NEMATOCIDAL AND INSECTICIDAL COMPOSITION AND METHOD FOR THE CONTROL OF THE SAID PESTS

Abstract: Granules for the control of nematodes and soil dwelling pests which contain in total, 0.1-20% by weight of a hydro­ gen carbonate (I) of the formula MHCO₃ and/or a carbonate (II) of the formula (M) n CO₃ (wherein M is a mono- or divalent metal ion or an ammonium group and n is 1 or 2) and an or­ ganic acid (the weight ratio of the hydrogen carbonate (I) and/or the carbonate (II) to the organic acid being 1:10 - 10:1), in admixture with one or more organic or inorganic carriers. An insecticidal-nematocidal compound may also be included. The granules may be applied at a level of 1-100 hydrogen carbonate and/or carbonate and organic acid may be provided in one type of granule and the insecticidal-­ nematocidal compound in another type of granule, the two types of granule being mixed on site.

Description: Nematocidal and insecticidal composition and method for the control of the said pests This invention relates to a composition and method for the control of netuatoaes and soil dwelling insects. More particularly it is directed to a nematocidal and insecticidal composition based on attractant effect. The composition of the present invention can be used per se or in combination with soil disinfectants. It is known that nematodes and terricolous pests of cultivated plants can be controlled with so-called general or total soil disinfectants (fumigants) and insecticides and insecticides-neniatocides, respectively of the known compositions the general or total soil disinfectants exhibit the highest biological activity, eg. methyl bromide, carbon disulfide, methyl isocyanate (Di-tropex), 1,3-dichloro-propene + 1,2dichloro-propane (Shell DD), Dazomet (tetrahydro-3,5 dimethyl-1,3,5-thiadiazin-2-thiore; Basinid)° Although the known fumigants possess high biological activity, they also possess several properties which restrict their application. For this reason the said known fumigants can be practically used only under greenhouse, tree and vine nursery conditions. However, nematode and terricolous insect pests endanger agricultural and horticultural plants cultivated on overland as well (e.g. Heterodera, Meloidogyna, Xyphynoma, Longidorus, Agroites sp,, Melolontha sp. larva on grape, fruits, vegetables, ornamental plants etc.), The said pests can be controlled by phosphoric acid ester and carbamate derivatives having insecticidal and insecticidal-nematocidal activity, respectively. The said compositions may be formulated in the form of granules (G), emulsifiable liquid concentrates (EC), aqueous suspensions (FW), wettable powders (WP), preferably granules (G). The following compositions are the most well-known: 1. Chinufur 10 G (carbofuran: 2,3-dihydro-2,2-dimethyl- 7-benzofuranyl-N-methyl-carbamate) 2. Furadan 10 G (carbofuran) 3. Furadan 4 F (carbofuran) 4. Vydate 10 G (Oxamyl: -methyl-N', N'-dimethyl-N- /methylcarbamoyloxy/-l-thio-oxamimidate) 5. Teinik 15 G aIdicarb: 2-methyl-2-methylthio-propion aldehyde-O-(methyl-carbonyl)-oxime] 6. Thimet 10 G [phorat: 0,0-diethyl-S-(ethylthiomethyl)- phosphorodithioate] 7. Mocap 10 G [etoprop: 0-ethyl-S,S-dipropyl-phosphoro- dithioate) 8. Counter 15 G [terbuphos: S-(/1,1-dimethyl-ethyl/-thio- methyl-O,O-diethyl-phosphorodithioate] 9. Nemacur 15 G (phenaminphos: ethyl-4-methylthio-m tolyl-isopropyl-phosphoramidate) 10. Hasudin (diazinon: 0,0-diethyl-0-2-isopropyl-6 methyl-pyrimidine-4-yl-phosphorothioate) 11. Ekalux (quinalphos: 0 ,0-dietWyl-0-quinoxalyl-2- yl-phosphorothioate) According to the known pest control methods granules are applied to the soil before or during sowing. The active ingredient gets into the soil from the granules by desorption and the toxic (poison) zone formed in the vicinity of the granules contains a lethal amount of active ingredient. In the case of contact pesticides (e.g. diazinon) the killing effect is exerted by contact between the active ingredient and the pest. Systemic compositions exett their killing effect either by contact (as dernal poison) or by absorption in the roots of the host plant; in the latter case the active ingredient gets into the organism of the pest sooner or later with the foodstuff and acts as gastric poison. Certain active ingredients - e-,g. phorat, etoprop - exhibit in addition to an excellent systemic activity a significant "as effect" by exerting their toxi effect against soil dwelling insects in gaseous phase. The vapour pressures (v.p.) of some significant fumigant and insecticidal fumigant granules are summarised in the following Table. FUMIGANTS v.p. C A. carbon disulfide 357.1 Hgmm 25,0 Ethylene bromide 1131 IIgmm 25,0 1,2-Dichloro-propane 210.0 Hgmm 19.0 Shell DD 35.0 Hgmm 20.0 Methyl isocyanate 20.7 Hgmm 20.0 INSECTICIDAL-NEMATOCIDAL granules B. Carbofuran 2 x 10-5 Hgmm 33.0 Oxamil 2,3 x 10-4 Hgmm 25.0 Diva zion 1.4 x 10-4 Hgmm 20,0 Etoprop 3.5 x 10-4 Hgmm 26.0 Phorat 8.4 x 10-4 Hgmm 20.0 Thus the v.p. of the active ingredients of insecticidal-neeatocidal granules are from six to nine orders of magnitude lower than those of fumigants In group B, on the basis of the v.p. propertis, carbofuran shows the lowest and phorat the highest value. For this reason the pesticidal effect of phorat having a "high" v.p. value is not so strongly dependent on the incidental meeting of the active ingredient and the pest. The efficiency of both contact and systemic insecticides is fundamentally influenced by the physico chemical properties of the soil, the desorption characteristics of the active ingredient and the formulation, the localization of the pests in the soil, the stage of development of the pest (egg, larva, nymph, developed organism); it is also relevant whether the pest is in a state of dormancy (anabiosis, diapausa) or has already passed this stage. The high efficiency of treatment carried out in springtime on the complete area or in the rows is ensured by the following factors: - attractant effect of the plants: - "sensitivity" and active vital functions of the pests: - simultaneous presence of the pest and the 1,toxic zone" (or poison strip ) in the case of row treat ment) in the same soil. In the searching for sources of foodstuffs, the substsnces secreted by the vital functions of the roots of the plants (e.g. carbon dioxide, organic acids, amino acids etc) exhibit an attractant effect on the soil dwelling pests. A large number of pests (nematodes, terricolous insect pests) respond to the attractant effect of carbon dioxide and thus their movement becomes automatic. The "wheat luring forecast method of Manniger (Bognár-Huzián: Növényvédelmi #llattan, Mez#gazdadági Könyvkiadó, 1974; Benedek-Surján-Fésüs: Növényvédelmi El#rejelzés, Mez#gazdadági Kiadó, 1974) is based on the attractant effect of carbon dioxide produced by the roots of germinating wheat. The said attractant effect enables the forecast of wireworms and grubs and the prediction of the risk of damage. According to Balachowsky (Entomologie appliqued, Paris, Masson et Cie, 1963) the larvae of the insect Ortiorrhynchus ovatus perceive the delivery of carbon dioxide at a distance of 10 cm and a change of the carbon dioxide concentration assists the larvae in the search for roots. The present invention is based on the recognition that the efficiency of compositions for the control of nematodes and soil dwelling pests can be increased by using a stimulus (carbon dioxide evolution) which affects and preferably directs the seeking of foodstuff and the direction of movement. The said effect is particularly enhanced if active ingredients having a low vapour pressure (e.g. carbofuran, oxamil) are used for the control of soil dwelling pests and nematodes. According to a further aspect of the present invention certain nematode species can be controlled by using carbon dioxide stimulus without adding a nematocidal active ingredient; this is based on the recognition that infecting larvae can survive without foodstuff (host plant) for a short time only. The invention thus provides a composition for the control of nematodes and soil dwelling pests which comprises a hydrogen carbonate and/or carbonate and an organic acid, together with one or more solid carriers and optionally an insecticidal-nematocidal compound, the hydrogen carbonate and/or carbonate and the organic acid being present in amounts such that the composition evolves carbon dioxide after application in the presence of moisture. In particular the invention provides granules for the control of nematodes and soil dwelling pests which comprise 0-50% by weight an insecticidal-nematocidal compound and a total amount of 0.1-20% by weight preferably 5-10 % by weight-of a hydrogen carbonate (I) of the formula MHCO3 and/or a carbonate (II) of the formula (M)nCO3 (wherein M is a mono- or divalent metal ion or an ammonium group and n is 1 or 2) and an organic acid; the weight ratio of the hydrogen carbonate (I) and/or the carbonate (II) to the organic acid being 1:10 - 10:1 - preferably 3:1 - 1:3; in admixture with solid organic or inorganic carriers and optionally further auxiliary agents, such as hydrophobic silicic acid, sodium aluminium silicate, polyvinyl-pyrrolidonepolyvinyl acetate copolymer, magnesium sterate and oils of animal, vegetable or mineral origin. When an insecticidal-nematocidal compoun is used, it can be provided either in the same granules as the other ingredients or in separate granules for on site mixing. The composition is generally applied at a rate of 1-100 (preferably 20-50) kg/ha. As hydrogen carbonate of the general Foi-mula I preferably sodium, ammonium or potassium hydrogen carbonate - particularly potassium bicarbonate - can be used. As carbonate of the general Formula II preferably calcium carbonate can be used. Fron the group of organic acids for the present invention those organic acids are preferable which have a dissociation equilibrum constant between 10-5 and 10 2, e.g. citric acid, tartaric acid, oxalic acid, ascorbic acid, succinic acid, butyric acid, maleic acid, salicylic acid, particularly citric acid and succinic acid. The salts thus formed can be easily adsorbed as a result of their good water-solubility. Sunflower oil is preferably used as an oil additive. The compositions of the present invention can be produced by preparing a homogeneous mixture from the organic acid (e.. citric acid) and the hydrogen carbonate of the general Formula I (e.g. potassium bicarbonate) and/or carbonate of the general Formula II (e.g. calcium carbonate) in a conventional mixer and applying the premix thus obtained onto an organic or inorganic carrier - preferably onto a carrier of vegetable origin or synthetic - optio nally in the presence of an auxiliary agent. As inorganic carrier quartz sand, dlatomaeous earth or ground limestone can for example be used. As organic carrier Fugran (a carrier prepared fromily-drolysed agricultural waste materials, see DOS TO. 2,655,398) or agricultural grist can for example be used. As insecticidal-rtematocidal compound the products listed above or Chinufur 5 and 10 G, Wydate 10 G, Temik 10 G and DTemacur can for example be used. The pre-mix can also contain a water-repellant agent, such as colloidal silicic acid or hydrophobic sodium-silico aluminate (e.g. HDK H 15 , HDK H 20, HDK H 30, HDK H 2000 and HDK H 2 F manufactured by 'Macker,or Aerosil R 972 or advantageously Aerosil R 972 produced by Degussa). The composition of the present invention can further contain hydrophobic auxiliary agents and know film-forming'agents and adhesives (e.g. polivinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, carbomethoxy cellulose magnesium stearate, sugar, gelatine, resins of natural origin etc) which ensure the stability of the composition during storage, Thus during storage carbon dioxide is not evolved or only to a small extent, but is liberated gradually in use, under the effect of the natural humiditv of the soil. The desired desorption-velocity can be adjusted by appropriate modification of the ratio of the components and thus nematocidal granules having different durations of effect can be obtained. The following effects and activities are demonstrated by laboratory, small-scale and industrial scale field experiments. 1) The granules of the present invention comprising a hydrogen carbonate and/or carbonate and an organic acid evolve carbon dioxide and exhibit biological activity (attractant effect). 2) The nematocidal effect is exhibited by simulating (feigning) the carbon dioxide production of the roots of the plants. 3) The activity of the insecticidal-nematocidal compositions - preferably granules - is increased by the attractant effect of carbon dioxide. 4) By using the combination of the present invention the amount of active ingredient applied onto a unit of area can be decreased without any loss of activity. The components used in the composition must meet the following requirements: 1) They do not adversely effect in the applied doses the physico-chemical characteristics of the soil. 2) They do not effect the physiological properties, germination and further growth of the plants in an adverse manner. 3) The substances which are formed during the reaction of the components beside the carbon dioxide comply with the conditions under 1 and 2. 4) They can be formulated with insecticides and nematocides (granules). 5) The composition can be applied onto the soil by usual methods (adapter). 6) Their toxicity is low. Further details of the present invention are to be found in the following Examples without limiting the scope of protection to the said Examples. The biological activity is also demonstrated in the Examples. Example 1 4.84 parts by weight of citric acid and 0.04 parts by weight of Aerosil 972 R are admixed in a slowly moving homogenizer, whereupon 14.64 parts by weight of potassium hydrogen carbonate are added. The pre-mix thus obtained is subjected to dry homogenization with 174.6 parts by weight of granules (Fugran) in a rolling drum. In a separate apparatus 6 parts by weight of a co-polymer of polivinyl pyrrolidone and polivinyl acetate (Luviskol VA 64:, film forming agent) are dissolved in 40 parts by weight of dichloro methane. The solution thus obtained is sprayed onto the homogenized granules. After drying 200.12 parts by weight of granules are obtained, particle size 0.2-1.0 mm. Example 2 One proceeds according to Example 1 except that in the place of Fugran 174.6 g. parts by weight of Chinufur 10 G are weighed in. Thus 200.12 parts by weight of granules are obtained which contain 20.0 parts by weight of carbofuran. (The Chinufur 10 G is a composition comprising 10 % by weight of carbofuran on Fugran carrier). Example 3 4*84 g. citric acid are admixed 0.03 part by weight of rosol R 972 and the mixture is homogenized with a mixture of 14.64 parts by weight of potassium hydrogen carbonate and 0.03 part by weight of Aerosil R 972. The pre-mix thus obtained is subjected to dry homogenization with 149 parts by weight of granules (Fugran). A solution of 10 parts by weight of carbofuran and 22 parts by weight of dimethyl formamide is sprayed onto the pre-homogenized granules. Thus 200,64 parts by weight of granules are obtained which contain 10 parts by weight of carbofuran, Examples 4-10. The process according to Example 3 is carried out except that the following components are admixed: Example 4 Component Amount, parts by weight tartaric acid 4.84 Potassium hydrogen carbonate 14.64 Aerosil R 972 0.04 Carbofuran 10.00 Dimethyl formamide 22.00 Fugran 149.00 Example 5 Component Amount, parts by weight tartaric acid 4.84 Potassium hydrogen carbonate 14,64 Aerosil R 972 0.04 Suviskal VA 64 6.00 Fugran 174.60 Example 6 Component Amount, parts by weight Tartaric acid 4.84 Potassium hydrogen carbonate 14,64 Aerosil R 972 0.04 Luviskal VA 64 6.00 Carbofuran 20.90 Fugran 153.70 Example 7 Component Amount, parts by weight Citric acid 4,84 Potassium hydrogen carbonate 14.64 Aerosil R 972 0.06 Quinalphos 10.30 Fugran 171.00 Example 8 Component Amount, parts by weight Citric acid 4.84 Potassium hydrogen carbonate 14.o4 Aerosil R 972 0.06 Quinalphos 10.30 Fugran 171.00 Example 9 Component Amount, parts by weight Citric acid 4.84 Pctassium hydrogen carbonate 14.04 Aerosil R 972 0.06 Prophos (etotrop) 20.60 Fugran 171.00 Example 10 Component Amount, parts by weight Tartaric acid 4.81 Potassium hydrogen carbonate 14.04 Aerosil R 972 0.06 Prophos (etoprop) 20.60 Fugran 171.00 Example 11 A mixture of 0.52 part by weight of paraffin oil and 0.13 part by weight of Triton x-45 is applied onto quartz sand. The pre-moistened quartz sand is llomogenized with a homogenized prefix of 2.7 parts by weight of citric acid, 3.63 parts by weight of potassium hydrogen carbonate and 0 015 part by weight of Aerosil R 972 in a rolling drum. A solution of 0.91 part by weight of magnesium stearate, 4.09 parts b weight of paraffin oil and 10 parts by weight of dichloro methane is sprayed onto the homogenized granules. After drying the granules are coated with with a solution of 3.0 parts by weight of Luviskol VA and 10.5 parts by weight of dichloro methane and the dichloro methane is evaporated. Thus 49.99 parts by weight of granules are obtained. Example 12 2.7 parts by weight of citric acid are admixed with 0,015 part by weight of Aerosil R 972 in a slowly moving homogenizer whereupon 3.63 parts by weight of potassium hydrogen carbonate are added* The pre-mix is subjected to dry homogenization with 42.2 parts by weight of Temik 10 G granules in a rolling drum, The granules are coated with a solution of 1.5 pats by weight of Luviskol VA 64 and 10 parts by weight of dichloro methane. After drying 50.0 parts by weight of granules are obtained, aldicarb content 8.4 b by weight. Example 13 2.7 parts by weight of citric acid are admixed with 0.015 part by weight of Aerosil R 972 in a slowly moving homogenizer whereupon 3.63 parts by weight of potassium hydrogen carbonate are added. The pre-mix thus obtained is subjected to dry homogenization with 42.2 parts by weight of Nemacur 10 G granules in a rolling drum. The granules are coated with a solution of 1.5 parts by weight of Luviskol VA 64 and 10 parts by weight of dichloro methane. After drying 50,0 parts by weight of granules are obtained, phenamiphos content 8.4 %. Example 14 2.7 parts by weight of citric acid and 0,015 part by weight of Aerosil R 972 are admixed in a slowly moving homogenizer, whereupon 3.63 parts by weight of potassium bicarbonate are added. The pre-mix thus obtained is subjected to dry homogenization with 42.2 parts by weight of Vydate 10 G granules in a rolling drum. The granules are coated with a solution of 1.5 parts by weight of Luviskol VA 64 and 10 parts by weight of dichloro methane. After drying 50.045 parts b weight of granules are obtained, oxamin content 8.4 %. Example 15 The contact toxicity of the components of the composition of the present invention is tested on chemorabditis elegans and Meloidogyne incognita nematode species. Description of the test: The substances and combinations tested are added in the given amounts to agar in which the test animals are raised (see tests 1-7), As test organism chemorabditis elegans and Meloidogne incognita infective larves obtained from eggs are used; 25 organisms per plate (Tetri-dish) are applied, The effect is evaluated 24 hours after the animals are placard on the plate and the number of organisms killed during the test is determined as well. The results are expressed as the percentage of the starting organism number (Table I). These date mean the percentage of the killed nematodes, 4 replicates are carried out. The ratio of the components of the combina tions is given below: 1. Carbofuran : tartaric acid = 2.06 : 1 2. Carbofuran : citric acid = 4.13 : 1 3. Carbofuran : KHC03 .1,38 : 1 4. Carbofuran : tartaric acid : KHC03= 2.06 : 1 : 3 5, Carbofuran : citric acid : KHCO3 = 4.13 : 1 : 3 6. Tartaric Acid : KHCO3 = 1 : 3 7. Citric acid : KHCO3 = 1 : 3. Table I Tested components M o r t a 1 i t y (%) ( g./ml.) Chenorabditid E. Meloidogynes 1 l 10 100 1000 1 10 100 1000 1. Carbofuran 5.0 7.5 95.0 100.0 0 10 27.5 85,0 2. Fugran 2.5 2.5 0,0 0.0 2,8 0.0 0.0 0,0 3. Tartaric acid 2.5 1.0 0.0 0.0 0,0 2.5 2.5 0.0 4. Citric acid 0.0 0.0 0.0 0.0 0.0 2.8 0.0 0.0 5. KHCO3 0.0 5.0 0.0 0.0 0.0 2.5 0.0 0.0 6. Carbofuran + 0.0 5.0 23.0 100.0 2.7 2.5 2.5 27. tartaric acid 7. Carbofuran + 8 citric acid 0.0 12.5 30.0 100.0 0.0 2.8 10.5 35.0 8. Carbofuran + KHCO3 5.0 7.5 20.0 100.0 0.0 2.6 15.0 30.0 9. Tartaric Acid + 2.5 2.5 0.0 5.0 0.0 0.0 0.0 0.0 KHCO3 10. Citric acid + 0.0 0.0 2.5 0.0 0.0 0.0 0.0 KHCO3 0.0 0.0 2.5 0.0 0.0 0.0 0.0 0.0 11. Carbofuran + citric acid + 0.0 2.5 25.0 0.0 4.0 0.0 38.5 KHC03 12. Carbofuran + tartaric acid 2.5 5.0 10.0 100.0 0,0 0,0 10,0 27,5 +KHCO3 She object of the test is to determine the biological efficiency of the components of the compositions of the present invention per se and in combinations in concentrations of 1, 10, 100 and 1000 ppm., respectively. The data obtained in the Petri-dish experiments illustrate the contact tonicity of the components and combinations thereof. Treatments Nos. 1-5 show unambiguousla that the "additives" per se are completely inactive as contact poison (nematocide). These components are Fugran carrier, tartaric acid, citric acid, KHCO3. In the double and triple combinations the efficiency of the individual treatments (contact toxicity) does not increase as compared to the pure active ingredient (Carbofuran) in the concentrations used, Example 16 Effect on Meloidogyne incognita Description of the test Cultivating plates (diameter 12 cm,) are filled with soil strongly infected by root gall threadworm (Meloidog.yne incognita). The weighed granules are applied into the soil placed in the plate: (on the complete surface, at a depth of 4 cm,). As test plant stiff stemed tomato (species Recskemét) is used. The seedlings are cultured under sterile conditions on a perlite medium until 9 weeks' age; there was no Meloidogne incognita infection during the first treatment. The plants are grown at an air temperature of 22-24 0C for 6 weeks until the safe growth of the Meloidogyne incognita generation. The sol is washed off from the roots and the number of galls' on each plant is determined, The efficiency of the treatments is calculated by means of the ABBOT formula. The tess are carried out by using the composition according to Example 1. The ABBOT formula is the following: Efficiency = 100 x treated mortality % - untreated 100 - untreated mortality % mortality % 100 - untreated mortality %3 The results are summarized in Table II. Table II Dose Sown tomato Transplanted tomato Treatment kg./ha. average No. Activity Average No. Activity of galls pro related to of galls pro related to plant control, % plant control, % 10 days before sowing and planting 1. Citric acid + KHCO3 20 6.1 27.4 6.0 52.0 granules 40 0.4 95.2 2.0 84.0 2. Citric acid + KHCO3 40 0.4 95.2 2.0 84.0 granules 3. Chinufur 10 G (10 % by weight of 20 1.6 80.95 3.5 72.0 carbofuran) 4. Chinufur 10 G (10 % by weigth of 40 0.9 89.3 2.0 84.0 carbofuran) 5. Control - 8.1 - 12.5 Simultaneously with sowing and planting 1. Citric acid + KHCO3 20 1.7 94.4 7.5 66.3 granules 2. Citric acid + KHCO3 40 4.1 86.4 5.25 76.4 granules 3. Chinufur 10 G (10 % by weight of 20 7.8 74.4 6.5 70.8 carbofuran) 4. Chinufur 10 G (10 % by weigth of 40 0.2 99.9 3.0 86.5 carbofuran) 5. Control - 30.1 - 22.3 - Example 17 Test carried out in a growth dish 2 stage (invasion) larves of Meloidogyne in cognita threadworm are added to soil in pots having a diameter of 12 cm.; 100 larves are applied into each pot. The test granules are applied into the root zone of tomato seedlings (three weeks old, Kecskemét species) just before the planting of the seedlings. Thirty days after planting the test plants are removed from the pots and their roots are made free from soil with running water. The evaluation is carried out by determining the number of galls (diameter 3-5 mm.) on the roots of the plants. The efficiency is related to the untreated control and calculated with the aid of the ABBOT formula. The number of replicates is } (in each replicate 10 plants are used; thus each data is the result of 40 measurements. Table III Treatment Dose Average No. Efficiency kg./ha. of galls pro plant (AEBOT) 1. Chinufur 10 G 30 1.75 84.9 2. Composition accord- 30 3.25 70.5 ing to Example 1 3. Chinufur 10 G + citric acidm KHCO3 30 0.00 100.0 composition accod- ing to Example 2 Table III (continued) Treatment Dose Average No. Efficiency kg./ha. of galls pro plant (ABBOT) 4. 5 V carbofuran + citric acid, KHC03 30 0.50 95.46 composition accord ing to Example 3 5. 5 % carbofuran + tartaric acid, KEiCO3 30 0.00 100.0 composition accord ing to Example 4 6. Control - 11.0 Tests carried out in a laboratory growth dish In this test the effect of compositions comprising with or without carbofuran is evaluated. The medium (soil) into which the granules are applied enable - the formation of point-like sources of stimulus, - the formation of concentration gradient, According to the test results the granules containing no carbofuran exhibit significant effect on the basis of tha dose dependence both when sown together with the seeds of the tomato test plant and when applied into the dishes 10 days before the sowing of the sterile seedlings. The effect of the combinations comprising carbofuran is striking already when comparing the 10 G formulations but the surplus effect of the compositions of the present invention manifests itself particularly when 5 G formulations are used. Example 18 Activity against Heterodora sachti Description of the test The test is carried out in a "cs'ernozjom son having an organic substance content of 2.1 %. Sugarbeet (species Monopoli N 1) 15 sown in a depth of 4 cm. on the 10th April, the germ rumber is 95.000 95,000/stem/ha. Treatments are carried out simultaneously with sowing by means of an adapter mounted on a Ran Exacta sowing machine, the rows are treated. The average number of Heterodora sachti vesicles amounts to 12.3 pro 100 g. soil. The following characteristic data are measured: 1) Heterodora sachti infection index and efficiency of the treatment. 2) Infectedness of the plants on the 24th July. 3) Number of vesicles in 100 g. of soil, on the 24th July. The results are summarized in Table IV. Table IV Treatment Dose Infection index Efficiency, No. of vesicles kg./ha. of the plants, on July 24 on July 24 on July 24 1. 10 % carbofuran 20 0.22 56.86 9.0 (Chinufur 10 G) 2. 10 % carbofuran + citric acid +KHCO3 20 0.09 82.35 3.2 3. 5 % carbofuran + tartaric acid +KHCO3 20 0.29 43.13 14.0 (composition according to Example 4) 4. Thimet 10 G 20 0.09 13.72 32.4 5. Control - 0.51 0.0 26.0 Under field condition8 the Heterodera sachti threadworm is the most dangerous nematode pest of sugar-beet. In our tests the compositions containing 5 % by weight of carbofuran + additive and 10 % by weight of carbofuran + additive, respectively are compared to the most widespreadly used known insecticidal-nematodidal granules. It has been found that the activity of the compositions of the present invention is superior to that of the known pesticides. The results obtained with the compositions of the present invention are better for all the measured characteristics than those of known compositions generally used for the control of soil dwelling pests of sugar-beet (Chinufur 10 G and particularly Thimer 10 G). Example 19 Tests carried out in vine nursery The tests are carried out in medium hard brown forest soil (Arany number 37-42; pH 7.5). Three replicates are made for each treatment. The granules are applied onto the surface of soil by means of a dense row sowing machine and the working into the soil is accomplished with the aid of a rigal-plow equipped with a pre-plough. The SHELL DD is applied in a dose of 1000 l./ha. by means of a special apparatus mounted on a rigal-plough. The survey. of the soil dwelling pests is carried out for each treatment and replicate by the usual survey and application methods (Baerman-type funnel application); three times of 100 g. of soil, each are used pro replicate. The efficiency against soil dwelling pests is calculated by means of the Schneider-Orelli formula, while the nematocidal activity is calculated with the aid of the Hendenson -Tilton formula, Schneider-Orelli formula Soil dwelling pests E = efficiency, % T-c = ##### x 100 T = larves killed during the treatment, % c = larves killed in the control, % Nematocidal effect with the Henderson-Tilton formula t xU Effect % = 1- 2 1 x 100 t1 x U2 tl - t2 = organism frequency of the treated area, before and after treatment U1- U2 = organism frequency of the control, before and after treatment The results are summarized in Table V. Table V Treatment Survey before treatment After treatment No. of worms, on 2.5 mê Efficiency, % wireworms grubs wireworms grubs 1. Chinufur 10 G 15.5 4 76.8 100.0 2. 5 % carbofuran + tartaric acid CO2 15.5 4 93.37 100.0 (composition according to Example 4) 3. 3 % carbofuran + citric acid CO2 14.0 4 70.65 100.0 (composition according to Example 3) 4. Shell DD 19.5 1 11.03 5. Control 19.0 3 0.0 0.0 1-3. 50-50 kg./ha. 4. 1000 l./ha., applied with a rigal-plough Table V (continued) Dose Number of nemathodes in 100 g. Efficiency, Treatment kg./ha./l. of soil % Before treatment after treatment 0-30 30-60 0-30 30-60 0-30 30-60 cm. cm. cm. cm. cm. cm. 1. Chinufur 10 G 50.0 347.3 381.8 45.5 47.6 85.2 89.1 2. Citric acid + KHCO3 (Example 1) 50.0 244.6 405.1 33.0 25.8 85.5 94.5 3. 5% by weight carbofuran + citric 50.0 257.8 271.1 17.0 11.5 92.9 96.3 acid + KHCO3 (Example 3) 4. 5 % carbofuran + tartaric acid + 50.0 191.0 246.0 33.3 46.6 81.3 83.5 KHCO3 (Example 4) 5. Shell DD 1000 142.6 160.0 18.3 18.6 86.2 89.9 6. Control - 265.8 211.0 247.3 242.3 - - The phytotoxicity is determined 3 days after soil ventillation according to the known mustard method. The results are summarized in Table VI, Table VI Results of phytotoxicity tests Dose Shooting so, in the soil Treatment kg./ha./l. sample 0-20 cm. 20-40 cm. 40-60 cm. 1, Chinufur 10 g 50 93 92 93 2. Citric acid + KHCO3 (Example 50 95 93 93 1) 3. 5 so by weight carbofuran + citric acid + 5 94 93 94 KHCO3 (Example 3) 4, 5 % by weight carbofuran + tartaric acid + 30 95 55 55 KHC03 (Example 4) 5, Shell DD 1000 35 31 35 6, Control - 95 96 96 The composition of the present invention having a lower active ingredient content give in a dose of fO kg./hae against wireworms and grubs/soil dwelling pests better results than Chinufur 10 G and the same results as Shell DD, respectively. Compositions containing. no active ingredient and the half amount of carbofuran , respectively show high efficiency against nematodes. The results are particularly striking if they are compared to those obtained with the fumigant Shell DD, The efficiency of treatments 2., 3. and 4. is identical with or better than, respectively that of Shell DD in various soil levels and at the same time there is no risk of phitotoxicity. Example 20 5.4 g, parts by weight of citric acid, 0.03 part by weight of Aerosil R-972 and 6.3 parts by weight of sodium bicarbonate are thoroughly admixed in a pug mill. 85.3 parts by weight of Chinufur 5 G are weighed in a roundbottomed flask and subjected to dry homogenization with the pre-mix prepared above. Finally 3.0 parts by weight of sunflower oil are applied onto the mixture and it is thoroughly admixed. 100.03 parts by weight of granules are obtained, carbofuran content 4.27 parts by weight. (The Chinufur 5 G is a composition comprising 5 % bey weight of carbofuran on a Fugran carrier). Example 21 84,3 parts by weight of Cninufur 5 G and 4 parts by weight of sunflower oil are admixed in a round- bottomed flask, whereupon 5.4 parts by weight of citric acid are added, the mixture is homogenised and 6.3 parts by weight of sodium bicarbonate are added. The mixture is coated with 0.03 part by weight of Aerosil R 972 under vigorous shaking. Thus 100.03 g. of granules are obtained, carbofuran content 4.22 parts by weight. Example 22 2.8 parts by weight of carbofuran (purity 90 %) are added to 5 parts by weight of dimethyl formamide and warmed until it is dissolved (at a temperature of about 50-55 C). The solution thus obtained is poured onto 34,3 parts by weight of fugran, stirred, whereupon 2.7 parts by weight of citric acid, 3.15 parts by weight of sodium bicarbonate, 2 parts by weight of sunflower oil and 0,05 part by weight of Aerosil R 972 are added. The mixture is vigorously stirred after the addition of each component. Thus 50.0 parts by weight of granules are obtained, carbofuran content 2.52 parts by weight. Example 23 A mixture of 2.8 parts by weight of carbofuran (purity 90 %) and 5.0 parts by weight of dimethyl formamide is heated to about 55 C. The solution is poured onto 3.55 parts by weight of Fugran, thoroughly admixed and the following components are added under stirring: 5.5 parts by weight of citric acid, 3.65 parts by weight of kalcium carbonate, 1.5 parts by weight of sunflower oil. Thus 50.0 parts by weight of granules containing carbofuran are obtained, Example 24 5.6 parts by weight of carbofuran (purity 90 are dissolved in 10 parts by weight of dimethyl formamide at a temperature of about 50-55 C. The solution is applied onto 64 parts by weight of Fugran and admixed, whereupon a pre-mix consisting of 11 parts by weight of citric acid and 0.1 part by weight of Aerosil R 972 is added under stirring. Finally 7.3 parts by weight of calcium carbonate and 2 parts by weight of sunflower oil are added, to yield 100 parts by weight of granules containing 5,04 parts by weight of carbofuran. Example 25 41.7 parts by weight of Chinufur 5 G are admixed with 3.15 parts by weight of oxalic acid whereupon 3.15 parts by weight of sodium bicarbonate and thereafter 1.0 parts by weight of sunflower oil are added under stirring and the mixture is homogenised. Thus 48 parts b weight of granules are obtained, carbofuran content 2,09 parts by weight. Example 26 39.85 parts by weight of Chinufur G are admixed with 5.5 parts by weight of citric acid, whereupon 3.65 parts by weight of calcium carbonate and there; after 1.0 part by weight of sunflower oil are added. After homogenisation 50 parts by weight of granules are obtained, containing 2 parts by weight of active ingredient. Example 27 A solution of 2.8 parts b weight of carbofuran (purity 90 %) formed with 5 parts by weight of di- methyl formamide is poured onto 31.05 parts by weight of fugran whereupon the following components are added under homogenisation: 5.5 parts by weight of citric acid, 2.0 parts by weight of sunflower oil and 3.65 parts by weight of calcium carbonate. Thus 50.0 parts by weight of granules' are obtained, carbofuran content 2.5 parts by weight. Example 28 5.5 parts by weight of citric acid are added to 31.05 parts by weight of Fugran whereupon a solution of 2.8 parts by weight of carbofuran (purity 90 %) and 5 parts by weight of dimethyl formamide, and thereafter 1.5 parts by weight of sunflower oil, 3.65 parts by weight of calcium carbonate and 0,5 part by weight of sunflower oil are added under stirring, Thus 50.0 parts by weight of granules are obtained, active ingredient content 2.5 parts by weight. Example 29 To 88 parts by weight of dimethyl formamide 28 parts by weight of carbofuran (90 % purity) and 55.0 parts by weight of citric acid are added at 55 0C. The mixture is poured onto 266 parts by weight of fugran under stirring whereupon 15 parts by weight of sunflower oil and 36.5 parts by weight of calcium carbonate '- are added and the mixture is coated with 5 parts by weight of sunflower oil. Thus 493.5 parts by weight of granules are obtained, carbofuran content 25.2 parts by weight. Example 30 In 61.0 parts by weight of dimethyl formamide 28 parts by weight of carbofuran (purity 90 %) and 20 parts by weight of oxalic acid are dissolved at 55 C whereupon the solution is poured onto 334 parts by weight of Fugran. The mixture is homogenised with 15 parts by weight of sunflower oil, 31.5 parts by weight of sodium bicarbonate are added and it is finally coated with 5 parts by weight of sunflower oil. Thus 494.5 parts by weight of granules are obtained, carbofuran content 25.2 parts by weight.

Claims: CLAIMS: 1. Granules for the control of nematodes and soil dwelling pests which contain, in total, 0.1-20% by weight of a hydrogen carbonate (I) of the formula MHCO3 and/or a carbonate (II) of the formula (M) nCO3 (wherein M is a mono- or divalent metal ion or an ammonium group and n is 1 or 2) and an organic acid (the weight ratio of the hydrogen carbonate (I) and/or the carbonate (II) to the organic acid being 1:10 - 10:1, in admixture with one or more solid organic or inorganic carriers. 2. Granules according to claim 1 which additionally contain up to 50% by weight of an insecticidal hematocidal compound. 3. Granules according to claim 2 comprising as insecticidal-nematocidal compound one or more of the following compounds: 2,3-dShydro-2,2-dimethyl-7-benzofuranyl-N-ethyl-carbamate 0,0-diethyl-0-quinoxalin-2-yl-phosphorothioate; 0-ethyl-S,S-dipropyl-phosphorodioate; S-methyl-N',N'-dinethyl-}-(methylcarbonyloxy)-l-thio- oxamimidate; O,O-diethyl-S-(ethylthiometilyl)-phosphorodithioate; 2-methyl-2-methylthio-propionaldehyde-0-(methyl carbamoyl )-oxime; ethyl-4-methylthio-m-tolyl-isopropyl-phosphorimidate; S-[(/1,1-dimethyl-ethyl/-thio)-methyl]-0,0-diethylphosphorodionate; 0,0-diethyl-0-(2-isopropyl)-6-methyl-pyrimidine-4-yl phosphorothioate a 4. Granules according to any preceding claim in which the bicarbonate (I) is sodium potassium or ammonium bicarbonate. 5. Granules according to any preceding claim in which the carbonate (II) is calcium carbonate. 6. Granules according to any preceding claim in which the organic acid has a dissociation equilibrum constant between 10-5 and 10-2. 7. Granules according to claim 5 in which the organic acid is citric acid, tartaric acid, oxalic acid, ascorbic acid, succinic acid, butyric acid, maleic acid or salicyclic acid. 8. Granules according to any preceding claim containing a total of 5-10% of the hydrogen carbonate and/or carbonate and the organic acid. 9. Granules according to any preceding claim in which the ratio of the hydrogen carbonate and/or carbonate to the organic acid is 3:1 - 1:3. 10. Granules according to any preceding claim which further contain hydrophobic silicic acid, sodium aluminium silicate, polyvinylpyrrolidone-polyvinylacetate copolymer, magnesium stearate, an animal, vegetable or mineral oil or other auxiliary agents. 11. A method for the control of nematodes and soil dwelling pests which comprises treating the surface to be protected with 1-100 kg/ha of granules as claimed in any one of the preceding claims. 12. A method according to claim 11 in which granules containing the hydrogen carbonate and/or carbonate and the organic acid are mixed on site with granules containing an insecticidal-nematocidal compound.

Inventors: ANGYAN, SANDOR, PETERDI, VIKTORIA, RACS, ISTVAN, RACZ, ISTVAN, SOS, JOZSEF
Applicants: CHINOIN GYOGYSZER ES VEGYESZETI TERMEKEK GYARA RT.
Application year: 1983
Main classification: A01N59
IPC codes: A01N25, A01N59, A01P7, A01N43