NZ531078A - Fertiliser compositions for reducing the progress of the production of nitrates in the soil - Google Patents

Abstract

A method of producing a composition suitable to be applied to the soil and/or pasture is disclosed, wherein the method comprises the steps of: (i) formulating an aqueous slurry of a particulate nitrification inhibitor agent or particulate nitrification inhibitor agents having at least one zeolite as a potential carrier in a particulate form, and optionally having a suitable suspension stabilising agent, and (ii) drying the slurry to at least a substantially dried particulate form which has the nitrification inhibitor(s) adhered to or otherwise carried by the zeolite(s) ("the zeolite(s) carrier").

Description

531078 *10056536139* NEW ZEALAND PATENTS ACT, 1953 No: 531078 Date: 9 February 2004 COMPLETE SPECIFICATION FERTILIZER COMPOSITIONS We, BALLANCE AGRI-NUTRIENTS LIMITED, a company duly incorporated under the laws of New Zealand of Hewletts Road, Mount Maunganui, New Zealand, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: 1"- n 5 ■ ' "> d k. .n n c r c I INTEtt€CTUAL PROPERTY OFFICE OE, N.Z. 119 mar 2006 RECEIVED The present invention relates to the treatment of the soil and/or pasture, compositions for application to the soil and/or pasture, procedures for preparing such compositions, compositions thus formed, fertiliser compositions and related uses.

Nitrification is the process of conversion of a relatively immobile form of nitrogen (N) from an ammonium (NH4+) form into the more mobile nitrate (NO3") form. During nitrification the NH4+ is believed to be first oxidised to nitrite (NCY) and that this conversion is largely brought about by Nitrosomonas bacteria. Thereafter the N02" in turn, it is believed, is oxidised to N03" by Nitrobacter bacteria.

Nitrates, produced from the nitrification process, is subject to losses by leaching from soils and can potentially contaminate surface and ground water. Nitrates can also undergo denitrification in the absence of oxygen by a taxonomically diverse group of microorganisms to gaseous oxides of N (e.g. N20) and nitrogen gas (N2), which are commonly lost to the atmosphere. These losses of N account for inefficiencies in the use of applied N by plants, whether from N including fertilisers or urine, or both. N20 is one of the greenhouse gases and also has a catalytic effect on the destruction of stratospheric ozone.

An approach previously proposed to increase plant N use efficiency and minimise potential adverse environmental effects by nitrogeneous compounds is the use of nitrification inhibitors. Since NH4+ is less subject to loss from soils, delaying the microbial transformation (nitrification process) of NH4+ to NO3" through the use of nitrification inhibitors can result in an increase in potential N availability for plant growth and a decrease in N03" and N20 production.

Nitrification inhibitors are compounds that delay the microbial oxidation of NH4+ to N02" (the first step of the nitrification process) for a certain period by depressing the activity of Nitrosomonas bacteria in soils. The second step of nitrification it is believed normally is not influenced.

An ideal nitrification inhibitor should have the following characteristics: Specificity. It should block the conversion of NH4+to N03" and be nontoxic to other soil organisms, animals and humans.

Mobility. It should move with N fertilisers or nutrient solution. Persistence. It should stay in soils for an adequate period.

Int«si'-T.v;!4i Property Olsiufo of M.2. 0 9 NAR 2006 flCitofioofc i'?1 NOW AMENDED Economy. It should be cheap as it is frequently to be used as an additivf to fertilisers.

Examples of compositions that hitherto have been considered for appti&rfion to soils or pasture include those disclosed by Sumitomo Chemical Co Ltd New Zealand Patent Specification No. 161791 where they disclose a ni^rophosphate fertiliser containing a nitrification inhibitor in the amount of from 1 to^0% by weight based on total nitrogen content and where the fertiliser contains jutrate nitrogen of from 20 to 80% by weight based on total nitrogen content. Ex^ples of nitrification inhibitors given in New Zealand are as follows: N-2,5-dichlorophenyl succinamic acid 2-chloro-6-trichloromethyl pyridine ("Nitarfj$rin") dicyandiamide ("DCD or "DCDIN"")^ch is HN=C(NH2)-NH-CN zinc ethylene-bis-dithiocarbamate 2,4,6-trichloroaniline pentachlorophenol thio-urea.

Other known nitrification inlfrtfitors include ATS (ammonium thiosulphate) and water soluble DMPP (3,4-dyythypyrazole phosphate). Still other options are discussed in the prior art.

The term "nitrificat^^inhibitor" or its plural refers to any suitable compound or compounds and is incUfsfve of those discussed above.

As used here«f%eolite" or "zeolites" means mineral sourced alumino-silicates of a porous three dimensional form. Examples include Clinoptilolite and Mordenite. It is an object ojwq present invention to provide advantageous compositions inclusive of nitrificati9<yfnhibitor(s) capable of agricultural use.

Ii/one aspect the invention is a method of producing a composition suitable (alone/y^ in conjunction with at least one other material) to be applied to the soil an#?#? pasture, said method comprising or including formulating a slurry of at least one zeolite as a particulate carrier with a liquid (preferably at least water) after, as and/or prior to the inclusion of at least one nitrification inhibitor therein, and ^ h .1 ' Q\ O ■ f O i* Vi , C l 1 * 9^0 Iv.«<<« D cr* p i i/ intellectual property office bf fe" 03 mar 2006.... receivcb ^ / |JAU| j\JHEHBEOEc0n0m>' ^ s^ou^ c^eaP as it is frequently to be used as an additi^ to fertilisers.

Examples of compositions that hitherto have been considered for apptftajfon to soils or pasture include those disclosed by Sumitomo Chemical Co Ltd bf it/ New Zealand Patent Specification No. 161791 where they disclose a nijropfiosphate fertiliser containing a nitrification inhibitor in the amount of from 1 to^OSC by weight based on total nitrogen content and where the fertiliser contains jfitmte nitrogen of from 20 to 80% by weight based on total nitrogen content. Examples of nitrification inhibitors given in New Zealand are as follows: N-2,5-dichlorophenyl succinamic acid _ - 2-chloro-6-trichloromethyl pyridine ("Niti^fpyfin") ^ - dicyandiamide ("DCD or "DCDIN"") y^i;rfi is HN=C(NH2)-NH-CN zinc ethylene-bis-dithiocarbamate 2,4,6-trichloroaniline pentachlorophenol thio-urea.

Other known nitrification inbfbjlbrs include ATS (ammonium thiosulphate) and water soluble DMPP (3,4-digretJrfypyrazole phosphate). Still other options are discussed in the prior art.

The term "nitrification i#mibitor" or its plural refers to any suitable compound or compounds and is 'mo\x&v4 of those discussed above.

As used herein/z^61ite" or "zeolites" means mineral sourced alumino-silicates of a porous three diifieftsional form. Examples include Clinoptilolite and Mordenite. It is an object ofmypresent invention to provide advantageous compositions inclusive of nitrificatioiyinmbitor(s) capable of agricultural use.

In />n£ aspect the invention is a method of producing a particulate composition suitable (alone or in conjunction with at least one other material) to be |no the soil and/or pasture, said method comprising or including (A) formulating and establishing an aqueous (i) at least one particulate )lite, (ii) at least one particulate nitrification inhibitor without substantial dissolation ''and (iii) a tackifier, wherein the particulate nitrification inhibitor(s) on average is (are) finer than the zeolite(s), and wherein the tackifier has the capability in the aqueous intellectual property office of N2. - jun2w AS AMENDED Economy. It should be cheap as it is frequently to be used as an additive to fertilisers.

Examples of compositions that hitherto have been considered for application to soils or pasture include those disclosed by Sumitomo Chemical Co Ltd in its New Zealand Patent Specification No. 161791 where they disclose a nitrophosphate fertiliser containing a nitrification inhibitor in the amount of from 1 to 20% by weight based on total nitrogen content and where the fertiliser contains nitrate nitrogen of from 20 to 80% by weight based on total nitrogen content. Examples of nitrification inhibitors given in New Zealand are as follows: N-2,5-dichlorophenyl succinamic acid 2-chloro-6-trichloromethyl pyridine ("Nitrapyrin") ® - dicyandiamide ("DCD or "DCDIN"") which is HN=C(NH2)-NH-CN zinc ethylene-bis-dithiocarbamate 2,4,6-trichloroaniline pentachlorophenol thio-urea.

Other known nitrification inhibitors include ATS (ammonium thiosulphate) and water soluble DMPP (3,4-dimethypyrazole phosphate). Still other options are discussed in the prior art.

The term "nitrification inhibitor" or its plural refers to any suitable compound or compounds and is inclusive of those discussed above.

^ As used herein "zeolite" or "zeolites" means mineral sourced alumino-silicates of a porous three dimensional form. Examples include Clinoptilolite and Mordenite. It is an object of the present invention to provide advantageous compositions inclusive of nitrification inhibitor(s) capable of agricultural use.

In one aspect the invention is a method of producing a particulate composition suitable (alone or in conjunction with at least one other material) to be applied to the soil and/or pasture, said method comprising or including (A) formulating and establishing an aqueous slurry of (i) at least one particulate zeolite, (ii) at least one particulate nitrification inhibitor without substantial dissolation and (iii) a tackifier, wherein the particulate nitrification inhibitor(s) on average is (are) finer than the zeolite(s), and wherein the tackifier has the capability in the aqueous Intellectual Property Office of M.2. 1 9 nov 2007 RECEIVED AMENDED drying the slurry to result in an at least substantially dry particulate material sjth the zeolite carrying the nitrification inhibitors).

The nitrification inhibitors) may be soluble to some extent in the liquid but prefe^ly is present as a particle prior to the drying step. jferred particle size ranges for the solid carrier or zeolite is from 1 to 3mm (typically N&% passing a 3mm screen and < 1% a 1mm screen).

Cherm^Jly preferably the zeolite is 65 to 95% w/w mordenite and 5 to 20% smectite.

The nitrific&^qn inhibitor is preferably (but optionally) able to pass through a 200fj.ni screen.

The nitrification rolubitor(s) prior to drying is supported in the liquid by a suspension agent (preferablyVWm).

Preferably the slurry pnok to drying (preferably to a dryness of less than 8 % w/w water/composition) includesN^ the suspension agent or otherwise a tackifier (e.g. a gum).

Examples of suitable gums fdrV>ne or both purposes include microbial polysaccharides such as dextran, gella^X rhamsan, guar and xanthan gums; polysaccharide derivatives such as hydroxymtohylcellulose, hydroxyethylcellulose, microcrystalline cellulose and modified starchesKand synthetic polymers such as polyvinyl alcohols, polyvinyl acetates and cross-linK^cKpolyacrylates.

In another aspect the invention is a methoovfc producing a composition suitable (alone or in conjunction with at least one other imperial) to be applied to the soil and/or pasture, said method comprising or including thes^ps of formulating an aqueous slurry of a particulate nitrification agent or agents together with one or both of a suitable suspension stabilising agentVW a zeolite carrier or carriers in a particulate form, and drying the slurry to at least a substantially dried particulate formVkich has the nitrification inhibitor(s) adhered to or otherwise carried by the zeolite(s) caA\& Preferably the formation of said slurry is a stage wise process.

Preferably said stage wise process involves optionally milling in wat& nitrification inhibitor(s).

UTfl.;'-; OT o s i::z zoos p C I \/ c intellectuatproperty OFFICE OF W.z. 89 MAR 2006 ;/ RIOIIVItt NOW AMENDED environment of contacting both the particulate zeolite(s) and the particulate Snitrification inhibitor(s), and Vs. (B) drying the slurry to result in an at least substantially dry particulate marmal with the zeolite particles carrying as a coating the tackifier adhered particles of the nhrification inhibitor(s).

Tflknitrification inhibitor(s) may be soluble to some extent in the liquid but preferably iswesent as a particle smaller than the average zeolite particles from the outset as well aSvprior to the drying step.

Preferred particle size ranges for the solid carrier or zeolite is from 1 to 3mm (typically 100% passing^ 3 mm screen and < 1% a 1mm screen).

Chemically preferably the zeolite is 65 to 95% w/w mordenite and 5 to 20% smectite. YV The nitrification inhibnot is preferably (but optionally) able to pass through a 200|xm screen. \V The nitrification inhibitorsJNprior to drying is supported in the liquid by a suspension agent (preferably a gum). \\ Preferably the slurry prior to dryin^\preferably to a dryness of less than 8 % w/w water/composition) includes as the suspension agent or otherwise a tackifier (e.g. a gum). \\ Examples of suitable gums for one or purposes include microbial polysaccharides such as dextran, gellan, rhamsanAguar and xanthan gums; polysaccharide derivatives such as hydroxymethylcellutobe, hydroxyethylcellulose, microcrystalline cellulose and modified starches; and symntoic polymers such as polyvinyl alcohols, polyvinyl acetates and cross-linked polyacryrattes.

In another aspect the invention is a method of producmk a composition suitable (alone or in conjunction with at least one other material) to D^V>plied to the soil and/or pasture, said method comprising or including the steps of \\ formulating an aqueous slurry of a particulate nitrification agentSokagents together with one or both of a suitable suspension stabilising agent and a zeoliteArrier or carriers in a particulate form, and \\ drying the slurry to at least a substantially dried particulate form which has tlre^ nitrification inhibitor(s) adhered to or otherwise carried by the zeolite(s) carrier. intellectual property office 0FN2. - jun 2007 \ environment of contacting both the particulate zeolite(s) and the particulate nitrification inhibitor(s), and (B) drying the slurry to result in an at least substantially dry particulate material with the zeolite particles carrying as a coating the tackifier adhered particles of the nitrification inhibitor(s).

The nitrification inhibitor(s) may be soluble to some extent in the liquid but preferably is present as a particle smaller than the average zeolite particles from the outset as well as prior to the drying step.

Preferred particle size ranges for the solid carrier or zeolite is from 1 to 3mm (typically 100% passing a 3mm screen and < 1% a 1mm screen).

Chemically preferably the zeolite is 65 to 95% w/w mordenite and 5 to 20% smectite.

The nitrification inhibitor is preferably (but optionally) able to pass through a 200(o,m screen.

The nitrification inhibitor(s) prior to drying is supported in the liquid by a suspension agent (preferably a gum).

Preferably the slurry prior to drying (preferably to a dryness of less than 8 % w/w water/composition) includes as the suspension agent or otherwise a tackifier (e.g. a gum).

Examples of suitable gums for one or both purposes include microbial polysaccharides such as dextran, gellan, rhamsan, guar and xanthan gums; polysaccharide derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, microcrystalline cellulose and modified starches; and synthetic polymers such as polyvinyl alcohols, polyvinyl acetates and cross-linked polyacrylates.

In another aspect the invention is a method of producing a composition suitable (alone or in conjunction with at least one other material) to be applied to the soil and/or pasture as defined in the first aspect, said method further comprising or including the steps of formulating an aqueous slurry of a particulate nitrification inhibitor or inhibitors together with one or both of a suitable suspension stabilising agent and a zeolite carrier or carriers in a particulate form, and drying the slurry to at least a substantially dried particulate form which has the nitrification inhibitor(s) adhered to or otherwise carried by the zeolite(s) carrier. intellectual Property j Office of H.z. ' I 19 nov 2007 IOW AMENDED -5 Preferably the suspension stabilising agent and/or tack providing agent is added to the initial slurry and thereafter the zeolite(s) carrier is added. In preferred of the present invention the nitrification agent is selected from the range of particulate nitrification agents including DCD and ATS.

^Preferably said suspension stabilising agent and/or tack providing agent is a gum. Preferably said gum is a polysaccharide gum such as, by way of example, one or more of xanthan gum, guar gum, etc. [e.g. as earlier exemplified]. the composition produced by the process is any of the compositions hereinafter descKted.

In yet a fih^er aspect the present invention consists in the aforementioned process(es) and the optimal additional step of adding a flow enhancing agent such as a particulate agent such asialc to the dried product.

In still a further aspect the present invention consists in the aforementioned process(es) and the additiona\V>tional step (irrespective of whether or not a flow enhancing agent has been utilise^Vof admixing or otherwise associating the zeolite carried nitrification inhibitor(s) wim\a fertilising agent, compound or composition irrespective of whether or not it inclu(|e| nitrogen. Preferably however it includes nitrogen and may be, by way of example In another aspect the present inventforiNconsists in a composition for pasture application in the form of particulate zeolit^\or zeolites carrying at least one nitrification inhibitor.

Preferably said composition has a tack provicflokagent and/or adhesive at least in part binding the at least one nitrification inhibitor to tH^Jiarticulate zeolite(s) Preferably but not necessarily the nitrification inhH^ftpifs) is (are) low water solubility.

Preferably said tack providing agent and/or adhesive is a Preferably said gum is a polysaccharide gum (e.g. at lea: xanthan gum and/or guar gum).

Preferably the composition has a composition of 30 to 70% w/w zeolite(s), 1 to 50% w/w nitrification inhibitor(s), and or both of 0.1 to 5% w/w tack providing agent/adhesive, and optionally 0 property 2006 RICH i.'.i 03 u K £uj3 i-AMEMW AMENDED' Preferably the formation of said slurry is a stage wise process. \ Preferably said stage wise process involves optionally milling in water the Verification inhibitor(s).

\\ Preferably the suspension stabilising agent and/or tack providing agent is addeaStVthe initial slurry and thereafter the zeolite(s) carrier is added. In preferred forms orSpe present invention the nitrification agent is selected from the range of particulate nitrification agents including DCD and ATS.

Preferable said suspension stabilising agent and/or tack providing agent is a gum. Preferably sartl gum is a polysaccharide gum such as, by way of example, one or more of xanthan gunVguar gum, etc. [e.g. as earlier exemplified].

Preferably the composition produced by the process is any of the compositions hereinafter described. Y\ In yet a further aspectHhe present invention consists in the aforementioned process(es) and the optional additional step of adding a flow enhancing agent such as a particulate agent such as talc to the omd product.

In still a further aspect the present invention consists in the aforementioned process(es) and the additional optional sreft (irrespective of whether or not a flow enhancing agent has been utilised) of admixing or otherwise associating the zeolite carried nitrification inhibitors) with a fertilismk agent, compound or composition irrespective of whether or not it includes nitrogekVPreferably however it includes nitrogen and may be, by way of example, urea. \\ In another aspect the present invention consists nra composition for pasture application in the form of particulate zeolite or zeoliiesv carrying at least one nitrification inhibitor. \\ Preferably said composition has a tack providing agent ana/or adhesive at least in part binding the at least one nitrification inhibitor to the particulateN^eolite(s).

Preferably but not necessarily the nitrification inhibitor(s) is (ami low water solubility. \\ Preferably said tack providing agent and/or adhesive is a gum. \\ Preferably said gum is a polysaccharide gum (e.g. at least one or bofflVof xanthan gum and/or guar gum). \\ Preferably the composition has a composition of intellectual property office of n2. - jun 2007 received AS AMENDED Preferably the formation of said slurry is a stage wise process.

Preferably said stage wise process involves optionally milling in water the nitrification inhibitor(s).

Preferably the suspension stabilising agent and/or tack providing agent is added to the initial slurry and thereafter the zeolite(s) carrier is added. In preferred forms of the present invention the nitrification inhibitor is selected from the range of particulate nitrification inhibitors including DCD and ATS.

Preferably said suspension stabilising agent and/or tack providing agent is a gum. Preferably said gum is a polysaccharide gum such as, by way of example, one or more of xanthan gum, guar gum, etc. [e.g. as earlier exemplified].

Preferably the composition produced by the process is any of the compositions hereinafter described.

In yet a further aspect the present invention consists in the aforementioned process(es) and the optional additional step of adding a flow enhancing agent such as a particulate agent such as talc to the dried product.

In still a further aspect the present invention consists in the aforementioned process(es) and the additional optional step (irrespective of whether or not a flow enhancing agent has been utilised) of admixing or otherwise associating the zeolite carried nitrification inhibitor(s) with a fertilising agent, compound or composition irrespective of whether or not it includes nitrogen. Preferably however it includes nitrogen and may be, by way of example, urea.

In another aspect the present invention consists in a composition for pasture application in the form of particulate zeolite or zeolites carrying at least one nitrification inhibitor.

Preferably said composition has a tack providing agent and/or adhesive at least in part binding the at least one nitrification inhibitor to the particulate zeolite(s).

Preferably but not necessarily the nitrification inhibitor(s) has (have) low water solubility.

Preferably said tack providing agent and/or adhesive is a gum.

Preferably said gum is a polysaccharide gum (e.g. at least one or both of xanthan gum and/or guar gum).

P"""' *""" Preferably the composition has a composition of Intellectual Proy,-, v Office ot <\t z. 1 9 nov 2007 AMEND /i RE C rrv 0 to 5% w/w flow enhancing agent.

In a further aspect the present invention consists in a composition of aiwyof the preceding kinds in admixture with a fertiliser. // Preferably said fertiliser is a nitrogen containing fertiliser. In other Jqpiis it is or can include trace elements or other fertilising elements. // In another aspect the present invention consists in a fertilise/composition comprising f/ to 80% w/w fertilisers), // to 70% w/w zeolite(s), // 1 to 45% w/w nitrification inhibitor(s), // 0.05 to 5% w/w tackifying and/or suspension ag&f(s) and optionally other inclusion(s) (e.g. flow enhancing agent£/tc.).

Preferably the fertiliser is from 50 to 80%/mv of the composition.

The fertiliser may be urea. The urea ma/be about 60% of the composition. Preferably the nitrification inhibitcowone or both of DCD and ATS.

Preferably said the compositioiyyformed by any of the methods hereinbefore described and/or hereinafter described^with or without reference to any example thereof and/or any of the accompeuramg drawings.

In still a further asn^&r the present invention consists in a method of potentiating the nitrificatuwinhibition of a nitrification inhibitor (preferably but optionally selected from Am or both of DCD and ATS) which comprises or includes coupling the nitrificatldmnhibitor with a zeolite.

In yet a i&ther aspect the present invention consists in a synergistic nitrification inhabiting composition comprising or including an effective amount of a particulate zeoLire carrying an effective amount of at least one nitrification inhibitor.

Pr^Mably the w/w ratio of zeolite(s) to nitrification inhibitor(s) is from 95% / 5%to3^W65%(i.e. 9:1 to7:13).

//Preferably the nitrification inhibitor is one or both of DCD and ATS. // In still a further aspect the present invention consists in, in a fertiliser delivery "System, particulate zeolite(s) carrying (optionally adhered) nitrification inhibitor(s).

In another aspect, as a broadcastable or selectively applicable fertilising composition, (I) liquid and/or solid material(s) having an N and/or other fertilising li i ' « ^ice ot t\j.z.

S MAR 2098 amende to 70% w/w zeolite(s), 1 to 50% w/w nitrification inhibitors), and 0.1 to 5% w/w tack providing agent/adhesive, and optionally 0 to 5% w/w flow enhancing agent.

In a further aspect the present invention consists in a composition of any of the preceding kinds in admixture with a fertiliser.

Preferably said fertiliser is a nitrogen containing fertiliser. In other forms it is or can include trace elements or other fertilising elements.

In another aspect the present invention consists in a fertiliser composition comprising to 80% w/w fertiliser(s), to 70% w/w zeolite(s), 1 to 45% w/w nitrification inhibitor(s), 0.05 to 5% w/w tackifying and/or suspension agent(s) and optionally other inclusion(s) (e.g. flow enhancing agents, etc.).

Preferably the fertiliser is from 50 to 80% w/w of the composition.

The fertiliser may be urea. The urea may be about 60% of the composition.

Preferably the nitrification inhibitor is one or both of DCD and ATS.

Preferably said the composition is formed by any of the methods hereinbefore described and/or hereinafter described with or without reference to any example thereof and/or any of the accompanying drawings.

In still a further aspect the present invention consists in a method of potentiating the nitrification inhibition of a nitrification inhibitor (preferably but optionally selected from one or both of DCD and ATS) which comprises or includes coupling the nitrification inhibitor with a zeolite.

In yet a further aspect the present invention consists in a synergistic nitrification inhibiting composition comprising or including an effective amount of a particulate zeolite carrying an effective amount of at least one nitrification inhibitor.

Preferably the w/w ratio of zeolite(s) to nitrification inhibitor(s) is from 95% / 5% to 35% / 65% (i.e. 9:1 to7:13).

Preferably the nitrification inhibitor is one or both of DCD and ATS. intellectual property office 0FN2. - jun 2007 NOW AMENDED elemental content together with (II) particulate zeolite(s) carrying a nitrificati inhibitor or nitrification inhibitors.

In still another aspect the invention is the use of any composition, fe#Ji!ser or product of the present invention on soil and/or pasture As used herein the term "zeolite" includes a zeolite of a kind (see^ftachment) As used herein the term "slurry" is not restrictive to wate/^irried particle mixtures but preferably includes water in the liquid or has water asAe sole liquid.

As used herein "nitrification inhibitors)" includes one/pr more inhibitor and preferably, but not only, one of those previously referred to.y^amples include N-2,5-dichlorophenyl succinamic acid, 2-chloro-6-trichloromethyl pyridine ("N^^yrin") dicyandiamide ("DCD or "DCDIN zinc ethylene-bis-dithiocarbamate 2,4,6-trichloroaniline pentachlorophenol, thio-urea, ATS (ammonium thiosdifShate), and DMPP (3,4-dimethywTazole phosphate).

As used herein the ter^/and/or" means "and" and "or", or both.

As used herein the/fafm "s" following a noun means the singular and plural forms of that noun.

Nothing herejfL^recludes other agents in addition to the nitrification agent(s) also being carried Jfythe zeolite(s).

A preferaa form of the present invention will now be described with reference to the accopu&nying drawings in which ire 1 shows a flow diagram of one form of preparative method in ice with the present invention leading either to a particulate form having a niccrfication inhibitor or inhibitors carried by a particulate carrier or carriers or to a jsultant mix thereof with a fertiliser, Figure 2 shows a more specific procedure of which the procedure of Figure 1 is generic, and iwellectual property offfce of n.7 0 s MAR 2006 ricetve is Oi'i'ic© Ot iiVi.Z. on '1 2008 O cr r~ i \ / r— i 1 "r NOW AMENDED ■- In still a further aspect the present invention consists in, in a fertiliser delivery system, particulate zeolite(s) carrying (optionally adhered) nitrification inhibitor(s).

In another aspect, as a broadcastable or selectively applicable fertilising composition, (I) liquid and/or solid material(s) having an N and/or other fecfifising elemental content together with (II) particulate zeolite(s) carrying a nj#mcation inhibitor or nitrification inhibitors.

In still another aspect the invention is the use of any composj^ftfh, fertiliser or product of the present invention on soil and/or pasture.

As used herein the term "zeolite" includes a zeolite of aJGfid (see attachment) As used herein the term "slurry" is not restrictive^© water carried particle mixtures but preferably includes water in the liquid or ha&water as the sole liquid.

As used herein "nitrification inhibitor(s)" incfcMes one or more inhibitor and preferably, but not only, one of those previously rejqjred to. Examples include N-2,5-dichlorophenyl succinamic 2-chloro-6-trichloromethyl pyruurfe ("Nitrapyrin"), dicyandiamide ("DCD or "DGDIN""), zinc ethylene-bis-dithioc^amate, 2,4,6-trichloroaniline, pentachlorophenol thio-urea, ATS (ammojiMn thiosulphate), and DMPP (SArolimethypyrazole phosphate).

As used hemjrthe term "and/or" means "and" and "or", or both. As used/fiaifein the term "s" following a noun means the singular and plural forms of that aoon.

Npfbmg herein precludes other agents in addition to the nitrification agent(s) also bejfiafcarried by the zeolite(s).

(A preferred form of the present invention will now be described with reference tb/tle accompanying drawings in which Figure 1 shows a flow diagram of one form of preparative method in accordance with the present invention leading either to a particulate form having a intellectual property office 0FN2. - jun 2007 In still a further aspect the present invention consists in, in a fertiliser delivery system, particulate zeolite(s) carrying (optionally adhered) nitrification inhibitor(s).

In another aspect, as a broadcastable or selectively applicable fertilising composition, (I) liquid and/or solid material(s) having an N and/or other fertilising elemental content together with (II) particulate zeolite(s) carrying a nitrification inhibitor or nitrification inhibitors.

In still another aspect the invention is the use of any composition, fertiliser or product of the present invention on soil and/or pasture.

As used herein the term "zeolite" includes a zeolite of a kind (see attachment) As used herein the term "slurry" is not restrictive to water carried particle mixtures but preferably includes water in the liquid or has water as the sole liquid.

As used herein "nitrification inhibitor(s)" includes one or more inhibitor and preferably, but not only, one of those previously referred to. Examples include N-2,5-dichlorophenyl succinamic acid, 2-chloro-6-trichloromethyl pyridine ("Nitrapyrin"), dicyandiamide ("DCD or "DCDIN""), zinc ethylene-bis-dithiocarbamate, 2,4,6-trichloroaniline, pentachlorophenol, thio-urea, ATS (ammonium thiosulphate), and DMPP (3,4-dimethypyrazole phosphate).

As used herein the term "and/or" means "and" and "or", or both.

As used herein the term "s" following a noun means the singular and plural forms of that noun.

Nothing herein precludes other agents in addition to the nitrification inhibitor(s) also being carried by the zeolite(s).

A preferred form of the present invention will now be described with reference to the accompanying drawings in which Figure 1 shows a flow diagram of one form of preparative method in accordance with the present invention leading either to a particulate form having a Intellectual Property Office of N.z. 19 nov 2007 JRECEI VED AMENDED -8 Figure 3 demonstrates efficacy as explained hereinafter.

In the preferred form of the present invention the zeolite is of a kind that is [ably with a substantially w/w Mordinite presence (preferably at least 20%, more ijy greater than 40% and most preferably at least 50% e.g. 55 to 95%). aspects of the present invention will now be demonstrated by the following e%h^ples which are not limiting of the invention.

Example\\hows one suitable zeolite form.

Example 1 Composition: ClinopfeiMite Mordenitfc Smectite Opal C K Feldspar -65% 25-65% <5% -20% -20% Density Porosity Slurry pH CEC Internal surface area Colour Absorbencies Water Oil 1.2 g.cm 60% .6 80 meq/lOOg 35 m2/g Opaque 55% 45% ® 3 mar 2006 muveD Example 2 shows a more preferred higher mordenite containing zeolite fo* Example 2 Composition: Mordenite Smectite 65-95% 5-20% I>'iot 0 S f4AR 20; A AS AM! y nitrification inhibitor or inhibitors carried by a particulate carrier or carriers or to a resultant mix thereof with a fertiliser, Figure 2 shows a more specific procedure of which the procedure of Figure 1 is generic, and Figure 3 demonstrates efficacy as explained hereinafter.

In the preferred form of the present invention the zeolite is of a kind that is preferably with a substantially w/w Mordinite presence (preferably at least 20%, more preferably greater than 40% and most preferably at least 50% e.g. 55 to 95%).

Various aspects of the present invention will now be demonstrated by the following examples which are not limiting of the invention.

Example 1 shows one suitable zeolite form.

Example 1 Composition: Clinoptilolite Mordenite Smectite Opal C K Feldspar -65% 25-65% <5% -20% -20% Density Porosity Slurry pH CEC Internal surface area Colour Absorbencies Water Oil 1.2 g.cm 60% .6 80 meq/lOOg 35 m2/g Opaque 55% 45% Example 2 shows a more preferred higher mordenite containing zeolite form. intellectual property office 0FN1. - jun 2007 NOW AMEN Opal C K Feldspar <5% 5-20% Density Porosity Slurry pH CEC Internal surface area Pore size Colour Absorbencies Water Oil 0.89g.cm 60% to 6 for 20%w/v 120 meq/lOOg 48m2/g 7 Angstroms Off white 55% 45% ,NTofnSAAePROPERTY w"ce of n.z. "s mar 2006 riciivcd Examples 3 and 4 show two conreosition forms where the nitrification agent is DCD alone. Analogous examples /ran be formed with other nitrification agents disclosed herein or blends of any sunt agents disclosed herein. The more soluble nitrification agents will be more ads»ued into the zeolite rather than to adhere to the zeolite as is the case with the less/oluble nitrification agents.

Example 3 - AyCD/Zeolite composition 250 gram/jKCD (ground until 100% passing 200(j,m screen) 250 g«wn Water fQ.ter and DCD were blended until a smooth slurry was formed. To this slurry 5 'grams of xanthan gum was added and stirred until fully hydrated (approx 15 min).

O'isiiJri Ot e S MAR 2008 ! r* it" i \ / g— A NOW AMENDED Example 2 Composition: Mordenite Smectite Opal C K Feldspar 65-95% 5-20% <5% 5-20% Density Porosity Slurry pH CEC Internal surface area Pore size Colour Absorbencies Water Oil 0.89g.cm 60% to 6 for 20%w/v 120 meq/lOOg 48m2/g 7 Angstror Offwh Examples 3 and/Yshow two composition forms where the nitrification agent is DCD alone. Analogous examples can be formed with other nitrification agents disclosed herein or J^ends of any such agents disclosed herein. The more soluble nitrification agents Mil be more adsorbed into the zeolite rather than to adhere to the zeolite as is the #gse with the less soluble nitrification agents.

Example 3 - A PCD/Zeolite composition 250 gram DCD (ground until 100% passing 200|im screen) intellectual property office of n.z. - jun 2007 I AS ARMED Example 2 Composition: Mordenite Smectite Opal C K Feldspar 65-95% 5-20% <5% 5-20% Density Porosity Slurry pH CEC Internal surface area Pore size Colour Absorbencies Water Oil 0.89g.cm 60% to 6 for 20%w/v 120 meq/lOOg 48m2/g 7 Angstroms Off white 55% 45% Examples 3 and 4 show two composition forms where the nitrification inhibitor is DCD alone. Analogous examples can be formed with other nitrification inhibitors disclosed herein or blends of any such inhibitors disclosed herein. The more soluble nitrification inhibitors will be more adsorbed into the zeolite rather than to adhere to the zeolite as is the case with the less soluble nitrification inhibitors.

Example 3 - A PCD/Zeolite composition 250 gram DCD (ground until 100% passing 200]_im screen) IW AMEND! The suspension was then added to 500 gram of zeolite (l-3mm) and mixed until the zeolite grains were evenly coated and the mix was the consistency of bread crumbs. 50 grams of talc was then added to form a free flowing, granular DCD product.

Final pro^W contains 23.7% DCD and 0.47% xanthan gum.

The product orEkample 3 is a heterogeneous mix of granules typically l-3mm particle size range. This\j«£terial is relatively free flowing and is stable in blends with fertilisers.

Example 4 - A PCD/ZeohtXcomposition 165 grams of DCD 300 grams of 55% w/w ATS soluticfc DCD and ATS were mixed and blended f^pS minutes with a Silverstone type blender. 4.65 grams of xanthan gum was added and aHxVed to fully hydrate.

The above mix was added to 470 grams of zeonle\(l-3mm) and stirred until bread crumb like granules were formed. The wet granulesN^e dried to yield 800 grams of product.

The product of Example 4 is a heterogeneous mix of granules typically l-3mm particle size range. This material is relatively free flowing and is st^h|e in blends with fertilisers.

These Example's 3 and 4 products are mixable in all proportions with u^e\which is the preferred product for delivery to enhance the nitrogen use efficacy of the area.

AMENDED 250 gram Water Water and DCD were blended until a smooth slurry was formed. To this slurry 5 grams of xanthan gum was added and stirred until folly hydrated (approx 15 min).

The suspension was then added to 500 gram of zeolite (l-3mm) and mixed until the zeolite grains were evenly coated and the mix was the consistency of bread crumbs. 50 grams of talc was then added to form a free flowing, granular DCD product.

Final product contains 23.7% DCD and 0.47% xanthan gum.

The product of Example 3 is a heterogeneous mix of granules typically l-3mm particle size range. This material is relatively free flowing and is stable in blends with fertilisers.

Example 4 - A PCD/Zeolite composition 165 grams of DCD 300 grams of 55% w/w ATS solution DCD and ATS were mixed and blended for 5 minutes with a Silverstone type blender. 4.65 grams of xanthan gum was added and allowed to fully hydrate.

The above mix was added to 470 grams of zeolite (l-3mm) and stirred until bread crumb like granules were formed. The wet granules were dried to yield 800 grams of product.

The product of Example 4 is a heterogeneous mix of granules typically l-3mm particle size range. This material is relatively free flowing and is stable in blends with fertilisers. intellectual property office 0FN2. - jun 2007 received Trial Performance The uniform placement of a fertiliser or nitrification inhibitor is most uniform ^efficacious if applied as a liquid or suspension.

When applied as a DCD zeolite granule of the present invention (e.g. a compcNutton of Example 3), we have found the granule application surprisingly gave equal or S^rior efficacy to such liquid or suspension applications as either measured as nitrate orXftunonia reduction or expressed as dry matter production. See Figure 3 in respect of nitro^eto losses and Table 1.

This is ilft^rated from field trial data showing statistically the same efficacy in terms of soil N f^Mions but a statistically significant advantage in terms of dry matter production.

This may be duW a release characteristic from the zeolite core or an absorption property of the rik&rial. In any event, the association with the zeolite in such scenarios of application provide advantages.

Field trials show, almost wWwut exception, at least equality of performance from the particulate (zeolite) application V> that of a liquid vehicle application.

The following data presents some f^sV^lts from a range of field trials evaluating the DCD carried in/on zeolite particles wbefe applied dry versus dissolved DCD formulations when applied as a spray, where higfaVitrogen application rates of order of 600 kg/ha of N have been applied to all treatments^ Pasture measurements were assessed by mowii% 8uts.

DCD N Care trial 1 Woodlands. The granule composition wc Table 1 Inte^e^'iai srty of sX'.Z. 0 3 i iLiJO I \/ e n> in Example 3 Form Total yield (kg/ha) Control 1715 Liquid DCD (15 kg DCD/ha) 3194 Zeolite DCD granule (15 kg DCD /ha) 3957 Lsd 294 PROPERTY n.z.

RECEI as amended These Example's 3 and 4 products are mixable in all proportions with urea which is the preferred product for delivery to enhance the nitrogen use efficacy of the urea.

Trial Performance The uniform placement of a fertiliser or nitrification inhibitor is most uniform and efficacious if applied as a liquid or suspension.

When applied as a DCD zeolite granule of the present invention (e.g. a composition of Example 3), we have found the granule application surprisingly gave equal or superior efficacy to such liquid or suspension applications as either measured as nitrate or ammonia reduction or expressed as dry matter production. See Figure 3 in respect of nitrogen losses and Table 1.

This is illustrated from field trial data showing statistically the same efficacy in terms of soil N fractions but a statistically significant advantage in terms of dry matter production.

This may be due to a release characteristic from the zeolite core or an absorption property of the material. In any event, the association with the zeolite in such scenarios of application provide advantages.

Field trials show, almost without exception, at least equality of performance from the particulate (zeolite) application to that of a liquid vehicle application.

The following data presents some results from a range of field trials evaluating the DCD carried in/on zeolite particles when applied dry versus dissolved DCD formulations when applied as a spray, where high nitrogen application rates of order of 600 kg/ha of N have been applied to all treatments.

Pasture measurements were assessed by mowing cuts.

DCD N Care trial 1 Woodlands. The granule composition was as in Example 3 Table 1 Form Total yield (kg/ha) Control 1715 Liquid DCD (15 kg DCD/ha) 3194 intellectual property c 0FN2. - jun 2007 receive IW AMEHDEC DCD N Care trial 2 Rotorua. The granule composition was as in Example 3 Table 2 Foijk Total yield (kg/ha) Contm^\ 4254 Zeolite IXSDsgranule (30 kg/ha DCD) 5202 Lsd (5%) V\ 493 DCD N Care trial 3 Rhakura.

The granule composition was as in Example 3 Table 3 Form \ \ Y\ Total leaching (kg N/ha) V Control (no urine) %A 11 v\ Urine \\ \ * 210 \ Urine plus Zeolite DCD granule (12 kg5 DCD /ha) \ 145 \\ Lsd V w V. 0 y fc t LiV'WU WEI t u t iW' intellectual OFFICE OF $ 3 mar 200&' RECEIVED 1 Zeolite DCD granule (15 kg DCD /ha) 3957 Lsd 294 DCD N Care trial 2 Rotorua. The granule composition was as in Example 3 Table 2 Form Total yield (kg/ha) Control 4254 Zeolite DCD granule (30 kg/ha DCD) 5202 Lsd (5%) 493 DCD N Care trial 3 Ruakura. The granule composition was as in Example 3 Table 3 Form Total leaching (kg N/ha) Control (no urine) 11 Urine 210 Urine plus Zeolite DCD granule (12 kg DCD /ha) 145 Lsd INTELLECTUAL property office of N2. - jun 2007 received m amend!. -13 Table 4 is that table identified as Table 1 in our priority specification (the provisional specification of NZ Patent Application No. 531078). This table shows a range of DCD libitor rates and formulations including liquid (DCD L) and their impact on pasture prcMtaction parameters. Urine was applied at 600 kg N/ha.

Table 4 Treat Form V\ Urine .12.03 .01.04 Total Kg/ha Grass Clover Kg/ha Grass Clover Yield (kg/ha) DM % % DM % % 1 Control 641 66.1 .1 392 52.0 40.3 1715 2 Urea 1099 63.3 31.1 508 52.5 38.8 2795 3 Urea + v\ 1771 75.3 .8 503 67.4 22.3 3301 4 Super U o \\ V 1243 66.8 28.3 384 53.6 39.2 2952 Super U + \ \2104 72.4 17.4 479 65.2 29.2 3852 6 Coated N 0 \\j68 67.2 29.4 394 58.6 .0 2877 7 Coated N + 80.3 11.2 637 71.6 21.8 3565 8 DCD (L) 15 + mzt 77.4 18.5 443 73.2 19.7 3194 9 DCD (L) 30 + 18®t\S 76.2 17.0 611 74.9 19.4 3636 Zeolite 15 + 2104V V 77.0 18.7 636 74.7 19.9 3957 11 Zeolite 30 + 2020 0*5.3 21.1 618 71.8 16.8 3792 12 Urea 0 988 vl9 27.9 380 54.7 33.9 2356 13 Urea + 2065 18.4 662 80.7 .0 3780 *** * *** *** SED 182 6.9 \\ .9 124 7.3 .7 294 Contra + - Urine ** \\*» * *** *** *** sts Urea v Super U NS NS NS NS t t Super U v Coated N NS NS N§\ NS NS NS NS Urea v Coated N NS NS NS V VNS NS NS NS Urine v Super U v Coated N NS NS NS 1 VVNS NS NS NS Urea v Coated N & Super U NS NS NS vts NS NS NS 2 Urea v DCD (all) NS NS NS NS NS NS All Super U v Coated N NS NS NS NSV V NS NS . NS with Urine Urea v DCD (Zeolite & Liq DCD) NS NS NS NS Vtos f NS 30kg/ha v 15 kg/ha NS NS NS NS NS NS Zeolite v Liquid DCD NS NS NS NS NS\H . NS * Interaction NS NS NS NS NS \ \ NS NS h eto'r n ': J V\ Of si CB Qt hi./.

P 1 cr n L 1 V t ij INTELLECTUAL OFFICE OF ?ERTY mar 20$ RECEIVED \v LW AMENDED WHAT WE CLAIM IS: A method of producing a composition suitable to be applied to the soil aim/or pasture, said method comprising or including formulating a slurry of at least one zeolite as a particulate carrier with at least water afflff, as and/or prior to the inclusion of at least one nitrification inhibitor therein, and dryin|Mie slurry to result in an at least substantially dry particulate material with the zeolite drying the nitrification inhibitor(s). 2. A method S^laim 1 wherein the nitrification inhibitor(s) is soluble to some extent in water. 3. A method of clafl^M or 2 wherein the nitrification inhibitor(s) is present as a particle prior to the drying; 4. A method of any one cKNhe preceding claims wherein particle size ranges for the particulate carrier or zeolite r\Sjom 1 to 3 mm (typically 100% passing a 3 mm screen and < 1% a 1mm screen).

. A method of any one of the preS^ng claims wherein the zeolite is 65 to 95% w/w mordenite and 5 to 20% smectite. 6. A method of any one of the preceding%Mms wherein the nitrification inhibitor is able to pass through a 200(im screen. 7. A method of any one of the preceding' ;\0ims wherein the nitrification inhibitor(s) prior to drying is supported in the water by' ^spension agent. 8. A method of claim 7 wherein the suspension agen^M gum. 9. A method of any one of the preceding claims wrc^jn the drying is to a dryness of less than 8 % w/w water/composition).

. A method of claim 7 wherein the slurry prior to drying ha^\§ the suspension agent, a tackifier. 11. A method of claim 10 wherein the trackifier is a gum. 12. A method of claim 8 or 11 wherein the gum(s) is (are) selected frorAifticrobial polysaccharides such as dextran, gellan, rhamsan, guar and xanthan gums; polysaccharide derivatives such as hydroxymethylcellul hydroxyethylcellulose, microcrystalline cellulose and modified starches; and Intellectual Property Office of N.2. 3 0 JUN 2006 n r r r | \/ r n as amended 14-

Claims (49)

WHAT WE CLAIM IS:

1. A method of producing a particulate composition suitable to be applied to the soil and/or pasture, said method comprising or including (A) formulating and establishing an aqueous slurry of (i) at least one particulate zeolite, (ii) at least one particulate nitrification inhibitor without substantial dissolution and (iii) a tackifier, wherein the particulate nitrification inhibitor(s) on average is(are) finer than the zeolite(s), and wherein the tackifier has the capability in the aqueous environment of contacting both the particulate zeolite(s) and the particulate nitrification inhibitor(s), and (B) drying the slurry to result in an at least substantially dry particulate material with the zeolite particles carrying as a coating the tackifier adhered particles of the nitrification inhibitor(s).

2. A method of claim 1 wherein there is one nitrification inhibitor only and it is soluble only to some small extent in water.

3. A method of claim 1 or 2 wherein the aqueous slurry, at least in part has resulted from milling in water of at least the nitrification inhibitor(s).

4. A method of claim 1, 2 or 3 wherein said tackifier is added to a slurry of the nitrification inhibitor(s) prior to the addition of the zeolite(s) carrier.

5. A method of claim 1 or 2 wherein the nitrification inhibitor(s) is present as a particles smaller than the average zeolite particles from the outset as well as prior to the drying step.

6. A method of any one of the preceding claims wherein particle size ranges for the particulate carrier or zeolite is from 1 to 3mm (typically 100% passing a 3mm screen and < 1% a 1mm screen).

7. A method of any one of the preceding claims wherein the zeolite is 65 to 95% w/w mordenite and 5 to 20% smectite.

8. A method of any one of the preceding claims wherein the nitrification inhibitor is able to pass through a 200|im screen.

9. A method of any one of the preceding claims wherein the nitrification inhibitor(s) prior to drying is supported in the water by a suspension agent.

10. A method of claim 9 wherein the suspension agent is a gum.

11. A method of claim 9 or 10 wherein the slurry prior to drying has, as the suspension agent, the tackifier. intellectual property office of nx 5 - jun 2007 MENDED -15- synthetic polymers such as polyvinyl alcohols, polyvinyl acetates and cross-linkB^polyacrylates. 13. W method of producing a composition suitable to be applied to the soil and/or pmlure, said method comprising or including the steps of: (i) Xjbrmulating an aqueous slurry of a particulate nitrification inhibitor or particulate nitrffiWion inhibitors having at least one zeolite as a potential carrier in a particulate form, aMLopotionally having a suitable suspension stabilising agent, and (ii) drying\|te slurry to at least a substantially dried particulate form which has the nitrification inn^or(s) adhered to or otherwise carried by the zeolite(s) ("the zeolite(s) carrier"). 14. A method of claim 13 herein the aqueous slurry has resulted from milling in water of at least the nitrification inVkutor(s). 15. A method of claim 13 or clK(\ 14 wherein a suitable suspension stabilising agent is present. 16. A method of claim 13 or 14 wherefa\aid suspension stabilising agent or a tack providing agent, or an agent which is both aJ?uspension stabilising agent and a tack providing agent, or both a suspension stabilisink\gent and a tack providing agent, is added to the slurry of the nitrification inhibitor(s) to the addition of the zeolite(s) carrier. 17. A method of claim 16 wherein said suspensioft^^bilising agent and/or tack providing agent is a gum 18. A method of claim 17 wherein said gum is a polysacch^de gum. 19. A method of any one of the preceding claims whSc^P the nitrification inhibitor(s) is(are) selected from the range of particulate nitrificatio^^hibitors N-2,5-dichlorophenyl succinamic acid, 2-chloro-6-trichloromethyl pyridine ("Nitrapyrin"), dicyandiamide ("DCD or "DCDIN""), zinc ethylene-bis-dithiocarbamate, 2,4,6-trichloroaniline, pentachlorophenol, thio-urea, Intellectual Property^ Office of N.Z. 3 0 JUN 2006 received AS A

12. A method of claim 1 or 11 wherein the tackifier is a gum.

13. A method of claim 10, 11 or 12 wherein the gum(s) is (are) selected from microbial polysaccharides such as dextran, gellan, rhamsan, guar and xanthan gums; polysaccharide derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, microcrystalline cellulose and modified starches; and synthetic polymers such as polyvinyl alcohols, polyvinyl acetates and cross-linked polyacrylates.

14. A method of claim 12 or 13 wherein said gum is a polysaccharide gum.

15. A method of any one of the preceding claims wherein the drying is to a dryness of less than 8 % w/w water/composition).

16. A method of any one of the preceding claims wherein the nitrification inhibitors) is(are) selected from the range of particulate nitrification inhibitors N-2,5-dichlorophenyl succinamic acid, 2-chloro-6-trichloromethyl pyridine ("Nitrapyrin"), dicyandiamide ("DCD or "DCDIN""), zinc ethylene-bis-dithiocarbamate, 2,4,6-trichloroaniline, pentachlorophenol, thio-urea, ATS (ammonium thiosulphate), and DMPP (3,4-dimethypyrazole phosphate).

17. A method of any one of the preceding claims wherein the nitrification inhibitor is DCD and/or ATS.

18. A method of claim 17 wherein DCD is present and ATS is not present.

19. A method of any one of the preceding claims with the optional additional step of adding a flow enhancing agent such as a particulate agent to the dried product.

20. A method of claim 19 wherein the flow enhancing agent is a particulate agent and/or talc.

21. A method of any one of the preceding claims with the additional optional step (irrespective of whether or not a flow enhancing agent has been utilised) of admixing intellectual property office of nz 5 - jun 2007 NOW AMENDED -16- ATS (ammonium thiosulphate), and DMPP (3,4-dimethypyrazole phosphate). A method of claim 19 wherein the nitrification inhibitor is DCD and/or ATS. A method of claim 20 wherein DCD is present and ATS is not present. 22. \\A method of any one of the preceding claims with the optional additional step of adding\a flow enhancing agent such as a particulate agent to the dried product. 23. A trtethod of claim 22 wherein the flow enhancing agent is a particulate agent \ and/or talc. 24. A methotKpf any one of the preceding claims with the additional optional step (irrespective of wfMfaer or not a flow enhancing agent has been utilised) of admixing or associating the zewrte carried nitrification inhibitor(s) with a fertilising agent compound or compositia 25. A method of claim Miwherein the fertilising compound is urea 26. A composition produc©jM>y a method of any one of the preceding claims. 27. A composition of claim Mtfor pasture application in the form of particulate zeolite or zeolites carrying at least on^oitrification inhibitor. 28. A composition of claim 27 whek^p the nitrification inhibitor(s) has (have) low water solubility. 29. A composition of claim 27 or 28\Vherein said composition has a tack providing agent and/or adhesive at least in paraj^jinding the at least one nitrification inhibitor to the particulate zeolite(s). 30. A composition of claim 29 wherein said tack^gviding agent and/or adhesive is a gum 31. A composition of claim 30 wherein said gum is a polysaccharide gum 32. A composition of claim 31 with at least one or bothN^xanthan gum and/or guar gum. 33. A composition of any one of claim 26 to 31 with 30 to 70% w/w zeolite(s), 1 to 50% w/w nitrification inhibitor(s), and 0.1 to 5% w/w tack providing agent/adhesive, and optionally 0 to 5% w/w flow enhancing agent. 34. A composition of any one of claims 27 to 33 in admixture with a fertiliser. Intellectual Property Office of N.Z. 3 0 JUN 2006 R^C E I V E ameh -16- or associating the zeolite carried nitrification inhibitors) with a fertilising agent, compound or composition.

22. A method of claim 21 wherein the fertilising compound is urea.

23. A composition produced by a method of any one of the preceding claims.

24. A composition of claim 23 for pasture application in the form of particulate zeolite or zeolites carrying at least one nitrification inhibitor.

25. A composition of claim 24 with at least one or both of xanthan gum and/or guar gum.

26. A composition of 24 or 25 with 30 to 70% w/w zeolite(s), 1 to 50% w/w nitrification inhibitor(s), and 0.1 to 5% w/w tack providing agent/adhesive, and optionally 0 to 5% w/w flow enhancing agent.

27. A composition of any one of claims 24 to 26 in admixture with a fertiliser.

28. A composition of claim 27 wherein said fertiliser is a nitrogen containing fertiliser or a trace element or both.

29. A fertiliser composition of claim 27 or 28 comprising 10 to 80% w/w fertiliser(s), 10 to 70% w/w zeolite(s), 1 to 45% w/w nitrification inhibitor(s), 0.05 to 5% w/w tackifying and/or suspension agent(s), and optionally, additives.

30. A composition of claim 29 wherein the fertiliser is from 50 to 80% w/w of the composition.

31. A composition of claim 29 or 30 wherein the fertiliser is urea.

32. A composition of claim 31 wherein the urea is about 60% w/w of the composition.

33. A composition of any one of claims 29 to 33 wherein the nitrification inhibitor(s) is(are) one (or both) of DCD and ATS.

34. A composition of any one of claims 29 to 33 is formed by any of the methods hereinbefore described and/or hereinbefore described with or without reference to any example thereof and/or any of the accompanying drawings. r-~— intellectual property office of NZ 5- JUN 2007 DCori m AMENDED 17-

35. A composition of claim 34 wherein said fertiliser is a nitrogen containing fertiliser or a trace element or both.

A fertiliser composition of claim 36 comprising 10 to 80% w/w fertiliser(s), to 70% w/w zeolite(s), l\ds^5% w/w nitrification inhibitors), 0.05\<S5% w/w tackifying and/or suspension agent(s), and optionally, additiv^

37. A composKAstfi of claim 36 wherein the fertiliser is from 50 to 80% w/w of the composition.

38. A composition dfbJaim 36 or 37 wherein the fertiliser is urea.

39. A composition of\p^im 38 wherein the urea is about 60% w/w of the composition.

40. A composition of any of claims 36 to 39 wherein the nitrification inhibitor(s) is(are) one (or both) of DCD and ATS.

41. A composition of any one of cMtos 36 to 40 is formed by any of the methods hereinbefore described and/or hereinbefore, described with or without reference to any example thereof and/or any of the accompanying drawings.

42. A method of potentiating the nitrification inhibition of a nitrification inhibitor which comprises or includes couplingMke nitrification inhibitor with a zeolite using a composition of claim 26.

43. A method of claim 42 wherein the inhibitor is \(Hected from one or both of DCD and ATS.

44. A synergistic nitrification inhibiting composition of\ m 26 comprising or including an effective amount of a particulate zeolite carrying ^ective amount of at least one nitrification inhibitor.

45. A synergistic nitrification inhibiting composition of claim \vherein the w/w ratio of zeolite(s) to nitrification inhibitor(s) is from 9:1 to 7:13.

46. A composition of claim 44 or 45 wherein the nitrification inhibitor & \ne or both of DCD and ATS.

47. A fertiliser delivery system comprising particulate zeolite(s) carry! (optionally adhered) nitrification inhibitor(s) as a composition ef claim 26.—— Intellectual Property Office ot N.Z. 3 0 JUN 20(6 35. A method of potentiating the nitrification inhibition of a nitrification inhibitor which comprises or includes coupling the nitrification inhibitor with a zeolite using a composition of claim 23. 36. A method of claim 35 wherein the inhibitor is selected from one or both of DCD and ATS. 37. A synergistic nitrification inhibiting composition of claim 23 comprising or including an effective amount of a particulate zeolite carrying an effective amount of at least one nitrification inhibitor. 38. A synergistic nitrification inhibiting composition of claim 23 wherein the w/w ratio of zeolite(s) to nitrification inhibitor(s) is from 9:1 to 7:13. 39. A composition of claim 37 or 38 wherein the nitrification inhibitor is one or both of DCD and ATS. 40. A fertiliser delivery system comprising particulate zeolite(s) carrying (optionally adhered) nitrification inhibitor(s) as a composition of claim 23. 41. A fertilising composition for use in broadcasting or selective application, consisting of (I) liquid and/or solid material(s) including an N fertilising elemental content together with (II) , as a composition of claim 23, particulate zeolite(s) carrying a nitrification inhibitor or nitrification inhibitors. 42. The use of a composition of any one of claims 23 to 34, 37 to 39 and 41 on soil and/or pasture. DATED THIS 2) DAY OFCJUAC 3oc AJ Park 0 PER /j yjXOj-UAd AGENTS FOR THE APPLICANT & IW AMENDED -18-

48. A fertilising composition for use in broadcasting or selective application, consisting of (I) liquid and/or solid material(s) including an N fertilising elemental content togto^er with <P) , as a composition of claim 26, particulate zeolite(s) carrying a nitrification inhibitor (^.nitrification inhibitors.

49. TheSke of a composition of any one of claims 26 to 41, 44 to 46 and 48 on soil and/or past Intellectual Property Office of M.Z. 3 0 jun 2006 received