WO2016018155A1 - Calcium carbonate beads as carrier for plant protection agents and/or nutrition products - Google Patents

Calcium carbonate beads as carrier for plant protection agents and/or nutrition products Download PDF

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Publication number
WO2016018155A1
WO2016018155A1 PCT/NL2015/050561 NL2015050561W WO2016018155A1 WO 2016018155 A1 WO2016018155 A1 WO 2016018155A1 NL 2015050561 W NL2015050561 W NL 2015050561W WO 2016018155 A1 WO2016018155 A1 WO 2016018155A1
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Prior art keywords
plant
beads
composition
calcium carbonate
substrate
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PCT/NL2015/050561
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French (fr)
Inventor
Wilhelmus Maria Van Der Krieken
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Vadaflor B.V.
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Publication of WO2016018155A1 publication Critical patent/WO2016018155A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12Powders or granules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents

Definitions

  • the invention relates to compositions for use mainly in agriculture, but also in all activities related to plants such as gardening, amenities, nurseries, and pot plants. More specifically, the invention relates to compositions comprising calcium carbonate beads and one or more active ingredients selected from the groups consisting of plant protection agents, and/or plant nutrition products such as biostimulants.
  • Acid soil reduces plant growth by inhibiting the intake of major plant nutrient such as nitrogen, phosphorus and potassium.
  • major plant nutrient such as nitrogen, phosphorus and potassium.
  • neutralizers such as lime is vital for them to maximize crop yield.
  • a further contributor to the acidification of soil acid is the application of modern chemical fertilizers which include nitrogen compounds, as these nitrogen compounds produce nitrous and nitric acid when oxidized in the process of nitrification.
  • Yet a further contributor is plant material that is incorporated into the soil, which results in the production of acids such as acetic acid, humic acid, oxalic acid, and tannic acid.
  • Spraying requires significant investments and is very energy consuming.
  • granules for example based on different types of clay, are used for the application of plant protection agents when the pathogens are mainly present in the soil.
  • the amounts that are required per hectare is important to obtain a sufficient repartition in the soil. This amount ranges from about 12 kg/ha located close to the future roots system when the crop is drilled or planted in a row, such as sugar beet, potato, corn, etc., to about 300 kg/ha when all the surface is covered by the seedlings like for some vegetables.
  • the present inventors surprisingly found that a specific form of calcium carbonate can be combined with a plant protection agent or a plant nutrition product and can easily be applied into the soil, on the soil and/or on a plant or plant part.
  • the invention provides a composition comprising calcium carbonate beads and one or more active ingredients selected from the group consisting of a plant protection agent or/and a plant nutrition product.
  • the specific calcium carbonate beads are produced from a pellet reactor process directed to softening of water, especially drinking water.
  • the beads are produced in a reactor in which a bed of fine sand is maintained in fluidization.
  • the sand is used as a crystallization seed for calcium carbonate that is present in the water.
  • the calcium carbonate precipitates on the surface of the sand particles under basic pH conditions. Following drainage, the water content of the calcium carbonate beads is lower than 5%.
  • These beads are presently used as road embankment material, pipeline trench sublayers and cement raw material (ACTINATM, "Reducing water hardness with pellet softening”. Veolia Water Solutions & Technologies, Saint- Maurice Cedex, France).
  • Calcium carbonate beads are spherical, in fact almost perfectly round, and composed of about 98 % of calcium carbonate (see Figure 1).
  • the diameter of the beads is between 0.1 and 5 mm, normally between 0.8 and 2.4 mm, or between 0.1 and 2 mm.
  • the beads are often present in two different sizes: between 0.1 and 1.2 mm having an average diameter of 0.4- 0.8 mm) and between 1.6 and 2.4 mm, as determined by passing through a mesh with appropriate mesh size.
  • a preferred diameter of the beads is below 1 mm. Most preferably, the calcium carbonate beads have an average diameter of about 0.4 mm. A preferred method for determining the average particle size of the beads is sieve analysis or gradation test, which is commonly used to assess the particle size distribution of a granular material. A sieve is also preferably used to select calcium carbonate beads have a diameter of less than 1 mm, and/or beads that have an average diameter of about 0.4 mm.
  • the hardness of calcium carbonate beads is between 10-100, as determined with a sclerometer, for example a Turner-sclerometer.
  • the hardness of calcium carbonate beads is higher than of calcite, which is about 9.
  • the density of calcium carbonate beads is about 2800 kg/m 3 , which is much higher than the density of, for example, crushed calcium carbonate stone or marble which both are about 1500 kg/m 3 (see
  • Calcium carbonate beads as herein described, are produced during the water softening process.
  • the beads consist of solid CaC03 that is layered around a very small sand nucleus with high density of at least 2,8 (Mohs hardness) and having channels that are directed from the center to the surface).
  • the clay granules that are used today for soil application with impregnated pesticides are based on sepiolite or attapulgite. These are fibrous and open clay minerals (hydrous aluminium silicates).
  • the hardness on Mohs scale of the present CaC03 beads is at least 2.5 (between 2.5 and 3.5), while the hardness of the currently used sepiolite and attapulgite clays is lower than 2 on the Mohs scale.
  • the hardness of composite CaC03 granules (granules made out of compressed CaC03 dust) is between 1 and 2 on Mohs scale.
  • the features of the present calcium carbonate beads including round shape, high density and hardness, differentiates these calcium carbonate beads from any of the existing clay and/or calcium carbonate-containing particles.
  • Calcium carbonate beads as described herein may be applied to the soil in order to neutralize, or to reduce the acidity of, acidic soil. It may be used instead of lime, or in addition to lime. The slow dissolution of the beads provides an effective means to control the pH of a soil over time.
  • small beads between 0.1 and 1.2 mm, preferably beads having an average diameter of about 0.4 mm.
  • beads having an average diameter of 0.4 mm have a volume of about 0.03 mm 3 , with a density of 2.8 mg/mm 3 . This means that 1 bead weighs, on average, about 8.04058 E -5 gram. 8 kg of calcium carbonate equals about 100 E 6 beads, When applying 8 kg/ha of land, on average 1 bead per cm 2 is obtained.
  • dehydrated calcium carbonate beads having a water content of less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%, preferably less than 1%, absorb liquids onto or in the beads, including one or more active ingredients selected from the group consisting of a plant protection agent and/or a plant nutrition product.
  • large beads between 1.6 and 2.4 mm
  • small beads between 0.1 and 1.2 mm
  • the calcium carbonate beads slowly dissolve over time, thereby providing immediate but also slow release of the plant protection agent and/or the plant nutrition product.
  • Said slow release is, amongst other factors, dependent on the pH of the soil, plant or plant part, and the temperature, as is known to a person skilled in the art.
  • said release preferably is over a period of at least two weeks, preferably over a period of at least one month, preferably over a period of at least two months.
  • an immediate release of a part of the product is preferred, which is followed by slow release on a period of about two months.
  • the plant protection agent and/or the plant nutrition product is adsorbed onto the calcium carbonate beads in a composition according to the invention.
  • a binder such as, for example, a polyacrylic acid ester binder, for example RHOPLEX HA-8 manufactured by Rohm and Haas Company; or a polyvinyl acetate binder, for example DUR-O-SET SBX manufactured by Chas. S. Tanner Company.
  • the presence of a binder helps to prevent release of the plant protection agent and/or the plant nutrition product prior to dissolution of the calcium carbonate beads, thereby also providing a slow release formulation
  • absorbed refers to the intake of a liquid, preferably an aqueous liquid, including a plant protection agent and/or a plant nutrition product including a biostimulant, onto or in the calcium carbonate beads through the many small pores or channels.
  • adsorbed refers to the adhesion of a plant protection agent and/or a plant nutrition product to a surface of the calcium carbonate beads.
  • dissolution of the calcium carbonate beads depends inter alia on the pH of the soil, plant or plant part.
  • Calcium carbonate that is released from the calcium carbonate beads will act as a buffer essentially resulting in basic conditions with a pH above 8.
  • the dissolution of calcium carbonate beads in basic conditions is slow, thereby effectively retarding the dissolution of the calcium carbonate beads under basic condition.
  • the slow release of a plant protection agent and/or a plant nutrition product may result in less leaching in the soil, which is better for environment, for example in areas where ground water is collected.
  • a more stable, basic environment may increase the time period that live microorganisms are present in or on the soil, plant or plant part.
  • Calcium carbonate beads through their slow release of calcium carbonate, may also result in an increased pH around the roots of plants, thereby resulting in better absorption of a plant nutrition product by the plants.
  • shelf life of a plant protection agent and/or plant nutrition product that is based on the presence of beneficial microorganisms, when present in a composition comprising calcium carbonate beads according to the invention, is better when compared to the same microorganisms in another formulation such as a wettable powder, a soluble concentrate and/or organic based granules.
  • a further advantage of a composition according to the invention is that the calcium carbonate beads will dissolve completely over time, preferably within a year, more preferably within a period of 3-6 months, leaving no remnants behind, except for calcium, such as in the case of clay particles or other granules.
  • Said plant nutrition product preferably is a biostimulant.
  • biostimulant refers to a substance and/or material that, when applied to a plant, seed or growth substrate, has the capacity to modify physiological processes in said plant which provide benefit to growth, development and/or stress response of said plant.
  • Biostimulants include humic substances, organic materials such as brassinosteroids, chemical elements, inorganic salts such as phosphite, seaweed extract, and chitin, chitan and derivatives thereof.
  • brassinosteroids refers to a class of poly hydroxy steroids that have been recognized as plant hormones.
  • a preferred brassinosteroid is 24-epibrassinolide ((22R,23R,24R)-2a,3a,22,23- tetrahydroxy-24-methyl-6-homo-7-oxa-5-cholestan-6-one) or 28- homobrassinolide (22R,23R,24R-2a,3a,22,23-tetrahydroxy-B-homo-7-oxa-5a- ergostan-6-one).
  • Said plant nutrition product preferably is a chemical element and/or compound that is necessary for plant growth.
  • Primary macronutrient or growth stimulants for plants comprise nitrogen (N), phosphorus (P), potassium (K), the three secondary macronutrient calcium (Ca), sulphur (S), magnesium (Mg).
  • Trace minerals include boron (B), chlorine (CI),
  • Nutrient or growth stimulant uptake from the soil is achieved by cation exchange, where root hairs pump hydrogen ions (H+) into the soil through proton pumps. These hydrogen ions displace cations attached to negatively charged soil particles so that the cations are available for uptake by the root.
  • H+ hydrogen ions
  • the increased pH and buffering capacity of a composition according to the invention will prevent acidification of the soil, thereby increasing the intake of major plant nutrient or growth stimulants such as nitrogen, phosphorus and potassium.
  • the buffering capacity at a slightly basic pH will prevent leaching of especially cationic nutrient or growth stimulants through the soil.
  • a composition of the invention therefore, results in improved and prolonged availability of nutrient or growth stimulants to a plant.
  • a preferred composition comprising a plant nutrition product according to the invention comprises 10-300 g/kg phosphor (P), 5-250 g/kg magnesium (Mg), 0.5-25 g/kg of iron (Fe), 2-100 g/kg manganese (Mn), 5-250 mg/kg boron (B), 0.1-5 mg/kg molybdenum (Mo), and 0.05-2.5 mg/kg zinc (Zn), based on dry weights.
  • Said plant nutrition product including a nutrient and/or or growth stimulant, preferably is absorbed/adsorbed on or into the calcium carbonate beads.
  • said plant nutrition product is added to the water before or during the production of the calcium carbonate beads.
  • a plant protection agent is preferably selected from microorganism, a plant extract or a natural or synthesized compound. These plant
  • protection agents may have insecticide, fungicide, nematicide, miticide, bactericide, molluscicide and/or herbicide activity, as is known to a skilled person.
  • natural or synthesized compound refers to compounds that occur in nature, or that are biologically synthesized, for example with the use of a microorganism, or chemically synthesized, for example through one or more reaction steps.
  • Said microorganism preferably is already known or registered for its biocontrol activity.
  • Said microorganism preferably comprises at least one fungus and/or bacterium, or spores thereof.
  • Preferred fungi include Streptomyces species, Paecilomyces species, Talaromyces species,
  • Trichoderma species Beauveria species, Ampelomyces species,
  • Preferred bacterial species include lactic acid bacteria such as Lactococcus lactis, Lactococcus lactis subsp. lactis, Pediococcus acidilactici, P. pentosaceus, P. damnosus,
  • Lactobacillus plantarum Lactobacillus reuteri, Lactobacillus sake
  • propionic acid bacteria such as Propionibacterium jensenii and Propionibacterium freudenreichii subsp. shermanii
  • Bacillus species such as Bacillus
  • biocontrol agents examples are provided in a world wide web-based report, entitled “Alternatives to Copper for Disease Control in the Australian Organic Industry; A report for the Rural Industries Research and Development Corporation", by Van Zwieten, Stovold, and Van Zwieten (authors). The report is available at
  • biocontrol agents have been applied in the past, including Agrobacterium radiobacter, for control of Crown gal, Ampelomyces quisqualis, for control of powdery mildew, Arthrobotrys dactyloides, for control of root knot and nematodes, Ascocoryne sarcoides, for control of various decay organisms, Bacillus licheniformis for control of anthracnose and stem end rot, Bacillus subtilis for control of green and blue moulds and stem canker, Chaetomium globosum for control of black spot, Cladosporium oxysporum for control of petal blight, Cladosporium
  • cladosporioides for control oiBotrytis cinerea, Coniothyrium minitans for control of Sclerotinia sclerotiorum, Dactylella leptospora for control of nematodes, hypovirulent strains of Cryphonectria for control of
  • Cryphonectria a hrp mutant of Erwinia amylovora for control of Erwinia amylovora, hypovirulent strains oiFusarium oxysporum for control of Fusarium oxysporum, Gliocladium virens for control of Sclerotium rolfsii, Gliocladium roseum for control of Botrytis cinerea, Hansfordia pulvinata for control oiFulvia fulva, Laetisaria arvalis for control of aerial blight and root rot, Myrothecium verrucaria for control of Sclerotium rolfsii,
  • Nematophthora species for control of nematodes Penicillium oxalicum for control of fusarium wilt and verticillium wilt, Phlebiopsis gigantean for control of root and butt rot, Phialophora radicicola for control of Ophiobolus patch disease, Pseudomonas aeruginosa and Pseudomonas fluorescens for control of Pythium, Pythium oligandrum for control of Pythium ultimum, Scytalidium uredinicola for control of Endocronartium harknessii,
  • Botrytis cinerea Sclerotinia sclerotiorum and Cladosporium fulvum
  • Trichoderma harzianum for control of Fusarium udum
  • Trichoderma harzianum for control of Sclerotium rolfsii and Fusarium oxysporum
  • Trichoderma koningii for control of Phytophthora parasitica
  • Trichoderma viride for control of Rhizoctonia solani
  • Trichoderma viride for control of Botrytis cinerea
  • Trichothecium roseum for control of Sclerotinia
  • sclerotiorum Tuberculina maxima for control of Cronartium quercuum
  • Verticillium biguttatum for control of Rhizoctonia solani
  • Verticillium chlamydosporium for control of nematodes
  • Verticillium lecanii for control of mites.
  • Further examples include Trichoderma virens, for control of soilborne Rhizoctonia, Fusarium and Pythium moulds, and Streptomyces griseoviridis for control of Pythium, Fusarium, Alternaria, Phomopsis, Rhizoctonia, Phytophthora and Botrytis.
  • One or more of these agents is prefereably included as biocontrol agent in a composition according to the invention.
  • a preferred microorganism is or comprises at least one Beauveria species, CoUetotrichum species, Trichoderma species, Ampelomyces species, Gliocladium species, Bacillus species and/or Pseudomonas species, and/or spores thereof.
  • Said microorganism is preferably present in a composition according to the invention in an amount of between 10 4 and 10 9 colony forming units (cfu), preferably between 10 6 and 10 9 cfu.
  • Said microorganism may benefit from the increase in pH that is provided by dissolution of the calcium carbonate as most microorganisms grow better under non-acidic conditions.
  • a further preferred plant protection agent in a composition according to the invention is a natural of chemically synthesized compound with fungicide, herbicide, insecticide, bactericide, molluscicide and/or nematocide activity.
  • a composition of the invention may also comprise two plant protection agents, such as two or more fungicides, two or more herbicides, two or more insecticides, two or more nematocides, or
  • At least one fungicide and at least one insecticide at least one fungicide and at least one herbicide, at least one fungicide and at least one nematocide, at least one herbicide and at least one nematocide, at least one herbicide and at least one insecticide, and/or at least one insecticide and at least one nematocide.
  • Some plant protection agents have a wide range of target organisms, as is known to the skilled person, and may therefore be included in more than one subgroup of plant protection agents.
  • a plant protection agent selected from natural or chemically synthesized compounds is preferably present in a concentration of between 0, 1 and 90 w/v%, more preferred between 1 and 70 w/v%, more preferred between 10 and 50 w/v%.
  • An insecticide is a compound used to control (including prevention, reduction or elimination) parasitic insects.
  • Said insecticide preferably is or comprises a neonicotinoid such as imidacloprid (commercial product:
  • a composition of the invention may comprise two or more insecticides.
  • a fungicide is a compound used to control (including prevention, reduction or elimination) parasitic fungi.
  • a preferred antifungal compound or fungicide is or comprises 2-phenylphenol; 8 -hydroxy quinoline sulphate; acibenzolar-5-methyl; actinovate; aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azoxystrobin; benalaxyl;
  • benodanil benomyl (methyl l-(butylcarbamoyl)benzimidazol-2- ylcarbamate); benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; blasticidin-S; boscalid; bupirimate;
  • buthiobate butylamine; calcium polysulphide; capsimycin; captafol; captan (N-(trichloromethylthio)cyclohex-4-ene-l,2-dicarboximide); carbendazim; carboxin; carpropamid; carvone; chinomethionat; chlobenthiazone;
  • chlorfenazole chloroneb; chlorothalonil; chlozolinate; cis-l-(4-chlorophenyl)- 2-(lH-l,2,4-triazol-l-yl)-cycloheptanol; clozylacon; a conazole fungicide such as, for example, (RS)-l-(6-allyloxy-2,4-dichlorophenethyl)imidazole (imazalil; Janssen Pharmaceutica NV, Belgium) and N-propyl-N-[2-(2,4,6- trichlorophenoxy)ethyl] imidazole- 1-carboxamide (prochloraz); cyazofamid; cyflufenamid; cymoxanil; cyprodinil; cyprofuram; Dagger G; debacarb;
  • a conazole fungicide such as, for example, (RS)-l-(6-ally
  • dichlofluanid dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine;
  • drazoxolon edifenphos; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenfuram; fenhexamid; fenitropan; fenoxanil;
  • fenpiclonil fenpropidin; fenpropimorph; ferbam; fluazinam (3-chloro-N-(3- chloro-5-trifluoromethyl-2-pyridyl)-a,a,a-trifluoro-2,6-dinitro-p-toluidin flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; flurprimidol; flusulfamide; flutolanil; folpet (N-
  • phosdiphen phosphite (a salt and/or ester of phosphonic acid (phosphorous acid, preferably ethyl-phosphite); phthalide; picobenzamid; picoxystrobin; piperalin; polyoxins; polyoxorim; procymidone; propamocarb; propanosine- sodium; propineb; proquinazid; pyraclostrobin; pyrazophos; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine, quinconazole; quinoxyfen; quintozene; silthiofam; sodium tetrathiocarbonate; spiroxamine; sulphur; tecloftalam; tecnazene; tetcyclacis; thiazole fungicide such as, for example, 2-(thiazol-4- yl)benzimidazole (thiabendazole; e.g.
  • Preferred fungicides include tebuconazole, mefenoxam,
  • propamocarb ethylphosphosphonate and/or hymexazol.
  • a nematocide is a compound used to control (including prevention, reduction or elimination) parasitic nematodes, including wireworms.
  • a preferred nematocide is or comprises aldicarb, imicyafos, oxamyl and/or fenamiphos.
  • a herbicide is a compound used to control (including prevention, reduction or elimination) unwanted plants.
  • a preferred herbicide is or comprises glyphosate, an acetamide such as diphenamid, naprop amide, naproanilide, acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, and flufenacetan, triallate (S -(2,3,3 -trichloro ally) - diisopropylthiocarbamate), an acetyl coenzyme A carboxylase inhibitor; an acetolactate synthase inhibitor such as sulfonylurea, imidazolinone, triazolopyrimidine, pyrimidinyl oxybenzoate, and sulfonylamino carbonyl triazolinone; enolpyruvylshikimate 3-phosphate synthase inhibitor such as glyphosate; a synthetic auxin such as 2,4-dichlorophenoxyacetic acid; a photosystem II inhibitor such
  • Said herbicide preferably is a residual herbicide, which remains active for at least four weeks after application.
  • residual herbicides include, but are not limited to, Anthem® (FMC Agricultural Solutions), which is a pre-mix of pyroxasulfone) and fluthiacet-methyl);
  • FirstRate® (3-chloro-2-[[(5-ethoxy-7-fluoro[l,2,4]triazolo[l,5-c]pyrimidin-2- yl)sulfonyl]amino]benzoic acid; Dow Agrosciences); Prefix® (a pre-mix of S- 2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(l-methoxypropan-2-yl)acetamide and the sodium salt of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-
  • a most preferred herbicide is Allie® SX (metsulfuron methyl (methyl 2-[[[[[(4-methoxy-6- methyl -l,3,5-triazin-2-yl)amino]carbonyl] amino] -sulfonyl]benzoate;
  • a composition of the invention preferably comprises a binder, a spreader and/or a surfactant, especially in the case when the plant protection agent and/or plant nutrition product, including a nutrient and/or growth stimulant, is adsorbed to a calcium carbonate bead.
  • a binder is preferably selected from artificial latex (commercial product: Prolong, Holland Fyto, Netherlands); ethylene vinyl acetate copolymer (commercial product: Atlox Semkote E-105, Uniqema, USA) and/or polyvinyl acetate.
  • a binder may further be selected from pinolene (commercial product: Nu-film 17, (Miller Chemical and Fertilizer
  • xanthan commercial product: Rhodopol, Rhodia, France
  • succinoglycan commercial product: Rheozan, Rhodia, France
  • polyvinylpyrolidone commercial product:
  • a spreader is preferably a nonionic surfactant such as
  • polyoxy ethylene sorbitan ester polyoxyethylene alkyl (or aryl) ether or polyoxy ethylene fatty acid ester, an anionic surfactant such as straight- chain alkylbenzene sulfonate, dialkylsulfosuccinate, lignin sulfonate or polynaphthyl sulfonate, or a high molecular compound such as polyacrylate.
  • anionic surfactant such as straight- chain alkylbenzene sulfonate, dialkylsulfosuccinate, lignin sulfonate or polynaphthyl sulfonate, or a high molecular compound such as polyacrylate.
  • a surfactant is preferably an anionic tenside such as sodium lauryl sulphate, polyethylene alkyl ether or polyoxyethylether, e.g Tween® 60, 61 or 65; organo silicone, sulfosuccinate, alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid propoxylate and the commercial product Zipper® (Moodify BV, The Netherlands).
  • anionic tenside such as sodium lauryl sulphate, polyethylene alkyl ether or polyoxyethylether, e.g Tween® 60, 61 or 65; organo silicone, sulfosuccinate, alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid propoxylate and the commercial product Zipper® (Moodify BV, The Netherlands).
  • a composition of the invention preferably comprises between 0.1 gram/liter and up to 100 gram/liter of a binder, a spreader and/or a surfactant, preferably between 1 and 10 gram/liter.
  • the calcium carbonate beads preferably have an average diameter of about 0.4 mm. Calcium carbonate beads having a diameter between 1.6 and 2.4 mm are particularly suitable as molluscicide. Said beads preferably are impregnated with
  • iron(iii)phosphate and/or ammonium sulfate are iron(iii)phosphate and/or ammonium sulfate.
  • the invention further provides a method of protecting an agricultural product or substrate, comprising a) providing the composition according to the invention, and b) contacting the agricultural product or substrate with the composition. Said method preferably protects a plant from a pathogenic microorganism.
  • the invention further provides a method of preventing, reducing and/or eliminating the presence of a pathogen on a substrate, on a plant or on one or more plant parts, comprising applying to said substrate, plant or plant part a composition comprising at least one plant protection agent according to the invention, or a composition according to the invention.
  • a composition of the invention is preferably diluted with water to contain between 0.001 and 20%, more preferred between 0.01 and 1 % (w/v) of a biocontrol agent, prior to applying it to a substrate, a plant or a plant part.
  • a preferred composition of the invention comprising a herbicide, preferably a residual herbicide, is preferably applied to a substrate preferably in the period between October and April, preferably between October and March.
  • Said residual herbicides are preferably applied to, for example, winter barley or winter wheat, when the daily temperature is 10 degrees Celcius or higher.
  • compositions according to the invention are combined prior to contacting an agricultural product or substrate with the combination of compositions.
  • mixing of two or more impregnated beads, wherein each of the beads is impregnated with a different active ingredient would allow the combination of different active ingredients.
  • the mixing of two or more impregnated beads will reduce or pre-empt numerous formulation studies and regulatory studies that are normally required when two or more active ingredients are mixed.
  • the mixing of two or more impregnated beads will allow a combination of two or more active ingredients that otherwise would not be compatible.
  • the invention therefore provides a mixture of at least two compositions according to the invention, wherein the active ingredient differs between said at least two compositions.
  • the mixture preferably comprises a composition comprising calcium carbonate beads and a fungicide, preferably azoxystrobin (methyl (2E)-2-(2- ⁇ [6-(2- cyanophenoxy)pyrimidin-4-yl]oxy ⁇ phenyl)-3-methoxyacrylate), and a composition comprising calcium carbonate beads and a biostimulant.
  • a further preferred mixture comprises a composition comprising calcium carbonate beads and an insecticide, preferably a pyrethroid such as imidacloprid ((E)- l-(6-chloor- 3-pyridinylmethyl)-N-nitro-imidazolidin-2-ylideenamine) ), and a pyrethroid such as imidacloprid ((E)- l-(6-chloor- 3-pyridinylmethyl)-N-nitro-imidazolidin-2-ylideenamine) ), and a pyrethroid such as imidacloprid ((E)- l-(6-chloor- 3-pyridinylmethyl)-N-nitro-imidazolidin-2-ylideenamine) ), and a pyrethroid such as imidacloprid ((E)- l-(6-chloor- 3-pyridinylmethyl)-N-nitro-imidazolidin-2-yl
  • composition comprising calcium carbonate beads and a herbicide such as Allie®.
  • the mixture of impregnated beads is preferably made after preparation of the compositions according to the invention. Said mixture preferably is made before application so that an optimal mixture is prepare that fits with the pests or weeds of the crop to be protected.
  • the mixture of two of more impregnated beads can be made in a 1: 1 ratio in the case of two active ingredients, or in a 1: 1: 1 ratio in case there are three different impregnated beads. The skilled person will understand that the
  • compositions according to the invention will allow mixing the impregnated beads at any ratio, for example 10:90, 20:80; 30:70, 40:60, or 10: 10:80, 20: 10:70, 30: 10:60, 40: 10:50, 20:20:60 and so on, as will be clear to a skiUed person.
  • clay granules such as granules that are based on sepiolite or attapulgite, that are impregnated with different active ingredients, may be combined prior to contacting an agricultural product or substrate with the combination of granules. Again, the mixing of two or more impregnated granules will reduce or pre-empt numerous formulation studies and regulatory studies that are normally required when two or more active ingredients are mixed.
  • a mixture comprising beads impregnated with one or more of an insecticide, fungicide, nematocide, miticide, bactericide, molluscicide and/or herbicide is preferably applied prior to emergence of the weed and/or pests, or shortly after emergence of undesired vegetation from soil.
  • Said mixture is preferably applied in the winter or spring before the seeds of the crops germinate and begin growing.
  • Said herbicide preferably prevents the emergence of hypocotyl and epicotyl from unwanted seed such as, for example, dicotyl seed.
  • impregnated beads include beads impregnated with a broad-spectrum herbicide, for example from the chemical class sulfonylurea, preferably l-(4,6- dimethoxypyrimidin-2-yl)-3-(3-trifluoromethyl-2-pyridylsulphonyl)urea (flazasulfuron) and beads impregnated with a benzenesulfonamide herbicide, preferably 2-(2,2-chfluoroethoxy)-N-(5,8- dimethoxy [1,2,4] triazolo [ 1 , 5 -c]pyrimidin-2 -yl) -6 -
  • a further preferred example includes a combination of beads impregnated with a winter wheat herbicide such as a sulfonylamino-carbonyl- triazolinone, preferably propoxycarbazone-sodium (Olympus ®), or with pyroxsulam, preferably N- (5,7-dimethoxy[l,2,4]triazolo[l,5-a]pyrimidin-2-yl)-2-methoxy-4- (trifluoromethyl)pyridine-3-sulfonamide (POWERFLEX®), and beads impregnated with a dicots killer such as 2,4-dichlorophenoxyacetic acid, a synthetic auxin.
  • a winter wheat herbicide such as a sulfonylamino-carbonyl- triazolinone, preferably propoxycarbazone-sodium (Olympus ®), or with pyroxsulam, preferably N- (5,7-dimethoxy[l,2,4]
  • Said agricultural product preferably is a seed, fruit, leaf, bulb or a corn, or a post-harvest fruit, such as a citrus, for example an orange.
  • Said product preferably is an edible product, selected from a plant or part of a plant, preferably a seed, a vegetable, a processed food or feed product.
  • a preferred part of a plant is selected from seed, fruit and leaf.
  • a most preferred part of a plant comprises or is a leaf.
  • a further preferred part is a seed such as a vegetable seed, a bulb or a corn, or a post-harvest fruit, such as a citrus, for example an orange.
  • substrate includes soil, an artificial substrate and/or a growth substrate that is used in agriculture and/or horticulture, such as a growth substrate for mushrooms, tomatoes, and/or cucumber, as is known to a skilled person.
  • a composition of the invention provides a slow, continuous release of a plant protection agent and/or plant nutrition product such as a nutrient and/or growth stimulant, over time, thereby providing a longer lasting activity of the plant protection agent and/or plant nutrition product such as a nutrient and/or growth stimulant.
  • the effective amount of a plant protection product and/or a plant nutrition product such as a nutrient and/or growth stimulant depends on the type of plant protection agent and/or nutrient or growth stimulant, the type of crop to be protected, the growth phase of the crop, environmental conditions, weather conditions such as rainfall and the type of soil to which a composition of this invention is added.
  • the required concentration may differ depending on the efficacy of the individual compound in certain applications and the required level of protection, as is well known to the person skilled in the art and of course is recommended by the producer of the plant protection agent and/or plant nutrition product such as a nutrient and/or growth stimulant.
  • a preferred amount of a composition of the invention comprising a plant protection agent selected from a natural or chemically synthesized compound that is applied to an agricultural product or substrate is 0.2-100 kg/ha, preferably in an amount of 1-20 kg/ha, calculated by dry weight of the composition.
  • a plant nutrition product such as a nutrient and/or growth stimulant that is applied to an agricultural product or substrate is 1-250 kg/ha, preferably in an amount of 5-100 kg/ha, calculated by dry weight of the composition.
  • the invention further provides a method for protecting a plant or plant part against biotic stress caused by microorganisms, which method comprises providing the composition according to any one of claims 1-6, and contacting the plant or plant part with the composition, wherein the active ingredient of the composition is a plant protection agent.
  • Biotic stress occurs as a result of damage done to plants by other living organisms, such as bacteria, viruses, fungi, parasites, nematodes, beneficial and harmful insects, weeds, and cultivated or native plants. It is a major focus of agricultural research, due to the vast economic losses caused by biotic stress. Biotic stress also impacts horticultural plant health and natural habitats ecology.
  • the invention further provides a method for preventing, reducing and/or eliminating poor edaphic conditions of a plant or substrate, comprising a) providing the composition according to any one of claims 1-6, wherein the active ingredient is a plant nutrition product such as a nutrient and/or growth stimulant; and b) adding the composition to the plant or substrate.
  • a plant nutrition product such as a nutrient and/or growth stimulant
  • composition of the invention comprising one or more plant nutrition products such as nutrients and/or growth stimulants, is preferably used to prevent, reduce and/or eliminate such poor edaphic conditions.
  • the invention further provides the use of a composition according to the invention for preventing, reducing and/or eliminating the presence of pathogenic microorganisms, especially fungi, in or on a plant, plant part or substrate.
  • FIGURE LEGENDS are examples of pathogenic microorganisms, especially fungi, in or on a plant, plant part or substrate.
  • Figure 1 Exemplary picture of calcium carbonate beads.
  • Figure 2. Scattering of calcium carbonate beads when dropped from a height of 30 cm (A), when compared to clay particles (B).
  • Example 1 Water absorption capacity of the CaC03 beads. Water saturated beads were dried for 4 hours at 70 °C. The beads were spread in a layer of about 3 mm on a flat surface and left for cooling for about one hour at room temperature. Subsequently, 100 g of beads were transferred into a beaker glass of 250 ml. To the beads, 2 ml of tap water was added. The beads were then stirred for 1 minute and left for 10 minutes. Six additional portions of 2 ml of water were added as described above after which free water between the beads became visible. The beads were then dried with a filter paper to remove the access water, after which the weight increase of the filter paper was measured.
  • Example 2 Use of calcium carbonate beads to lengthen the survival rate of microorganisms.
  • a microorganism from the Fusarium family was coated on calcium carbonate beads using the following method: the beads were impregnated with the spores collected from the fermenters at the level of 4.5 x 10 6 CFU/g. Three months later, the survival percentage of the microorganisms on the beads was measured by microbial analysis on a Petri dish. Result l,6xl0 6 CFU/g were found present on the beads. As a control, the same microorganism was coated on an common organic granule substrate at the same time as the beads and at the same level of concentration of cfu. The subsequent microbial analysis on a Petri dish gave no CFU, which means all spores where dead. In conclusion: CaC03 beads used as carrier for microorganisms leads to a prolonged survival at room temperature. Example 3. Use of CaC03 beads with impregnated insecticide based on pyrethroid for soil application against wireworm.
  • Treatment 1 and 2 provide the same quantity of pyrethroid per ha.
  • the CaC03 composite granules were made from compressed CaC03 dust, and have a hardness of between 1,5 and 2 on the Mohs scale. In contrast, the CaC03 beads have a hardness of about 3 (Mohs scale).
  • Allie® SX (20% metsulfuron - methyl; DuPont de Nemours, Mechelen, Belgium) was dissolved in 8 ml water by 20 minutes continuous stirring. Once the Allie® SX was dissolved, 1 gram of the sticker polyvinylacetate was slowly added and dissolved under continuous stirring (about 20 minutes). 1 kg of beads or granules were "stirred” in a Hobart mixer and the Allie® SX solution was slowly added to the beads or granules. After mixing for 15 minutes, the beads or granules were spread out (thin layer of about 1 cm height) over a clean plastic plate and left for drying to the air overnight. Finally, the impregnated beads or granules were collected and stored for 1 week in a closed bottle and used in the germination and growth inhibition experiment.
  • Incubation was performed in closed plastic containers of 22 X 36 X 12 cm (length x width x height) cm, on two layers of filter paper, onto which 5 ml water was sprayed uniformly. 100 grass seeds were evenly spread (1 grass seed per 7,5 square cm). To these containers, 0,75 g of Allie® SX impregnated beads or granules (diameter 1 mm) were added. The beads or granules were either evenly spread over the filter paper or they were dropped at a height of 20 cm above the center of the plastic container and bounced randomly over the filter paper. Finally, 20 ml of water was uniformly sprayed in the container.
  • Results show that incubation of grass seeds (100 seeds per incubation in two-fold) with Allie® SX-impregnated beads resulted in a lower germination percentage compared to Allie® SX-impregnated granules (see Table 3). This especially was the case when the Allie® SX-impregnated beads were dropped from 20 cm height (germination percentage is 30 % less than the control). This is caused by the good repartitioning of the beads compared to the granules.
  • Example 5 Effect of the combined application of beads coated with the herbicide Allie and beads coated with the plant growth regulator EpinTM (24-epibrassinolide) on germination and growth of grass.
  • the Allie beads were coated as described in example 4 (5 g Allie® SX per kg of beads with a diameter of 0,5 to 1 mm).
  • 5 mg of Epin was dissolved in 2,5 ml glycerol, which was mixed with 6 ml water.
  • 1 gram of the sticker polyvinylacetate was slowly added and dissolved under continuous stirring (about 20 minutes).
  • 1 kg of beads were "stirred” in a Hobart mixer and the Epin solution was slowly added to the beads. After mixing for 15 minutes, the beads were spread out (thin layer of about 1 cm height) over a clean plastic plate and left for drying to the air overnight.
  • impregnated beads were collected and stored in a closed bottle until use. Incubation was performed in closed plastic containers of 22 X 36 X 12 cm (length x width x height) cm, on two layers of filter paper, onto which 25 ml water was sprayed uniformly. 100 grass seeds were evenly spread (1 grass seed per 7,5 square cm). To these containers, 0,50 g of the Allie® SX and/or Epin impregnated beads were added. The beads were evenly spread over the filter paper.
  • the calcium carbonate beads bounced away from the center where they hit the towels, and the beads were found to scatter over a substantial area.
  • the clay granules formed a pile at the center where they hit the towels.

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Abstract

The invention relates to a composition comprising calcium carbonate beads and one or more active ingredients. The invention additionally relates to methods of protecting an agricultural product or substrate, methods for protecting a plant or plant part against biotic stress, methods for preventing the development of a pathogenic microorganism, methods for preventing, reducing and/or eliminating poor edaphic conditions of a plant or substrate, comprising providing the composition according to the invention to the plant or substrate, as well as the use of a composition according to the invention.

Description

Title: Calcium carbonate beads as carrier for plant protection agents and/or plant nutrition products
The invention relates to compositions for use mainly in agriculture, but also in all activities related to plants such as gardening, amenities, nurseries, and pot plants. More specifically, the invention relates to compositions comprising calcium carbonate beads and one or more active ingredients selected from the groups consisting of plant protection agents, and/or plant nutrition products such as biostimulants.
Farmers, especially in areas with acidic soil, regularly apply different types of lime to correct acidity in the soil. Acid soil reduces plant growth by inhibiting the intake of major plant nutrient such as nitrogen, phosphorus and potassium. In addition, several plants, for example legumes, will not grow in highly acidic soils. The neutralization of acidic soil by application of neutralizers such as lime is vital for them to maximize crop yield.
Soils become acidic in a number of ways. Locations that have high rainfall levels become acidic through leaching. Land used for crop and livestock purposes lose minerals over time by crop removal and become acidic. A further contributor to the acidification of soil acid is the application of modern chemical fertilizers which include nitrogen compounds, as these nitrogen compounds produce nitrous and nitric acid when oxidized in the process of nitrification. Yet a further contributor is plant material that is incorporated into the soil, which results in the production of acids such as acetic acid, humic acid, oxalic acid, and tannic acid.
Because the acids in soils are relatively weak, agricultural lime is preferably milled to a small particle size to be effective. In general, it is thought that particles smaller than 0.3 mm (about 50 mesh) are more effective than larger particles (Stone et al., 1998. Acid Sulfate Soils Manual 1998. (Acid Sulfate Soils Management Advisory Committee; Wollongbar, NSW)). Farmers in addition routinely apply plant protection agents such as herbicides, nematocides, insecticides, miticides, fungicides, bactericides, and molluscicides, to soil, or to plants that are growing on a soil. The most widely used technique for this is spraying of a solution or emulsion comprising a plant protection agent. Spraying requires significant investments and is very energy consuming. As an alternative, granules, for example based on different types of clay, are used for the application of plant protection agents when the pathogens are mainly present in the soil. The amounts that are required per hectare is important to obtain a sufficient repartition in the soil. This amount ranges from about 12 kg/ha located close to the future roots system when the crop is drilled or planted in a row, such as sugar beet, potato, corn, etc., to about 300 kg/ha when all the surface is covered by the seedlings like for some vegetables.
The present inventors surprisingly found that a specific form of calcium carbonate can be combined with a plant protection agent or a plant nutrition product and can easily be applied into the soil, on the soil and/or on a plant or plant part.
Therefore, the invention provides a composition comprising calcium carbonate beads and one or more active ingredients selected from the group consisting of a plant protection agent or/and a plant nutrition product.
The specific calcium carbonate beads are produced from a pellet reactor process directed to softening of water, especially drinking water. The beads are produced in a reactor in which a bed of fine sand is maintained in fluidization. The sand is used as a crystallization seed for calcium carbonate that is present in the water. The calcium carbonate precipitates on the surface of the sand particles under basic pH conditions. Following drainage, the water content of the calcium carbonate beads is lower than 5%. These beads are presently used as road embankment material, pipeline trench sublayers and cement raw material (ACTINA™, "Reducing water hardness with pellet softening". Veolia Water Solutions & Technologies, Saint- Maurice Cedex, France).
Calcium carbonate beads are spherical, in fact almost perfectly round, and composed of about 98 % of calcium carbonate (see Figure 1). The diameter of the beads is between 0.1 and 5 mm, normally between 0.8 and 2.4 mm, or between 0.1 and 2 mm. The beads are often present in two different sizes: between 0.1 and 1.2 mm having an average diameter of 0.4- 0.8 mm) and between 1.6 and 2.4 mm, as determined by passing through a mesh with appropriate mesh size.
A preferred diameter of the beads is below 1 mm. Most preferably, the calcium carbonate beads have an average diameter of about 0.4 mm. A preferred method for determining the average particle size of the beads is sieve analysis or gradation test, which is commonly used to assess the particle size distribution of a granular material. A sieve is also preferably used to select calcium carbonate beads have a diameter of less than 1 mm, and/or beads that have an average diameter of about 0.4 mm.
The hardness of calcium carbonate beads is between 10-100, as determined with a sclerometer, for example a Turner-sclerometer. The hardness of calcium carbonate beads is higher than of calcite, which is about 9. The density of calcium carbonate beads is about 2800 kg/m3, which is much higher than the density of, for example, crushed calcium carbonate stone or marble which both are about 1500 kg/m3 (see
worldwideweb.engineeringtoolbox.com/density-materials-d_1652.html).
Calcium carbonate beads, as herein described, are produced during the water softening process. The beads consist of solid CaC03 that is layered around a very small sand nucleus with high density of at least 2,8 (Mohs hardness) and having channels that are directed from the center to the surface).
Most of the clay granules that are used today for soil application with impregnated pesticides are based on sepiolite or attapulgite. These are fibrous and open clay minerals (hydrous aluminium silicates). The hardness on Mohs scale of the present CaC03 beads is at least 2.5 (between 2.5 and 3.5), while the hardness of the currently used sepiolite and attapulgite clays is lower than 2 on the Mohs scale. The hardness of composite CaC03 granules (granules made out of compressed CaC03 dust) is between 1 and 2 on Mohs scale. The features of the present calcium carbonate beads, including round shape, high density and hardness, differentiates these calcium carbonate beads from any of the existing clay and/or calcium carbonate-containing particles.
As a consequence of the round shape, high density and hardness, calcium carbonate beads that fall on a surface bounce or scatter in all directions. This greatly improves their distribution on any surface, such as soil, for example during the period following the harvest of the previous crop and the plantation of the new crop, but also including the row bottom or planting hole that is made by drilling or planting equipment to place, for example, seed, grain, the seed tuber, seed bulb, or young plants from nurseries, resulting in a better repartition of the plant protection agent and/or the plant nutrition product.
Calcium carbonate beads as described herein may be applied to the soil in order to neutralize, or to reduce the acidity of, acidic soil. It may be used instead of lime, or in addition to lime. The slow dissolution of the beads provides an effective means to control the pH of a soil over time.
Particularly preferred are small beads (between 0.1 and 1.2 mm, preferably beads having an average diameter of about 0.4 mm). For example, beads having an average diameter of 0.4 mm have a volume of about 0.03 mm3, with a density of 2.8 mg/mm3. This means that 1 bead weighs, on average, about 8.04058 E-5 gram. 8 kg of calcium carbonate equals about 100 E6 beads, When applying 8 kg/ha of land, on average 1 bead per cm2 is obtained. It was found that dehydrated calcium carbonate beads, having a water content of less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%, preferably less than 1%, absorb liquids onto or in the beads, including one or more active ingredients selected from the group consisting of a plant protection agent and/or a plant nutrition product. In general, large beads (between 1.6 and 2.4 mm) may absorb about at max. about 15% of their volumes in water, while small beads (between 0.1 and 1.2 mm) may absorb about 1-10% of their volumes in water. Once applied onto or into a soil, plant or plant part, the calcium carbonate beads slowly dissolve over time, thereby providing immediate but also slow release of the plant protection agent and/or the plant nutrition product. Said slow release is, amongst other factors, dependent on the pH of the soil, plant or plant part, and the temperature, as is known to a person skilled in the art. For plant nutrition products, including growth stimulants and biostimulants such as brassinosteroids, said release preferably is over a period of at least two weeks, preferably over a period of at least one month, preferably over a period of at least two months. For plant protection agents, an immediate release of a part of the product is preferred, which is followed by slow release on a period of about two months.
As an alternative, the plant protection agent and/or the plant nutrition product is adsorbed onto the calcium carbonate beads in a composition according to the invention. If required, a binder such as, for example, a polyacrylic acid ester binder, for example RHOPLEX HA-8 manufactured by Rohm and Haas Company; or a polyvinyl acetate binder, for example DUR-O-SET SBX manufactured by Chas. S. Tanner Company. The presence of a binder helps to prevent release of the plant protection agent and/or the plant nutrition product prior to dissolution of the calcium carbonate beads, thereby also providing a slow release formulation
preferably over a period of at least two weeks, preferably over a period of at least one month, preferably over a period of at least two months. The term absorbed, as used herein, refers to the intake of a liquid, preferably an aqueous liquid, including a plant protection agent and/or a plant nutrition product including a biostimulant, onto or in the calcium carbonate beads through the many small pores or channels.
The term adsorbed, as used herein, refers to the adhesion of a plant protection agent and/or a plant nutrition product to a surface of the calcium carbonate beads.
As is indicated herein above, dissolution of the calcium carbonate beads depends inter alia on the pH of the soil, plant or plant part. Calcium carbonate that is released from the calcium carbonate beads will act as a buffer essentially resulting in basic conditions with a pH above 8. The dissolution of calcium carbonate beads in basic conditions is slow, thereby effectively retarding the dissolution of the calcium carbonate beads under basic condition. The slow release of a plant protection agent and/or a plant nutrition product may result in less leaching in the soil, which is better for environment, for example in areas where ground water is collected. An increased pH to about pH=8 is also very important for effective application of beneficiary microorganisms such as bacteria, mycorrhizae and fungi. These microorganisms are very sensitive to low pH. A more stable, basic environment may increase the time period that live microorganisms are present in or on the soil, plant or plant part.
Calcium carbonate beads, through their slow release of calcium carbonate, may also result in an increased pH around the roots of plants, thereby resulting in better absorption of a plant nutrition product by the plants.
It was further found that the shelf life of a plant protection agent and/or plant nutrition product that is based on the presence of beneficial microorganisms, when present in a composition comprising calcium carbonate beads according to the invention, is better when compared to the same microorganisms in another formulation such as a wettable powder, a soluble concentrate and/or organic based granules.
A further advantage of a composition according to the invention is that the calcium carbonate beads will dissolve completely over time, preferably within a year, more preferably within a period of 3-6 months, leaving no remnants behind, except for calcium, such as in the case of clay particles or other granules.
Said plant nutrition product preferably is a biostimulant. The term biostimulant, as is used herein, refers to a substance and/or material that, when applied to a plant, seed or growth substrate, has the capacity to modify physiological processes in said plant which provide benefit to growth, development and/or stress response of said plant. Biostimulants include humic substances, organic materials such as brassinosteroids, chemical elements, inorganic salts such as phosphite, seaweed extract, and chitin, chitan and derivatives thereof.
The term brassinosteroids, as is used herein, refers to a class of poly hydroxy steroids that have been recognized as plant hormones. A preferred brassinosteroid is 24-epibrassinolide ((22R,23R,24R)-2a,3a,22,23- tetrahydroxy-24-methyl-6-homo-7-oxa-5-cholestan-6-one) or 28- homobrassinolide (22R,23R,24R-2a,3a,22,23-tetrahydroxy-B-homo-7-oxa-5a- ergostan-6-one).
Said plant nutrition product preferably is a chemical element and/or compound that is necessary for plant growth. Primary macronutrient or growth stimulants for plants comprise nitrogen (N), phosphorus (P), potassium (K), the three secondary macronutrient calcium (Ca), sulphur (S), magnesium (Mg). Trace minerals include boron (B), chlorine (CI),
manganese (Mn), iron (Fe), zinc (Zn), copper (Cu), molybdenum (Mo), nickel (Ni). Nutrient or growth stimulant uptake from the soil is achieved by cation exchange, where root hairs pump hydrogen ions (H+) into the soil through proton pumps. These hydrogen ions displace cations attached to negatively charged soil particles so that the cations are available for uptake by the root. As is indicated herein above, the increased pH and buffering capacity of a composition according to the invention will prevent acidification of the soil, thereby increasing the intake of major plant nutrient or growth stimulants such as nitrogen, phosphorus and potassium. In addition, the buffering capacity at a slightly basic pH will prevent leaching of especially cationic nutrient or growth stimulants through the soil. A composition of the invention, therefore, results in improved and prolonged availability of nutrient or growth stimulants to a plant.
A preferred composition comprising a plant nutrition product according to the invention comprises 10-300 g/kg phosphor (P), 5-250 g/kg magnesium (Mg), 0.5-25 g/kg of iron (Fe), 2-100 g/kg manganese (Mn), 5-250 mg/kg boron (B), 0.1-5 mg/kg molybdenum (Mo), and 0.05-2.5 mg/kg zinc (Zn), based on dry weights.
Said plant nutrition product, including a nutrient and/or or growth stimulant, preferably is absorbed/adsorbed on or into the calcium carbonate beads. As an alternative, said plant nutrition product is added to the water before or during the production of the calcium carbonate beads.
A plant protection agent is preferably selected from microorganism, a plant extract or a natural or synthesized compound. These plant
protection agents may have insecticide, fungicide, nematicide, miticide, bactericide, molluscicide and/or herbicide activity, as is known to a skilled person.
The term natural or synthesized compound, as used herein, refers to compounds that occur in nature, or that are biologically synthesized, for example with the use of a microorganism, or chemically synthesized, for example through one or more reaction steps.
Said microorganism preferably is already known or registered for its biocontrol activity. Said microorganism preferably comprises at least one fungus and/or bacterium, or spores thereof. Preferred fungi include Streptomyces species, Paecilomyces species, Talaromyces species,
Trichoderma species, Beauveria species, Ampelomyces species,
Coniothyrium species and Gliocladium species. Preferred bacterial species include lactic acid bacteria such as Lactococcus lactis, Lactococcus lactis subsp. lactis, Pediococcus acidilactici, P. pentosaceus, P. damnosus,
Lactobacillus plantarum, Lactobacillus reuteri, Lactobacillus sake; propionic acid bacteria such as Propionibacterium jensenii and Propionibacterium freudenreichii subsp. shermanii; Bacillus species such as Bacillus
thuringiensis and Bacillus subtilis; Pseudomonas species such as
Pseudomonas aeruginosa and Pseudomonas fluorescens.
Examples of biocontrol agents and their applications are provided in a world wide web-based report, entitled "Alternatives to Copper for Disease Control in the Australian Organic Industry; A report for the Rural Industries Research and Development Corporation", by Van Zwieten, Stovold, and Van Zwieten (authors). The report is available at
https://rirdc.infoservices.com.au/items/07-110.
As is indicated in the report, biocontrol agents have been applied in the past, including Agrobacterium radiobacter, for control of Crown gal, Ampelomyces quisqualis, for control of powdery mildew, Arthrobotrys dactyloides, for control of root knot and nematodes, Ascocoryne sarcoides, for control of various decay organisms, Bacillus licheniformis for control of anthracnose and stem end rot, Bacillus subtilis for control of green and blue moulds and stem canker, Chaetomium globosum for control of black spot, Cladosporium oxysporum for control of petal blight, Cladosporium
cladosporioides for control oiBotrytis cinerea, Coniothyrium minitans for control of Sclerotinia sclerotiorum, Dactylella leptospora for control of nematodes, hypovirulent strains of Cryphonectria for control of
Cryphonectria, a hrp mutant of Erwinia amylovora for control of Erwinia amylovora, hypovirulent strains oiFusarium oxysporum for control of Fusarium oxysporum, Gliocladium virens for control of Sclerotium rolfsii, Gliocladium roseum for control of Botrytis cinerea, Hansfordia pulvinata for control oiFulvia fulva, Laetisaria arvalis for control of aerial blight and root rot, Myrothecium verrucaria for control of Sclerotium rolfsii,
Nematophthora species for control of nematodes, Penicillium oxalicum for control of fusarium wilt and verticillium wilt, Phlebiopsis gigantean for control of root and butt rot, Phialophora radicicola for control of Ophiobolus patch disease, Pseudomonas aeruginosa and Pseudomonas fluorescens for control of Pythium, Pythium oligandrum for control of Pythium ultimum, Scytalidium uredinicola for control of Endocronartium harknessii,
Sphaerellopsis filum for control of Melampsora species, Sporidesmium sclerotivorum for control of Sclerotinia, Botrytis, Amphobotrys and
Monilinia species, Streptomyces species for control of Pythium ultimum, Taloromyces flavus for control of stem rot, Trichoderma asperellim for control of Fusarium oxisporum, Trichoderma harzianum for control of
Botrytis cinerea, Sclerotinia sclerotiorum and Cladosporium fulvum,
Trichoderma harzianum for control of Fusarium udum, Trichoderma harzianum for control of Sclerotium rolfsii and Fusarium oxysporum, Trichoderma koningii for control of Phytophthora parasitica, Trichoderma viride for control of Rhizoctonia solani, Trichoderma viride for control of Botrytis cinerea, Trichothecium roseum for control of Sclerotinia
sclerotiorum, Tuberculina maxima for control of Cronartium quercuum, Verticillium biguttatum for control of Rhizoctonia solani, Verticillium chlamydosporium for control of nematodes, and Verticillium lecanii for control of mites. Further examples include Trichoderma virens, for control of soilborne Rhizoctonia, Fusarium and Pythium moulds, and Streptomyces griseoviridis for control of Pythium, Fusarium, Alternaria, Phomopsis, Rhizoctonia, Phytophthora and Botrytis. One or more of these agents is prefereably included as biocontrol agent in a composition according to the invention. A preferred microorganism is or comprises at least one Beauveria species, CoUetotrichum species, Trichoderma species, Ampelomyces species, Gliocladium species, Bacillus species and/or Pseudomonas species, and/or spores thereof.
Said microorganism is preferably present in a composition according to the invention in an amount of between 104 and 109 colony forming units (cfu), preferably between 106 and 109 cfu.
Said microorganism may benefit from the increase in pH that is provided by dissolution of the calcium carbonate as most microorganisms grow better under non-acidic conditions.
A further preferred plant protection agent in a composition according to the invention is a natural of chemically synthesized compound with fungicide, herbicide, insecticide, bactericide, molluscicide and/or nematocide activity. A composition of the invention may also comprise two plant protection agents, such as two or more fungicides, two or more herbicides, two or more insecticides, two or more nematocides, or
combinations thereof such as, for example, at least one fungicide and at least one insecticide, at least one fungicide and at least one herbicide, at least one fungicide and at least one nematocide, at least one herbicide and at least one nematocide, at least one herbicide and at least one insecticide, and/or at least one insecticide and at least one nematocide. Some plant protection agents have a wide range of target organisms, as is known to the skilled person, and may therefore be included in more than one subgroup of plant protection agents.
A plant protection agent selected from natural or chemically synthesized compounds is preferably present in a concentration of between 0, 1 and 90 w/v%, more preferred between 1 and 70 w/v%, more preferred between 10 and 50 w/v%.
An insecticide is a compound used to control (including prevention, reduction or elimination) parasitic insects. Said insecticide preferably is or comprises a neonicotinoid such as imidacloprid (commercial product:
ADMIRE®, Bayer) and thiamethoxam (Syngenta), teflubenzuron
(commercial product: NOMOLT®, BASF), pymetrozine (commercial product: PLENUM®, Syngenta), acetamiprid (commercial product: GAZELLE®, Certis Europe), pirimiphos-methyl (commercial product: ACTELLIC®
Syngenta, Switserland), pyrethroids (commercial product BAYGON®
(Bayer) and cypermethrine (cyano-(3-phenoxyphenyl)methyl]3-(2,2- dichloroethenyl)-2,2-dimethylcyclopropane-l-carboxylate)), bifenazate (e.g. Uniroyal), dichlorvos (e.g. Amvac Chemical Corporation), imidacloprid (e.g. Bayer), fenamiphos (e.g. Mobay Chemical Corporation), orange oil, D- limonene, oxamyl (e.g. Dupont), organophosphate (an ester of phosphoric acid), neem oil, and sulfur-based insecticides. A most preferred insecticide is a pyrethroid, organophoshate, andor a neonicotinoid. A composition of the invention may comprise two or more insecticides.
A fungicide is a compound used to control (including prevention, reduction or elimination) parasitic fungi. A preferred antifungal compound or fungicide is or comprises 2-phenylphenol; 8 -hydroxy quinoline sulphate; acibenzolar-5-methyl; actinovate; aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azoxystrobin; benalaxyl;
benodanil; benomyl (methyl l-(butylcarbamoyl)benzimidazol-2- ylcarbamate); benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; blasticidin-S; boscalid; bupirimate;
buthiobate; butylamine; calcium polysulphide; capsimycin; captafol; captan (N-(trichloromethylthio)cyclohex-4-ene-l,2-dicarboximide); carbendazim; carboxin; carpropamid; carvone; chinomethionat; chlobenthiazone;
chlorfenazole; chloroneb; chlorothalonil; chlozolinate; cis-l-(4-chlorophenyl)- 2-(lH-l,2,4-triazol-l-yl)-cycloheptanol; clozylacon; a conazole fungicide such as, for example, (RS)-l-(6-allyloxy-2,4-dichlorophenethyl)imidazole (imazalil; Janssen Pharmaceutica NV, Belgium) and N-propyl-N-[2-(2,4,6- trichlorophenoxy)ethyl] imidazole- 1-carboxamide (prochloraz); cyazofamid; cyflufenamid; cymoxanil; cyprodinil; cyprofuram; Dagger G; debacarb;
dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine;
drazoxolon; edifenphos; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenfuram; fenhexamid; fenitropan; fenoxanil;
fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam (3-chloro-N-(3- chloro-5-trifluoromethyl-2-pyridyl)-a,a,a-trifluoro-2,6-dinitro-p-toluidin flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; flurprimidol; flusulfamide; flutolanil; folpet (N-
(trichloromethylthio)phthalimide); fosetyl-Al; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine;
hexachlorobenzene; hymexazol; iminoctadine triacetate; iminoctadine tris(albesilate); iodocarb; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoxim -methyl; mancozeb; maneb; mefenoxam ((-)-Metalaxyl , (R)-2{(2,6-dimethylphenyl)- methoxyacetylamino}- propionic acid methyl ester , (R)-Metalaxyl;
Syngenta); meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; methasulfocarb; methfiroxam; methyl l-(2,3-dihydro-2,2-dimethyl- lH- inden-l-yl)- lH-imidazole-5-carboxylate; methyl 2-[[[cyclopropyl[(4- methoxyphenyl)imino] methyl] thio] -methyl] - . alph- a. - (methoxymethylene)benzeneacetate; methyl 2-[2-[3-(4-chlorophenyl)-l- methyl-allylideneaminooxymethyl]phenyl]-3-meth- oxyacrylate; metiram; metominostrobin; metrafenone; metsulfovax; mildiomycin; monopotassium carbonate; myclozolin; N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formylamino- 2-hydroxybenzamide; N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide; N-butyl-8-(l, l-dimethylethyl)-l-oxaspiro[4.5]decan-3-amine; a polyene fungicide such a natamycin (pimaricin ((1R,3S,5R,7R,8E, 12R, 14E, 16E, 18E, 20E,22R,24S,25R, 26S) -22-[(3-amino-3,6-dideoxy-D-mannopyranosyl)oxy]- l,3,26-trihydroxy-12-methyl-10-oxo-6, 11,28- trioxatricyclo[22.3.1.05,7]octacosa-8, 14, 16, 18,20-pentaene-25-carboxylic acid); nitrothal-isopropyl; noviflumuron; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxycarboxin; oxyfenthiin; pencycuron; penthiopyrad;
phosdiphen; phosphite (a salt and/or ester of phosphonic acid (phosphorous acid, preferably ethyl-phosphite); phthalide; picobenzamid; picoxystrobin; piperalin; polyoxins; polyoxorim; procymidone; propamocarb; propanosine- sodium; propineb; proquinazid; pyraclostrobin; pyrazophos; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine, quinconazole; quinoxyfen; quintozene; silthiofam; sodium tetrathiocarbonate; spiroxamine; sulphur; tecloftalam; tecnazene; tetcyclacis; thiazole fungicide such as, for example, 2-(thiazol-4- yl)benzimidazole (thiabendazole; e.g. the commercial product TECTO® Flowable SC of Syngenta, USA), thicyofen; thifluzamide; thiophanate- methyl; thiram; tiadinil; tioxymid; tolclofos-methyl; tolylfluanid; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin;
validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)- N-[2-[4-[[3-(4- chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-met- hyl-2- [(methylsulphonyl)amino]butanamide; l-(l-naphthalenyl)-lH-pyrrole-2,5- dione; 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine; 2,4-dihydro-5- methoxy-2-methyl-4-[[[[l-[3-(trifluoromethyl)phenyl]-ethyli- dene]amino]oxy]methyl]phenyl]-3H-l,2,3-triazol-3-one; 2-amino-4-methyl-N- phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro- l, l,3-trimethyl-lH- inden-4-yl)-3-pyridinecarboxam- ide; 3,4,5-trichloro-2,6- pyridinedicarbonitrile; and/or 3-[(3-bromo-6-fluoro-2-methyl-lH-indol- l- yl)sulphonyl]-N,N-dimethyl-lH-l,- 2,4-triazole-l-sulphonamide.
Preferred fungicides include tebuconazole, mefenoxam,
propamocarb, ethylphosphosphonate and/or hymexazol.
A nematocide is a compound used to control (including prevention, reduction or elimination) parasitic nematodes, including wireworms. A preferred nematocide is or comprises aldicarb, imicyafos, oxamyl and/or fenamiphos. A herbicide is a compound used to control (including prevention, reduction or elimination) unwanted plants. A preferred herbicide is or comprises glyphosate, an acetamide such as diphenamid, naprop amide, naproanilide, acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, and flufenacetan, triallate (S -(2,3,3 -trichloro ally) - diisopropylthiocarbamate), an acetyl coenzyme A carboxylase inhibitor; an acetolactate synthase inhibitor such as sulfonylurea, imidazolinone, triazolopyrimidine, pyrimidinyl oxybenzoate, and sulfonylamino carbonyl triazolinone; enolpyruvylshikimate 3-phosphate synthase inhibitor such as glyphosate; a synthetic auxin such as 2,4-dichlorophenoxyacetic acid; a photosystem II inhibitor such as triazine, including atrazine, and urea derivatives such as diuron; a photosystem I inhibitor for example a bipyridinium herbicide such as diquat and paraquat, a diphenyl ether such as nitrofen, nitrofluorfen, and acifluorfen; an 4-hydroxyphenylpyruvate dioxygenase inhibitor such as mesotrione and sulcotrione. A preferred herbicide is or comprises glyphosate, napropamide, triallate, a sulfonylurea and/or triazine.
Said herbicide preferably is a residual herbicide, which remains active for at least four weeks after application. Examples of residual herbicides include, but are not limited to, Anthem® (FMC Agricultural Solutions), which is a pre-mix of pyroxasulfone) and fluthiacet-methyl);
FirstRate® (3-chloro-2-[[(5-ethoxy-7-fluoro[l,2,4]triazolo[l,5-c]pyrimidin-2- yl)sulfonyl]amino]benzoic acid; Dow Agrosciences); Prefix® (a pre-mix of S- 2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(l-methoxypropan-2-yl)acetamide and the sodium salt of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-
(methylsulfonyl)-2-nitrobenzamide; Syngenta); Sharpen® (N'-{2-Chloro-4- fluoro-5-[l,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin- l-yl]benzoyl}-N-isopropyl-N-methylsulfamide; BASF); Valor® (fLumioxazin (2-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-l,4-benzoxazin-6-yl]- 4,5,6,7-tetrahydro-lHisoindole-l,3(2H)-dione; Valent)). A most preferred herbicide is Allie® SX (metsulfuron methyl (methyl 2-[[[[(4-methoxy-6- methyl -l,3,5-triazin-2-yl)amino]carbonyl] amino] -sulfonyl]benzoate;
DuPont de Nemours, Mechelen, Belgium).
A composition of the invention preferably comprises a binder, a spreader and/or a surfactant, especially in the case when the plant protection agent and/or plant nutrition product, including a nutrient and/or growth stimulant, is adsorbed to a calcium carbonate bead.
A binder is preferably selected from artificial latex (commercial product: Prolong, Holland Fyto, Netherlands); ethylene vinyl acetate copolymer (commercial product: Atlox Semkote E-105, Uniqema, USA) and/or polyvinyl acetate. A binder may further be selected from pinolene (commercial product: Nu-film 17, (Miller Chemical and Fertilizer
Corporation, USA), xanthan (commercial product: Rhodopol, Rhodia, France), succinoglycan (commercial product: Rheozan, Rhodia, France), and/or polyvinylpyrolidone.
A spreader is preferably a nonionic surfactant such as
polyoxy ethylene sorbitan ester, polyoxyethylene alkyl (or aryl) ether or polyoxy ethylene fatty acid ester, an anionic surfactant such as straight- chain alkylbenzene sulfonate, dialkylsulfosuccinate, lignin sulfonate or polynaphthyl sulfonate, or a high molecular compound such as polyacrylate.
A surfactant is preferably an anionic tenside such as sodium lauryl sulphate, polyethylene alkyl ether or polyoxyethylether, e.g Tween® 60, 61 or 65; organo silicone, sulfosuccinate, alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid propoxylate and the commercial product Zipper® (Moodify BV, The Netherlands).
A composition of the invention preferably comprises between 0.1 gram/liter and up to 100 gram/liter of a binder, a spreader and/or a surfactant, preferably between 1 and 10 gram/liter.
As is indicated herein above, the calcium carbonate beads preferably have an average diameter of about 0.4 mm. Calcium carbonate beads having a diameter between 1.6 and 2.4 mm are particularly suitable as molluscicide. Said beads preferably are impregnated with
iron(iii)phosphate and/or ammonium sulfate.
The invention further provides a method of protecting an agricultural product or substrate, comprising a) providing the composition according to the invention, and b) contacting the agricultural product or substrate with the composition. Said method preferably protects a plant from a pathogenic microorganism. The invention further provides a method of preventing, reducing and/or eliminating the presence of a pathogen on a substrate, on a plant or on one or more plant parts, comprising applying to said substrate, plant or plant part a composition comprising at least one plant protection agent according to the invention, or a composition according to the invention. A composition of the invention is preferably diluted with water to contain between 0.001 and 20%, more preferred between 0.01 and 1 % (w/v) of a biocontrol agent, prior to applying it to a substrate, a plant or a plant part.
A preferred composition of the invention comprising a herbicide, preferably a residual herbicide, is preferably applied to a substrate preferably in the period between October and April, preferably between October and March. Said residual herbicides are preferably applied to, for example, winter barley or winter wheat, when the daily temperature is 10 degrees Celcius or higher.
It is further preferred that two or more compositions according to the invention are combined prior to contacting an agricultural product or substrate with the combination of compositions. For example, mixing of two or more impregnated beads, wherein each of the beads is impregnated with a different active ingredient, would allow the combination of different active ingredients. The mixing of two or more impregnated beads will reduce or pre-empt numerous formulation studies and regulatory studies that are normally required when two or more active ingredients are mixed. In addition, the mixing of two or more impregnated beads will allow a combination of two or more active ingredients that otherwise would not be compatible.
The invention therefore provides a mixture of at least two compositions according to the invention, wherein the active ingredient differs between said at least two compositions. The mixture preferably comprises a composition comprising calcium carbonate beads and a fungicide, preferably azoxystrobin (methyl (2E)-2-(2-{[6-(2- cyanophenoxy)pyrimidin-4-yl]oxy}phenyl)-3-methoxyacrylate), and a composition comprising calcium carbonate beads and a biostimulant. A further preferred mixture comprises a composition comprising calcium carbonate beads and an insecticide, preferably a pyrethroid such as imidacloprid ((E)- l-(6-chloor- 3-pyridinylmethyl)-N-nitro-imidazolidin-2-ylideenamine) ), and a
composition comprising calcium carbonate beads and a herbicide such as Allie®.
The mixture of impregnated beads is preferably made after preparation of the compositions according to the invention. Said mixture preferably is made before application so that an optimal mixture is prepare that fits with the pests or weeds of the crop to be protected. The mixture of two of more impregnated beads can be made in a 1: 1 ratio in the case of two active ingredients, or in a 1: 1: 1 ratio in case there are three different impregnated beads. The skilled person will understand that the
compositions according to the invention will allow mixing the impregnated beads at any ratio, for example 10:90, 20:80; 30:70, 40:60, or 10: 10:80, 20: 10:70, 30: 10:60, 40: 10:50, 20:20:60 and so on, as will be clear to a skiUed person.
A person skilled in the art will appreciate that also clay granules, such as granules that are based on sepiolite or attapulgite, that are impregnated with different active ingredients, may be combined prior to contacting an agricultural product or substrate with the combination of granules. Again, the mixing of two or more impregnated granules will reduce or pre-empt numerous formulation studies and regulatory studies that are normally required when two or more active ingredients are mixed.
A mixture comprising beads impregnated with one or more of an insecticide, fungicide, nematocide, miticide, bactericide, molluscicide and/or herbicide is preferably applied prior to emergence of the weed and/or pests, or shortly after emergence of undesired vegetation from soil. Said mixture is preferably applied in the winter or spring before the seeds of the crops germinate and begin growing. Said herbicide preferably prevents the emergence of hypocotyl and epicotyl from unwanted seed such as, for example, dicotyl seed. An example of preferred combinations of impregnated beads include beads impregnated with a broad-spectrum herbicide, for example from the chemical class sulfonylurea, preferably l-(4,6- dimethoxypyrimidin-2-yl)-3-(3-trifluoromethyl-2-pyridylsulphonyl)urea (flazasulfuron) and beads impregnated with a benzenesulfonamide herbicide, preferably 2-(2,2-chfluoroethoxy)-N-(5,8- dimethoxy [1,2,4] triazolo [ 1 , 5 -c]pyrimidin-2 -yl) -6 -
(trifluoromethyl)benzenesulfonamide (penoxsulame). A further preferred example includes a combination of beads impregnated with a winter wheat herbicide such as a sulfonylamino-carbonyl- triazolinone, preferably propoxycarbazone-sodium (Olympus ®), or with pyroxsulam, preferably N- (5,7-dimethoxy[l,2,4]triazolo[l,5-a]pyrimidin-2-yl)-2-methoxy-4- (trifluoromethyl)pyridine-3-sulfonamide (POWERFLEX®), and beads impregnated with a dicots killer such as 2,4-dichlorophenoxyacetic acid, a synthetic auxin.
Said agricultural product preferably is a seed, fruit, leaf, bulb or a corn, or a post-harvest fruit, such as a citrus, for example an orange. Said product preferably is an edible product, selected from a plant or part of a plant, preferably a seed, a vegetable, a processed food or feed product. A preferred part of a plant is selected from seed, fruit and leaf. A most preferred part of a plant comprises or is a leaf. A further preferred part is a seed such as a vegetable seed, a bulb or a corn, or a post-harvest fruit, such as a citrus, for example an orange.
The term substrate, as is used herein, includes soil, an artificial substrate and/or a growth substrate that is used in agriculture and/or horticulture, such as a growth substrate for mushrooms, tomatoes, and/or cucumber, as is known to a skilled person. A composition of the invention provides a slow, continuous release of a plant protection agent and/or plant nutrition product such as a nutrient and/or growth stimulant, over time, thereby providing a longer lasting activity of the plant protection agent and/or plant nutrition product such as a nutrient and/or growth stimulant.
The effective amount of a plant protection product and/or a plant nutrition product such as a nutrient and/or growth stimulant, depends on the type of plant protection agent and/or nutrient or growth stimulant, the type of crop to be protected, the growth phase of the crop, environmental conditions, weather conditions such as rainfall and the type of soil to which a composition of this invention is added. Thus, the required concentration may differ depending on the efficacy of the individual compound in certain applications and the required level of protection, as is well known to the person skilled in the art and of course is recommended by the producer of the plant protection agent and/or plant nutrition product such as a nutrient and/or growth stimulant.
A preferred amount of a composition of the invention comprising a plant protection agent selected from a natural or chemically synthesized compound that is applied to an agricultural product or substrate is 0.2-100 kg/ha, preferably in an amount of 1-20 kg/ha, calculated by dry weight of the composition. A preferred amount of a composition of the invention
comprising a plant nutrition product such as a nutrient and/or growth stimulant that is applied to an agricultural product or substrate is 1-250 kg/ha, preferably in an amount of 5-100 kg/ha, calculated by dry weight of the composition.
The invention further provides a method for protecting a plant or plant part against biotic stress caused by microorganisms, which method comprises providing the composition according to any one of claims 1-6, and contacting the plant or plant part with the composition, wherein the active ingredient of the composition is a plant protection agent.
Biotic stress occurs as a result of damage done to plants by other living organisms, such as bacteria, viruses, fungi, parasites, nematodes, beneficial and harmful insects, weeds, and cultivated or native plants. It is a major focus of agricultural research, due to the vast economic losses caused by biotic stress. Biotic stress also impacts horticultural plant health and natural habitats ecology.
The invention further provides a method for preventing, reducing and/or eliminating poor edaphic conditions of a plant or substrate, comprising a) providing the composition according to any one of claims 1-6, wherein the active ingredient is a plant nutrition product such as a nutrient and/or growth stimulant; and b) adding the composition to the plant or substrate.
Poor edaphic conditions like pH levels and poor nutrient or growth stimulant availability may cause abiotic stress. These abiotic stress factors also lead to a lower yield and reduce the quality of the products. A
composition of the invention, comprising one or more plant nutrition products such as nutrients and/or growth stimulants, is preferably used to prevent, reduce and/or eliminate such poor edaphic conditions.
The invention further provides the use of a composition according to the invention for preventing, reducing and/or eliminating the presence of pathogenic microorganisms, especially fungi, in or on a plant, plant part or substrate. FIGURE LEGENDS
Figure 1. Exemplary picture of calcium carbonate beads. Figure 2. Scattering of calcium carbonate beads when dropped from a height of 30 cm (A), when compared to clay particles (B).
Examples
Example 1. Water absorption capacity of the CaC03 beads. Water saturated beads were dried for 4 hours at 70 °C. The beads were spread in a layer of about 3 mm on a flat surface and left for cooling for about one hour at room temperature. Subsequently, 100 g of beads were transferred into a beaker glass of 250 ml. To the beads, 2 ml of tap water was added. The beads were then stirred for 1 minute and left for 10 minutes. Six additional portions of 2 ml of water were added as described above after which free water between the beads became visible. The beads were then dried with a filter paper to remove the access water, after which the weight increase of the filter paper was measured. After calculating the amount of water added (14 ml), minus the amount of water absorbed in the filter paper (3.2 g) it was concluded that 100 g of the beads absorbed 10.8 g of water. Since the density of the beads is 2.8 g per cubic cm, this means that 1 cubic cm of beads may contain about 0.30 ml of water.
Example 2. Use of calcium carbonate beads to lengthen the survival rate of microorganisms.
A microorganism from the Fusarium family was coated on calcium carbonate beads using the following method: the beads were impregnated with the spores collected from the fermenters at the level of 4.5 x 106 CFU/g. Three months later, the survival percentage of the microorganisms on the beads was measured by microbial analysis on a Petri dish. Result l,6xl06 CFU/g were found present on the beads. As a control, the same microorganism was coated on an common organic granule substrate at the same time as the beads and at the same level of concentration of cfu. The subsequent microbial analysis on a Petri dish gave no CFU, which means all spores where dead. In conclusion: CaC03 beads used as carrier for microorganisms leads to a prolonged survival at room temperature. Example 3. Use of CaC03 beads with impregnated insecticide based on pyrethroid for soil application against wireworm.
Application took place at the drilling time with a microgranulator attached to the drilling equipment. Treatment 1 and 2 provide the same quantity of pyrethroid per ha.
Results are shown in table 2.
Table 2
Figure imgf000025_0001
Conclusion : reduction of the weight of insecticide granules per ha from 15 kg to 6 kg provides the same efficiency of pyrethroid per hectare. This allows a major reduction of logistic work and costs. Example 4. Comparison of efficacy of the herbicide Allie
impregnated on CaC03 beads versus CaC03 composite granules on germination and growth of grass. The CaC03 composite granules were made from compressed CaC03 dust, and have a hardness of between 1,5 and 2 on the Mohs scale. In contrast, the CaC03 beads have a hardness of about 3 (Mohs scale).
5 g Allie® SX (20% metsulfuron - methyl; DuPont de Nemours, Mechelen, Belgium) was dissolved in 8 ml water by 20 minutes continuous stirring. Once the Allie® SX was dissolved, 1 gram of the sticker polyvinylacetate was slowly added and dissolved under continuous stirring (about 20 minutes). 1 kg of beads or granules were "stirred" in a Hobart mixer and the Allie® SX solution was slowly added to the beads or granules. After mixing for 15 minutes, the beads or granules were spread out (thin layer of about 1 cm height) over a clean plastic plate and left for drying to the air overnight. Finally, the impregnated beads or granules were collected and stored for 1 week in a closed bottle and used in the germination and growth inhibition experiment.
Incubation was performed in closed plastic containers of 22 X 36 X 12 cm (length x width x height) cm, on two layers of filter paper, onto which 5 ml water was sprayed uniformly. 100 grass seeds were evenly spread (1 grass seed per 7,5 square cm). To these containers, 0,75 g of Allie® SX impregnated beads or granules (diameter 1 mm) were added. The beads or granules were either evenly spread over the filter paper or they were dropped at a height of 20 cm above the center of the plastic container and bounced randomly over the filter paper. Finally, 20 ml of water was uniformly sprayed in the container.
The following incubations were performed (in two-fold):
1. Beads impregnated with Allie® SX fallen from 20 cm
2. Granules impregnated with Allie® SX fallen from 20 cm
3. Beads impregnated with Allie® SX evenly spread over filter paper
4. Granules impregnated with Allie® SX evenly spread over filter paper
5. No addition of beads or granules (untreated control)
After two weeks the average germination percentage and average length of the germinated grass were assessed.
Results: The results show that incubation of grass seeds (100 seeds per incubation in two-fold) with Allie® SX-impregnated beads resulted in a lower germination percentage compared to Allie® SX-impregnated granules (see Table 3). This especially was the case when the Allie® SX-impregnated beads were dropped from 20 cm height (germination percentage is 30 % less than the control). This is caused by the good repartitioning of the beads compared to the granules.
Table 3. Effect of Allie® SX-impregnated beads and granules germinated percentage of grass.
I ncubat ion ( K -m i nal ion ( )
Beads impregnated with Allie® i: >X fallen from 39,5
20 cm
Granules impregnated with Allie ® SX fallen 54,5
from 20 cm
Beads impregnated with Allie® i: 5X evenly 35,0
spread over filter paper
Granules impregnated with Allie ® SX evenly 44,5
spread over filter paper
No addition of beads or granules (untreated 84,5
control without Allie® SX)
The results presented in Table 4 show that incubation of grass seeds (100 seeds per incubation in two-fold) with Allie® SX-impregnated beads resulted in a lower length of the germinated seeds compared to Allie® SX-impregnated granules. This is especially the case when the Allie® SX- impregnated beads/granules were fallen from 20 cm height (length is 25% less). Table 4. Effect of Allie® SX-impregnated beads and granules on the length of the germinated grass.
Figure imgf000028_0001
Example 5. Effect of the combined application of beads coated with the herbicide Allie and beads coated with the plant growth regulator Epin™ (24-epibrassinolide) on germination and growth of grass.
In this experiment, Epin was used because we found in a separate experiment that application of Epin led to reduced lateral root formation of germinated grass seeds. The experiment in this example shows the combined effect of Allie® SX and Epin on germination and growth of grass.
Coating of beads. The Allie beads were coated as described in example 4 (5 g Allie® SX per kg of beads with a diameter of 0,5 to 1 mm). For the Epin coated beads, 5 mg of Epin was dissolved in 2,5 ml glycerol, which was mixed with 6 ml water. To this mixture, 1 gram of the sticker polyvinylacetate was slowly added and dissolved under continuous stirring (about 20 minutes). 1 kg of beads were "stirred" in a Hobart mixer and the Epin solution was slowly added to the beads. After mixing for 15 minutes, the beads were spread out (thin layer of about 1 cm height) over a clean plastic plate and left for drying to the air overnight. Finally, the
impregnated beads were collected and stored in a closed bottle until use. Incubation was performed in closed plastic containers of 22 X 36 X 12 cm (length x width x height) cm, on two layers of filter paper, onto which 25 ml water was sprayed uniformly. 100 grass seeds were evenly spread (1 grass seed per 7,5 square cm). To these containers, 0,50 g of the Allie® SX and/or Epin impregnated beads were added. The beads were evenly spread over the filter paper.
The following incubations were performed:
1. Beads impregnated with Allie® SX
2. Beads impregnated with Epin
3. Beads impregnated with both Allie® SX and Epin
4. No addition of beads or granules (untreated control)
After two weeks the average germination percentage and average length of the germinated grass were determined.
The results related to germination (Table 5) show that incubation of grass seeds (100 seeds per incubation) with Allie® SX -impregnated beads led to a 42% lower germination percentage compared to the control. Beads impregnated with Epin had a 6% lower germination percentage. The germination percentage of the combined Allie® SX + Epin application was 51% lower. From these results it can be concluded that combining different beads leads to an combined (additive) effect.
Table 5. Effect of Allie® SX, Epin and Allie® SX + Ep
gnated beads on the germination percentage of grass.
I ncu ba t i on ( icrin i n a l i on (" n)
Beads impregnated with Allie® SX 51
Beads impregnated with Epin 87
Beads impregnated with Allie® SX + Epin 42
No addition of beads 93
The results related to growth (Table 6) show that incubation of grass seeds (100 seeds per incubation) with Allie® SX -impregnated beads led to a 5,5 cm lower growth compared to the control. Beads impregnated with Epin had a 1,2 cm lower growth. The growth of the combined Allie® SX + Epin application was 5,9 cm lower. From these results it can be concluded that combining different beads led to a combined (additive) effect.
Table 6. Effect of Allie® SX, Epin and Allie® SX + Ep
gnated beads on the length of germinated grass.
I ncubat ion Lengt h (nun)
Beads impregnated with Allie ® SX 14
Beads impregnated with Epin L 57
Beads impregnated with Allie ® SX + Epin 10
No addition of beads 69
Example 5. Scattering of calcium carbonate beads. In this
experiment, the scaterring of calcium carbonate beads according to the invention was compared to the scattering of clay granules of similar size.
Materials and methods.
4 gram of beads or 4 gram of clay granules were impregnated with AUie® as described herein above. The beads or granules were dropped from a spoon at a height of 30 cm onto 3 layers of moistened absorbent paper (kitchen towels). For moistening, 10 ml of tap water was dispersed on a surface of 25x35 cm. The soft and moistened towels served as a soil mimic.
Results
As can be seen in Figure 2, the calcium carbonate beads bounced away from the center where they hit the towels, and the beads were found to scatter over a substantial area. In contrast, the clay granules formed a pile at the center where they hit the towels.
From these results, it can be concluded that the calcium carbonate beads according to the invention scatter over a wide area when dropped on a surface, in contrast to clay particles.

Claims

1. A composition comprising calcium carbonate beads and one or more active ingredients selected from the group consisting of a plant protection agent and/or a plant nutrition product.
2. Composition according to claim 1, wherein the plant protection agent and/or plant nutrition product is absorbed onto or in the calcium carbonate beads or adsorbed onto the calcium carbonate beads.
3. Composition according to claim 1 or claim 2, wherein the one or more active ingredients comprise a plant protection agent selected from a biocontrol agent such as a microorganism, a plant extract, and/or a natural or synthesized compound.
4. Composition according to claim 3, wherein the microorganism comprises at least one of Trichoderma species, Ampelomyces species, Coniothyrium species, Paecilomyces species, Talaromyces species,
Gliocladium species, Bacillus species and/or Pseudomonas species, and/or spores thereof.
5. Composition according to any one of claims 1-4, wherein the one or more active ingredients comprise a plant nutrition product, preferably a biostimulant.
6. Composition according to any one of claims 1-5, wherein the composition further comprises a binder, a spreader and/or a surfactant.
7. Mixture of at least two compositions according to any one of claims
1-6, wherein the active ingredient differs between said at least two compositions.
8. A method of protecting an agricultural product or substrate, comprising
a) providing the composition according to any one of claims 1-6, or the mixture according to claim 7, and
b) contacting the agricultural product or substrate with the composition.
9. The method according to claim 8, wherein the agricultural product is an edible product, selected from a plant or part of a plant, preferably a seed, a vegetable, a processed food or feed product, a fruit and/or a leaf.
10. The method according to claim 8, wherein the substrate is soil.
11. Method according to any one of claims 8-10, wherein the
composition is applied, calculated by dry weight of the composition, in an amount of 0.2-250 kg/ha, preferably in an amount of 1-20 kg/ha.
12. Method for protecting a plant or plant part against biotic stress which method comprises providing the composition according to any one of claims 1-6, or the mixture according to claim 7, and contacting the plant or plant part with the composition or mixture, wherein the active ingredient of the composition is a plant protection agent.
13. Method for preventing the development of a pathogenic
microorganism in and/or on a plant, plant part or substrate, comprising a) providing the composition according to any one of claims 1-6, or the mixture according to claim 7,
wherein the active ingredient is a plant protection agent; and
b) adding the composition to the plant, plant part or substrate.
14. Method for preventing, reducing and/or eliminating poor edaphic conditions of a plant or substrate, comprising
a) providing the composition according to any one of claims 1-6, or the mixture according to claim 7,
wherein the active ingredient is a plant nutrition product; and
b) adding the composition to the plant or substrate.
15. Use of a composition according to any one of claims 1-6, or the mixture according to claim 7, for preventing, reducing and/or eliminating the presence of weeds, pathogenic microorganisms, especially fungi, insects and/or nematodes, in or on a plant, plant part or substrate.
PCT/NL2015/050561 2014-08-01 2015-08-03 Calcium carbonate beads as carrier for plant protection agents and/or nutrition products WO2016018155A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109717679A (en) * 2019-02-20 2019-05-07 安徽笄山生态农业有限公司 A kind of product display shelf for the ecological agriculture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056299A2 (en) * 2005-11-04 2007-05-18 The Anderson's Agriservices, Inc. Pesticide delivery granule
WO2008001946A2 (en) * 2006-06-29 2008-01-03 Sumitomo Chemical Company, Limited Pesticidal composition comprising tetrafluorobenzyl cyclopropane carboxylates
WO2009060012A2 (en) * 2007-11-06 2009-05-14 Basf Se Plant health compositions comprising a beneficial microorganism and a pesticide
US20090263437A1 (en) * 2008-04-16 2009-10-22 Talmor Giora Pesticide compositions
US20110174898A1 (en) * 2008-06-25 2011-07-21 Sbm Developpement Method for controlling soil insects
US20110223228A1 (en) * 2009-09-16 2011-09-15 Eric Pipkin Repellant for Ground Rooting Animals

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056299A2 (en) * 2005-11-04 2007-05-18 The Anderson's Agriservices, Inc. Pesticide delivery granule
WO2008001946A2 (en) * 2006-06-29 2008-01-03 Sumitomo Chemical Company, Limited Pesticidal composition comprising tetrafluorobenzyl cyclopropane carboxylates
WO2009060012A2 (en) * 2007-11-06 2009-05-14 Basf Se Plant health compositions comprising a beneficial microorganism and a pesticide
US20090263437A1 (en) * 2008-04-16 2009-10-22 Talmor Giora Pesticide compositions
US20110174898A1 (en) * 2008-06-25 2011-07-21 Sbm Developpement Method for controlling soil insects
US20110223228A1 (en) * 2009-09-16 2011-09-15 Eric Pipkin Repellant for Ground Rooting Animals

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"ACTINA (TM) Reducing water hardness with pellet softening", 1 December 2013 (2013-12-01), Saint-Maurice Cedex, pages 1 - 4, XP055227791, Retrieved from the Internet <URL:http://technomaps.veoliawatertechnologies.com/processes/lib/pdfs/2751,Brochure_Actina_VWS_ENG_LR_Draft_v0.pdf> [retrieved on 20151111] *
STONE ET AL.: "Acid Sulfate Soils Manual", 1998

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109717679A (en) * 2019-02-20 2019-05-07 安徽笄山生态农业有限公司 A kind of product display shelf for the ecological agriculture
CN109717679B (en) * 2019-02-20 2020-07-03 安徽笄山生态农业有限公司 A product show shelf for ecological agriculture

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