WO1993000311A2 - Traitement therapeutique et preventif de l'etat anaerobie de plantes et du sol - Google Patents

Traitement therapeutique et preventif de l'etat anaerobie de plantes et du sol Download PDF

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Publication number
WO1993000311A2
WO1993000311A2 PCT/US1992/005058 US9205058W WO9300311A2 WO 1993000311 A2 WO1993000311 A2 WO 1993000311A2 US 9205058 W US9205058 W US 9205058W WO 9300311 A2 WO9300311 A2 WO 9300311A2
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Prior art keywords
peroxide
phosphate
plant
oxygen
surfactant
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PCT/US1992/005058
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English (en)
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WO1993000311A3 (fr
Inventor
William A. Farone
Stephen Koenigsberg
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Plant Research Laboratories
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Publication of WO1993000311A2 publication Critical patent/WO1993000311A2/fr
Publication of WO1993000311A3 publication Critical patent/WO1993000311A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/50—Surfactants; Emulsifiers

Definitions

  • the present invention relates to the use of certain peroxides, and mixtures of these peroxides with phosphates or surfactants, or both, as agents which release oxygen to the soil.
  • this invention relates to a method of using certain metal peroxides or metal peroxide/phosphate/surfactant mixtures as a preventative or therapeutic treatment of anaerobic soil conditions, by directly applying the metal peroxide or mixtures thereof to the soil, or blending the metal peroxide or mixtures thereof with plant nutrients, growth regulators or other beneficial additives, and then applying to the soil.
  • a variety of oxygen delivery vehicles are known in the art. For example, U.S. Patent No. 3,912,490 to Malcolm B.
  • Boghosian discloses aqueous plant nutrient systems involving the use of urea peroxide or hydrogen peroxide as supplements to fertilizers which release oxygen to the soil.
  • the solution is applied to the soil or other media in which the plant grows.
  • the solution penetrates the soil, releasing oxygen to the root zone.
  • This oxygen treatment is stated to improve plant appearance and prevent injury to the plant due to over watering.
  • the Boghosian supplement may include nitrogen, phosphorus and potassium in the appropriate ratios and concentrations as required by the particular plant being fertilized.
  • the nitrogen, potassium and phosphorus are macronutrients.
  • the application of nutrients is controlled by the amount in the fertilizer formulation and the rate at which the fertilizer is applied through mixing with water.
  • the Boghosian formulation requires-an aqueous system which is limited to relatively low amounts of included macronutrients due to the solution becoming unstable and prematurely releasing hydrogen peroxide which, in turn, releases oxygen.
  • Urea peroxide is a complex of urea and hydrogen peroxide with rather low binding energy.
  • the aqueous Boghosian formulation is limited in the use of micronutrients such as trace metals because the micronutrients react with the urea peroxide releasing hydrogen peroxide which, in turn, releases oxygen.
  • a method of treating media in which plants grow is particularly effective in media of the type having a relatively negative reduction- oxidation potential.
  • a composition containing peroxide is applied to the media in an amount which releases to the media an effective amount of atomic oxygen to provide an initial increase in the reduction- oxidation potential.
  • a composition containing an oxygen release rate mediated peroxide is used. This initial shift of the reduction oxidation potential in the positive direction offsets the negative effects of having a relatively negative reduction oxidation potential, thereby enhancing plant growth and appearance.
  • the peroxide is selected from the group consisting of calcium peroxide, potassium peroxide and magnesium peroxide.
  • the oxygen release rate modifier preferably comprises a compound which provides a source of phosphate ion, such as potassium dihydrogen phosphate, dipotassium hydrogen phosphate, urea phosphate, monoammonium phosphate, diammonium phosphate and mixtures thereof.
  • the composition preferably also includes a surfactant in an amount which is substantially non-toxic to plants, and preferably is within the range of from about 0.03 to about 1.60 g per gram of peroxide.
  • a method of treating black layer in turf comprising the steps of identifying a turf region which exhibits indicia of, or the potential to develop black layer, and administering to the affected turf and effective amount of a composition comprising an oxygen delivery compound selected from the group consisting of calcium peroxide, magnesium peroxide, potassium peroxide and combinations thereof.
  • the compound also includes a phosphate ion source and/or a surfactant.
  • a method of treating potato soft rot comprising administering to a harvested potato an effective soft rot treating amount of a composition comprising a compound selected from the group consisting of magnesium peroxide, calcium peroxide, potassium peroxide and mixtures thereof, preferably in combination with an intercalated phosphate source.
  • a method of treating plants or plant portions such as from potatoes, or any other susceptible crop, prior to planting said portions is provided.
  • the plant or plant portions are contacted with an effective amount of a composition comprising a compound selected from the group consisting of magnesium peroxide, calcium peroxide, potassium peroxide and mixtures thereof, preferably in combination with an intercalated phosphate source, to inhibit the onset of detrimental conditions of the type which are treatable by said composition.
  • a method of storing plants or plant parts such as with post-harvest storage prior to use, shipment or prior to planting or any other post-harvest treatment.
  • the plant or plant part is contacted with an effective amount of a compound selected from the group consisting of magnesium peroxide, calcium peroxide, potassium peroxide and mixtures thereof, preferably in combination with an intercalated phosphate source, for inhibiting the onset of detrimental conditions of the type which are treatable by said compound.
  • a compound selected from the group consisting of magnesium peroxide, calcium peroxide, potassium peroxide and mixtures thereof preferably in combination with an intercalated phosphate source
  • a plant crop having a propensity to develop or already having symptoms of undesirable levels of anaerobic microorganism activity are identified.
  • An effective anaerobic microorganism activity inhibiting or treating amount of a composition comprising a compound selected from the group consisting of calcium peroxide, magnesium peroxide, potassium peroxide and combinations thereof, preferably in combination with an intercalated phosphate source, is administered to the crop to either treat or inhibit the condition.
  • Figure 1 illustrates the improved storability of calla rhizomes when treated in accordance with the present invention.
  • Figure 2 illustrates the dose response of five species of phythium as a result of treatment in accordance with the present invention.
  • Figure 3 illustrates the effect of ORC treatment at the pre-use, pre-shipment, pre-storage or pre-planting stage on potato sections in accordance with the present invention.
  • ORCs oxygen releasing compounds
  • compositions and methods in accordance with the present invention are useful, but not limited to, the control of black layer in turf grass, post harvest soft rot in potatoes, and as a pre-plant treatment in potatoes.
  • the basis of the preventative and therapeutic actions of ORC is believed by the inventors herein to involve, inter alia, its ability to release oxygen.
  • the complex chemical reactions of the soil environment are beyond complete description, using the current state of the art, the empirical evidence developed by the inventors leads them to conclude that the oxygen release characteristics of the compounds and formulations disclosed herein, have beneficial effects in the control of black layer and harmful microorganisms.
  • a central parameter in soil chemistry is the reduction- oxidation potential.
  • the so-called "redox" potential is an electrochemical background condition, which controls the chemical reactivity of ions in soil.
  • the present invention is directed to making negative redox potential media "less negative,” or slightly positive redox potential media “more positive.”
  • references to moving the redox potential from negative to positive refers to the direction of the change, not necessarily a change from absolute negative (below zero) to absolute positive (above zero) .
  • a positive redox potential referred to as an oxidized environment
  • an oxidized environment is generally beneficial to plant growth.
  • unhealthy soils tend to have a negative redox potential, which is detrimental to plant growth.
  • the common terms, sweet and sour soil relate respectively to the above descriptions and the characteristic smells are a function of the different chemistry in each condition.
  • Black layer develops under negative redox potentials.
  • the condition is characterized by the presence of iron and manganese sulfides (FeS and MnS) , which are relatively insoluble dark to black compounds that precipitate and become visually apparent in the soil column.
  • the sulfides are formed and are stable in relatively negative redox environments and may transform to the soluble, lighter colored sulfates (FeS0 4 and MnS0 4 ) , in relatively positive redox environments.
  • ORCs by virtue of their oxygen release capability, tend to provide an initial increase in the redox potential in the positive direction. As sulfides turn into sulfates, the dark to black coloration disappears, the accompanying odor disappears, and iron and manganese become available to the plants. As an additional benefit of the foregoing solubility changes, the resulting increase in available iron is particularly important in turf management. Furthermore, the phosphates which are present in certain time release ORC formulations in accordance with the present invention, will form complexes with Fe and Mn thereby minimizing the formation or reformation of the respective sulfides.
  • the sulfides form insoluble precipitates, which in turn have a detrimental effect on the water status of turf by reducing soil porosity.
  • zone an impervious black layer zone or zones
  • zone can cause a perched water table, which in turn can lead to anoxic conditions in the root zone.
  • the black layer zone is toxic and therefore impenetrable to plant roots.
  • Malodorous conditions is a function of several genera of anaerobic, sulfur reducing bacteria such as, but not limited to, Desulfovibrio. Desulfoto aculum. Desulfomonas, Desulfonema. and Desulfobacter. These bacteria will convert sulfur to a variety of detrimental sulfur compounds including hydrogen sulfide gas (H 2 S) which has the characteristic smell of rotten eggs and various mercaptan compounds which also have very disagreeable odors.
  • H 2 S hydrogen sulfide gas
  • the redox potential is a function, not only of the charged species, but also of the concentration of the species and the temperature of the solution.
  • the two important “half reactions” (written as "standard” potentials for unit concentration at 25°C) are:
  • equation [1] has a voltage given by:
  • [1] can be controlled by the concentration of oxygen and the temperature of the system.
  • any of a variety of pH adjusters may be used as will be understood by one of skill in the art, including KOH and H 2 S0.
  • pH adjustment can detrimentally affect the desirable microorganisms as will be well known by those of skill in the art.
  • Nitrate is used in plant nutrition as a nitrogen source.
  • Mg0 2 oxygen reacts roughly as per [1] and [2] and, consequently, it is not in the range, such as with H-0 2 concentrates and 0 3 , where damage to microbes and the plants of interest and other detrimental chemistry can occur.
  • Mg0 2 has a lower redox value than H 2 0 2 , under the same (standard) conditions, because Mg0 2 is made from H 2 0 ⁇ .
  • this could not occur if Mg0 2 could oxidize water to give H 2 0 2 .
  • Concentrated hydrogen peroxide is a stronger oxidizing agent (higher redox potential) and thus is more difficult to control.
  • one objective of the invention is to beneficially increase the amount of oxygen for the microbes and the plants of interest without unwanted side reactions due to oxidative mechanisms.
  • Introduction of oxygen into the soil by ORC has been determined by the inventors herein to function both as a preventative and as a therapeutic to the development of black layer.
  • a preventative or therapeutic treatment for any anaerobic soil conditions comprising the application of any feasible peroxides, as agents which release oxygen to the soil.
  • the anaerobic soil conditions that merit preventative or therapeutic measures include, but are not limited to, those that generate malodorous or otherwise undesirable conditions.
  • Feasible peroxides are defined as any peroxide which can be used in a soil system, within defined limits, in a safe and effective manner.
  • a given oxygen delivery system i.e., feasible peroxides
  • suitable oxygen delivery systems are best determined empirically, to determine the actual impact on microbes and the plants of interest.
  • feasible peroxides can be identified by one of skill in the art through routine experimentation. The objective would be to increase the redox potential, preferably to above zero, near about 0.1 volts.
  • Feasible peroxides include, but are not limited to, hydrogen peroxide, urea hydrogen peroxide, sodium percarbonate, calcium peroxide, potassium peroxide and magnesium peroxide.
  • zinc peroxide may be used in combination with others.
  • the present invention incorporates certain properly sized metal peroxides and mixtures of these metal peroxides with phosphates or surfactants, or both, as agents which release oxygen to the soil.
  • the specific invention is utilized as a preventative and therapeutic treatment, including such agronomic condition(s) as that referred to as black layer, defined as an anaerobic soil condition detrimental to plant growth and development.
  • particles having a mesh size of smaller than about 100, but generally no smaller than about 400 mesh Preferably, mesh size in the range of from about 200 to about 400 will be used. Particles of less than 400 mesh are relatively unstable and generally unable to deliver oxygen over a sufficient treatment period to effectively carry out the required reactions. In addition, production of excessively small particle size adds to manufacturing costs. However, the smaller particle sizes result in superior particle mobility. Thus, the smallest particle size obtainable, which also exhibits sufficient stability for a given application, is most preferred. Stabilizing relatively small particle size is preferably accomplished in accordance with the "intercalation" method of the present invention, disclosed infra. Alternatively, particle sizes even larger than 100 mesh may be desired to facilitate handling of the product, especially for dry applications.
  • magnesium peroxide Mg0 2
  • the calcium peroxide, magnesium peroxide, potassium peroxide or mixtures thereof are preferably present in an amount ranging from about 5 to about 100 and more preferably, from about 5 to about 60 weight percent of the preferred formulation.
  • the rate at which the metal peroxides will release oxygen to the soil may be inhibited by including an oxygen release rate modifier such as a source of phosphate ion (P0 "3 ) , in the formulation.
  • an oxygen release rate modifier such as a source of phosphate ion (P0 "3 )
  • P0 "3 phosphate ion
  • intercalation method it takes a substantially longer period of time for the metal peroxide to decompose to release the oxygen.
  • simple phosphate ion (not polyphosphate) will be used.
  • Polyphosphates are less effective per unit weight, less available to plants, and more prone to cause various colloidal effects.
  • the active oxygen content of the phosphate-intercalated, time-release magnesium peroxide was higher in all 11 of the pairs of batches than the regular magnesium peroxide.
  • the average percentage increase for the active oxygen content with phosphate intercalation was 22.6%.
  • the amount of phosphate used varies, depending on the desired characteristics sought to be achieved, but generally from about 0.03 to about 1.60 grams of phosphate compound is used per gram of metal peroxide.
  • phosphate ion potassium dihydrogen phosphate, dipotassium hydrogen phosphate, urea phosphate, monoammonium phosphate and diammonium phosphate.
  • a surfactant with the metal peroxides.
  • the surfactant has been observed to improve germination of seeds.
  • the surfactant is also desirable because it tends to increase the dispersibility of the metal peroxide in water and in the soil upon application.
  • from about 0.005 to about 0.020 grams of surfactant is used per gram of metal peroxide.
  • the surfactant will generally be present within the range of from about 0.05% to about 2.0% of the ORC composition.
  • the surfactant will be present in the range of from about 0.1% to about 1%, and most preferably about .1 weight percent of surfactant will be used. For specific applications, however, significantly more surfactant may be desirable.
  • surfactants which are generally non-toxic to plants and which have been found useful in germinating seeds, are disclosed, for example, in U.S. Patent No. 4,171,968, the disclosure of which is hereby incorporated by reference.
  • suitable surfactants include alcohol ethoxylate sulfates, acyl taurides and ethoxylated alcohols.
  • the following classes of surfactants are contemplated by the inventors herein:
  • long chain alcohol ethoxylate sulfates of the formula RO - (CH 2 CH 2 0) - _ SO-Na where R is about C 12 to C 18 , and n is no greater than about 9 to 10;
  • long chain acyl taurides of the formula RCON(CH 3 )C 2 H 4 S0 3 Na where R is about C 14 to C 20 ;
  • long chain ethoxylated alcohols of the formula RO - (CH 2 CH 2 0) - _ H where R is about C 14 to C 20 , and n is no greater than about 9 to 10.
  • Class 2 surfactants may be obtained from Rhone Poulenc under the trade name Igepon.
  • Other compounds are also suitable surfactants in the context of the present invention.
  • the surfactant is a monolaurate, monopalmitate, monostearate and monooleate esters of sorbitol, or mixtures thereof, either with or without ethoxylation. These compounds are sold by ICI America under the brand names of Tween and Span.
  • fertilizer nutrients for the treatment of black layer and other anaerobic soil conditions which detrimentally affect plant growth, it may also be desirable to include fertilizer nutrients, growth regulators or other beneficial additives in the ORC composition. Fertilizer nutrients will generally not be included, however, in the treatment of some types of conditions such as post harvest control of potato soft rot, but could be incorporated into ORCs which are applied to potato seed pieces as a pre-planting treatment.
  • the fertilizer nutrients of this invention includes the macronutrients, nitrogen (N) , phosphorous (P) and potassium (K) .
  • the nitrogen expressed as atomic nitrogen, is preferably present in the range from about 1 to about 35 weight percent.
  • the phosphorous expressed as phosphorous pentoxide (P 2 0_)
  • P 2 0_ phosphorous pentoxide
  • the potassium expressed as potassium oxide (K-O) , is preferably present in the range from about 1 to about 35 weight percent.
  • the ratio of nitrogen, phosphorous and potassium may be varied throughout a relatively wide range depending upon the application, as will be appreciated by one of skill in the art.
  • a fertilizer including relatively high levels of nitrogen, potassium and phosphorous, and a metal peroxide.
  • fertilizers with an N-K-P value in excess of 15:15:15 are readily achievable in a dry formulation containing metal peroxides.
  • the fertilizer of this invention may also include micronutrients such as trace amounts of iron and manganese, and other ingredients known to be beneficial to plants. Typically, these micronutrients are in amounts ranging from about 0 to about 5 weight percent, preferably 0.1 to 2.0 weight percent.
  • the N-P-K ratio is 20:15:15 for general application.
  • the formulation for use in accordance with the present invention preferably also include small, but effective amounts of certain metals.
  • Suitable metals are selected from the group consisting of zinc, copper, molybdenum, boron, selenium, cobalt, aluminum, manganese, iron, and nickel.
  • Such metals are bioactive agents which either suppress or enhance the growth of selected microorganisms.
  • An effective amount of metal is sufficiently low that upon application of the composition, to the soil, toxic effects with respect to plants is avoided, and is sufficiently high to affect the microorganisms in the vicinity of the plant roots.
  • the trace elements will generally be in the range of 0.005% to 0.1% for copper; 0.001% to 0.05% for cobalt and nickel; 0.001% to 0.2% for molybdenum; 0.001% to 0.2% for aluminum; 0.01% to 0.4% for zinc; and 0.01% to 0.8% for manganese and iron.
  • an effective amount of metal is less than about 1000 parts per million of the composition (0.1%).
  • formulations in accordance with the present invention will include sufficient quantities of metals to inhibit the first and enhance the second and third of the above classes.
  • formulations useful in practicing the methods in accordance with the present invention optimally include the following four types of ingredients.
  • Oxygen releasing metal peroxides are applied to provide oxygen to select the beneficial microorganisms from the pathogenic microorganisms. This is a function in addition to the function discussed above, i.e., providing oxygen to the media or plant tissue. Oxygen release is accomplished in a controlled profile through the use of release rate modifiers to select the beneficial microorganisms over an extended period.
  • Surfactants are also preferably included to improve suspension of the product in a slurry (as it is essentially insoluble) , and to improve dispersion of the composition in the soil during and after application.
  • Appropriate nutrients can be included in formulations for use in treating black layer and other undesirable conditions which have resulted from or are associated with anaerobic soil conditions. Such nutrients are not only beneficial to the plant but can also help maintain a desirable microorganism population. In accordance with other aspects of the present invention, such as the post harvest control of undesirable conditions such as potato soft rot, plant nutrients may not necessarily be included.
  • Trace metals at levels which are effective in controlling the enzymatic secretions of the damaging microorganisms are also preferably included.
  • the trace metals can be added in such levels such that the predominant activity is on the microorganisms while the excess, not used in reacting with the microorganism's enzyme systems, can be beneficially used by the plants themselves.
  • compositions of this invention and method of using such compositions can both aid the plants and interact in the desired favorable fashion with microorganisms in the soil that help or hurt the plants.
  • a variety of bacterial diseases of interest to commercial growers include the following: Cornebacterium insidiosum causes alfalfa wilt; Xanthomonas malyaqearum causes leaf spot in cotton; Xanthomonas stewartii causes wilt in corn; Erwinia thacheipilia causes wilt in cucurbits; Xanthomonas phaseoli causes blight of beans; Xanthomonas campestris causes black rot of crucifers; Erwinia amyloyora causes fire blight in some fruits; Streptomyces scabies causes potato scab; Cornebacterium sepedonicum causes ring rot in potato; Erwinia carotovora causes soft rot in cabbage, lettuce, potato (and other root crops) ; and Pseudomonas malkyace
  • Rhizopus spp. and Tilletia spp. cause smut in oats, wheat, rye, barley, sorghum and corn; and Fusarium and Verticillium spp. cause wilt in many plants. Mildew, damping off and root rot have been controlled in experiments with sensitive seedlings.
  • a combination of the surfactants with the oxygen-releasing peroxides provided evidence of earlier and higher frequency of germination of seedlings with no evidence of these fungal diseases in geraniums, impatien ⁇ , and other bedding plants.
  • formulations containing copper in the range of 0.1-5 ppm have been found to be useful for control of many of the fungi, particularly Taphrina, Pvthium, Tilletia. Ustiaqo and Fusarium.
  • Copper salts are preferably included in the formulation in an amount so that when applied dry to the soil and then watered, or when the formulation is diluted with water before application, from about 0.1 to about 5 ppm of copper is delivered.
  • ORC in accordance with the present invention, exhibits both preventative and therapeutic effects. Turf grass was grown within 4" dia. x 3" deep pots (approx. 600 cc soil) in the greenhouse, for the purpose of proving ORC alleviated flooding stress (anaerobic stress) which it did. An unexpected result was control of algae. A minimum 100 mg of ORC (20% activity) was added per pot every two days. This minimum dosage in the experiment demonstrated preventative results. This work was repeated using pots in the greenhouse with algae already growing. The addition of 100 mg/pot twice per week controlled algae, demonstrating therapeutic action as well. In these experiments, 20 mg 0 2 was added each treatment to a soil volume of about 600 cc. Thus, since soil has a bulk density of about 1.25 g/cc, each 0 2 dosage was approximately 26 ppm.
  • beneficial bacteria such as Bacillus thurinqiensis or Bacillus popilliae are added to the soil.
  • Entomophthora spp. Beauveria bassiana, Metarhizium anisopliae and Hirsutella thompsonii.
  • the natural fungi associated with plant roots will benefit from the oxygen, trace metals, macro nutrients and other beneficial additives supplied by the ORC formulations of the present invention in aqueous carrier assisted to the soil area by the surfactant.
  • These organisms include, but are not limited to, members of the species Pisolithus. Boletus, Cenococum and Thelephora.
  • a wide variety of different formulations of fertilizers may be made utilizing the principles of this invention.
  • the nominal percentages of the various macronutrients, micronutrients, other beneficial additives and surfactant could be varied to provide fertilizers having formulations tailored to the specific plants and environments in which they are used.
  • the ingredients of these formulations and typical weight ranges are as follows: Ingredient Weight Percent magnesium peroxide 5-60 potassium dihydrogen phosphate 0-40 dipotassium hydrogen phosphate 0-40 diammonium phosphate 0-45 potassium nitrate 0-40 ammonium nitrate 0-50 urea 0-60 trace metals 0.0-5.0 surfactants 0.0-0.2
  • the preferred fertilizers of this invention have the following compositions: Fertilizer I: from 10 to 25 weight percent magnesium peroxide, from 10 to 25 weight percent potassium dihydrogen phosphate, from 15 to 25 weight percent dipotassium hydrogen phosphate, from 40 to 60 weight percent urea, from 0 to 2.0 weight percent trace metals, and from 0 to 0.2 weight percent surfactant.
  • Fertilizer II from 10 to 25 weight percent magnesium peroxide, from 30 to 50 weight percent diammonium phosphate, from 15 to 30 weight percent potassium nitrate, from 15 to 25 weight percent urea, from 0 to 2.0 weight percent trace metals, and from 0 to 0.2 weight percent surfactant.
  • Fertilizer III from 10 to 25 weight percent magnesium peroxide, from 30 to 45 weight percent diammonium phosphate, from 5 to 30 weight percent potassium nitrate, from 15 to 50 weight percent ammonium nitrate, from 0 to 2.0 weight percent trace metals, and from 0 to 0.2 weight percent surfactant.
  • Typical formulations are as follows: Formulation A
  • the above Formulation A is based upon employing chemical quality ingredients and the nominal percentages may vary slightly as a consequence.
  • the magnesium peroxide could be as low as 5 percent in the above formulation and still provide adequate oxygen release. In fertilizers, where a very high oxygen release is required, such as severely flooded soils, the above formulation may contain as much as 50 percent magnesium peroxide.
  • the above Formulation A gives an N-P-K value of 21.74-15.30-15.01, with the P expressed as P 2 0 5 and K expressed as K 2 0.
  • the potassium dihydrogen phosphate appears to be slightly preferred when it is desired that the product release oxygen over a one to two week period. Thus, it may be desirable to employ only this phosphate and not a mixture of the potassium dihydrogen phosphate and the dipotassium hydrogen phosphate. Either or both of these phosphates are added during the preparation of the magnesium peroxide.
  • the following Formulation B illustrates such a product.
  • Formulation B has a N-P-K value of 23.98:17.04:16.27.
  • Formulation C has a N-P-K value of 23.98:17.04:16.27.
  • Formulation C provides magnesium peroxide at an active oxygen concentration of 15 percent, and has about 30 mg of atomic oxygen per gram of fertilizer. 19.96% magnesium peroxide 38.26% diammonium phosphate 21.62% potassium nitrate 19.96% urea
  • Formulation C is a less expensive fertilizer. Again the diammonium phosphate is added to the magnesium peroxide prior to drying. Diammonium phosphate is slightly hygroscopic and needs to be protected from pickup of moisture. Mixing the magnesium peroxide and the diammonium phosphate before drying is effective in preventing hygroscopic behavior. Formulation C nominally has an N-P-K value of 20.43:20.56:20.15. Formulation D
  • Formulation D is based upon the magnesium oxide being present at least 25 percent active oxygen purity. The amount of peroxide may be reduced to provide 29 mg of oxygen per gram of fertilizer. Formulation D is: 11.74% magnesium peroxide
  • the active oxygen is as low as 15%, and the oxygen release is about 30 mg oxygen per gram of fertilizer:
  • the active oxygen is greater than 25%, and the oxygen release is 29 mg/g of fertilizer: 11.74% magnesium peroxide 42.19% diammonium phosphate
  • the active oxygen is at least 15%, and the oxygen release is about 27 mg/g of fertilizer: 17.96% magnesium peroxide 33.27% potassium dihydrogen phosphate
  • the active oxygen is at least 25%, and the oxygen release is about 29 mg/g of fertilizer: 11.49% magnesium peroxide 35.89% potassium dihydrogen phosphate
  • the metal peroxide is first prepared in an aqueous solution.
  • the metal oxide, metal hydroxide or metal carbonate, or combination thereof is reacted with hydrogen peroxide to produce the metal peroxide.
  • the reactions are generally non- stoichiometric.
  • magnesium peroxide could be prepared by one of the following three reactions:
  • Mg0 2 magnesium peroxide
  • H 2 0 2 is hydrogen peroxide
  • MgO magnesium oxide, also called magnesia H 2 0 is water
  • Mg (OH) 2 is magnesium hydroxide
  • MgC0 3 magnesium carbonate
  • C0 2 is carbon dioxide gas
  • the magnesium oxide and hydrogen peroxide reaction is the preferred way to produce the magnesium peroxide utilized in this invention, from the viewpoint of providing highest oxygen activity.
  • the magnesium carbonate could be used as the starting material and it does not require cooling, but it is more costly.
  • Any suitable source of magnesium oxide, commercial grade, is acceptable, preferably 100 to 400 mesh particles are used if the magnesium peroxide is to be dispersed in water. Particle size is not as important if the magnesium peroxide is to be applied in a dry form. Due to surface area reactivity characteristics, finer particle sizes result in higher activity in the final product.
  • the hydrogen peroxide is sold as a water solution containing from about 3 to 70 percent by weight of hydrogen peroxide.
  • the commercial grade solution of hydrogen peroxide contains 30 to 35 percent of the hydrogen peroxide and this is the material typically utilized in the method of this invention.
  • the reaction of magnesium oxide and hydrogen peroxide is exothermic, and the temperature must be controlled so that excess heating does not occur. Moreover, water is removed after the reaction is completed to produce a dry product. The drying must be done in a manner which does not destroy the metal peroxide which, for example in the case of magnesium peroxide, decomposes at 160°C or 320°F. In general, the heating process is preferably controlled so that the temperature does not exceed about 110°C. Temperature as low as 40°C with vacuum may also be used. The magnesium peroxide does not decompose in any significant quantities under such temperature conditions. It is important that the magnesium peroxide formed be maintained as a peroxide, so that the desired oxygen release characteristic is attained when applied to soil. The best way to make magnesium peroxide with the highest oxygen activity, presently known to the inventors, is to vacuum dry at the lowest possible temperature.
  • metal peroxide It is desirable during the production of the metal peroxide that the maximum amount of metal peroxide be produced.
  • magnesium peroxide if perfectly pure, would contain 28.4 percent by weight oxygen for release.
  • percent by weight oxygen is 22.2 percent.
  • potassium peroxide the percent by weight oxygen is 14.5 percent. Consequently, on a weight-for-weight basis, none of the other metal peroxides match magnesium peroxide. Moreover, at equal levels of active oxygen, the magnesium peroxide will always have the lowest weight in the formulation.
  • the magnesium oxide is mixed with an aqueous solution of hydrogen peroxide to produce a metal peroxide having an acceptable purity so that it contains at least about 5% and preferably at least about 15% by weight oxygen to be released to the soil.
  • the temperature of the reaction must be controlled. This may be accomplished by blending the hydrogen peroxide with the magnesium oxide in two steps.
  • the aqueous hydrogen peroxide solution for a given batch is divided approximately into equal portions.
  • the magnesium oxide is slowly added to one of these portions, allowing the heat to dissipate slowly to avoid explosive or extremely ebullient reaction conditions occurring in the reaction vessel, which is preferably a water-cooled, jacketed container.
  • Magnesium oxide powder is added to the first portion, preferably in portions or metered at a rate to maintain the temperature of the reacting mixture at about 40°C, with vacuum. After all the magnesium oxide is added, the temperature of the reaction mixture is lowered to about 35 ⁇ C and then the balance of the aqueous hydrogen peroxide solution is slowly added with stirring and cooling to avoid an excessively high reaction temperature. This aqueous slurry of magnesium peroxide, which consists of fine particles dispersed throughout the water, is then dried to produce a granular material. This can be accomplished by heating under vacuum, oven drying or spray drying.
  • a phosphate-intercalated material such as has been previously described is added to the aqueous medium before completion of drying.
  • the phosphate- containing material in addition to regulating the rate at which oxygen is released, also provides the macronutrient phosphorous.
  • the dried product containing the magnesium peroxide is then dry-blended with any other desired ingredients, for example urea, which provides the nitrogen and ingredients containing potassium and other supplements such as trace minerals.
  • the surfactant is added to the aqueous medium prior to drying, if the surfactant is stable in water. If the surfactant is unstable in water, such as the istheionates, it may be dry blended after drying.
  • EXAMPLE 1 PREPARATION OF MAGNESIUM PEROXIDE To produce 56.3 grams of magnesium peroxide, 40.3 grams of magnesium oxide and 94 cubic centimeters of a 34 weight percent aqueous hydrogen peroxide solution are used. To ensure completeness of the reaction between the magnesium oxide and hydrogen peroxide, excess hydrogen peroxide, for example, approximately 150 cubic centimeters of the aqueous hydrogen peroxide is acceptable. This is divided into approximately two equal portions. The first portion, or 75 cubic centimeters, is placed in a water-jacketed reaction vessel and the powdered magnesium oxide is added slowly, keeping the temperature of the reaction ingredients at approximately 40°C.
  • the temperature is lowered to 35°C and the second half of the hydrogen peroxide solution is added to the reaction vessel, with stirring and cooling to prevent the liquid reaction slurry from bubbling out of the reaction vessel.
  • the liquid slurry produced is then dried by heating at. a temperature of 90-110°C in an oven provided with vacuum to produce a fine granular powdery magnesium .peroxide having a mesh size of approximately 325. It is preferable that the magnesium peroxide be in a highly powdered form so that if it is subsequently mixed with water, it can be easily dispersed in the water, since neither magnesium peroxide nor the resulting magnesium oxide produced after release of oxygen is soluble in water.
  • Example 2 This example is similar to Example l in that essentially the same amounts of reagents are used.
  • 43.2 grams of potassium dihydrogen phosphate is dry blended with the magnesium oxide prior to mixing with the hydrogen peroxide solution. The drying is conducted at 40°C under vacuum. A product with a higher oxygen activity is produced using the procedure of this example than produced in Example 1.
  • EXAMPLE 3 TIME RELEASE ORC This example is essentially the same as Example 1, except the potassium dihydrogen phosphate is added to the liquid slurry prior to drying.
  • Example 2 This example is essentially the same as Example 2, except 0.3 gram of the surfactant monolaurate sorbitol ester is added to the aqueous slurry of the magnesium peroxide and the potassium dihydrogen phosphate before drying, or following drying in accordance with milling techniques, known in the art.
  • EXAMPLE 6 PEROXIDE/SURFACTANT This example is essentially the same as Example 1, except 0.3 gram of the surfactant is added to the aqueous slurry of magnesium peroxide. Upon drying, a powder is provided having a mesh size of 325. This powder may be dispersed readily in water and applied either directly to the soil or used as a seed treatment prior to planting.
  • the dried material containing the phosphate stabilized calcium peroxide is optimally then dried blended with 116.6 grams of urea, 45 grams of dipotassium hydrogen phosphate to provide a fertilizer with an N-P-K of 20:15:15.
  • EXAMPLE 8 PREPARATION OF POTASSIUM PEROXIDE ORC To prepare 50 grams of potassium peroxide, 62.7 grams of potassium carbonate mixed with 38.3 grams of potassium dihydrogen phosphate and 0.3 gram of surfactant is added slowly to 70 milliliters of 34% hydrogen peroxide solution. The reaction is carried out inside a vacuum oven so that immediately after the reaction is completed the mixture is dried at 40°C or less under high vacuum.
  • the dry reaction product may thereafter be dry blended with 116.6 grams of urea and 45 grams of dipotassium hydrogen phosphate to provide a fertilizer of N-P-K of 20:15:32.
  • ORC is defined as 0-1 or 3-1. This defines the percentages of phosphate (as, but not restricted to, KH 2 P0 4 and surfactant (as, but not restricted to, Na istheionate) , respectively. Therefore, 0-1 is pure Mg0 2 of a * given activity with 0% phosphate and 1% surfactant, while 3-1 is pure Mg0 2 of a given activity with 3% phosphate and 1% surfactant.
  • a 0-0 formulation would be essentially pure metal peroxide, such as the unamended product of Example 1.
  • 10 lbs. of 0-1 or 3-1 ORC is mixed in 50 gal. of water for a concentration of .2 lbs./gal.
  • the amount of water being applied is somewhat negligible relative to the area to which it is applied and the slurry dries quickly to a powder. Every time the area is watered, the ORC can release oxygen until it is spent. A full irrigation followed each application, to activate the product in a timely fashion, which constitutes a product use recommendation. This is of particular importance if the product is used in conjunction with core aeration techniques. It has been determined that the efficacy of the ORC is maximized if applied following a core aeration treatment, or presumably also following any other method that allows greater physical penetration of the ORC.
  • EXAMPLE 10 THERAPEUTIC EFFECT ON BLACK LAYER A series of greens having Bentgrass overseeded with Bermuda grass variety turf at a golf course in Florida, were diagnosed as affected by black layer. Diagnosis was accomplished by visual observation from above the ground, which revealed signs of anaerobic stress. Upon core sampling of the visibly affected area, a characteristic black layer ⁇ ymptomology was observed, including a marked, single or multiple color zonation and odor.
  • a series of sections of the affected turf were utilized, to demonstrate the efficacy and dose dependency relationship, in practicing the method in accordance with the present invention.
  • a therapeutic ORC formulation made in accordance with Example 6 modified to produce an ORC having approximately 99% Mg0 2 and 1% surfactant, identified below as 0-1.”
  • a second ORC formulation was prepared in accordance with Example 5, modified by the use of Na istheionate as the surfactant, to produce an ORC having approximately 96% Mg0 2 , 3% phosphate and 1% surfactant, identified below as "3-1.”
  • the formulations were applied to each of the test zones for a total test period of 12 weeks as follows:
  • a series of greens having Bermuda grass turf at a golf course in Florida was diagnosed as affected by black layer. Diagnosis was accomplished as described in Example 10.
  • a series of sections of the affected turf were utilized to demonstrate the dose dependency in practicing the method in accordance with the present invention.
  • a therapeutic formulation made as described in Example 10 was applied to each of the test zones over a total test period of 12 weeks as follows:
  • EXAMPLE 13 - BLACK LAYER PREVENTATIVE EFFECT A series of greens with Bentgrass overseeded with Bermuda grass located at a golf course in Virginia which had demonstrated a propensity of black layer in summer months, was selected to demonstrate the preventative effect of methods in accordance with the present invention. Two pounds, 4 pounds and 8 pounds per 1000 square feet were added, respectively, to each of nine separate greens as follows:
  • Root growth was reduced in control areas, but vigorous and healthy in test plots. Root growth was approximately 2-1/2 inches greater in depth in the 8 pound per 1000 square foot test plot as compared to the control area.
  • ORCs can be critical in the maintenance of key biochemical mechanisms in the past, implicated in the maintenance of disease resistance.
  • facultative anaerobes which can tolerate or stay virulent at relatively low levels of oxygen, control would be achieved with higher dosages, as will be apparent to one of skill in the art based upon the disclosure herein.
  • Post harvest physiology is a branch of agricultural science that concerns itself with preservation of the harvest.
  • Certain major commodities such as potatoes are susceptible to soft rot during storage.
  • the causal organism is Erwinia carotovora discussed previously. When a potato becomes wet, the layer of water, in particular the water that can infiltrate a wound, can become anaerobic. In this instance, E. carotovora can become "armed and dangerous,” genetically speaking. This scenario also applies to any other anaerobic organisms and their potential impact on other susceptible crops.
  • ORC utilized in the following Experiment, is unstable above about 160°C and releases oxygen when wet. 1 gram of material holds .14 grams of oxygen (14% available oxygen). This material is prepared by reacting lOOg MgO with sufficient H 2 0 2 to produce 48.95g Mg0 2 and 51.05g of MgO.
  • E. Carotovora (Ecc) grows in the presence of ORC, the compound was added to cooled, molten agar (55°C; 1.5% Difco bacteriological agar in water) in the bottom of 90 cm petri dishes.
  • the specific ORC utilized herein is 14% available oxygen Mg0 2 .
  • PEM (0.1% polygalacturonic acid, 0.5% tryptone, and 0.5% yeast extract; pH 7.0) was inoculated with an overnight static culture of Ecc in LB (Miller, 1972) to a turbidity of ⁇ 0.00 at 600 nm ( ⁇ 10 6 cfu/ml) and dispensed in 10 ml portions into the petri dishes on top of the hardened agar containing ORC.
  • ORC Oxygen-Releasing Compound
  • ORC affects the growth of Ecc in a positive manner at low concentration (0.01%) in anaerobic conditions
  • Example I above. The results were dramatic. After one week an average of 14.93 grams of tissue had rotted in the control as compared to .83 grams among the treated pieces.
  • ORC Enhanced sprouting.
  • Table 1 the evidence shows that ORC suppresses growth of Ecc, see Table 1, and releases 0 2 in cultures.
  • ORC demonstrated both the ability to substantially prevent post harvest soft rot in potatoes, via the controls of Ecc and support of host defense mechanisms, and the ability to enhance sprouting when utilized as a pre-planting treatment of potato sections.
  • EXAMPLE 16 POST HARVEST STORAGE OF CALLA LILY RHIZOMES Calla lilies are produced from rhizomes (fleshy storage roots) . When these rhizomes are planted, they sprout and produce the saleable crop.
  • a mature plant can be dug up to collect rhizomes which are often stored for future planting. Erwinia carotovora can devastate the stored rhizomes as well as planted rhizomes or whole plants.
  • Petri dishes were inoculated with plugs of the phythium fungi. The experiments began with a 5 mm diameter plug. Effects on growth are then a function of the increase in diameter of this plug (colony size in mm) .
  • the control was 0.0 mg ORC and tests were conducted at
  • Plant organs for consumption which may or may not be capable of utility in propagation, preferentially asexual propagation, or for direct consumption or reuse, such as tubers, rhizomes, bulbs and corm are all potentially beneficially treated.

Abstract

L'invention concerne l'utilisation de véhicules d'apport d'oxygène comprenant des peroxydes de calcium, de potassium et de magnésium, afin de traiter des milieux de plantes présentant un potentiel d'oxydo-réduction négatif. Les peroxydes sont de préférence intercalés avec un ion phosphate prolongeant la durée pendant laquelle l'oxygène est libéré. On peut mélanger les peroxydes à des macro-substances nutritives, des micro-substances nutritives ou d'autres additifs ou amendements avantageux, afin de produire des engrais, ou on peut les appliquer directement aux milieux. On utilise des quantités efficaces de métaux comme agents bioacitfs pour supprimer ou améliorer l'activité de micro-organismes se trouvant dans le sol, selon que lesdits micro-organismes sont soit nuisibles soit avantageux pour les plantes. Les formulations sont utiles dans le traitement d'états pathologiques anaérobies associés tels que l'apparition d'une couche noire dans le gazon. Les formulations sont aussi utiles pour combattre la pourriture molle de la pommede terre après récolte ainsi que d'autres infections et maladies d'origine microbienne chez les plantes.
PCT/US1992/005058 1991-06-21 1992-06-17 Traitement therapeutique et preventif de l'etat anaerobie de plantes et du sol WO1993000311A2 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016112425A1 (fr) 2015-01-14 2016-07-21 Calix Ltd Inhibiteur d'agents pathogènes améliorée
WO2022234582A1 (fr) 2021-05-06 2022-11-10 Dead Sea Bromine Company Ltd. Dispersions aqueuses de composés de magnésium destinées à être utilisées dans la conservation de produits récoltés

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS49117244A (fr) * 1973-03-23 1974-11-08
EP0063844A1 (fr) * 1981-04-27 1982-11-03 INTEROX Société Anonyme Utilisation pour l'amendement des sols de particules solides contenant un peroxyde métallique
WO1991009821A1 (fr) * 1989-12-22 1991-07-11 Plant Research Laboratories Peroxydes metalliques comprenant des metaux a enzymes actives comme complements pour les plantes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49117244A (fr) * 1973-03-23 1974-11-08
EP0063844A1 (fr) * 1981-04-27 1982-11-03 INTEROX Société Anonyme Utilisation pour l'amendement des sols de particules solides contenant un peroxyde métallique
WO1991009821A1 (fr) * 1989-12-22 1991-07-11 Plant Research Laboratories Peroxydes metalliques comprenant des metaux a enzymes actives comme complements pour les plantes

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Title
Database WPI, no. 75-41683w; Derwent Publications Ltd., (London, GB) & JP, A, 49117244 (HIRYO K.K.) 8 November 1974, see the abstract *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016112425A1 (fr) 2015-01-14 2016-07-21 Calix Ltd Inhibiteur d'agents pathogènes améliorée
CN107105671A (zh) * 2015-01-14 2017-08-29 卡利有限公司 改进的病原体抑制剂
EP3244735A4 (fr) * 2015-01-14 2018-07-04 Calix Ltd Inhibiteur d'agents pathogènes améliorée
AU2015376853B2 (en) * 2015-01-14 2019-09-12 Calix Ltd Improved pathogen inhibitor
EP3735828A1 (fr) * 2015-01-14 2020-11-11 Calix Limited Inhibiteur pathogène amélioré
WO2022234582A1 (fr) 2021-05-06 2022-11-10 Dead Sea Bromine Company Ltd. Dispersions aqueuses de composés de magnésium destinées à être utilisées dans la conservation de produits récoltés

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