H2O2→Fe3++OH−+OH.  (1)

This reaction requires stoichiometric amounts of Fe2+ and hydrogen peroxide to produce an equivalent molar quantity of hydroxyl radicals. The Fenton reaction is catalytic, however, to the extent that the iron (III) product compound is reduced in the presence of hydrogen peroxide:

Fe3++H2O2→Fe2++H++HOO.  (2)

In the conventional Fenton process, reaction (2) is several orders of magnitude slower than reaction (1), and thus becomes the rate-limiting step in environments where an excess of H2O2 is present. Alternative pathways for reduction of Fe(III) to Fe(II), however, are known in the art, and are predominantly used in many applications of Fenton chemistry for water or soil treatment.
For example, an alternative version of reaction (2) uses photochemical energy, rather than ambient thermal energy, to reduce the Fe(III) species to Fe(II):

Fe3++H2O2→hvFe2++H++HOO.  (2B)

In this reaction, the Fe(OH)2+ ion absorbs light at wavelengths up to about 410 nm, which falls in the near-UV region of the spectrum. The photochemical reduction process including the combined process of reactions (1) and (2B) is generally known as the photo-assisted Fenton (or photo-Fenton) reaction.
Advantageously, the present method has been shown to work without the requirement of UV lighting or other photons to assist the reaction. This is beneficial, in part, because the UV lighting and other equipment required to carry out the photo-Fenton reaction can be fragile, unwieldy, and expensive, particularly when the reaction is scaled up to the level required for the agricultural uses described herein. Experiments were conducted using foil-wrapped containers, wherein the present method was used to degrade herbicidal residue in the absence of UV light. The foil-wrapped container results showed no significant differences in reaction kinetics as compared to equivalent experiments conducted in the presence of UV light. As a result, the present method does not require the cleaning mixture to be subjected to an artificial light source while in the tank. The tank material may be substantially opaque to ultraviolet light. In addition, the present method is suitable for use in large-scale agricultural operations.
As a further alternative to the UV-induced catalysis described above, an applied electric current may be used to reduce the iron (III) species, thereby regenerating the iron ions in solution. Advantageously, the present method does not require the use of electrochemistry, in that it does not require the cleaning mixture to be subjected to an applied electric current while in the tank.
Kits
The present invention is further directed to kits for use in connection with the methods described herein.
Generally, the kit comprises a source of polyvalent iron ions and a source of hydrogen peroxide. The sources of polyvalent iron ions and hydrogen peroxide, respectively, may be selected as described above. The kit may further comprise instructions for carrying out the methods described herein.
Typically, the source of hydrogen peroxide and the source of polyvalent iron ions should be packaged separately, such that they do not interact prior to the formation of the cleaning solution.
Following are Examples presented to illustrate the present invention and are not intended to limit the scope of this invention. The examples will permit better understanding of the invention and perception of its advantages and certain variations of execution.
EXAMPLES
Example 1
An experiment was conducted to measure the reaction kinetics of the present method with respect to dicamba. Ferric chloride (FeCl3) was used as the source of iron. Aqueous hydrogen peroxide (30% w/w) was used as the peroxide source.
An additional sample was prepared with glyphosate to measure the effect of iron chelation on the dicamba degradation process.
Hydrogen peroxide was added to the reaction vessel in a molar ratio of 100:1 with respect to dicamba. In the absence of glyphosate, the results show that the dicamba concentration was degraded to below detectable limits in 24 hours. In the sample containing glyphosate, however, the reaction was effectively stopped due to chelation of the iron species. The results of these trials are summarized in Table 1 below.







TABLE 1







100× Molar Ratio of Hydrogen Peroxide to Dicamba 


Over 24 Hours














Dicamba
Dicamba
Dicamba
Dicamba


Sam-

% 
% 
% 
% 


ple

Change
Change
Change
Change


No.
Ingredients
0-2 Hr.
2-4 Hr.
4-6 Hr.
24 Hr.















723-10 
glyphosate/
 4%
 4%
 5%
 6%



dicamba/







H2O2/FeCl3






723-11
dicamba/
35%
58%
70%
92%



H2O2/FeCl3









Additional trials were conducted to evaluate the effectiveness of sodium percarbonate and OXICLEAN, respectively, as alternative sources of hydrogen peroxide. The results of these trials are summarized in Table 2 below.







TABLE 2







100× Molar Ratio of Hydrogen Peroxide to Dicamba Over 24 Hours












Dicamba 
Dicamba %


Sample

%
Change 


No.
Ingredients
wt. 24 Hr.
24 Hr.













723-16
glyphosate/dicamba/H2O2/FeCl3
0.116
 7.9%


723-17
dicamba/H2O2/FeCl3
0.01
  92%


723-18
glyphosate/dicamba/
0.103
  18%



2(Na2CO3)•3(H2O2)/FeCl3




723-19
dicamba/2(Na2CO3)•3(H2O2)/FeCl3
0.122
  7%


723-20
glyphosate/dicamba/OXICLEAN/FeCl3
ND
 100%


723-21
dicamba/OXICLEAN/FeCl3
ND
 100%









Example 2
Additional experiments were conducted to further investigate the effect of varying peroxide levels on the degradation reaction kinetics. Aqueous hydrogen peroxide, sodium percarbonate, and OXICLEAN were each used at 100:1 and 10:1 molar ratios with respect to dicamba, in samples both with and without the presence of glyphosate. Control samples were also prepared with one or more herbicides in the absence of a source of hydrogen peroxide, a source of iron, or both.
The samples were measured after 24 hours to determine the concentration of dicamba remaining in the reaction mixture. The pH of the reaction mixture was also recorded. The results of these trials are summarized in Table 3, below.







TABLE 3







Degradation of Dicamba after 24 Hours












Sample

Iron
Hydrogen
% Change



No.
Herbicide(s)
Source
Peroxide Source 
dicamba
pH















1435-1
Dicamba
None
None
 0%
6.36


1435-6
Dicamba
FeCl3
H2O2 (100×)
 8%
3.97


1435-24
Dicamba
FeCl3
H2O2 (10×)
100%
1.84


1435-12
Dicamba
FeCl3
H2O2 (100×)
100%
1.91


1435-18
Dicamba
FeCl3
H2O2 (100×)
100%
1.86


1435-20
Dicamba
FeCl3
Sodium Percarb.
 2%
10.78





(10×)




1435-14
Dicamba
FeCl3
Sodium Percarb.
 9%
11.42





(100×)




1435-22
Dicamba
FeCl3
OXICLEAN (10×)
 5%
10.93


1435-16
Dicamba
FeCl3
OXICLEAN
100%
10.82





(100×)




1435-7
Dicamba
None
Sodium Percarb.
 8%
11.54





(100×)




1435-8
Dicamba +
None
Sodium Percarb.
 13%
10.51



Glyphosate

(100×)




1435-23
Dicamba +
FeCl3
H2O2 (10×)
 7%
3.38



Glyphosate






1435-11
Dicamba +
FeCl3
H2O2 (100×)
 12%
3.3



Glyphosate


 



1435-17
Dicamba +
FeCl3
H2O2 (100×)
 11%
3.28



Glyphosate


 



1435-19
Dicamba +
FeCl3
Sodium Percarb.
 17%
9.43



Glyphosate

(10×)
 



1435-13
Dicamba +
FeCl3
Sodium Percarb.
 25%
10.63



Glyphosate

(100×)
 



1435-21
Dicamba +
FeCl3
OXICLEAN (10×)
 13%
10.32



Glyphosate






1435-15
Dicamba +
FeCl3
OXICLEAN
100%
10.84



Glyphosate

(100×)




1435-2
Dicamba +
None
None
 0%
4.29



Glyphosate


 



1435-10
Dicamba +
FeCl3
None
 3%
3.51



Glyphosate


 



1435-3
Dicamba +
None
H2O2 (100×)
 7%
4.14



Glyphosate






1435-9
Dicamba +
None
H2O2 + Sodium
 17%
10.45



Glyphosate

Percarb. (100×)




1435-5
Dicamba +
None
OXICLEAN
100%
10.73



Glyphosate

(100×)




1435-4
Dicamba +
None
Sodium Percarb. 
 9%
10.52



Glyphosate

(100×)




1435-25
Glyphosate
FeCl3
Sodium Percarb.

11.12





(100×)









Example 3
An experiment was conducted to investigate whether the chelation effect of glyphosate can be overwhelmed by including additional amounts of iron. Samples were prepared using ferric chloride (FeCl3) and ferrous sulfate (FeSO4), respectively, which were incorporated at molar ratios of 1:1 and 2:1 with respect to glyphosate.
Aqueous hydrogen peroxide (30% w/w) was used as the peroxide source, and was provided in a 100:1 molar ratio with respect to dicamba. A small number of control samples, as shown in the table below, were prepared in the absence of a peroxide source.
For samples comprising both glyphosate and dicamba, the herbicides were present in a molar ratio of 1.5:1, respectively.
The results showed that at both 1:1 and 2:1 molar ratios of iron salt to glyphosate, the dicamba was fully degraded after 24 hours, with the concentration being either not detectable (ND) or detectable but not quantifiable (<5 ppm) (DBNQ).
The results are summarized in Table 4, below. Iron concentration is provided in terms of the molar ratio with respect to glyphosate. Where no glyphosate is present, the concentrations used were either a 1.5:1 molar ratio to dicamba (1×) or a 3:1 molar ratio to dicamba (2×).







TABLE 4







Effect of Iron Concentration on Dicamba Degradation Rate in 


the Presence of Glyphosate

















Dicamba 


Sample

Peroxide
Iron
Iron
%


No.
Herbicide(s)
Conc.
Source
Conc.
24 Hr.















08578911-1
Dicamba
None
None
—
0.1021


08578911-2
Dicamba + Glyphosate
None
None
—
0.1044


08578911-3
Dicamba
100×
None
—
0.0952


08578911-4
Dicamba + Glyphosate
100×
None
—
0.0981


08578911-5
Dicamba + Glyphosate
None
FeCl3
1X
0.0939


08578911-6
Dicamba
100×
FeCl3
1X
DBNQ


08578911-7
Dicamba
100×
FeCl3
2X
0.0711


08578911-8
Dicamba + Glyphosate
100×
FeCl3
1X
DBNQ


08578911-9
Dicamba + Glyphosate
100×
FeCl3
2X
ND


08578911-10
Dicamba + Glyphosate
None
FeSO4
1X
0.0924


08578911-11
Dicamba
100×
FeSO4
1X
ND


08578911-12
Dicamba
100×
FeSO4
2X
0.0972


08578911-13
Dicamba + Glyphosate
100×
FeSO4
1X
DBNQ


08578911-14
Dicamba + Glyphosate
100×
FeSO4
2X
ND









Example 4
Experiments were conducted using a dicamba/glyphosate tank mix formulation.
The herbicidal formulation was diluted to a concentration of 0.6% (g/g), which is appropriate for commercial spray applications. Further dilutions were made from this stock solution. Ferric chloride hexahydrate was provided by FISHER and diluted to a 10% (g/g) solution on an anhydrous basis with distilled water. Aqueous hydrogen peroxide (30%) was provided by SIGMA-ALDRICH and was used as received.
Experiments were performed in the hood using 8 drachm ( ̃30 ml) glass vials. Reagents were added to the vials in the following order: dicamba solution, ferric chloride solution, and aqueous hydrogen peroxide. One milliliter samples were taken from each vial at 5, 15, 30, 60, and 120 minute intervals and placed into HPLC vials containing a 10% solution of N-(phosphonomethyl)iminodiacetic acid (PMIDA). The PMIDA quenched the reaction by rapidly chelating iron and preventing it from degrading peroxide. The amount of PMIDA solution in each vial was calculated such that the sum of the moles of glyphosate and PMIDA were a 10% excess of the moles of iron present.
Samples were analyzed using ion chromatography coupled with mass spectroscopy (IC/MS/MS) to determine the dicamba concentration with time. Results were reported on a mass basis in parts-per-million (ppm) of the sample.
Tables 5-7 summarize the experiments designed for analyzing the impact of initial iron, peroxide, and dicamba concentrations on dicamba degradation rates.







TABLE 5







Reagent amounts for experiments looking at the effect of initial iron


concentration on dicamba degradation rate.












Dicamba,
Hydrogen
10% FeCl3
PMIDA in analytical


Sample ID
mg/kg
Peroxide, μL
Solution, μL
vial, uL














1.75XFe
1493.5
1725
960
125


2XFe
1493.5
1725
1097
125


2.5XFe
1493.5
1725
1371
125


3XFe
1493.5
1725
1645
125
















TABLE 6







Reagent amounts for experiments looking at the effect of initial peroxide


concentration on dicamba degradation rate. (NBP 08615439)












Dicamba,
Hydrogen 
Iron,
PMIDA in 


Sample ID
mg/kg
Peroxide, μL
μL
analytical vial, uL














25XHOOH
1500
350
2200
160


50XHOOH
1500
700
2200
160


75XHOOH
1500
1050
2200
160


100XHOOH
1500
1400
2200
160


125XHOOH
1500
1750
2200
160
















TABLE 7







Reagent amounts for experiments looking at the effect of initial dicamba


concentration on dicamba degradation rate.











Sample
Dicamba,
Hydrogen 
Iron,
PMIDA in 


ID
mg/kg
Peroxide, μL
μL
analytical vial, uL














D/1
6000
3466
4458
400


D/2
3000
1733
2229
400


D/4
1500
867
1115
400


D/8
750
433
557
400


D/16
375
217
279
400


D0
0
867
1115
400









Example 5
Using data generated in connection with the experiments described in Example 4, reaction kinetics were calculated for degradation of dicamba in the presence of glyphosate. The results are generally consistent with first order kinetics for all of the reagents.
For example, FIG. 1 shows the expected concentration of dicamba with respect to time on a logarithmic scale. The reaction rate constant (represented by the slope of the line) is not significantly impacted by the initial dicamba concentration, implying first-order behavior. FIG. 2 depicts the reaction rate constant as a function of initial hydrogen peroxide concentration. Generally, the data indicate that hydrogen peroxide has a first order effect on reaction rate. FIG. 3 depicts the reaction rate constant as a function of the iron to glyphosate molar ratio. Note that approximately 1.56 molar equivalents of iron are required to start the reaction in the presence of glyphosate. Also noteworthy is that the impact of increasing iron concentration is approximately 10 times greater than that achieved by increasing the concentration of hydrogen peroxide.
The reaction rate can reasonably be described by the equation below




  
    
      
        
          r
          d
        
        =
        
          
            -
            
              
                d
                
                  [
                  D
                  ]
                
              
              
                d
                t
              
            
          
          =
          
            
              
                k
                ⁡
                
                  [
                  
                    F
                    -
                    
                      F
                      0
                    
                  
                  ]
                
              
              ⁡
              
                [
                P
                ]
              
            
            ⁡
            
              [
              D
              ]
            
          
        
      
    
    
      
        (
        1
        )
      
    
  




Where D is the dicamba concentration in ppm, F is the molar ratio of total iron to glyphosate, and P is the peroxide concentration. From the kinetic data, k=7.2×10−7 min−1 and F0=1.56 mol iron/mol glyphosate. The rate equation is able to accurately fit the observations made in Examples 1-4 regarding changing peroxide and dicamba concentrations.

Example 6
The Fenton method, which was applied to degrade dicamba in Examples 1-4, was applied to 2,4-D to investigate whether this herbicide could also be degraded. The solutions set forth in Table 8, below, were prepared and placed in separate glass vials. The solutions were then analyzed by high performance liquid chromatography at 12 days following the first mixing. As shown in the table below, no dicamba or 2,4-D was detected in any of the samples comprising Fenton reagents.







TABLE 8







Analysis of dicamba and 2,4-D samples

















0.1% wt
Dicamba acid
2,4-D



10% w/w
30% w/w
0.1% wt
2,4-D
(% wt/vol),
(% wt/vol),



Fe salt
H2O2
Clarity
amine
remaining
remaining


Sample #
(μL)
(μL)
(g)
(g)
after 12 days
after 12 days
















08488968-1
0
0
30
0
0.1058
ND


(dicamba)








08488968-2
0
0
0
30
ND
0.1158


(2,4-D)








08488968-3
1050
1890
30
0
ND
ND


(dicamba/peroxide/








FeCl3)








08488968-4
1050
1890
30
0
ND
ND


(dicamba/peroxide/








FeCl3)








08488968-5
1050
1890
30
0
ND
ND


(dicamba/peroxide/








FeCl3)








08488968-6
1050
1890
0
30
ND
ND


(2,4-D/peroxide/








FeCl3)








08488968-7
1050
1890
0
30
ND
ND


(2,4-D/peroxide/








FeCl3)








08488968-8
1050
1890
0
30
ND
ND


(2,4-D/peroxide/








FeCl3)









Example 7
The following tables represent exemplary formulations, applications, and environmental conditions of the compositions and methods described herein. Unless otherwise noted, all values pertain to the cleaning of a full size spray tank with a capacity of 26 gallons (approximately equivalent to 100 kilograms).










TABLE 9







Dicamba Use Rate, lb/A
0.01
0.25
0.5


Glyphosate Use Rate, lb/A
0.03
0.75
1.5


FeCl3, molar equivalent to glyphosate
1
1.25
1.5


Hydrogen Peroxide, molar eq. to dicamba
25
50
100


Temperature, C.
15
25
35






















TABLE 10







Dicamba Use Rate, lb/acre
0.25
0.5
0.05
0.005
0.4518
2.56E−04


Application Rate, gallons/acre
10
10
10
10
10
10


Dicamba Concentration, % (g/g)
0.2998
0.5995
0.0600
0.0060
0.5417
3.069 × 10−6


Holdup Volume, gallons
6
6
6
6
6
6


Rinse Volume, gallons
20
20
20
20
20
20


Rinse 1 Dicamba Concentration,
691.75
1383.5
138.35
13.835
1250
0.70836


mg/kg






















TABLE 11







Glyphosate Use Rate, lb/acre
0.75
1.5
0.15
0.015
1.355
1


Application Rate, gallons/acre
10
10
10
10
10
10


Glyphosate Concentration, % (g/g)
0.899
1.799
0.180
0.018
1.625
1.199


Holdup Volume, gallons
6
6
6
6
6
6


Rinse Volume, gallons
20
20
20
20
20
20


Rinse 1 Dicamba Concentration,
2075.3
4150.5
415.05
41.505
3750
2767.02


mg/kg









Tables 12A and 12B generally relate to an application of the present method to clean a full size spray tank, wherein the source of transition metal ions is ferric chloride, and the source of hydrogen peroxide is aqueous hydrogen peroxide. In addition to glyphosate acid, a relatively small amount N-(phosphonomethyl)iminodiacetic acid, an intermediate produced during the production of glyphosate that is present in some glyphosate formulations, was also incorporated into the test herbicidal mixture. The test mixture was also pH adjusted to approximately 4.0 using sodium hydroxide, as necessary.










TABLE 12A









Dicamba, mg/kg
1500



Glyphosate, mg/kg
3035.16



FeCl3 Basis Amount, mol/mol glyphosate
1.3



H2O2 Basis Amount, mol/mol dicamba
25

























TABLE 12B






Amount
Density
Mass
Amount
MW
Amount
Conc.
Conc.


Component
(uL)
(mg/ul)
Frac.
(mg)
(g/mol)
(mmol)
(mol/L)
(mg/kg)























Dicamba acid
30000
1
0.0015
45
221.04
0.20
0.01
1456


Glyphosate
30000
1
0.003
91.05
169.07
0.54
0.02
2946


acid










FeCl3
392
2.898
0.1
113.56
162.2
0.70
0.02
3674


(10% soln)










H2O2
520
1.11
0.3
173.12
34.015
5.09
0.16
5600


(30% soln)










Total
30912


422.73






PMIDA 10%
429
1
0.094
40.36
227.11
0.18
5.67E−03
1288


(g/g) solution









Tables 13A and 13B generally relate to an application of the present method to clean a full size spray tank, wherein the source of transition metal ions is ferrous sulfate, and the source of hydrogen peroxide is aqueous hydrogen peroxide.










TABLE 13A









Dicamba Basis, mg/kg
1250



Glyphosate Basis, mg/kg
3750



FeCl3 Basis Amount, uL
50



H2O2 Basis Amount, uL
567

























TABLE 13B






Amount
Density
Mass
Amount
MW
Amount
Conc.
Conc.


Component
(uL)
(mg/ul)
Frac.
(mg)
(g/mol)
(mmol)
(mol/L)
(mg/kg)























Dicamba acid
30000
1
0.0013
37.5
221.04
0.17
4.77 × 10−3
1055


Glyphosate
30000
1
0.0038
112.5
169.07
0.67
0.02
3164


acid










FeSO4•7H2O
3662
1.898
0.1
695.03
278.02
2.50
0.07
19550


(10% soln)










Hydrogen
1890
1.11
0.3
629.37
34.015
18.50
0.52
17703


Peroxide










(30% soln)










Total
35552


1474.41









Tables 14A and 14B generally relate to an application of the present method to clean a full size spray tank, wherein the source of transition metal ions is ferric chloride, and the source of hydrogen peroxide is sodium perborate.










TABLE 14A









Dicamba Basis, mg/kg
1250



Glyphosate Basis, mg/kg
3750



FeCl3 Basis Amount, uL
50



H2O2 Basis Amount, uL
567

























TABLE 14B






Amount
Density
Mass
Amount
MW
Amount
Conc.
Conc.


Component
(uL)
(mg/ul)
Frac.
(mg)
(g/mol)
(mmol)
(mol/L)
(mg/kg)























Dicamba acid
30000
1
0.0013
37.5
221.04
0.17
0.01
1143


Glyphosate
30000
1
0.0038
112.5
169.07
0.67
0.02
3430


acid










FeCl3
1400
2.898
0.1
405.72
162.2
2.50
0.08
12369


(10% soln)










Sodium
1401
1.31
1
1835.57
100
18.36
0.56
55961


Perborate










(μg)










Total
32801


2391.29









Tables 15A and 15B generally relate to an application of the present method to clean a full size spray tank, wherein the source of transition metal ions is ferric chloride, and the source of hydrogen peroxide is aqueous hydrogen peroxide. In addition to glyphosate acid, a relatively small amount N-(phosphonomethyl)iminodiacetic acid, an intermediate produced during the production of glyphosate that is present in some glyphosate formulations, was also incorporated into the test herbicidal mixture. The test mixture was also pH adjusted to approximately 4.0 using sodium hydroxide.










TABLE 15A









Dicamba, mg/kg
1500



Glyphosate, mg/kg
3035.15625



FeCl3 Basis Amount, mol/mol glyphosate
4



H2O2 Basis Amount, mol/mol dicamba
125

























TABLE 15B






Amount
Density
Mass
Amount
MW
Amount
Conc.
Conc.


Component
(uL)
(mg/ul)
Frac.
(mg)
(g/mol)
(mmol)
(mol/L)
(mg/kg)























Dicamba acid
50000
1
0.0015
75
221.04
0.34
5.66 × 10−3
1252


Glyphosate
50000
1
0.00303
151.757
169.07
0.90
1.50 × 10−2
2533


acid










FeCl3
5573
1.045
0.1
582.37
162.2
3.59
5.99 × 10−2
9721


(10% soln.)










Hydrogen
4332
1.11
0.3
1,442.67
34.015
42.41
0.708
24083


Peroxide










(30% soln)










Total
59905


2251.79






PMIDA 10%
9542
1
0.094
896.96
227.11
3.95
5.69 × 10−2
12916


(g/g) soln.









Tables 16A and 16B generally relate to an application of the present method to clean a full size spray tank, wherein the source of transition metal ions is ferric chloride, and the source of hydrogen peroxide is aqueous hydrogen peroxide. In addition to glyphosate acid, a relatively small amount N-(phosphonomethyl)iminodiacetic acid, an intermediate produced during the production of glyphosate that is present in some glyphosate formulations, was also incorporated into the test herbicidal mixture. The test mixture was also pH adjusted to approximately 4.0 using sodium hydroxide.










TABLE 16A









Dicamba, mg/kg
1500



Glyphosate, mg/kg
3035.15625



FeCl3 Basis Amount, mol/mol glyphosate
4



H2O2 Basis Amount, mol/mol dicamba
125

























TABLE 16B






Amount
Density
Mass
Amount
MW
Amount
Conc.
Conc.


Component
(uL)
(mg/ul)
Frac.
(mg)
(g/mol)
(mmol)
(mol/L)
(mg/kg)























Dicamba acid
50000
1
0.0015
75
221.04
0.34
5.66 × 10−3
1252


Glyphosate
50000
1
3.03 × 10−3
151.757
169.07
0.90
1.50 × 10−2
2533


acid










FeCl3
5573
1.045
0.1
582.37
162.2
3.59
5.99 × 10−2
9721


(10% soln.)










Hydrogen
4332
1.11
0.3
1442.67
34.015
42.41
0.708
24083


Peroxide










(30% soln)










Total
59905


2251.79






PMIDA 10%
9542
1
0.094
896.96
227.11
3.95
5.69 × 10−2
12916


(g/g) soln.









Example 8
This example describes a small-scale demonstration of the efficacy of the present invention in largely eliminating injury to soy due to residual levels of three herbicides: dicamba, 2,4-D and flumioxazin, all in the presence of glyphosate. Four simulated spray solutions were prepared. All of the solutions were prepared assuming a 10 gallon/acre spray rate with a glyphosate rate of 1.0 lb acid equivalent (a.e.) per acre (1120 g/ha). The source of the glyphosate was Roundup Powermax® herbicide. In addition, the spray solutions contained dicamba diglycolamine salt (Clarity®) or 2,4-D amine sometimes in combination with flumioxazin derived from Valor® herbicide.
60 ml of the simulated spray solutions were transferred to 250 ml beakers. A ferrous sulfate solution (10% iron) was added to each solution in an amount that provided 3 moles of iron per mole of glyphosate. 30 moles of hydrogen peroxide per mole of dicamba or 15 or 30 moles of hydrogen peroxide per mole of 2,4-D was then added. The flask was swirled and allowed to stand for 20 minutes. Oxygen evolution occurred with mild foaming.
Immediately after 20 minutes had elapsed, the treated solutions were diluted 30× and sprayed over glyphosate-tolerant soybeans at a 10 gallon per acre rate. As a control, untreated solution, was diluted 30× and sprayed at the same rate. Soybean injury was rated 7 days after spraying. Injury to soy was dramatically reduced in all cases.







TABLE 17







Treatment protocols and soy injury


ratings for simulated tank cleaning













Treat-




Injury



ment
Glyphosate
Other
Rates
H2O2
un-
Injury


No.
rate (g/ha)
herbicides
(g/ha)
ratio†
treated
treated





1
1120
Dicamba
 560
30
26%
4%


3
1120
Dicamba/
 560/107
30
28%
7%




flumi*






4
1120
2,4-D
1120
30
38%
4%


5
1120
2,4-D
1120
15
38%
3%


6
1120
2,4-D/
1120/107
30
24%
4%




flumi*





*flumi = flumioxazin.


†Molar ratio of H2O2 to dicamba or 2,4-D.






When introducing elements of the present invention or the preferred embodiments(s) thereof, the articles “a”, “an”, “the” and “said” are intended to mean that there are one or more of the elements. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.
In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.
As various changes could be made in the above products and methods without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

## Claims

1. A method of preparing an agricultural spray tank for use in connection with a second pesticide following use of the tank in connection with a first pesticide, the method comprising:
introducing a cleaning mixture into the tank containing a residual amount of the first pesticide, wherein the cleaning mixture comprises
(a) a source of transition metal ions, and
(b) a source of hydrogen peroxide;

allowing the cleaning mixture to remain in the tank for a time sufficient to degrade at least about 50% by weight of the residual amount of the first pesticide, thereby forming a waste mixture comprising degradation products of the first pesticide; and
removing the waste mixture from the tank;
wherein the first pesticide comprises a first herbicide, and the first herbicide comprises glyphosate,
and wherein the transition metal ions are initially added to the tank in a molar ratio of at least about 3:1 with respect to the amount of glyphosate a.e. present in the pesticidal residue.

2. The method of claim 1 wherein the cleaning mixture further comprises water.

3. The method of claim 1 wherein the first herbicide further comprises an herbicide selected from the group consisting of 2,4-D, dicamba, and mixtures thereof.

4. The method of claim 1 wherein the first herbicide further comprises dicamba.

5. The method of claim 1 wherein the source of transition metal ions comprises a source of polyvalent iron ions.

6. The method of claim 5 wherein the source of iron ions is ferrous sulfate, ferric chloride, or a mixture thereof.

7. The method of claim 1 wherein the source of hydrogen peroxide is selected from the group consisting of sodium percarbonate, sodium perborate, and combinations thereof.

8. The method of claim 1 wherein the source of hydrogen peroxide is aqueous hydrogen peroxide.

9. The method of claim 1 wherein the duration between introduction of the cleaning mixture into the tank and removal of the waste mixture from the tank is less than about 2 hours.

10. The method of claim 1 wherein the waste mixture is removed from the tank by spraying.

11. The method of claim 1 further comprising a pre-rinse step prior to introducing the cleaning mixture into the tank, wherein the pre-rinse comprises introducing an aqueous medium into the tank to form a diluted pesticidal residue mixture comprising a portion of the first pesticide.

12. The method of claim 11 wherein at least a portion of the diluted pesticidal residue mixture is removed from the tank by spraying prior to introduction of the cleaning mixture into the tank.

13. The method of claim 2 wherein water constitutes at least about 50% by weight of the cleaning mixture.

14. The method of claim 1 wherein the cleaning mixture is not subjected to an artificial light source or an applied electric current while in the tank.

15. The method of claim 1 wherein the initial molar ratio of hydrogen peroxide to transition metal ions in the cleaning mixture is at least about 5:1.

16. The method of claim 1 wherein the molar ratio of hydrogen peroxide introduced into the tank to residual first pesticide is at least about 10:1.

17. The method of claim 1 wherein the cleaning mixture comprises transition metal ions in a molar ratio of at least about 4:1 with respect to the amount of glyphosate present in the pesticidal residue prior to introduction of the cleaning mixture into the tank.

18. The method of claim 1 wherein at least a portion of the first herbicide is present in an aqueous solution.

19. The method of claim 1 wherein the source of transition metal ions is introduced into the tank before the source of hydrogen peroxide is introduced into the tank.

20. The method of claim 1 wherein the duration between introduction of the cleaning mixture into the tank and removal of the waste mixture from the tank is less than about 20 minutes.

21. A method of preparing an agricultural spray tank for use in connection with a second pesticide following use of the tank in connection with a first pesticide, the method comprising:
introducing a cleaning mixture into the tank containing a residual amount of the first pesticide, wherein the cleaning mixture comprises
(a) a source of transition metal ions, and
(b) a source of hydrogen peroxide;

allowing the cleaning mixture to remain in the tank for a time sufficient to degrade at least about 50% by weight of the residual amount of the first pesticide, thereby forming a waste mixture comprising degradation products of the first pesticide; and
removing the waste mixture from the tank;
wherein the first pesticide comprises a first herbicide, and the first herbicide comprises glyphosate,
wherein the transition metal ions are initially added to the tank in a molar ratio of greater than 1:1 with respect to the amount of glyphosate a.e. present in the pesticidal residue,
and wherein the duration between introduction of the cleaning mixture into the tank and removal of the waste mixture from the tank is less than about 20 minutes, and the waste mixture is removed from the tank by spraying.