AU5718700A - Improvements in and relating to fertilisers - Google Patents

Description

WO 01/14285 PCT/NZOO/00I 11 IMPROVEMENTS IN AND RELATING TO FERTILISERS Technical Field This invention relates to improvements in and relating to fertilisers. More particularly, it relates to a method of, and compositions for, correcting soil pH and supplying nutrients to the soil, in accordance 5 with soil requirements, in a single application. Background Art Most soil is degraded. That is, because of nutrient loss caused by erosion, long periods of cultivation, building activities or simply poor inherent structure (for example, a clay or boggy soil), the soil 10 structure is commonly less than ideal for cultivation purposes and associated types of land use, for example: farming, planting, domestic lawns and gardens, and so on. Farmers and all users of fertilisers have numerous commercial products available to them that are known as conventional fertilisers. These consist of natural mined resources which are processed to form these products. Most of these commodities are subjected to losses when applied through 15 leaching or fixation. Most fertilisers are applied as solids. Problems that occur include: loss of fine particles (being blown away from the area where they want it applied); difficulty in drilling in damp conditions where they clog up the application machinery; and cleaning of equipment to continue application. A further important effect of fertiliser application is pollution of rivers, lakes, underground water and the sea, 20 seriously affecting the ecology. Mixtures of conventional fertilisers also have the problem of fixation, not only by the ingredients but also with the soil nutrients. Some of the materials are harmful to the soil itself and destroy humus as well as killing off the soil organisms, thus depleting the natural process that these organisms perform which maintain the fertility of soils. All these effects are expensive for a farmer to deal with. 25 Commercial fertilisers usually consist of the cheaper grades of mined products which are applied as a single application having one or a few more nutrients available when mixed together. The practice of adding trace elements as sulphates is impaired by the losses from leaching and immobilisation and the expense of adding complexes that contain polyvalent cations with the cation charge reduced to zero (chelates) is very expensive and subjected to huge losses from leaching. The cost to the farmer is WO 01/14285 PCT/NZOO/001 11 very high. Farmers plant seeds for crops that may firstly require a soil pH correction then apply a fertiliser that has a low nitrogen content and a high phosphate and potassium content, as well as a balance of the other nutrients. A commercial fertiliser needs to be applied separately to stop wasteful 5 immobilisation and to get the best nutrients for seed germination. Once the seed emerges from the ground, the shoots need to have more nitrogen in the balance of nutrients for the leaves to develop, so that photosynthesis will proceed at a maximum rate. Farmers normally apply a commercial nitrogenous fertiliser, without a balance of the other nutrients, which causes damage to the soil by loss of humus and is subjected to high leaching. Urea applied to 10 soil breaks down into ammonia, nitrates and nitrites. However, the nitrites are toxic and may cause death to stock feeding off pastures where it has been applied. Since the added nitrogenous fertiliser does not have a balance of the other nutrients, the crop is deprived, which results in impaired development. In the case of grazing pasture, this deprives the stock of the other balanced nutrients, causing metabolic diseases. The cost of a further application of 15 fertiliser and losses by leaching and fixation to the farmer is high. Some crops require the correct soil pH so that the root system is not infected by fungal development (for example a pineapple crop needs the soil pH to be below 5 to prevent fungal development leading to loss of the root system). Correcting this problem is expensive. Where a soil is acid, lime is usually applied. Lime, when mined, consists of calcium carbonate of 20 various grades of purity and exists as a solid mass that needs to be ground before being-applied on soils to correct acidity. The particle size is important, since the smaller the particle size the greater the surface area per unit volume, and thus the more easily of the material can pass into solution. Lime needs water to dissolve to begin its antacid action. Usually lime is applied by solid application, to lie on the ground surface to be washed into the soil by rainfall or by use of irrigation water. 25 Thus, lime is subjected to leaching and to immobilisation. Again, especially with crops where the pH or soil condition needs to be corrected before fertiliser is applied, the farmer is confronted with several preparation procedures of considerable cost. Using just lime is not the complete answer to correcting pH for the Base Saturation of the soil determines the soil pH. The ionic elements that determine the Base Saturation include: calcium, 30 magnesium, sodium and potassium cations. However, anions formed from acids or from fertiliser which is applied that break down to form acid also affect pH. 2 WO 01/14285 PCT/NZOO/001 11 The normal practice of applying lime and conventional fertilisers are all subjected to losses. The cation and anion holding ability of the soil is a function of the colloidal content of the soil and the amount of organic material present, which determines the Cation Exchange Capacity of that soil. Farmers are currently using more and more nitrogenous fertilisers to force the growth of pastures and 5 crops, at the expense of the soil fertility, as the fertiliser destroys humus. This is turn lowers the anion and cation carrying capacity of the soil and increases the losses through leaching. Alkaline soils that have a pH higher than 7 do not need lime. Instead they need acid-forming fertilisers to reduce the pH. Nitrogenous fertilisers are used for this task, and also elemental sulphur which, when acted upon by sulphonating bacteria in the soil, form sulphate, an acid radical which 10 lowers soil pH. With respect to the domestic situation, when new buildings are erected, the topsoil is removed to allow a solid foundation. After completion of the house only a thin layer of topsoil is replaced. The owner of the property has a problem with turning the resulting clay soil to workable fertile soil. When it rains the water collects in pools in the basins, where few plants can grow. The clay consists 15 of fine particles, causing muddy soil that dries out and becomes very hard. Nutrients needed for plants to grow are washed away and is difficult to dig. To correct these problems commercial products are prepared from bark, grinding it into coarse particles and mixing it with sand or pumice. However, the pH of this mix is approximately 5 which is very acid. To lift the pH by using commercial lime is not practicable, since large amounts would 20 need to be used and would be costly. The next problem found is that if the conventional fertilisers are applied, the large particle size means little is available and remains in the soil unused, while of the finer particles much is lost by leaching. Deserts exist in large areas throughout the world. To change deserts back to fertile land, water is needed and then lime is needed to raise the pH, and nutrients for a balance. Deserts consist of 25 comparatively large particles and in most cases have a high salt content, which means that the ground is not suitable for growing plants. The salt content needs to be washed out with water before fertiliser is applied. Deserts have very little organic matter present and little or no colloidal material. This is a condition which causes very high leaching of any commercially applied fertilisers. Immobilisation of the commercial fertilisers also takes place. Humus is virtually non-existent and needs to be added. 30 The expenses involved with growing pasture and crops in deserts, even when water is available, is very high and often uneconomic 3 WO 01/14285 PCT/NZOO/001 11 The leaching of fertilisers (especially conventional fertilisers) is a huge problem when the nutrients are leached down to a reservoir, causing contamination and the growth of harmful algae that produce toxic effects in the water. Hydroponics and the growing of flowers or other crops need to have corrections of pH of up to 5 several points quickly, and be supplied the balance of nutrients needed for growth to occur. The addition of the conventional fertilisers gives the grower many problems with fixation and leaching. It is the purpose of this invention to address these problems and offer alternatives. It is an object of the present invention to address the foregoing problems or at least to provide the public with a useful choice. 10 Further aspects and advantages of the present invention will become apparent from the ensuing description which is given by way of example only. Disclosure of Invention According to one aspect of the present invention there is provided a composition for application to a 15 substrate, said composition being a predetermined composition and pH, characterised in that said composition includes a protective material, which is selected from the group: a cellulose compound; a synthetic or a natural polymer; a carbohydrate compound; 20 an inorganic compound; and a combination of these; said protective material having clathratic properties and being further characterised in that: when said protective material is free of polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material is free of any 25 gel-forming property, but when polyvalent cations are introduced to the protective material in the presence of water, the protective material forms a gel that thickens; and further characterised in that: 4 WO 01/14285 PCT/NZOO/00 111 when said protective material includes polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material forms a gel that thickens. Thus, in the present invention polyvalent cations can be present in the protective material and/or in 5 the substrate. when water is added to protective material that has no polyvalent cations present, a gel only forms once the protective material is in contact with the substrate. If there are polyvalent cations present in the protective material, it can be added to water, a gel formed which can be shaped and worked. The resultant material can be dried, applied to the substrate and, in the presence of and water, forms a mucilaginous gel. 10 According to one aspect of the present invention there is provided a composition as described above in which the protective material is a carbohydrate compound and is selected from the monovalent alkali salts of carboxypolysaccharides. If the protective material includes a synthetic polymer, examples of such may include polyanionic polymers, such as sulphonated urea-melamine formaldehyde and urea-formaldehyde. 15 According to one aspect of the present invention there is provided a composition as described above in which the protective material is selected from: the sodium salt of 2-ethoxy-5-(2-hydroxyethoxymethyl)cellulose; the sodium salt of D mannuronic acid; sodium phthalate; 20 the sodium salt of carboxymethlycellulose; and a combination of these. According to one aspect of the present invention there is provided a composition as described above in which a mild acid is added to activate the protective material with or without in the presence of polyvalent cations. 25 According to one aspect of the present invention there is provided a composition as described above in which said polyvalent cations are selected from the salts of the group: boron, calcium, copper, iron, manganese, magnesium, cobalt, selenium, molybdenum, zinc, any other soluble or slightly soluble polyvalent salt and a combination of these. 5 WO 01/14285 PCT/NZOO/001 11 According to one aspect of the present invention there is provided a composition as described above in which said composition further includes enteric coating substances. The enteric coating substances are optionally selected from the group of carbohydrate based material and or any of the group of polymers: fats, fatty acids, waxes, wax mixtures, shellac, ammoniated shellac, cellulose acetate 5 phthalates, the sodium salt of carboxypolysaccharide; and a combination of these. Such substances can be used to effect a time span composition, releasing the contents of the composition at a pre-determined time. According to one aspect of the present invention there is provided a composition as described above in which said composition further includes a compound additive selected from the group: a nutrient, 10 an enzyme, a medication, a biological organism; and a combination of these compounds. Optionally said additive is incorporated into the enteric coating and or a combination of protective material as a separate pill with or without enteric coating(s). According to one aspect of the present invention there is provided a composition as described above in which said enteric coating is further characterised in having clathratic properties, and forming a gel 15 on contact with polyvalent cations and water or gels formed by mild acid. According to another aspect of the present invention there is provided a method of manufacturing a composition for application to a substrate, said method including the steps of: (a) selecting the substance(s) for addition to said substrate; (b) selecting the protective material (as described above); and 20 (c) forming a homogenous mixture of the substance and the protective material (to form the predetermined composition). According to another aspect of the present invention there is provided a method of manufacturing a composition for application to a substrate substantially as described above, wherein said method further includes the steps 25 (d) adding water sufficient to form a dough with the mixture from step (c); (e) extruding the dough to pre-selected size and shape tablets; and (f) drying the tablets. 6 WO 01/14285 PCT/NZOO/001 11 According to another aspect of the present invention there is provided a method of manufacturing a composition for application to a substrate as described above in which the method includes, after step (b), the step of selecting and adding an inert substance to the mixture. Optionally, the inert substance is bentonite or other material which expands slightly on mixing with water. 5 According to another aspect of the present invention there is provided a method of manufacturing a composition for application to a substrate as described above in which the method includes, after step (f) or step (e), the step of (g) coating the tablets with an enteric coating, as described above. These may be further dried. This step (g) may be repeated. 10 According to another aspect of the present invention there is provided a method of manufacturing a composition for application to a substrate as described above in which said composition is soluble in water and free of polyvalent cations, and the substance for addition to the substrate is a mixture of soluble monovalent cationic compounds. When such a composition is added to water a solution is obtained and is easily applied to the 15 substrate. When the composition is on, for example, leaves it forms a gel after reaction with the expired carbon dioxide. In the soil, where polyvalent cations are present, the mucilage gel is formed. Optionally, the step of extrusion (step (e)) and selection of tablet size is determined by selection of the size of the extrusion die, and finished length of extruded material. Optionally also, the tablets may be pill-sized (and so referred to). The step of drying may be by any known process, for example: 20 a drying rotating drum, rotating disc, hot air drier or a heated jacket drier. The protective material may be compositions of a single component, or a combination of more than one component, that has gelling properties when in contact with water and polyvalent cations. Many of these protective materials become viscous with water, making an ideal medium for producing a dough. These protective materials, having clathratic properties and gelling capabilities, can be used to 25 produce pills even with polyvalent materials, for in this case, instead of having a viscous formation, a gel is formed. This also aids in dough making. The shape of the pill or tablet is any shape, not just a spherical shape that has the largest surface area per unit volume compared with other shapes. A selection of the shape, size and the coating(s) and since the protective material(s) alter in physical and chemical properties depending upon the length of 30 the chain the selection of the protective material(s) determines the time release of nutrients or other useful chemicals that is required at a particular time. 7 WO 01/14285 PCT/NZOO/001 11 Other materials, that need not have clathratic properties, can be added to prepare pills and time release pills. These materials delay release of the chemicals enclosed in the pill when water is applied to the pill and the gel is formed A combination of materials with clathratic and non clathratic properties can be use to make pills and 5 time release pills. Coatings to enteric coated pills can be sprayed onto these pills, giving a first release chemical(s) followed by the enteric coated interior as a later time release. The dough, when extruded and cut into small particles or compressed to any shape or tablet, will form pills that become hard on drying. The tablets/pills produced in this way can consist of single material or combinations of more than one material. This allows pills to be designed that have all the soluble 10 components in solution but has no polyvalent cations, or has polyvalent cations in complexes where the positive charge has been reduced to zero by the complex (for example, chelates). This wholly soluble solution, when sprayed on plants or to the soil, forms a gel by coming in contact with polyvalent cations or under the conditions when the pH is reduced by acids from outside the solution (as is the case on the surface of leaves of live plants). The protective materials thus have more than 15 one use; they are used to make the dough for pill manufacture, time-span release, hold caged nutrients, they are a gel preventing leaching and fixation; act as a food for soil organisms; and are a soil conditioner. The pills, however, may be designed having polyvalent cations present. These pills can be applied as a solid to the soil such that when water is available the gel is formed. 20 The size of the pill is important as very small sized pills have greater surface area per unit volume than larger sized pills. If the pill is totally soluble then the smaller the size the more readily the pill will dissolve. The pills made by any combination, one compound or more than one blended together is applied as a solid that forms gels in the soil, when water is available. Then the small sized pills will gel in a separate environment, encasing the material within the pill and make the nutrients available to 25 the plant, before the larger pills can and provides protection from leaching and fixation. By designing the pill size and the protective material a change in composition of the nutrients for release as a time span is achieved. Since the pills can be made with all material singly or in combination, when applied, as a solid to the soil, and water is available, each pill will form its own shape environment gel. By this means lime 30 pills and other nutrient pills can be mixed together, as they are then protected from interaction with the other since each pill is protected form interaction with the soil chemicals. 8 WO 01/14285 PCT/NZOO/001 11 Numerous varieties of pills can thus be made, with single components, or more than one component, or as a time span pill. The selection of the pills of various types can then be blended together and used as any combination of one or more pills in the blend and applied at the one time to the soil or pasture. By this invention all materials used as a fertiliser can be applied together without the normal 5 interaction and leaching is minimised or completely prevented depending upon the protective material/s used and the quantity incorporated in the pill. Totally soluble pills, in which polyvalent cations are not present. can be put into solution and sprayed on plants or to the soil or both. In this case when the dissolved solution comes in contact with mild acids on the leaves of plants, where carbon dioxide is expired by the live plant's respiration dissolves 10 in water forming carbonic acid, a gel is formed. Also when the solution comes in contact with polyvalent cations present in the soil a mucilage gel is formed. The materials used to make the pills can include hormones, or any other medication, to be available at a time when wanted, once the pill(s) are activated by water. The pills can be made with time span coating, or protected by synthetically attaching the active hormone or medication to a prosthetic 15 group, that prevents the action of the medication. These medication protected materials can be made into pills that are released by smaller time span pills containing enzymes, within the larger pill that is released at a time calculated and then the enzyme will split off the inactive prosthetic portion from the molecule and make the medication active. Thus, it can be seen that pills need not be the only method of application. According to a further 20 aspect of the present invention, a method of preparing a composition in which fine particles of inorganic, organic, or a combination are blended together with the protective material (as defined above). This is applied to the substrate as a blended powder, or by application of water and spraying. On applying the blend as a powder, having the protective materials incorporated, a gel will form when water is available but, not have each component protected by the shape gel formation, 25 interaction will take place by the interaction of compounds monovalent with polyvalent material if present. This interaction can be protected from other interaction by separating the polyvalent material and applying it separately if in powder form where on the other hand pills combined with pills that normally would react will not now react because of the shape protected environment of each pill. Individual pills made of one or more ingredients alters the concept of a prescription formulation. In 30 the prescription formulation each component added makes up a percentage of the nutrients in the final formulation to be applied, for as one nutrient may need to be increased all the others are altered as a percentage. Many different types of pills may be blended together giving a quantity for application of 9 WO 01/14285 PCT/NZOO/001 11 each and is not limited by percentages. The more finely ground the materials used to make the pills, or when the composition is applied as a powder or with water or other liquids, the more efficient is the material is at becoming available by passing into solution because of the larger surface area to the unit volume. When pills are made with 5 very fine materials and the protective materials the addition of a material that with liquid will swell for example Bentonite can be added. Bentonite is a native colloidal hydrated aluminium silicate, the principal constituent being montmorillonite, A1203,4SiO2,H20. It is insoluble in water, but swells into homogeneous mass and absorbs water readily to form either sols or gels depending upon its concentration. In aqueous sols and gels bentonite particles are negatively charged and flocculation 10 occurs when electrolytes or cations are present that consequently when applied to the soil will hold more nutrients increasing the Cation Exchange Capacity and prevent leaching. On swelling the fine particles of the materials made into pills and with the bentonite becomes easily separated and is encapsulated by the gel formed by the protective materials. The material is available to the plant more readily. The swelling material in absorbing water readily increases the ability to hold water, helps to 15 aerate the soil and enhances soil organism activity as well. The protective materials) also has the ability to hold water. According to another aspect of the present invention there is provided a method of manufacturing a composition for application to a substrate as described above in which the method includes, after step (e), the following steps: 20 (g) mixing together one or more selections of tablets; (h) repeating steps (b) to (g) using a larger die in the extrusion step. By this addition step a tablet or pill can be made which incorporates a selection of a many smaller tablets which may be of the same composition, or of a variety of compositions, as is desired. According to one aspect of the present invention there is provided a method of adjusting soil pH 25 including the steps of : (a) analysing soil pH; (b) determining whether an acid or a alkali adjustment is required to bring the soil pH to an optimum pH; (c) preparing a substance for addition to a substrate by selecting one or more elements from 10 WO 01/14285 PCT/NZOO/001 11 the following: (i) a compound made by the selection of a weak acid with one or more of: calcium, magnesium, sodium or potassium; to produce a salt which has ant acid action when applied to soil; or 5 (ii) a compound of a strong acid with one or more of the following calcium, magnesium, sulphur; which combine to produce a salt having an acidifying effect on the soil; characterised in that said selection being made to effect a reversal of the pH to the optimum determined under two; and in that said substance is formed into the soluble composition as described above by the method as described above; and 10 (d) applied to the soil (being the substrate). One example of a weak acid is carbonic acid and thus the salts so produced by combination with carbonic acid are carbonates and bicarbonates. However, it will be appreciated that any other weak acid considered suitable, and known to the art-skilled worker, also falls within the ambit of the present invention, for example, acetic acid and citric acid. 15 Precipitated sulphur BP standard is approximately 99.9% w/w pure and of very fine particle size, yet insoluble in water. The soil however contains sulphonating bacteria that change the elemental sulphur to sulphates, thereby producing a pH lowering effect when this material is applied. It should be noted that a strong acid, such as nitric acid, when combined with calcium, magnesium, sodium and or potassium produces the corresponding nitrate having a pH approximately neutral. 20 Other examples of suitable strong acids include sulphuric acid, hydrochloric acid and phosphoric acid. Antacid and acid soil treatment compositions made by the methods disclosed herein are also within the scope of the present invention. According to another aspect of the present invention there is also provided a method of producing a 25 total soil and crop treatment regime comprising substrate treatments selected from the group: a pH correction; a nutrient adjustment and treatment; 11 WO 01/14285 PCT/NZOO/001 11 humus addition; and a combination of these; characterised in that said method and treatment are in a single application of compound to the substrate; further characterised in that said treatment regime method includes the steps of: 5 (a) identifying any soil pH requirements; (b) preparing a composition by the method described above, incorporating a compound selected by the pH adjustment method described above; (c) identifying any nutrient requirements; (d) preparing a composition by the method described above, incorporating one or more 10 compounds which address the nutrient needs; (e) identifying any humus requirements; (f) preparing a composition by the method described above, incorporating one or more compound which address the humus requirements; and (g) applying same to the substrate, 15 said composition being further characterised in that when the protective material is free of polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material is free of any gel-forming property, but when polyvalent cations are introduced to the protective material in the presence of water, the protective material forms a gel that thickens; and further characterised in that: 20 when said protective material includes polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material forms a gel that thickens. Whilst the substrate in the examples given below, and in the preferred embodiments, is a solid (generally a soil, clay, sand or desert (etc)), it will be appreciated by those skilled in the art that the 25 substrate can be a liquid, for example water in need of pH adjustment or other purification. Delivering the pH addressing salts to the soil in a form in which leaching is addressed will be in combination with a gelling agent, in a preferred embodiment. This may be a carbohydrate-based 12 WO 01/14285 PCT/NZOO/001 11 agent, preferably an alkali salt of carboxypolysaccharides, such as sodium carboxymethylcellulose. The reader of the specification is referred to the specification of the applicant's New Zealand Patent No. 265399 (the Script TM patent) which is directed to delivery of nutrients in a mixture containing such a gelling agent, the gelling agent being activated by the polyvalent cations in the soil, a mucilage 5 gel immediately forming in the soil once the soluble cations in water come into contact with polyvalent cations, preventing leaching. Such synthetic, water-soluble carbohydrates are also helpful in restoring soil humus and act as a soil conditioner and those with clathratic properties hold nutrients preventing leaching and fixation. Lime may also preferably be delivered with the above pH adjusting salt in an available form, 10 preferably a precipitated form and the attention of the reader is directed to the applicant's New Zealand Patent No. 280358 (the Aqualime TM patent), which discloses precipitated lime fertiliser. Alternatively the lime may be lime powder. Together with said precipitated lime and anti leaching agent may be elements required by the soil as determined by soil analysis, said elements being in a complexed form and thus whilst being soluble, 15 are not reactive to soil polyvalent cations and thus fixed by reaction with same. In this regard the attention of the reader is again directed to New Zealand Patent No. 265399 (the Script " patent) which further discusses this desirable aspect. Another aspect of the method described above for preventing leaching depends upon a different factor. A blended mixture of solid nutrient combinations as described above using Script T M and 20 AqualimeTM technology along with the alkali salt of carboxypolysaccharide or polymers, where sodium carboxymethylcellulose is an example, can be formulated by use of any one or more of the ingredients of these products in the method of preparation of the solid. The following materials can be mixed in any combination in the fine powder form, using one or more of these ingredients used in Aqualime and Script, together with ground bark blood and bone or any 25 other organic vegetable or animal matter, with alkali-carboxy-saccharide (for example, sodium carboxymethylcellulose). This material can then be applied as a solid blend along with seed at planting. Once water is applied or supplied by rainfall the mixture of multilime and nutrients, (which has in its composition the gelling material that is activated by the polyvalent cations which are present in the multilime) a mucilage gel is immediately formed to prevent leaching. 30 By using a similar combination as described in 1 above, and preparing pills by the method described above. These tablets are dried and made easy for solid application for cropping. 13 WO 01/14285 PCT/NZOO/001 11 The invention may provide for a range of pellet sizes or density releasing a further prescription over a period of time. This assists in altering the composition of nutrients in the soil according to plant needs during its life span. For example when shoots appear (nitrogen particularly is required for leaf formation) the nutrient composition can be altered according to this requirement so that nitrogen 5 containing parts of the fertiliser are time released at shoot appearance. Application of the pills, using water, is done readily either in solution or as a slurry. The mixture is 1 (or 2) of pills to water. If the ratio is 2, the particle size can be very small, so that when applied to water it will penetrate quickly and form the required mucilage gel. The sodium carboxymethylcellulose (as the protective material) in water forms a viscous solution, and the greater 10 the concentration the greater the viscosity. When polyvalent cations are present with the blend the physical nature of the gelling material alters by not forming a viscous solution, but rather going immediately to the mucilage gel. When the polyvalent cations are present much less water is needed to obtain a slurry that is not so viscous to apply. The less water needed, the less cost of application. Separate pills can be made with the Aqualime ingredients, as can the Script pills or humus enhancing 15 agents. These pills can then be mixed in any combination to be used in cropping or on pasture either as a solid application or with water. (a) The alkali salts of carboxysaccharides have the physical property of forming gels, hereinafter called the 'gelling material' The gelling material produces a gel on the surface of live leaves where the product of oxidation, carbon dioxide is released. When this gelling 20 material in contact with polyvalent cations, however, a mucilage gel is formed. By mixing to a blend one or more electrolytes containing monovalent cations and polyvalent cations, and, depending upon the acid to base formation of the salt, a mixture can be made to raise or lower pH. If the gelling material is added to the composition the mixture contains solid chemicals with no water. When water is added a mucilage gel is formed. 25 (b) As in method (a) a mucilage gel can be formed within the soil by applying the composition as a dry powder. When water is present the gel produced prevents leaching. When pills are made separately (for example, of Aqualime Trade Mark or Script Trade Mark or humus forming agent with gel forming agent) the pills form gels with water, and are protected in spherical gel bodies separated from the others. This prevents interaction one 30 with the other and from the soil chemicals, and thus no fixation occurs upon application. (c) As with methods (a) and (b) other materials can be added protected by being complexes and supplying electrons to the polyvalent cations. This reduces the charge to zero and any 14 WO 01/14285 PCT/NZOO/001 11 remaining soluble material is not reactive to soil polyvalent cations. There is no fixation of these nutrients. (d) In addition to methods (a) to (c) the pH control with calcium magnesium, sodium and potassium carbonates combinations, soil pH can be increased at root level. This allows all 5 other nutrients to be added at that level when planting crops. The ground is prepared first and, in one application, the pH control material, and all the nutrients are delivered and the seed is sown. Considerable saving is made by the farmer and reduces all losses from fixation and leaching. (e) The compounds in the blend have different pH values. Each ingredient is a percentage so 10 that by multiplying the percentage of each ingredient by its pH value then adding these values, the pH value of the compound is obtained, by known techniques. This is important where the pH at root level must be maintained at the desired level. (f) In addition to method (e) this mixture can be applied by addition of water that then forms the gel and slurry, which again can be applied at one time when drilling the seed. 15 (g) In addition to method (e) vegetable matter and animal matter can be added finely ground and applied at one time when sowing the seed. (h) In addition to method (a) pills can be made for correction of pH as can the nutrients balance be formulated by taking soil tests and foliage tests to correct the balance of all nutrients needed. These pills can be mixed to the required application rate to meet the needs 20 of pasture or crops either by applying as a solid or by slurry so that only one application is necessary. Again considerable cost savings are made by the farmer. (i) Clay soils can be converted by using high concentrations of ground bark with 10 to 20 percent of sand and then adding by prescription (from soil and foliage tests) all the nutrients needed in a balance to correct the in balance and the gelling material. The pH control 25 materials can also be added, as in method 1. The blended mixture is dug into the clay soil. Leaching is prevented and the particle size of the clay soil is changed with the added mixture humus is gradually formed and the clay soil becomes fertile. (j) As in method (I) amino acids, vitamins, polypeptides and large quantities of the alkali salt of carboxymethylcellulose will produce large amounts of cellulose gel and feed the biological 30 inhabitants of the soil allowing them to multiply. Enzymes are released by this activity that will break down the material of organic nature to humus. 15 WO 01/14285 PCT/NZOO/001 11 Best Modes for Carrying out the Invention EXAMPLE 1 A composition using AqualimeTM technology is set out below. 5 Separate pills can be made with the formulation as follows: (a) Superphosphate pills 1 mm in diameter containing superphosphate 94% sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. (b) AqualimeTM pills 1 mm in diameter containing commercial calcium carbonate finely ground 70%, magnesium carbonate 20%, sodium carbonate 0.5%, potassium carbonate 3%, 10 sodium salt of bentonite 1.5% and sodium salt of methylcarboxycellulose 5%. (c) Trace element pills 1 mm in diameter containing a mixture of the sulphates containing commercial copper sulphate 2%, cobalt sulphate 0.5%, iron sulphate 5%, manganese sulphate 0.5%, zinc sulphate 1% and also had added sodium molybdate 0.005%, borax 0.005%, starch 11.09%, glucose 73.4%, bentonite 1.5% and sodium salt of methylcarboxycellulose 5%. 15 (d) Macro nutrient pills 1 mm in diameter containing commercial Di-ammonium phosphate 20%, Di-potassium phosphate 30%, ammonium sulphate 30'%, potassium chloride 13.5%, sodium salt of D mannuronic acid 1.5% and sodium of salt of methylcarboxycellulose 5%. (e) Time span pills 5 mm in diameter (larger in size than all others) containing commercial urea 70%, Di-ammonium phosphate 5%, Di-potassium phosphate 5%, ammonium sulphate 20 12%, starch 4%, sodium polyvinylphthalate 0.5%, 2-ethoxy-5(2 hydroxyethoxymethyl)cellulose 0.5%, sodium D mannuronate 1% and sodium methylcarboxycellulose 2%. All percentages are by weight. A blend was made containing the following mixture: 25 above 100 Kg/Ha of (a); above 150 Kg/Ha of (b); 16 WO 01/14285 PCT/NZOO/001 11 above 5 Kg/Ha of (c); above 100 Kg/Ha of (d); and above 45 Kg/Ha of (e) All the blend of pills was applied at a rate 400 Kg/Ha. Seed potatoes are mixed with the blend and 5 planted at one time after the soil has been prepared. On planting, it is desirable that water be applied along with the seed and the fertiliser pills separately. The smaller pills may be released for the seed potato to germinate, giving all the nutrients needed at that time and lifting the pH to 5.8, which is required for the best development of a potato crop. After seven to ten days the larger protected pills are then released, giving the added nitrogen along 10 with a balance of the macro-nutrients needed for maximum leaf growth. Since each pill has its own shaped gel environment, they do not interact with other pills or with the soil chemicals and are not leached. Many blends of pills and formulations of pills can be devised and derived by a scientist to meet the needs to balance of nutrients needed for any crop, controlling the pH and the quantity of the nutrients 15 required during the phases of the plant's growth with a single application. Thus in one application the following is effected: correction of the soil pH, and at the same time, supply of a balance of nutrients to correct soil deficiencies supply of humus producing biological products for maximum yields and increases soil fertility. The invention allows less fertiliser to be applied since the large losses from conventional fertilisers 20 from leaching and fixation are prevented. All the nutrients can now be applied at one time saving the farmer this expense. EXAMPLE 2 Pastoral soil, having a low pH of 5.1 a leaching condition, has nutrient levels that are low and a poor 25 rate of growth on the pasture. The stock are experiencing metabolic diseases and are not getting enough feed. The farmer has to feed hay when the pasture should be providing adequate for the level of stock. The soil has been forced with nitrogenous fertiliser over a long period that has resulted in a loss of humus and the biological organisms are low. The farm located in a very high rainfall area. 17 WO 01/14285 PCT/NZOO/001 11 Separate pills were made with the formulation as follows (a) Superphosphate pills 1 mm diameter containing commercial superphosphate 94% sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. (b) Trace element pills 1 mm diameter containing a mixture of the sulphates containing 5 commercial copper sulphate 2%, cobalt sulphate 0.5%, iron sulphate 5%, manganese sulphate 0.5% zinc sulphate 1% and also sodium molybdate 0.005%, borax 0.005%, starch 11.09%, glucose 73.4% and bentonite 1.5% and sodium salt of methylcarboxycellulose 5%. (c) Commercial Di-ammonium Phosphate pills 1 mm diameter containing Di-ammonium phosphate 94% sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. 10 (d) Commercial Ammonium Sulphate pills 1 mm in diameter containing ammonium sulphate 94% sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. (e) Commercial magnesium carbonate 94% sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. (f) Commercial Sodium Carbonate pills 1 mm in diameter containing sodium carbonate 94% 15 sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. (g) Commercial Potassium Carbonate pills 1 mm in diameter containing potassium carbonate 94% sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. (h) Urea combination pills 1 mm in diameter containing Urea 70%, mono potassium phosphate 15%, ammonium sulphate 5%, dextrose 4% sodium salt of D mannuronic acid 1% and sodium salt of 20 methylcarboxycellulose 5%. (i) Commercial Potassium Chloride 93.5%, Potassium Iodide 0.5% sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. (j) Commercial finely ground lime 93%, bentonite 1%, sodium salt of D mannuronic acid 1% and sodium salt of methylcarboxycellulose 5%. These powders blended together. 25 For each 500 Kg of lime to be applied to each hectare the following quantities of pills are added to the finely ground lime blended together with the protective materials: 130 Kg of (a); 18 WO 01/14285 PCT/NZOO/001 11 5 Kg of (b); 75 Kg of (c); 75 Kg of (d); 20 Kg of (e); 5 5 Kg of (f); 10 Kg of (g); 40 Kg of (h); and 10 Kg of (i) Thus total to be applied per hectare is 870 Kg of blended compound. 10 To apply to the pasture, the powder mixture of pills is well blended and applied as a slurry. The slurry is formed by the addition of water in a 1 in 2 dilution. All the pills are protected by the protective materials contained in the respective pills from reacting with water. The polyvalent cations present in the lime form a gel in their own environment, with no leaching or fixation. The pH of the pasture is lifted up quickly and all the nutrients are available for the pasture growth. 15 Many blends of the pills mixed with the protected lime can be determined and devised to meet the balancing of nutrients needed for any pasture. The blend can control the pH and the quantity of the nutrients to maintain adequate growth by a single application. EXAMPLE 3 20 A citrus fruit farm has an area where little production of fruit has eventuated for the last two years. On analysis it was found that the nutrient levels were low and not balanced and that the soil had deficiencies of trace elements. Also, calcium and magnesium levels were incorrect. Though citrus fruit has a root system that is able to feed near the surface all the fertiliser applied were leached in huge quantities. The error made in the past was to apply nitrogenous fertilisers to force production 25 and disregard the importance of trace elements and the balance of nutrients. The trees were stunted 19 WO 01/14285 PCT/NZOO/001 11 and the new growth did not carry adequate fruit to be commercial. In this case two applications need to be applied, one to the soil around the roots of the citrus fruit, and a foliage spray upon the leaves of the trees The foliage spray incorporated food grade materials as they are purified and have no foreign material 5 present that may block the sprays. All the materials used dissolve in water and form a gel on the surface of the leaves. (a) The spray formula compound was made into 0.5 mm diameter pills consisting of the following: Potassium sulphate 20.83% Urea 8.47% 10 Mono-Potassium Phosphate 30.30% Mono-Ammonium Phosphate 18.93% Ammonium Sulphate 13.25% Calcium Chelate 0.20% Zinc Chelate 0.31% 15 Sodium Molbdate 0.38% Manganese Chelate 0.35% Magnesium Chelate 4.21% Iron Chelate 0.07% Copper Chelate 0.31% 20 Boric Acid 0.14% Sodium salt of D Mannuronic Acid 1.25% Sodium Salt methylcarboxycellulose 1.00% Total Of All Ingredients 100.00% 20 WO 01/14285 PCT/NZOO/001 11 (b) The following powders were homogeneously blended for the ground application compound, using commercial grade materials finely ground and made into pills 1 mm in diameter: Calcium Carbonate 60% Magnesium Carbonate 10% 5 Potassium Carbonate 25% Bentonite 1% Sodium salt methylcarboxycellulose 4% Total Of All Ingredients 100% The spray formula pills were added to water at the ratio of 1 in 10 in water. The application rate of 10 the spray pills was 30 Kg/Ha in divided applications. Immediate and fast response to the uptake of nutrients was then controlled by the foliage feeding. To 150 Kg of ground application pills the following was added: 30 Kg of spray formula pills; and 100 Kg pills of the type described in Example 2(a) above. 15 The total of 280 Kg mixture was applied around the roots of the trees, per hectare. These pills were applied as solid material. Irrigation water was applied to wash in the nutrients (which were all protected from one another and from soil chemical interaction). The plants now had the resources needed from root uptake. The roots developed to allow more nutrient uptake and the citrus fruit responded accordingly. 20 There was no leaching or fixation. Less application of fertiliser now was wanted. After application the largest crop ever was recorded. The yield was approximately twice the normal, and the fruit captured 90% of the export market at top prices. The fruit ripened all at the same time and the sizes were even, thus costing less with harvesting. The taste of the fruit was much sweeter. Pills of many combinations of materials, blended together, can be devised to meet the balance of 25 nutrients needed for citrus fruit farming. The pH and the quantity of the nutrients to maintain adequate growth is managed by foliage and ground application. 21 WO 01/14285 PCT/NZOO/00 11 From these results other crops were investigated. EXAMPLE 4 Vegetables were grown using the same method - ground application with divided foliage feed 5 applications. The results were again more than encouraging. The size of the crop was increased, and the quality was greatly increased. The keeping value of the vegetables was greater and the taste was greatly increased. The above is an example only; there are numerous crops that need special treatment and the reader can see that each farmers requirements alters as does the formulation and blending of components far 10 too many to take each into consideration. EXAMPLE 5. In this example the soil was compacted, such as a clay soil. The particles of the soil are very fine, for clay consists of small particles easily compacted. The pH is usually about 5.0 and requires lifting to 15 pH 6.0. The fertiliser to be added to the to the mixture needs to be alkaline and have a balance of all the nutrients needed. Once dug into the clay soil and mixed, the biological population with the soil breaks down the organic material into humus and the soil changes to become more crumbly, able to support plant life. Ingredients Kg 20 Ground bark 89.00 Sand 10.00 Calcium Carbonate 0.5 Magnesium Carbonate 0.2 Sodium Carbonate 0.01 25 Potassium Carbonate 0.01 22 WO 01/14285 PCT/NZOO/001 11 Potassium Nitrate 0.005 Mono Potassium Phosphate 0.2 Sodium carboxymethylcellulose 0.02 Trace elements as complexes or made from ethylenediaminetetraacetic acid to 0.01 Kg 5 Boron 600 parts per million Cobalt 300 Copper 400 Iron 50 Manganese 50 10 Molybdenum 200 Zinc 300 Total 100 Kg The fertiliser prepared using food grade materials that are 99.9% pure. The ingredients of the fertiliser, without the sand and ground bark, are mixed with a little water to form a dough extruded 15 and cut into pieces and rolled into pills by an inclining rotating pan. The pills are dried. These small pills are added to the ground bark and sand mixture. After applying to the clay soil and coming into contact with water, the sodium carboxymethylcellulose has with it the polyvalent cations of calcium and magnesium carbonates that changes the sodium carboxymethylcellulose to a gel, preventing leaching and fixation. 20 100 Kg of this mixture of fertiliser, sand and ground bark will treat 100 square meters of clay soil and will last for the year. A second application the next year can convert the clay to good fertile soil. Hundreds of formulations of the product of the present invention can be achieved for pasture and crops. Any formulation can be made and then formed into pills as described above. A method of having complete pH control as well as a balance of nutrients to grow crops is achieved. The 25 application rate is the other adjustment. 23 WO 01/14285 PCT/NZOO/00 111 It will be appreciated that what ever the medium, there is a method of dealing with the substrata and formulating a compound in accordance with the present invention to cope with the conditions. EXAMPLE 6 5 Dealing with deserts and poor fertile soils it is necessary to include micro-organisms that are low in count in the dessert. The above described embodiments enable the provision of the nutrients needed to enable the micro-organisms to multiply and supply the needs for sustained plant growth. Having water available in abundance is most necessary for life. To do this the area in consideration for application of a devised compound mixture may need washing. This removes any unwanted salts. 10 In this method the nutrients protected in accordance with the invention are supplied along with compounds to correct the pH and supply the micro-organisms as well. All the other requirements, apart from water, can now be supplied by this invention. All the added resources can be protected from leaching and fixation. Humus can be replaced and the nutrients held as well as holding the water applied. Plants and soil organisms will grow and multiply accordingly. 15 Nature is then assisted to carry on its role. Fertile arable land results. It will be appreciated that to go into the complexity of the requirements is covered by example only and that the methods to be used are in the thousands; too many to be described in detail. The commercial viability however is obvious since leaching and fixation are eliminated, the cost is now affordable. 20 Aspects of the present invention have been described by way of example only and it should be appreciated that the modifications and additions may be made thereto without departing from the scope thereof. 24

Claims (48)

1. A composition for application to a substrate, said composition being a predetermined composition and pH, characterised in that said composition includes a protective material, which is selected from the group: 5 a cellulose compound; a synthetic or a natural polymer; a carbohydrate compound; an inorganic compound; and a combination thereof; 10 said protective material having clathratic properties and being further characterised in that: when said protective material is free of polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material is free of any gel-forming property, but when polyvalent cations are introduced to the protective material in the presence of water, the protective material forms a gel that thickens; 15 and further characterised in that: when said protective material includes polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material forms a gel that thickens. 20

2. A composition for application to a substrate as claimed in claim 1 wherein the protective material is a carbohydrate compound and is selected from the monovalent alkali salts of carboxypolysaccharides.

3. A composition as claimed in claim I wherein the protective material is selected from: 25 the sodium salt of 2-ethoxy-5-(2-hydroxyethoxymethyl)cellulose; 25 WO 01/14285 PCT/NZOO/001 11 the sodium salt of D mannuronic acid; sodium phthalate; the sodium salt of carboxymethlycellulose; and a combination of these. 5

4. A composition as claimed in any one of claims I to 3 wherein said composition further includes a mild acid to activate the protective material with or without in the presence of polyvalent cations. 0

5. A composition as claimed in any one of claims 1 to 4 wherein said polyvalent cations are selected from the salts of the group: boron, calcium, copper, iron, manganese, magnesium, cobalt, selenium, molybdenum, zinc, any other soluble or slightly soluble polyvalent salt and a combination of these 5

6. A composition as claimed in any one of claims 1 to 5 wherein said composition further includes a compound additive selected from the group: a nutrient, an enzyme, a hormone, a medication, a biological organism, and a combination of these.

7. A composition as claimed in claim 6 wherein said compound additive is physically separate from said protective material, within the composition.

8. A composition as claimed in any one of claims 1 to 7 wherein said composition further includes at least one enteric coating substance.

9. A composition as claimed in claim 8 wherein said enteric coating substance is selected from 26 WO 01/14285 PCT/NZOO/001 11 the group of carbohydrate based material and or any of the group of polymers: fats, fatty acids, waxes, wax mixtures, shellac, ammoniated shellac, cellulose acetate phthalates, the sodium salt of carboxypolysaccharide; and a combination of these. 5

10. A composition as claimed in either claim 8 or claim 9 wherein said enteric coating substance is selected for the property of slow dissolution, effecting a delayed time effect on the introduction of polyvalent cations to the protective material.

11. A composition as claimed in any one of claims 8 to 10 wherein said enteric coating 10 incorporates at least one compound additive selected from the group: a nutrient, an enzyme, a hormone; a medication, a biological organism; and a combination of these.

12. A composition as claimed in any one of claims 8 to 11 wherein said enteric coating is further characterised in having clathratic properties, and forming a gel on contact with: polyvalent cations; 15 water; or gels formed by mild acid.

13 A method of manufacturing a composition for application to a substrate, said method including the steps of: (a) selecting the and each substance for addition to said substrate; 20 (b) selecting the and each protective material, which protective material is selected from the group: (i) a cellulose component; (ii) a synthetic or a natural polymer; (iii) a carbohrydrate compound; 25 (iv) an inorganic compound; and 27 WO 01/14285 PCT/NZOO/001 11 (v) a combination thereof; said protective material having clathratic properties and being further characterised in that: when said protective material is free of polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material is free 5 of any gel-forming property, but when polyvalent cations are introduced to the protective material in the presence of water, the protective material forms a gel that thickens; and further characterised in that: when said protective material includes polyvalent cations and the material is dissolved in water, added to water or when water is added to said material, the protective material forms a 10 gel that thickens; and (c) forming a homogenous mixture of the substance(s) and the protective material(s) (to form the predetermined composition).

14. A method of manufacturing a composition for application to a substrate as claimed in claim 15 13, in which the protective material includes polyvalent cations and said method further including the steps: (d) adding water sufficient to form a dough with the mixture from step (c); (e) extruding the dough to pre-selected size and shape tablets; and (f) drying the tablets. 20

15. A method of manufacturing a composition for application to a substrate as claimed in either claim 13 or 14, wherein said protective material is a carbohydrate compound and is selected from the monovalent alkali salts of carboxypolysaccharides. 25

16. A method of manufacturing a composition for application to a substrate as claimed in either claim 13 or claim 14 wherein each said protective material is selected from the group: 28 WO 01/14285 PCT/NZOO/001 11 the sodium salt of 2-ethoxy-5-(2-hydroxyethoxymethyl)cellulose; the sodium salt of D mannuronic acid; sodium phthalate; the sodium salt of carboxymethlycellulose; and 5 a combination of these.

17. A method of manufacturing a composition as claimed in any one of claims 13 to 16 wherein said method includes, includes, after step (b) the step of selecting and adding an inert substance to the 10 mixture.

18. A method of manufacturing a composition as claimed in claim 17 characterised in that said inert substance expands on mixing with water. 15

19. A method of manufacturing a composition as claimed in either claim 17 or claim 18 wherein said inert substance is bentonite.

20. A method of manufacturing a composition as claimed in any one of claims 13 to 19 wherein said method includes, after step (f) or step (e), the step of 20 (g) coating the tablets with an enteric coating.

21. A method of manufacturing a composition as claimed in claim 20 wherein said enteric coating substance is selected from the group of carbohydrate based material and or any of the group of polymers: fats, fatty acids, waxes, wax mixtures, shellac, ammoniated shellac, cellulose acetate 25 phthalates, the sodium salt of carboxypolysaccharide; and a combination of these. 29 WO 01/14285 PCT/NZOO/001 11

22. A method of manufacturing a composition as claimed in either claim 20 or claim 21 wherein said enteric coating substance is selected for the property of slow dissolution, effecting a delayed time effect either on the introduction of polyvalent cations to the protective material or on the introduction 5 of water to the protective material.

23. A method of manufacturing a composition as claimed in any one of claims 20 to 22 wherein said enteric coating incorporates at least one compound additive selected from the group: a nutrient, an enzyme, a hormone, a medication, a biological organism; and a combination of these. 10

24. A method of manufacturing a composition as claimed in any one of claims 20 to 23 wherein said enteric coating is further characterised in having clathratic properties, and forming a gel on contact with: polyvalent cations; water; or gels formed by mild acid. 15

25. A method of manufacturing a composition as claimed in any one of claims 20 to 24 wherein step (g) is repeated after further drying of the tablets, to apply a second enteric coating.

26. A method of manufacturing a composition as claimed in any one of claims 13 to 25 wherein said tablets are of a size in the range 0.1 mm to 10 mm. 20

27. A method of manufacturing a composition as claimed in any one of claims 13 to 26 wherein said tablets are spherical.

28. A method of manufacturing a composition as claimed in any one of claims 13 to 27 wherein 25 said composition is the composition as claimed in any one of claims I to 12. 30 WO 01/14285 PCT/NZOO/001 11

29. A method of manufacturing a composition wherein said method includes the steps of: (a) selection of a plurality of tablets made in accordance with the method of any one of claims 13 to 28; (b) selecting one or more protective materials; and 5 (c) forming a homogenous mixture of the substance(s) and the protective material(s) (to form the predetermined composition).

30. A method of manufacturing a composition as claimed in any one of claims 13 to 29 in which 10 the protective material includes polyvalent cations and wherein said method further includes the steps of: (d) adding water sufficient to form a dough with the mixture from step (c); (e) extruding the dough to pre-selected size and shape tablets; and (f) drying the tablets. 15

31. A method of application of a composition to a substrate, said method including the steps of: preparing a composition, as claimed in any one of claims 1 to 12, in a powder form; mixing said powder with water to form a slurry; and applying the slurry to the substrate at a predetermined rate per area of substrate. 20

32. A method of application of a composition to a substrate, said method including the steps of mixing the composition produced by the method of any one of claims 13 to 31 with seeds or seed material and sowing the seeds or seed material. 31 WO 01/14285 PCT/NZOO/001 11

33. A method of adjusting substrate pH including the steps of: (a) analysing soil pH, (b) determining whether an acid or a alkali adjustment is required to bring the soil pH to an optimum pH; 5 (c) preparing a substance for addition to a substrate by selecting one or more elements from the following: (i) a compound made by the selection of a weak acid with one or more of: calcium, magnesium, sodium or potassium; to produce a salt which has ant acid action when applied to soil; or 10 (ii) a compound of a strong acid with one or more of the following calcium, magnesium, sulphur; which combine to produce a salt having an acidifying effect on the soil; characterised in that said selection being made to effect a reversal of the pH to the optimum determined under two; and in that said substance is formed into the soluble composition as described above by the method as described above; and 15 (d) applied to the substrate.

34. A method of adjusting soil pH as claimed in claim 33 wherein after step (c) the step of adding lime in a precipitated form or as a finely ground powder. 20

35. A method of adjusting soil pH as claimed in claim 33 or claim 34 wherein the weak acid is selected from the group: carbonic acid, acetic acid, citric acid and a combination of these.

36. A method of adjusting soil pH as claimed in any one of claims 33 to 35 wherein the strong acid is selected from the group: nitric acid, sulphuric acid, hydrochloric acid, phosphoric acid, the 25 strong acid being in combination with calcium, magnesium, sodium or potassium or a combination thereof 32 WO 01/14285 PCT/NZOO/001 11

37. A method of adjusting soil pH as claimed in any one of claims 33 to 36 wherein said substance for addition to the substrate includes a gelling agent. 5

38. A method of adjusting soil pH as claimed in claim 37 wherein said gelling agent is carbohydrate based and is an alkali salt of carboxypolysaccharides.

39. A method of adjusting soil pH as claimed in claim 38 wherein said gelling agent is sodium carboxymethylcellulose. 10

40. A method of producing a total soil and crop treatment regime comprising substrate treatments selected from the group: a pH correction; a nutrient adjustment and treatment; 15 humus addition; and a combination of these; characterised in that said method and treatment are in a single application of compound to the substrate; further characterised in that said treatment regime method includes the steps of: (a) identifying any soil pH requirements; 20 (b) preparing a composition by the method as claimed in any one of claims 13 to 31, incorporating a compound selected by the pH adjustment method as claimed in any one of claims 33 to 39; (c) identifying any nutrient requirements; (d) preparing a composition by the method as claimed in any one of claims 13 to 31, 25 incorporating one or more compound which address the nutrient needs; 33 WO 01/14285 PCT/NZOO/001 11 (e) identifying any humus requirements; (f) preparing a composition by the method as claimed in any one of claims 13 to 31 above, incorporating one or more compound which address the humus requirements; and (g) applying same to the substrate. 5

41. A method of producing a total soil and crop treatment regime as claimed in claim 40 wherein the substrate to which the regime is applied is selected from the group: a soil, a clay, a sand, a desert, a liquid; a substrate in which plants re growing, and a combination of these. 10

42. A method of producing a total soil and crop treatment regime as claimed in claim 41 wherein said liquid is impure water.

43. A method of application of a composition to a substrate, said method further including the steps of 15 mixing the composition produced by the method as claimed in either claim 40 or claim 41 with seed or seed material; and sowing the seeds or seed material.

44. A soluble composition for application to a substrate, as claimed in any one of claims I to 12 20 and substantially as hereinbefore described with reference to any one of the Examples.

45. An anti-leaching agent for application to a substrate, said agent incorporating a compound selected from: the composition as claimed in any one of claims I to 12, the substance produced by the method of any one of claims 33 to 39, or a combination thereof. 25 34 WO 01/14285 PCT/NZOO/001 11

46. A method of manufacturing a soluble composition for application to a substrate, as claimed in any one of claims 13 to 31 and substantially as hereinbefore described with reference to any one of the Examples. 5

47. A method of adjusting soil pH, as claimed in any one of claims 33 to 39 and substantially as hereinbefore described with reference to any one of the Examples.

48. A method of producing a total soil and crop treatment regime, as claimed in any one of claims 40 to 42 and substantially as hereinbefore described with reference to any one of the 10 Examples. 35