WO1994024070A1

WO1994024070A1 - Improvements relating to soluble powder prescription fertiliser compositions incorporating special soil test systems

Info

Publication number: WO1994024070A1
Application number: PCT/NZ1994/000035
Authority: WO
Inventors: Gavin Frank Murdoch
Original assignee: Technical Patents Limited
Priority date: 1993-04-22
Filing date: 1994-04-18
Publication date: 1994-10-27
Also published as: AU6583994A; AU3608897A; AU696096B2

Abstract

The object of the invention provides a new technique of soil nutrient analysis using a photo-colourmetric determination system. The manufacture of soluble powdered chemical fertiliser containing certain protective chemicals ensures that all the chemicals are utilised by plants, protozoa life, bacteria and fungi and subsequently the animals eating produce grown in the soil. Prevention by use of the protective chemicals of the fertiliser chemicals being available for surface run-off, leaching and fixation. A prescribed protected chemical fertiliser will replace determined deficient chemicals in the soil providing sufficient balanced nutrients for crop or pastures needs in the next growing season. A controlled means of applying with the protected prescription fertilisers fungicides, herbicides, hormones, insecticides, medicines and/or antibiotics, vitamins or weedicides. Included in the prescription fertiliser are protective chemicals having channel-lattice properties which are either foods or fertiliser protecting the powdered fertiliser's organic and inorganic chemicals from reaction by humid conditions.

Description

DESCRIPTION

Title IMPROVEMENTS RELATING TO SOLUBLE POWDER PRESCRIPTION FERTILISER COMPOSITIONS INCORPORATING SPECIAL SOIL TEST SYSTEMS. TECHNICAL FIELD

This invention relates to improvements in fertiliser composition relating to soil test techniques and the mixture of chemicals that can be associated to produce a completely soluble powdered medium mixture for transport, protected from chemical reaction when made into solution for application, then with specific outside chemicals presence will bring about advantageous changes to give another method of protection against immobility, leaching, surface run-off, and insufficient nutrient application needed to give optimum growth of plants micro-organisms, fungi and protozoa life, necessary for healthy fertile soil reinstatement.

1. The object of this invention is to prepare from a new technique of soil analysis whereby the soil solution is tested for nutrient content by the use of special complexes enabling photo-colourmetric determination, for many elements, and opaque floccuation measurements, for some elements, of the macro and minor elements present in soil samples, and from this data and from finding the pH of the soil, determine a prescription of chemicals required to restore to the soil any deficiencies found. The prescription

1. will be prepared in fine well mixed soluble powdered materials including specially prepared protective chemicals also soluble and in powdered form, ready for transport as a highly concentrated product. Incorporated in this 5 heterogeneous mixture will be a dye to enable three objectives :-

A. To allow dilution to a predetermined concentration level compared by a colour strip supplied for the highest concentration allowable for application. 10B. To be able to analyse the product when sprayed on to the foliage determining the degree of concentration of the prescription when the product was sprayed.

C. To allow the product when sprayed to be easily seen where the spray has been applied. '^The prescription is therefore transported as a highly concentrated powdered mixture giving a less expensive cost for transport and then on application, since all the chemicals in the prescription are soluble, it is made into solution either with or other water containing products 0(such as whey) to a level of minimum high concentration and sprayed on the crops, pastures and soil, or any other location that will obtain benefit from the application. Along with the prescription fertiliser other chemicals which do not contain high concentrations of heavy metal ions that ⁵are not protected (chelated substances) can be applied along with the prescription solution, this includes weedicides, herbicides, hormones and insecticides, offering a method of lowering costs by one application rather than many.

TITUTE SHEET 2. Another objective is to limit the loss of prescription fertiliser chemicals and additives (by the use of protective chemicals) from surface run-off, or leaching by making prescription fertiliser into solution becoming a liquid and applying during a period setected allowing the liquid to soak into the soil, or becoming adhered to the foliage which provides a rapid method of foliage feeding from the protective chemicals applied. It is well known that with other fertilisers after applying onto the surface of the soil, remains on the surface and most of it is washed away from the surface or leeched during rainfall, and thus most of that fertiliser becomes unavailable to be utilised by the plants in the area of application.

3. It is a further object of this invention to include the specially prepared protective chemicals to prevent loss of the chemical prescription items applied in solution from reaction with soil chemicals which may result in rendering the prescription chemicals insoluble and therefore be unavailable to the life forms present in the soil. These protective prescription chemicals have four major objectives

A. To enable heavy metal minor trace elements and chelates to be incorporated in the prescription and when made into solution be protected from reaction with other ions in the prescription, and later in the soil where soil chemicals are present, to be protected from these chemicals from forming

3. insoluble precipitates and consequently rendering these minor trace elements unavailable to the life forms present in the soil.

B. To produce major element materials soluble in solution 5. but in complexes providing protection from unwanted chemical reaction with soil chemicals rendering them insoluble and therefore unavailable to life forms. In particular calcium and sulphur.

C. To offer a method of protection and ability of the 10 prescription chemicals to be held and available to plant life through foilage feeding by allowing the ions to be retained in solution but adhesive to the foliage.

D. To allow the prescription chemicals to be enveloped in the specially prepared protective chemicals thus on

15 application are soluble and change into a protective mucilage with clathratic properties, and sponge-like properties able to hold moisture incorporating the dissolved ions. This provides two objectives :-

a.) When in the case of contact on foliage a form of 0 adhesive compound is formed when some of the protective chemicals comes in contact with acid. ( On respiration of plants carbon dioxide is released which dissolves in water to produce carbonic acid, a mild acid ) . The prescription chemicals are enveloped and some adhere to the surface of -5 the foliage and remain in solution allowing immediate transfer to the plant according to its requirements. b.) When any of the protective chemicals along with the dissolved ions that did not adhere to the foliage comes in contact with heavy metal ions present in the soil a mucilage is formed enveloping again the prescription chemicals 5 present by the clathratic properties and holds the ions as a "guest" in the cage-like space created by this mucilage. The strength of the bonding allowing enveloping is not strong enough to disallow transfer to life forms by active absorption, but is strong enough to prevent the ions from 10 being washed away by leaching. This means that the problem which exists by the application of solid fertilisers and other liquid fertilisers from leaching is prevented with prescription fertiliser containing these special protective chemicals. The rate at which the mucilage is formed is 15 directly proportional to the concentration of the heavy metal ions present in the soil. This means that the prescription fertiliser is held at root level within the mucilage, and the balance of the chemicals become available to the plants and other life forms.

204. Another objective of this invention is to supply the life forms, including the plant life, nutrients in a form which is available but not to a concentrated level harmful to them. It is well known that bacteria, fungi and protozoa life forms are very necessary in the role played within

25 healthy fertile soil, and that by the conventional application of soild and highly concentrated other fertilisers these life forms including plants can be killed.

5. On the other hand prescription fertiliser is a balanced formulation with protective chemicals and contain only the desirable chemicals and at a predetermined level and pH when diluted with water which allows the absorption naturally by living organisms and plants, such nutrients as they require to promote healthy balanced growth.

5. Another objective of this invention is to offer a balance of nutrients to be available to life forms and for use with hydroponics. It is well known that if there is a deficiency of more than one element in the soil and that not all these elements are made available the plant may die. Again it is the same with all life forms that a balance of nutrients must be present and available as food and this includes all forms of food, carbohydrate, protein, fat, oils, vitamins and elements macro and minor. This includes stimulating hormones and medicine as well as antibiotics. Prescription fertiliser is a balanced formulation. Plants in particular are unable to actively absorb nutrients in some pH ranges. For most plants a pH of 5.3 to 6.4 is the recommended range. Prescription fertiliser is specially applied with the balance of the nutrients giving a pH close to the neutral point pH 7. This is obtained by dilution and using balanced soluble chemical compounds. All the ingredience of prescription fertiliser is a food, even the specially prepared protective chemicals and there is no harmful substances present.

6. 6. Another objective of this invention is to be able to apply prescription chemicals in a protective form to impregnated methyl cellulose, or paper strips which include seeds so that the seeds can be planted in strip form along with all the required nutrients needed for germination. The presence of water and correct temperatures begin germination. This provides a better method of propagation of plants devoid of weeds, and insect problems, if weedicides, insecticides, herbicides, and hormones are impregnated in the strips, along with the prescription chemicals and the seeds.

7. Another objective of this invention is to apply along with prescription fertiliser formulation sex hormones only when needed to give another method of controlling pests of the rodent family and insects suseptable to sex hormone application. Since these classifications are very small compared with that of stock animals very minute quantities of sex hormones are needed to be added because of body weight difference. The consequent application adhering to the foliage of grasses or crops produce conception in these insects or rodents thus controlling the population of these pests. Again the control of conception can also be used for any animals.

8. Another objective of this invention is to supply, as part of the prescription fertiliser, carbohydrate and their

7. derivatives, as a food for life forms. The mono-saccharides are easily assimulated, and metabolised giving energy through the energy rich phosphate bonds, rather than the di- saccharides and polysaccharides which need to be hydrolysised first to give the mono-saccharides. Since energy is obtained from this food quickly, it adds as a suppliment necessary for life form functions. Saccharides on oxidation produce the corresponding acids which when treated with alkali give highly soluble organic salts that have clathrate properties, holding as "guests" the ions in solution protected from chemical action outside the "host". At the same time these carbohydrates and their derivatives on crystallisation produce channel-latice complexes, providing a void or space within the crystal that can hold "guest" ions and become the "host" protecting reaction of these ions from outside the crystal. A good example of this is found with whey. This is immportant for the powdered prescription fertiliser product preparation where hygroscopic substances, for example can then be housed by these "hosts" and protected against the atmospheric humid conditions, or again any other chemicals can be housed protecting interaction of the mixture of chemicals present in prescription fertiliser, by being housed within the crystal as the powdered form. On rendering the prescription to a solution with water the "guest" ions are freed from the "host". The powdered material to be held in solution with the protective chemicals and on being triggered by mild acid on foliage to form a gel or by heavy metal ions present in

8. the soil to form mucilage is once more housed as a "guest" and totally available for absorption with no losses. It is found that the protective chemicals even protect the powdered prescription fertiliser prior to dissolving the material.

9.

Claims

CLAIMS RELATING TO THIS INVENTION

1. That by selection of balanced chemical compounds inorganic or organic, organic chelated products, carbohydrate and derived products exhibiting clathrate properties, channel-latice complexes, carbohydrate and carbohydrate derived complexes having sequestering properties, all soluble in water, can be selected to make up a prescription which is packed as a powdered mixture to enable the following claims :- A. That as a method of transporting the prescribed formulation of fertiliser as a concentrate lowers the cost of transport from those fertilisers in liquid form containing water, or powder containing insoluble material as a filler or impurity. When on site the prescription fertiliser is made into solution for application. Whilst in powder mixture form the contained chemicals are protected by chemicals possessing channel-latice properties holding the chemicals within the spacially formated latice and protecting these chemicals from interaction in particular from moist humid air where hygroscopic substances like salts of phosphate of sodium potassium and ammonium salts in moist air take up the water and dissolve in it, without this protection the powdered mixture would eventually become liquid and spoil the product. Carbohydrates and derivatives, of which there many possible molecules that can be prepared which has this properety of which we claim any of them along with urea which is not a carbohydrate or derivative of a carbohydrate.

10. B. The prescription fertiliser is a mixture of chemicals in a balance of compounds all a food with no harmful substances present, is completely soluble and therefore available to plants and to all forms of life present in the soil, or animals feeding from the pastures or crops, with benificial and not harmful affects.

C. That a prescription can be written to supply the elements found to be depleted in the soil or foliage by analysis of the nutrients present in the soil or foliar solution, to replace and build up the soil with replacement nutrients, supply carbohydrate and derivatives of carbohydrate to enhance the energy needed by life forms for their life functions, and material to increase the soil fertility and soil humus. This prescription is also a balance needed by life forms whereby if more than one element is absent from the soil, then the fertiliser prescription replaces all the elements in a balance for the life form assimilation.

D. That the prescription can be written for a total nutrient available product for use in hydroponics. E. That a prescription can be formulated and impregnated in a soluble methyl cellulose or paper strip along with seeds, insecticides, herbicides and or hormones necessary for the complete maturation of the seed and by additional application of prescribed fertiliser from time to time to provide the needs of nutrients to produce the crop.

F. That weedicides, insecticides, herbicides and or hormones along with medicines and antibiotics if so needed, except

11. those chemicals which contain high concentrations of heavy metal ions, can be included with the prescription fertiliser.

2. That the soluble powdered prescription fertiliser has included within the prescription a dye in a known weight in weight content which enables the following claims :- A. From a standard colour comparison strip supplied with the powdered fertiliser the prescription can be made into solution with water to compare with the colour intensity of that solution, so that a minimum high concentrated solution can be obtained that will not be harmful to apply, the colour can be less intense made by further diluting with water to suit the spraying equipment requirements but may not be applied with a higher colour intensity. B. If the prescription fertiliser is applied in the danger concentration level, then by analysis of the quantity of dye present on the foliage can be determined, hence the actual concentration of the spray. C. The dye will show the person spraying the product where it has been sprayed, and minimise over spraying.

3. Conventional fertilisers when applied solid are not controlled by the concentration of solution produced with rainfall, and consequently high concentrated solutions can result. These highly concentrated solutions when in contact with bacteria present in the soil invariably kill most of that bacteria and in so doing the soil bacteria, which exist with a population of millions per gram, is lowered, consequently the beneficial affect of these bacteria cannot

12. convert organic and inorganic material present in the soil to soluble nutrients ready for plant and other living organisms to assimulate. Again the high concentration of the solution is an irritant to protozoa life forms _> present in the soil, in particular earthworms, they surface and become prey to birds and can be washed away with drainage of surface water in heavy rainfall. The loss of earthworms has a dramatic effect towards the fertility of the soil. Again conventional fertilisers usually do not have

10 a balance of nutrients but contain insoluble carriers of little use due to the insolubility of the material and on application continuously will build up within the soil rendering eventually infertile conditions where plants and other life forms have difficulty in surviving.

15 Prescription fertiliser being applied as a liquid with a controlled dilution for application and a balance of all important required element nutrients being present including the protective chemicials, namely carbohydrates and their derivatives as described in claim 1 above, are in a powdered

20 mixture before application, and then rendered to solution with all the material being soluble to a predetermined pH close to neutral, at the same time all the ingredience are food to plants and other life forms which with the protective chemicals being triggered on foliage by the

25 mechanism mentioned previously to form a gel with mild acids as well as the triggering action within the soil by heavy metal ions present in the soil to form a mucilage

13. encapsulating the applied chemical nutrients prevents the problems so mentioned.

4. Conventional fertilisers provided on the market do not cater for the soil life forms and plants for energy producing foods, enabling ideal conditions to enhance growth and reproduction. Prescription fertiliser prescribes for this by the inclusion of the protective chemicals which have a carbohydrate base in a soluble form as well as the inclusion of carbohydrate itself. Though the protective chemicals being carbohydrate base forms muciliages encapsulating the prescribed nutrients is a semi-solid is not in a soluble form for immediate assimulation, but it is a food to bacterial action and protozoa life forms, in particular earthworms. The protective chemicals therefore are digested eventually. Bacterial counts and protozoa counts of the soil treated with prescription fertiliser increase.

Whey has present carbohydrate and can be used instead of water to render soluble the prescribed fertiliser, but it will be applied in very high dilution some forty times the usual recommended dilution when water is the sole dissolving agent, because of the presence of the carbohydrate in the whey and the addition of prescription fertiliser to the whey, a gel is produced slowly within the soil taking several days and once again giving a protection towards surface run-off, leaching, and interaction with soil chemicals rendering them insoluble which is known as immobility.

1 . 5. That the preparation of special complexes from carbohydrate, oxidised to produce the corresponding acid, esterified with organic or inorganic acids, and neutralised to produce the soluble salt with alkali will form complexes with elements. The intensity of the colour can be colourmetrically determined and compared from a standard known concentration colour intensity thereby giving a method of analysis of the soluble chemicals present in the soil solution of a test sample. 6. That carbohydrates and their derivatives in particular the oxidation products which produce the corresponding acid then neutralised with alkali produces a highly soluble product which will react beneficially to give protection with the following claims :- A. The prescription fertiliser is made into solution with ordinary water which usually contains very low concentration of heavy metal ions. The reaction which takes place with the prescription protection chemicals is brought about by the presence of heavy metal ions, but the speed of the reaction is directly proportional to the concentration of the heavy metal ions present. With most waters the concentration of these ions being low takes up to six to eight hours for the reaction to take place to form a mucilage. This fact allows ample time for the product to be made into solution and applied.

B. Soil solution contains higher concentration of heavy metal ions and the reaction to form a mucilage is one to two

15 hours. This allows this beneficial mucilage to be formed at root level.

C. That mild acids produce a different type of reaction forming a gum-like gel. D. The mucilages and gels mentioned above from these carbohydrate derived protection chemicals are able to absorb up to 60% weight in weight of water and has clathrate properties enveloping the ions present even in solution and then as a mucilage or gel when formed. The mucilage or gel 0 which ever way they are formed have clathrate properties thus giving protection against the following claims :- a.) The protection against unwanted chemical reaction from outside chemicals present in the soil solution is prevented from causing precipitation or rending the "guest" ions from 5 becoming insoluble and therefore unavailable as a food for life forms. The nutrients are protected against immobilisation. b. ) The mucliage prevents leaching, that is the "guest" ions are prevented from being washed away out of reach of ^ύ the plant roots, or from the other life forms present in the soil. c.) In the case of the gum-like gel formed on foilage the "guest" ions are prevented from being washed off from the foliage, thus enhancing foliage feeding. 5 d.) That both the mucilages and the gels being carbohydrate derivatives and therefore a food with no harmful ingredience. e.) The clathrate properties of the mucilages and gels have

16. the additional property of being able to from a bridge for the "guest" ions present within the "host" to be transported across the :-

-COOH or H-C I-OH groups spacially arranged in

I the ring structure, and also a bridge for the ions present outside the ring structure, by active absorption by life forms. This means that all the applied ions in prescription fertiliser and the ions present within the soil solution are available for life forms active absorption. f.) Surface run-off is a problem with all other fertilisers. Prescription fertiliser has not this problem since the protective chemicals when triggered on foliage or within or on the soil becomes a gel or mucilage then the chemicals are protected from run-off. This is very important because all other fertilisers with surface run-off and leaching contaminate rivers and lakes with the fertiliser with very harmful effects. Prescription fertiliser prevents this condition occuring. 7. That chelates can be produced from carbohydrates and their derivatives which produce soluble salts of a complex nature in the following claims :-

A. Glucose in solution with calcium salts produce complexes that are unaffected by sulphate ions and other ions which normally would cause precipitation, and remain in solution unaffected by these ions, giving a 1.8% weight in weight solution of available calcium, in a highly soluble form. The

17. application of calcium to the soil is conventionally applied with calcium carbonate, known as lime. The solubility of calcium carbonate is very small needing large amounts of rainfall to give small quantities in a soluble solution that would then be available to plants, it takes up to five years in some regions for the lime to be used depending upon the rainfall. The use of the highly soluble glucose calcium complex not only is protected from interaction of other soil chemicals, since it has clathrate property with the base being carbohydrate, but gives a method of supplying calcium nutrient easily to the soil, soluble and ready for assimulation by plants and other life forms. All other elements with a glucose base or carbohydrate base, of which there are many, will produce complexes that have chelated and clathratic properties.

B. That numerous chelates can be produced from mono, di- and polysaccharides to produce heavy metal soluble complexes, with clathratic properties, which allows a method of introducing macro and minor elements to the prescription fertiliser without fear of chemical reaction, and therefore preventing immobilisation by soil chemicals producing insoluble salts and making these nutrients unavailable to plants and other life forms.

C. That the higher the number of mono-saccharides joined together in a chain then the greater is the viscosity of the mucilage.

D. The smaller the number of mono-saccharide molecules in the chain the greater is the adhesive or gum-like property

18. of the mucilage or gel formed.

8. Crystalisation of urea, amylosee and other carbohydrate derivatives, and zeolites shows channel-latice complex ability enclosing and protecting ions of compounds of a size

5 able to be held in the void or space provided. This allows special compounds to be crystalised as "guests" with in the crystal "host" giving protection against unwanted chemical reaction of these "guest" ions whilst in powdered form. This allows the prescription to be mixed as a powder without fear

10 of interaction of the chemical ions so enclosed, with other enclosed ions. Ammonium Nitrate is an example inwhich being hygroscopic, that is it takes up moisture from the atmosphere and dissolves in that moisture, is protected against this happening when enclosed with urea crystal.

15 9. Hormones as an addition to prescription fertiliser of which some of these are able to be used as a controceptive in a mixture which have Oestrone effect are very slightly soluble in water or in alkali solutions most of these have a CHOLESTROL base, ethinyloestradiol for example is very

²⁰ slightly soluble in water others are insoluble in water but soluble in alcohol. The use of the combination of the sex hormones in minute quantities can be adhered to the foliage which pests, example mice, rodents, rabbits, or any other animal or insect, can be controlled by a controceptive

^5 action which makes them unable to propergate, preventing off-springs being produced and giving another method of pest control. 19. SUPPORT INFORMATION OF OBJECTIV S

Chemicals of the major elements are present in inorganic and organic compounds which are soluble in water, these elements include carbon, hydrogen, nitrogen, oxygen, calcium, potassium, phosporus, and sulphur. The minor- elements of importance are magnesium, iron, manganese, cobalt, copper, boron, selenium, zinc, and molybdenum however with the soluble salts of these in solution with other macro-elements, especially with alkaline solutions, are precipitated, thus making them unavailable to life forms, since they can only ingest the soluble ions. To prevent chemical reaction and have these ions available in solution complexes can be formed with organic compounds secondary coordinate complexes where the central atom is in complex with ligands in a coordination sphere and an ionisation sphere, and when the ligand forms a stable water- soluble metal complex resistant to chemical reaction, it becomes of importance to prescription fertiliser. Diagramatically it is known that :-

-Central Atom

In solution this compound will ionise to form [CoCl(NH3)5]++ and 2C1- ions. The chloride ion in the coordination sphere is not precipitated by silver nitrate. The groups which

20. combine with the central atom, by any type of bonding, are called LIGANDS. The type of bonding between the metal and ligand may be electrostatic or covalent. However, whether the bonding is ionic, covalent, or intermediate, the function of the ligand is always that of donating electrons to the central atom. The COORDINATE NUMBER is the maximum number of atoms or groups which can combine, in the combination sphere, with the central atom (usually an even number) . Ligands which have more than one electron pair available for coordination with the central ion are said to be bi, tri, or poly DENTATE.

A A' A A'

\ / \ / M M

/ \ / \ A" A"' A" A"' M has coordinate number Ligands A-A' and A"-A^,l of 4, and the ligands A, ARE BIDENTATE.

A', A", A"' ARE UNIDENTATE. A CHELATE.

A METAL COMPLEX.

Groups which occupy more than one coordination position in a complex form a ring with a central ion and are termed CHELATES. (Gr., claw).

Many groups have the ability to coordinate with the central atom, in the following order of decreasing affinity of coordinating groups :-

// -o⁷ > -NH2 > -N=N- > N > Ring Nitrogen > -COO' > - Enolate Amine Azo \ ion

/ -O- > ETHER > > -C=0 Carboxyl

CHELATES 21.

UBSTITUTE SHEET If the ligand forms a stable water-soluble METAL CHELATE IT IS SAID TO BE A SEQUESTERING AGENT. This means that the metal properties of the metal without removal of that metal from the system or phase by any process of precipitation or extraction is usually accomplished by CHELATION.

CITRIC ACID has been used to sequester metals in living systems, in foods, beverages and cosmetics.

METALLIC COMPLEXES of bi-valent cations with tartrates and citrates exist in a 1:1 molar ratio of tartrate or citrate to the metal.

ETHELENEDIAMINETETRAACETIC ACID (EDTA)

HOOC-CH2 CH2-COOH

\ /

N-CH2-CH2-N

/ \

HOOC-CH2 CH2-COOH

Ethylenediaminetetraacetic Acid

THE CALCIUM COMPLEX OF EDTA AS A TETRADENTRATE LIGAND

-OOC-CH2 CH2-C=0

\ / \

/ \ / -OOC-CH2 CH2

I have found that carbohydrate and derivatives of carbohydrate show ease of forming soluble salts complexes

22. with the trace elements and have sequestering properties.

The different types of carbohydrate derivatives used are prepared form mono, di and polysaccharides.

It is found that for example that calcium can be complexed with glucose, a mono-saccharide, in solution with calcium salts to produce a protected calcium ion having 1.8% weight in weight of calcium, it is not precipitated by sulphate ions. Again from the mono-saccharide by mild oxidation to the acid and neutralisation with sodium or potassium alkali produces a soluble acid salt. This salt forms a complex with solutions of the trace elements unaffected by weak acids or alkalis. This means that it will remain in solution in the presence of soil chemicals and be available to the life forms as nutrients.

From the di-saccharides example cane sugar complex is formed with acetic acid, or citric acid producing a soluble salt when treated with sodium, potassium or ammounium alkali, these soluble salts form a mucilage when coming in contact with ions of heavy metals in solution. The rate at which the mucilage is formed is directly proportional to the concentration of the heavy metal ion solution. These mucilages formed have sponge-like properties and will when dried and treated with water become a mucilage and absorb up to 60% of water depending upon the structure. It is also found that the mucilage has clathratic properties enveloping inorganic ions which are the "guest" ions within the molecule of these mucilages, the "host". The importance of

23. this property of the mucilage, allows protection against unwanted reaction with soil chemicals, for not only are the ions in solution and held with the ability of the mucilage to absorb water, but are held remote from interaction of

5 outside chemicals.

With poly-saccharides prepared by mild oxidation to the acid and neutralising with sodium, potassium or ammonium alkali these soluble acid salts in small concentrations of 1% will produce mucilages when in contact with heavy metal ions and

1 again the time of formation of the mucilage is directly proportional to the concentration of the heavy metal ions in solution. It is these compounds which are of importance to prescription fertiliser since the soluble solution containing the prescription chemicals and the protective

'5 carbohydrate dirivatives remain in solution providing sufficient time to apply. It is found that no mucilage is formed after four hours of mixing and even up to eight hours of mixing where the concentration of water heavy metal ions are in low concentration in ordinary water supply. After six ⁰ to eight hours mucilage begins forming, it is therefore a requirement to mix with water and spray on immediately. It is also found that with high concentration of heavy metal ions the mucilage is produced far more rapidly within a hour depending upon the concentration. What this means is that 5 the protective prescription chemicals become activated in the soil producing the mucilage protecting the chemicals of the prescription formulation by its clathratic properties

24. and providing a protection from leaching. It is also found that the chemical structure of these protective chemicals since they have, depending upon the length of the carbohydrate chain, a number of -COOH groups and H-CH-OH groups present, the H in the -COOH group can be replaced by a cation and therefore a bridge is formed within the molecule for transfer of cations across the -COOH groups to the root system by active absorption. The mucilage has the - COOH and the H-CH-OH , Space orientated in the chain and is therefore on the perimeter of the space where the "Host" molecule houses the "guests", this means that the bridge is in place for transport of ions even outside the "host" molecule allowing the ions present in the soil to be actively absorbed. Anions, example, Phosphate ions are bridged in a similar way as the cations, but by way of the -OH groups. Phosphate ions have either one, two or three salts formed from the parent ortho-phosphoric acid, H3P04, depending upon the number of H being replaced by a cation, this produces H2P04', HP04", or P04'" negatively charged ions. The -OH group is also negatively charged and therefore produces the bridge. This means the mucilage protects and at the same time gives a bridge for the transfer of cations and anions, inside the clathrate and outside the "host" for the soil chemicals. Again the clathrate property is afforded by the O in the

OH group transporting anions whilst the H in the -COOH and H-CH-OH attracts the cations since the -O is negatively charged and the -H is positively charged.

25. One of the chemicals extracted from seaweed is alginic acid which when neutralised with alkali, sodium, potassium, or ammonium forms soluble salts, of the corresponding alginates, and consists of d-manuronic acid molecules in a long chain :-

OH H COONa

O C -C C 0

\ /H OH \H H / \ /

C C C C / \ H / \ / \ OH OH/ \

OH C

COONa H H X sodium alginate

This material exhibits all the above properties of mucilage formation with heavy metal ions and displays the sponge-like properties able to absorb 60% of water as well as having the clathratic properties. It is found that the higher the number of molecules in the chain, as with sodium alginate where "x" is high, the mucilage, and its viscosity, the clathratic and sponge-like properties increase. It is also found that the gum type complexes occur more readily with the lower number of molecules in the chain. For example a complex made with cane sugar esterified with acetic acid and neutralised with sodium, potassium or ammonium alkali produced a gum type of mucilage. This mucilage has the important ability of forming in mild acid conditions. Carbon dioxide dissolved in water produces a mild acid which will cause the neutral to alkaline complex

26. to produce the gum mucilage. It is this material which is used for foilage feeding so that the gum mucilage will provide a sticking property to the prescription chemicals when coming in contact with the surface of foliage that has from respiration carbon dioxide dissolved on the surface of the foliage. This gum-mucilage has clathratic and sponge¬ like properties.

Sodium alginate will with mild acids form a gum-like gel also but does not have the same strength of adhesive properties as the shorter chain gum-gel. It is found however that the gel produced from mild acid with sodium alginate is very different to the mucilage formed with heavy metal ions. The former is sticky but slippery the latter is not sticky but very slippery and a thicker gel. Calcium Disodiumethylenetetraacetic acid cation complex is soluble in water but insoluble in organic solvents, and as the calcium ion is the central element will accept electrons and therefore allow complexes to be formed from the sodium salts when placed with a trace element heavy metallic ion. The effect with the complex formation for a particular trace element gives a change in colour for each element when further treated with diphenylthiocarbazone. The intensity of colour depends upon the concentration of the element ion present. A comparison with standard known element solutions give a photo-colourmetric evaluation of the sample and therefore the concentration of this element present in the known volume of solution. By this method analysis of soil

27. samples for any element can be determined except for calcium and chloride. This is determined by a known turbility comparison method. What it means is that instead of the usual method of analysing samples of soil by determining the elements present after extraction using a 1% to 2% citric acid solution, a method is now available whereby the elements can be analysed by determining the soluble material present in the soil water by use of deionised water. The extraction of the trace element to be determined is separated from the soil solution and all the other elements removed by known chemical methods. The photo-colourmetric evaluation is then taken.

For the determination of iron present a complex is formed by the use of glucose derived gluconic acid by mild oxidation then neutralising with sodium hydroxide solution. This solution form a complex with the iron in solution which when treated with dimethylglyoxime reagent produces a red colouration. The intensity of this red colouration deteriraes the concentration of the ferric ions present. In the same way copper extracted with sequestering gluconic acid complex treated with 7-iodo-8-hydroxyquinoline in sulphuric acid produces a green to greenish blue intensity colouration, which again on comparision colourmetrically gives the concentration of copper ions present. The Dye Methylene Blue has the imphirical formular [C16H18C1N3S3H20] is :-

3,7-Bis-(dimethylamino)Phenazathionium Chloride has very mild antiseptic action, but in the concentration that it

28. will be applied will not have harmful effect upon soil life forms. It is easily identified by tests and is soluble in water not affected by slightly acid to alkaline solutions but with pH below 3 is unstable. It is therefore ideal for inclusion in prescription fertiliser.

The chemicals used to make up the prescription especially with the macro-elements are combined molecules of inorganic elements and organic radicals utilising these elements in combination of soluble salts :- Potassium Dihydrogen Orthophosphate, KH2P04, has two macro¬ elements of importance. Potassium, K, 28.73% wt in wt of the crystalline powder, and Phosphorus, P, 22.76% wt in wt. A 5% solution in water produced a pH 4.1-4.5 at 25 degrees centigrade. Di-Potassium Hydrogen Orthophosphate, K2HP04, has 44.89% wt in wt of Potassium, K, and a7.79% wt in wt of Phosphorus, P. A 5% solution in water has a pH of 8.8 at 25 degrees centigrate. Ammonium D-Hydrogen Orthophosphate, NH4H2P04, has 12.18% Nitrogen, N, wt in wt and 26.93% Phosphorus, P, wt in wt. A 5% solution in water has a pH 3.8-4.4 at 25 degrees centigrade. Di-Ammonium Hydrogen Orthophosphate, (NH4)2HP04, has 21.22% Nitrogen, N, wt in wt, and Phosphorus, P, 23.46% wt in wt. A 5% solution in water has a pH of 7.7-8.1 at 25 degrees centigrade. Sodium Thiosulphate, Na2S203.5H20, is a convenient source of sulphur, since it is very soluble in water and contains 25.84% wt in wt of Sulphur, S. A 5% soultion in water has a

29. pH of 6. 0-8. 4 at 25 degrees centigrade .

Urea , NH2-C=0 is an organic compound and contains

\

NH2

46.65% wt in wt of Nitrogen, N. It is slightly hygroscopic.

5 Urea form channel-latice complexes on crystallisation where another "host" to "guest" property exists, however in this case the "guest" component must be of a shape which will fit into the void or channel :-

NH2 H2N CRYSTAL STRUCTURE OF UREA

-_|Q / \ showing cage-like space

O = C C = 0 within latice.

\ /

NH2 H2N

The space in this channel-latice is able to hold potassium and ammonium dihydrogen orthophosphate salts but is not large enough to hold the Tri-Potassium, or Tri-Ammonium, 5 othophosphate salts. This fact allows crystalline salts including the above "guests" to be housed within the crystal of the "host" urea. A number of other molecules are small enough to become "guests" to the "host" urea that can be used in this way, examples sodium thiosulphate and ammonium ⁰ nitrate. Amylose and the zeolites are examples of importance to prescription fertiliser in that they exhibit channel- latice complexes and will as "hosts" house "guests" of a larger size molecule. These crystals when disolved in water separate giving the "host" in solution and the "guests" in 5 solution. A balance of prescription fertiliser combinations can then be made using all kinds of concentrated chemicals,

30.

HEET either inorganic or organic, to obtain the prescription needed to replace soil tested deficient elements of macro or trace elements.

Carbohydrates are classified as mono, di- and poly- 5 saccharides. The di- and the poly-saccharides consists of two or more molecules of mono-saccharides joined together in a chain, and the molecule of a mono-saccharide is a ring structure, for example glucose in the ring structure is glucopyranose :-

¹⁰

H

C C glucopyranose

/ \ OH H / \ 3 dimentional ring 15 OH \ I I / OH structure.

C C Note the space inside the

I I ring.

H OH

\|/ oxidation

COOH

20 c O

H / I \ H

\ / H \ /

C C gluconic acid

/ \ / \ ₂₅ OH \ / OH

These specially configured structures exhibit clathrate properties and is of importance as an item of prescription -³⁰ fertiliser in that it becomes the "host" of the "guest" ions present in prescription fertiliser when made into solution, and in the case where the channel-latice crystal complexes

31. have been dissolved in water releasing the ion "guests" they hold, then these ions are attracted to be enclosed within the new "hosts" of these carbohydrate structures as their "guests" providing protection from outside unwanted chemical reaction.

The soil chemistry is very complex and it is due to the clathrate properties of carbohydrates and their derivatives that the addition of carbohydrate to the fertiliser contributes to the build up of humus of the soil. Organic chemicals can be added to prescription fertiliser if soluble, some of the additives that may be needed can be in a lot of cases rendered soluble either by reaction with alkali or first dissolving in alcohol. Most organic chemicals that react with alkali retain their properties, but however hormones can be destroyed by the addition of alkali, this fact being very useful when dealing with the control of pests using sex hormones, some of them are very slightly soluble in water, others are insoluble in water, minute quantities of these can be added by dissloving in alcohol first. Ethinyloestradiol for example is very slightly soluble in water whereas oesterone and norethisterone are both insoluble in water. The minute quantities are added to prescription fertiliser formulation for pest control, with insects, rodents, rabbits and other animals, by first dissolving the insoluble (in water) hormone mixture in the soluble medium of alcohol. These hormones are sensitive to light and can be rendered inactive by the application of lime. The alkali action of lime

32. destroys the hormone. Prescription fertiliser formulation contains the protective action of the gel-muciliage forming chemicals protecting the hormones added, therefore at any time the hormone action is need to become inactive lime (a fertiliser) is applied. The fact that the pests feed off the foliage provides a convenient method dosing them with the required hormone controceptive.

33.