Nitrification inhibitors to improve fertilizer efficiency
Disclosed are compositions and methods of making a liquid fertilizer additive of biodegradable polymeric and/or oligomeric nitrification inhibitors comprised of utilizing a non-aqueous polar, aprotic organo liquid (NAPAOL) as the reaction medium for the reaction of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more aldehyde reactive groups selected from the group consisting of a) primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxyls and f) phenols.
1. A liquid fertilizer additive composition comprising a) a non-aqueous polar, aprotic organic liquid (NAPAOL) and b) a nitrification inhibitor composition, wherein said NAPAOL comprises a) dimethyl sulfoxide and optionally b) one or more members selected from the group consisting of:
i) dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:
R 9 S(O) x R 10
wherein R 9 and R 10 are each independently a C 1-6 alkylene group, an aryl group, or C 1-3 alkylenearyl group or R 9 and R 10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 9 and R 10 together are a C 1-6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2,
ii) one or more alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate iv) 1-Methyl-2-pyrrolidone, v) one or more organo phosphorous liquids selected from the group consisting of hexamethylphosphoramide and one or more trialkylphosphates selected from the structure:
wherein:
R 22 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 23 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 24 is an alkyl radical —C 1 H 3 to —C 6 H 13
iii) 1,2-dimethyloxyethane, vii) 2-methoxyethyl ether, and viii) cyclohexylpyrrolidone,
and wherein the nitrification inhibitor composition comprises one or more members selected from the structures consisting of:
wherein R 43 , R 44 , R 45 and R 46 are one or more members independently selected from the group consisting of: H and —CH 2 OH wherein at least one of R 43 , R 44 , R 45 and R 46 is —CH 2 OH,
wherein R 47 , R 48 , R 49 R 50 , R 51 and R 52 are one or more members independently selected from the group consisting of: H, and —CH 2 OH, and
wherein R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 are one or more members independently selected from the group consisting of: H and —CH 2 OH wherein said liquid fertilizer additive composition is generated under non-aqueous conditions, and wherein the structures comprise more than 10% by weight of the nitrification inhibitor composition.
2. The liquid fertilizer additive composition of claim 1 further comprising:
wherein R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 are one or more members independently selected from the group consisting of: H and —CH 2 OH.
3. The liquid fertilizer additive composition of claim 1 further comprising one or more members selected from the group consisting of paraformaldehyde, dicyandiamide (DCD) and formaldehyde.
4. The liquid fertilizer additive composition of claim 1 , wherein the nitrification inhibitor composition further comprises one or more members selected from the group consisting of a) ammonia, b) one or more polyamines, c) one or more polyols, d) one or more primary amines, e) one or more secondary amines, f) one or more low molecular weight alcohols, and g) one or more non-cyano containing nitrification inhibitors wherein
the one or more polyamines are selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and aminoethylethanolamine, and wherein the polyamines comprise 0.01-5% of a polymer composition weight,
wherein the one or more polyols are selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, glycerin, poly(C 1-10 alkylene) glycols, ethylene, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, isopropylidene glycerol, tripropylene glycol methyl ether, tripropylene glycol butyl ether, dipropylene glycol butyl ether, and tripropylene glycol butyl ether wherein the one or more polyols comprise 0.1-5% of the polymer weight,
wherein the one or more secondary amines are selected from the group consisting of diethanolamine, diethylamine, cyclohexylamine, methylethanolamine, diisopropanolamine, methylispropylamine wherein the one or more secondary amines comprise 0.1-5% of the polymer composition,
wherein the one or more low molecular weight alcohols are selected from the group consisting of methanol, ethanol, butanol, pentanol, and hexanol wherein the one or more low molecular weight alcohols comprise 0.1-5% of the polymer composition weight,
wherein the one or more non-cyano containing nitrification inhibitors are selected from the group consisting of:
a) one or more pyrazoles represented by the structure:
wherein R 28 =—H, —CH 3 , —CH 2 CH 3 , —NH 2 or —NHCH 3 ,
wherein R 29 =—H, —OH, —SH, —CONH 2 or —CONHCH 3 ,
wherein R 30 =—H, —CH 3 , —CH 2 CH 3 , —NH 2 or —NHCH 3 , and
wherein R 31 =—H, —CH 3 , —CH 2 CH 3 , —NH 2 or —NHCH 3 ,
b) one or more members selected from the group consisting of 2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea, 2,4-diamino-6-trichloromethyl-5-triazine, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, and 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate.
5. The liquid fertilizer additive composition of claim 1 , wherein the composition further comprises one or more members selected from the group consisting of:
a) surfactants, buffers, fragrance/odor masking agents, colorants, flow modifiers, silicas, and hydrophobized silicas,
b) one or more non-aqueous organo liquids selected from the group consisting of one or more polar aprotic solvents, one or more aprotic solvents, and one or more protic organo solvents wherein:
the one or more aprotic solvents are selected from the group consisting of: i) one or more polyols capped with acetate or formate wherein a polyol portion is selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose and glycerin, ii) one or more alkylene glycol alkyl ether acetates selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and tripropylene glycol butyl ether acetate, iii) isophorone, iv) one or more diesters selected from the group consisting of dimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethyl glutarate, v) dimethylacetamide, vi) dimethylformamide, vii) dimethyl-2-imidazolidinone, viii) 1-Methyl-2-pyrrolidone and ix) limonene,
wherein the one or more protic solvents are selected from the group consisting of: i) an alcohol from the family of C 1-10 alkanols, ii) one or more polyols selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, iii) one or more poly(C 1-10 alkylene) glycols represented by the structure:
H(C t H u ) v OH, wherein
t is an integer: 1-10
u is an integer: 2-20
and v is an integer: 1-20,
iv) one or more alkylene glycols selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene glycol, v) isopropylidene glycerol vi) one or more alkylene glycol alkyl ethers selected from the group represented by the structure:
wherein R 1 is: CH 3 , C 2 H 5 , C 3 H 7 or C 4 H 9
wherein R 2 is: H or the structure
wherein R 3 is: H or CH 3
wherein R 4 is H or CH 3
and f is an integer between 1 and 15,
vii) one or more alkyl lactates selected from the group consisting of ethyl, propyl and butyl lactate, viii) one or more alkanolamines selected from the group represented by the structure:
wherein R 5 is: C 2 H 4 OR 8 or C 3 H 6 OH
wherein R 6 is: H, C 2 H 4 OR 8 or C 3 H 6 OH
wherein R 7 is: H, C 2 H 4 OR 8 or C 3 H 6 OH
wherein R 8 is: (C 2 H 4 O) g H
and g is an integer between 1-10
and ix) glycerol carbonate,
wherein the one or more polar aprotic solvents are selected from the group consisting of:
i) dimethyl sulfoxide,
ii) dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:
R 9 S(O) x R 10
wherein R 9 and R 10 are each independently a C 1-6 alkylene group, an aryl group, or C 1-3 alkylenearyl group, or R 9 and R 10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 9 and R 10 together are a C 1-6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2, and optionally further comprising
iii) one or more alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate iv) 1-Methyl-2-pyrrolidone, v) one or more organo phosphorous liquids selected from the group consisting of hexamethylphosphoramide and one or more trialkylphosphates selected from the group represented by the structure:
wherein:
R 22 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 23 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 24 is an alkyl radical —C 1 H 3 to —C 6 H 13
vi) 1,2-dimethyloxyethane, vii) 2-methoxyethyl ether and vii) cyclohexylpyrrolidone.
6. The liquid fertilizer additive composition of claim 1 , wherein the composition further comprises one or more members selected from the group consisting of:
a) one or more biologics selected from the group consisting of:
i) Bacillus biologics, ii) Azospirillum biologics, iii) Azobacter biologics iv) Gluconacetobacter biologics, v) Phosphobacteria , vi) Cyanobacteria , vii) Herbaspirillum , viii) Burkholderia , ix) Pseudomonas, x ) Gluconacetobacter , xi) Enterobacter , xii) Klebsiella , xiii) Burkholderia , xiv) Bradyrhiwbium species, xv) Bradyrhiwbium japonicum , xvi) Rhizobium meliloti , xvii) Laccaria bicolor, xviii) Glomus imraradices timanita , xix) Actinomyces , xx) Penicillium , xxi) Mesorhizobiwn cicero , xxii) one or more insecticidal or insect repellent microbial species and strains selected from the group consisting of:
Telenomus podisi, Baculovirus anticarsia; Trichogramma pretiosum, Trichogramma gallai, Chromobacterium subtsugae, Trichoderma fertile, Beauveria bassiana, Beauveria bassiana, Beauveria bassiana, Paecilomyces jknwsoroseu, Trichoderma harzianum, Verticillium lecanii, lsarfofumosarosea Lecanicillium muscarium, Streptomyces microflavus , and Muscodor albus,
xxiii) one or more nematodal microbial species and strains selected from the group consisting of:
Myrothecium verrucaria, Pasteuria species, Pasteuria Metarhizium species, and Flavobacteriwn species
xxiv) Reynoutria sachalinensis and
xxv) one or more antifungal, antimicrobial and/or plant growth promoting microbial species and strains selected from the group consisting of Gliocladium species, Pseudomonas species selected from the group consisting of:
Pseudomonas fluorescens, Pseudomonas fluorescens putida and P. chlororaphis, Pseudomonasfluorescens VP5, Pseudomonas diazotrophicus, Enterobacter cloacae, Trichodema species, Trichoderma virens, Trichoderma atroviride strains, Coniothyrium minitans, Gliocladium species, Gliacladium virens, Gliacladium roseum , and Trichodemw harzianum species,
b) and one or more biologically active agents selected from the group consisting of:
i) one or more urease inhibitors selected from the group consisting of aliphatic phosphoric triamide, phosphoramides, N-alkyl thiophosphoric triamides, (aminomethyl)phosphinic acids and their salts and aminomethyl (alkylaminomethyl)phosphinic acids and their salts,
ii) one or more additional nitrification inhibitors selected from the group consisting of 2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4,6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate, dimethylpyrazole organic and inorganic salts, and 2-amino-4-chloro-6-methylpyrimidine,
iii) and one or more members selected from the group consisting of pesticide(s), herbicides fungicides(s), and insecticide(s).
7. The liquid fertilizer additive composition of claim 1 , wherein the composition further comprises one or more organo polycarboxylic acids selected from the group consisting of a) organo polycarboxylic acid polymers and/or their salts wherein the organo polycarboxylic acid polymers are a homopolymer, a copolymer and/or a terpolymer comprised of one or more members selected from the group consisting of:
aspartic acid,
glutamic acid,
maleic anhydride,
itaconic anhydride,
citraconic anhydride,
citric acid, and
acrylic acid
b) one or more amino polycarboxylic acids and/or their salts selected from the group consisting of: ethylenediaminetetraacetic acid, N-hydroxyethylethlyenediaminetriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, propylenediaminetetraacetic acid, Iminodisuccinic acid, ethylenediamine-N,N′-disuccinic acid, Methylglycinediacetic acid, L-glutamic acid N,N-diacetic acid, nitrilotriacetic acid, N,N-bis(carboxymethyl)glutamic acid, Ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid, N,N′-Bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid, Glycine, N,N′-ethylenebis(N-salicyl) and Iminodisuccinic acid,
wherein the organo polycarboxylic acids are present in an amount that is about 1-50% of a total composition and wherein a cation of salts of the polyacids comprise one or more members selected from the group consisting of one or more metals and one or more organoamines wherein the one or more metals are selected from the group consisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, and Ni, and wherein the one or more organoamines are selected from the group consisting of mono C 1-6 amine, di C 1-6 amine, tri C 1-6 amine, mono ethanol amine, diethanol amine, triethanol amine, monoisopropyl amine, diisopropyl amine, triisopropyl amine, and diethyl amine.
8. The fertilizer composition of claim 1 , wherein the composition further comprises one or more members selected from the group consisting of:
a) surfactants, buffers, fragrance/odor masking agents, colorants, flow modifiers, silicas, and hydrophobized silicas,
b) one or more non-aqueous organo liquids selected from the group consisting of one or more polar aprotic solvents, one or more aprotic solvents, and one or more protic organo solvents wherein:
the one or more aprotic solvents are selected from the group consisting of: i) one or more polyols capped with acetate or formate wherein a polyol portion is selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose and glycerin, ii) one or more alkylene glycol alkyl ether acetates selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and tripropylene glycol butyl ether acetate, iii) isophorone, iv) one or more diesters selected from the group consisting of dimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethyl glutarate, v) dimethylacetamide, vi) dimethylformamide, vii) dimethyl-2-imidazolidinone, viii) 1-Methyl-2-pyrrolidone and ix) limonene,
wherein the one or more protic solvents are selected from the group consisting of: i) an alcohol from the family of C 1-10 alkanols, ii) one or more polyols selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, iii) one or more poly(C 1-10 alkylene) glycols represented by the structure:
H(C t H u ) v OH, wherein
t is an integer: 1-10
u is an integer: 2-20
and v is an integer: 1-20,
iv) one or more alkylene glycols selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene glycol, v) isopropylidene glycerol vi) one or more alkylene glycol alkyl ethers selected from the group represented by the structure:
wherein R 1 is: CH 3 , C 2 H 5 , C 3 H 7 or C 4 H 9
wherein R 2 is: H or the structure
wherein R 3 is: H or CH 3
wherein R 4 is H or CH 3
and f is an integer between 1 and 15,
vii) one or more alkyl lactates selected from the group consisting of ethyl, propyl and butyl lactate, viii) one or more alkanolamines selected from the group represented by the structure:
wherein R 5 is: C 2 H 4 OR 8 or C 3 H 6 OH
wherein R 6 is: H, C 2 H 4 OR 8 or C 3 H 6 OH
wherein R 7 is: H, C 2 H 4 OR 8 or C 3 H 6 OH
wherein R 8 is: (C 2 H 40 ) g H
and g is an integer between 1-10
ix) and glycerol carbonate,
wherein the one or more polar aprotic solvents are selected from the group consisting of
i) dimethyl sulfoxide,
ii) dialkyl, diaryl, and alkylaryl sulfoxide(s) having the formula:
R 9 S(O) x R 10
wherein R 9 and R 10 are each independently a C 1-6 alkylene group, an aryl group, or C 1-3 alkylenearyl group, or R 9 and R 10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 9 and R 10 together are a C 1-6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2, and optionally further comprising
iii) one or more alkylene carbonates are selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate iv) 1-Methyl-2-pyrrolidone, v) one or more organo phosphorous liquids are selected from the group consisting of hexamethylphosphoramide and one or more trialkylphosphates are selected from the group represented by the structure:
wherein:
R 22 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 23 is an alkyl radical —C 1 H 3 to —C 6 H 13
R 24 is an alkyl radical —C 1 H 3 to —C 6 H 13
vi) 1,2-dimethyloxyethane, vii) 2-methoxyethyl ether and vii) cyclohexylpyrrolidone.
9. The liquid fertilizer additive composition of claim 1 , wherein said liquid fertilizer additive composition further comprising soil, wherein the liquid fertilizer additive composition is applied to the soil directly either before or after application of a nitrogen source or in a composition with the nitrogen source to inhibit loss of the nitrogen source's nitrogen caused by a microbial process of nitrification.
10. A fertilizer composition comprised of:
a) one or more nitrogen sources selected from the group consisting of: i) urea, ii) urea formaldehyde reaction products, iii) ammonia, iv) urea formaldehyde and ammonia reaction products, v) ammonium nitrate, vi) ammonium sulfate, vii) manure viii) compost and ix) treated urea and
b) a liquid fertilizer additive composition comprising i) a non-aqueous polar, aprotic organic liquid (NAPAOL) and ii) a nitrification inhibitor composition, wherein NAPAOL comprises one or more members selected from the group consisting of:
(1) dimethyl sulfoxide,
(2) dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:
R 9 S(O) x R 10
wherein R 9 and R 10 are each independently a C 1-6 alkylene group, an aryl group, or C 1-3 alkylenearyl group or R 9 and R 10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 9 and R 10 together are a C 1-6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2,
(3) one or more alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate (4) 1-Methyl-2-pyrrolidone, (5) one or more organo phosphorous liquids selected from the group consisting of hexamethylphosphoramide and one or more trialkylphosphates selected from the structure:
wherein:
R 22 is an alkyl radical —C 1 H 3 to —C 6 H 3
R 23 is an alkyl radical —C 1 H 3 to —C 6 H 3
R 24 is an alkyl radical —C 1 H 3 to —C 6 H 13
(6) 1,2-dimethyloxyethane, (7) 2-methoxyethyl ether, and (8) cyclohexylpyrrolidone,
and wherein the nitrification inhibitor composition comprises one or more members selected from the structures consisting of:
wherein R 43 , R 44 , R 45 and R 46 are one or more members independently selected from the group consisting of: H and —CH 2 OH wherein at least one of R 43 , R 44 , R 45 and R 46 is —CH 2 OH,
wherein R 47 , R 48 , R 49 R 50 , R 51 and R 52 are one or more members independently selected from the group consisting of: H, and —CH 2 OH,
wherein R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 are one or more members independently selected from the group consisting of: H and —CH 2 OH wherein said liquid fertilizer additive composition is generated under non-aqueous conditions, and wherein the structures comprise more than 10% by weight of the nitrification inhibitor composition.
11. The fertilizer composition of claim 10 wherein the nitrification inhibitor composition further comprises the structure:
wherein R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 are one or more members independently selected from the group consisting of: H and —CH 2 OH.
12. The fertilizer composition of claim 10 wherein the composition further comprises one or more members selected from the group consisting of t paraformaldehyde, DCD and formaldehyde.
13. The fertilizer composition of claim 10 , wherein the nitrification inhibitor composition further comprises one or more members selected from the group consisting of a) ammonia, b) one or more polyamines, c) one or more polyols, d) one or more primary amines, e) one or more secondary amines, f) one or more low molecular weight alcohols, and g) one or more non-cyano containing nitrification inhibitors, wherein
the one or more polyamines are selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and aminoethylethanolamine, and wherein the one or more polyamines comprise 0.01-5% of a polymer composition weight,
wherein the one or more polyols are selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, glycerin, poly(C 1-10 alkylene) glycols, ethylene, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, isopropylidene glycerol, tripropylene glycol methyl ether, tripropylene glycol butyl ether, dipropylene glycol butyl ether, and tripropylene glycol butyl ether wherein the one or more polyols comprise 0.1-5% of the polymer weight,
wherein the one or more secondary amines are selected from the group consisting of diethanolamine, diethylamine, cyclohexylamine, methylethanolamine, diisopropanolamine, methylispropylamine wherein the one or more secondary amines comprise 0.1-5% of the polymer composition,
wherein the one or more low molecular weight alcohols are selected from the group consisting of methanol, ethanol, butanol, pentanol, and hexanol wherein the one or more low molecular weight alcohols comprise 0.1-5% of the polymer composition weight,
wherein the one or more non-cyano containing nitrification inhibitors are selected from the group consisting of:
a) one or more pyrazoles represented by the structure:
wherein R 28 =—H, —CH 3 , —CH 2 CH 3 , —NH 2 or —NHCH 3 ,
wherein R 29 =—H, —OH, —SH, —CONH 2 or —CONHCH 3 ,
wherein R 30 =—H, —CH 3 , —CH 2 CH 3 , —NH 2 or —NHCH 3 , and
wherein R 31 =—H, —CH 3 , —CH 2 CH 3 , —NH 2 or —NHCH 3 ,
b) one or more members selected from the group consisting of 2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea, 2,4-diamino-6-trichloromethyl-5-triazine, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, and 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate.
14. The fertilizer composition of claim 10 , wherein the composition further comprises one or more members selected from the group consisting of:
a) one or more biologics selected from the group consisting of:
i) Bacillus biologics, ii) Azospirillum biologics, iii) Azobacter biologics iv) Gluconacetobacter biologics, v) Phosphobacteria , vi) Cyanobacteria , vii) Herbaspirillum , viii) Burkholderia , ix) Pseudomonas, x ) Gluconacetobacter , xi) Enterobacter , xii) Klebsiella , xiii) Burkholderia , xiv) Bradyrhiwbium species, xv) Bradyrhiwbium japonicum , xvi) Rhizobium meliloti , xvii) Laccaria bicolor, xviii) Glomus imraradices timanita , xix) Actinomyces , xx) Penicillium , xxi) Mesorhizobiwn cicero , xxii) one or more insecticidal or insect repellent microbial species and strains selected from the group consisting of:
Telenomus podisi, Baculovirus anticarsia; Trichogramma pretiosum, Trichogramma gallai, Chromobacterium subtsugae, Trichoderma fertile, Beauveria bassiana, Beauveria bassiana, Beauveria bassiana, Paecilomyces jknwsoroseu, Trichoderma harzianum, Verticillium lecanii, lsarfofumosarosea Lecanicillium muscarium, Streptomyces microflavus , and Muscodor albus,
xxiii) one or more nematodal microbial species and strains are selected from the group consisting of:
Myrothecium verrucaria, Pasteuria species, Pasteuria
Metarhizium species, and Flavobacteriwn species
xxiv) Reynoutria sachalinensis and
xxv) one or more antifungal, antimicrobial and/or plant growth promoting microbial species and strains are selected from the group consisting of Gliocladium species, Pseudomonas species selected from the group consisting of:
Pseudomonas fluorescens, Pseudomonas fluorescens putida and P. chlororaphis, Pseudomonasfluorescens VP5, Pseudomonas diazotrophicus, Enterobacter cloacae, Trichodema species, Trichoderma virens, Trichoderma atroviride strains, Coniothyrium minitans, Gliocladium species, Gliacladium virens, Gliacladium roseum , and Trichodemw harzianum species,
b) and one or more biologically active agents are selected from the group consisting of:
i) one or more urease inhibitors are selected from the group consisting of aliphatic phosphoric triamide, phosphoramides, N-alkyl thiophosphoric triamides, (aminomethyl)phosphinic acids and their salts and aminomethyl (alkylaminomethyl)phosphinic acids and their salts,
ii) one or more additional nitrification inhibitors are selected from the group consisting of 2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4,6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate, dimethylpyrazole organic and inorganic salts, and 2-amino-4-chloro-6-methylpyrimidine,
iii) and one or more members selected from the group consisting of pesticide(s), herbicides fungicides(s), and insecticide(s).
15. The fertilizer composition of claim 10 , wherein the composition further comprises one or more organo polycarboxylic acids selected from the group consisting of a) organo polycarboxylic acid polymers and/or their salts wherein the polymer is a monomer homopolymer, a copolymer and/or a terpolymer comprised of one or more members selected from the group consisting of:
aspartic acid,
glutamic acid,
maleic anhydride,
itaconic anhydride,
citraconic anhydride,
citric acid, and
acrylic acid
b) one or more amino polycarboxylic acids and/or their salts selected from the group consisting of: ethylenediaminetetraacetic acid, N-hydroxyethylethlyenediaminetriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, propylenediaminetetraacetic acid, Iminodisuccinic acid, ethylenediamine-N,N′-disuccinic acid, Methylglycinediacetic acid, L-glutamic acid N,N-diacetic acid, nitrilotriacetic acid, N,Nbis(carboxymethyl)glutamic acid, Ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid, N,N′-Bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid, Glycine, N,N′-ethylenebis(N-salicyl) and Iminodisuccinic acid,
wherein the organo polycarboxylic acids are present in an amount that is about 1-50% of a total composition and wherein a cation of salts of the polyacids comprise one or more member selected from the group consisting of one or more metals and one or more organoamines wherein the one or more metals are selected from the group consisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, and Ni and wherein the one or more organoamines are selected from the group consisting of mono C 1-6 amine, di C 1-6 amine, tri C 1-6 amine, mono ethanol amine, diethanol amine, triethanol amine, monoisopropyl amine, diisopropyl amine, triisopropyl amine, and diethyl amine.
16. The fertilizer composition of claim 10 wherein treated urea is comprised of urea and one or more members selected from the group consisting of: a) urea formaldehyde polymer, b) urea formaldehyde reaction adducts, c) one or more biologics d) one or more biologically active agents and e) organo polycarboxylic acids and/or their salt wherein the one or more biologics are selected from the group consisting of:
i) Bacillus biologics, ii) Azospirillum biologics, iii) Azobacter biologics iv) Gluconacetobacter biologics, v) Phosphobacteria , vi) Cyanobacteria , vii) Herbaspirillum , viii) Burkholderia , ix) Pseudomonas, x ) Gluconacetobacter , xi) Enterobacter , xii) Klebsiella , xiii) Burkholderia , xiv) Bradyrhiwbium species, xv) Bradyrhiwbium japonicum , xvi) Rhizobium meliloti , xvii) Laccaria bicolor , xviii) Glomus imraradices timanita , xix) Actinomyces , xx) Penicillium , xxi) Mesorhizobiwn cicero , xxii) one or more insecticidal or insect repellent microbial species and strains selected from the group consisting of:
Telenomus podisi, Baculovirus anticarsia; Trichogramma pretiosum, Trichogramma gallai, Chromobacterium subtsugae, Trichoderma fertile, Beauveria bassiana, Beauveria bassiana, Beauveria bassiana, Paecilomyces jknwsoroseu, Trichoderma harzianum, Verticillium lecanii, lsarfofumosarosea Lecanicillium muscarium, Streptomyces microflavus , and Muscodor albus,
xxiii) one or more nematodal microbial species and strains selected from the group consisting of:
Myrothecium verrucaria, Pasteuria species, Pasteuria
Metarhizium species, and Flavobacteriwn species
xxiv) Reynoutria sachalinensis and
xxv) one or more antifungal, antimicrobial and/or plant growth promoting microbial species and strains selected from the group consisting of:
Gliocladium species, Pseudomonas species selected from the group consisting of:
Pseudomonas fluorescens, Pseudomonas fluorescens putida and P. chlororaphis, Pseudomonasfluorescens VP 5 , Pseudomonas diazotrophicus, Enterobacter cloacae, Trichodema species, Trichoderma virens, Trichoderma atroviride strains, Coniothyrium minitans, Gliocladium species, Gliacladium virens, Gliacladium roseum , and Trichodemw harzianum species,
and wherein the one or more biologically active agents are selected from the group consisting of:
i) one or more urease inhibitors selected from the group consisting of aliphatic phosphoric triamide, phosphoramides, N-alkyl thiophosphoric triamides, (aminomethyl)phosphinic acids and their salts and aminomethyl (alkylaminomethyl)phosphinic acids and their salts,
ii) one or more additional nitrification inhibitors selected from the group consisting of 2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4,6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate, dimethylpyrazole organic and inorganic salts, and 2-amino-4-chloro-6-methylpyrimidine,
iii) and one or more members selected from the group consisting of pesticide(s), herbicides fungicides(s), and insecticide(s).
17. The fertilizer composition of claim 10 wherein the NAPAOL comprises dimethyl sulfoxide.
18. The fertilizer composition of claim 10 wherein the composition is made using at least one of the following application techniques:
a) coating a nitrogen source with said liquid fertilizer additive composition utilizing spraying, metering or slowly pouring onto the surface of nitrogen source,
b) incorporating said liquid fertilizer additive composition during the processing of a nitrogen source wherein the liquid fertilizer additive can be added directly into the molten nitrogen source before formation of a particle, granule and/or a prill, applied/sprayed onto the surface of a molten nitrogen source during the formation of a particle, granule and/or a prill and/or sprayed onto a surface of a nitrogen source during the formation of a particle, granule and/or a prill,
c) dissolving said liquid fertilizer additive composition into aqueous liquid fertilizers, or
d) incorporating said liquid fertilizer additive composition into one or more non-aqueous liquid nitrogen sources selected from the group consisting of pressurized anhydrous ammonia gas and non-pressurized anhydrous ammonia gas.
19. The fertilizer composition of claim 10 wherein the composition of the nitrogen source comprises one or more members selected from the group consisting of urea and ammonium nitrate.
20. The fertilizer composition of claim 19 , wherein the composition further comprises water.