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Publication numberUSRE41789 E1
Publication typeGrant
Application numberUS 12/350,491
Publication dateOct 5, 2010
Filing dateJan 8, 2009
Priority dateFeb 7, 1994
Also published asCA2182300A1, CA2182300C, DE69532275D1, DE69532275T2, EP0743931A1, EP0743931A4, EP0743931B1, EP1386897A2, EP1386897A3, US5514200, US5514200, US5830255, US5830255, US6113665, US6645268, US6896714, US6929673, US7160349, US7160350, US20030101784, US20040226328, US20050126239, US20050178178, USRE43073, WO1995021142A1
Publication number12350491, 350491, US RE41789 E1, US RE41789E1, US-E1-RE41789, USRE41789 E1, USRE41789E1
InventorsCarol J. Lovatt
Original AssigneeThe Regents Of The University Of California
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
A buffered system based on phophorous acid, hypophosphorous acid and polyhypophosphorous acid and is phosphate-free; a second buffer system of carboxylic acid or salt, citric acid/ citrate; water-diluted to pH 6.5-7; leaf uptake; storage stability; materials handling; irrigation; plant/root health
US RE41789 E1
Abstract
Concentrated phosphorus fertilizers are disclosed that comprise a buffered composition of an organic acid and salts thereof and a phosphorous-containing acid and salts thereof. The concentrated phosphorus fertilizers can be diluted with water of pH ranging from about 6.5 to about 8.5 at ratios of concentrate to water at about 1:40 to about 1:600 to result in a fertilizer having a pH in the range acceptable for foliar uptake of phosphorus.
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Claims(110)
1. A multiple buffered phosphorus fertilizer comprising:
(i) a first buffer system comprising a phosphorous acid and a salt of a phosphorous acid; and
(ii) a second buffer system comprising an organic acid and a salt of an organic acid.
2. The multiple buffered phosphorus fertilizer according to claim 1, wherein phosphorus in said multiple buffered phosphorus fertilizer is present in an amount equivalent to about 0.30 kg/L or greater P2O5.
3. The multiple buffered phosphorus fertilizer according to claim 1, wherein said organic acid is a member selected from the group consisting of dicarboxylic acids, tricarboxylic acids and combinations thereof.
4. The multiple buffered phosphorus fertilizer according to claim 3, wherein said organic acid is citric acid.
5. The multiple buffered phosphorus fertilizer according to claim 1, wherein said phosphorous acid is a member selected from the group consisting of phosphorous acid, hypophosphorous acid, polyphosphorous acid, polyhypophosphorous acid and combinations thereof.
6. The multiple buffered phosphorus fertilizer according to claim 1, wherein said fertilizer has a pH of about 5.0 to about 7.0.
7. The multiple buffered phosphorus fertilizer according to claim 6, wherein said fertilizer has a pH of about 5.5 to about 6.5.
8. The multiple buffered phosphorus fertilizer according to claim 1, wherein the number of buffering systems is two.
9. A substantially fully solubilized use-dilution fertilizer having a pH acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphorus fertilizer according to claim 1; and
(ii) water.
10. The use-dilution fertilizer according to claim 9, wherein said use-dilution fertilizer comprises a ratio of said multiple buffered phosphorus fertilizer to said water of about 1:40 to about 1:600.
11. The use-dilution fertilizer according to claim 9, wherein said water has a pH of about 6.5 to about 8.5.
12. The multiple buffered phosphorus fertilizer according to claim 1, wherein said multiple buffered phosphorus fertilizer is essentially clear and devoid of precipitate.
13. The multiple buffered phosphorus fertilizer according to claim 1, further comprising a plant nutrient, wherein said plant nutrient is a member selected from the group consisting of nitrogen, potassium, sulfur, calcium, magnesium, boron, iron, manganese, molybdenum, zinc, ammonia and combinations thereof.
14. The multiple buffered phosphorus fertilizer according to claim 1, wherein said multiple buffered phosphorus fertilizer is in a liquid form.
15. The multiple buffered phosphorus fertilizer according to claim 1, wherein said multiple buffered phosphorus fertilizer is in a solid form.
16. The multiple buffered phosphorus fertilizer of claim 1, wherein phosphorus in said multiple buffered phosphorus fertilizer is present in an amount equivalent to from about 0.30 kg/L to about 0.40 kg/L P2O5.
17. The multiple buffered phosphorus fertilizer according to claim 16, wherein said organic acid is a member selected from the group consisting of dicarboxylic acids, tricarboxylic acids and combinations thereof.
18. The multiple buffered phosphorus fertilizer according to claim 17, wherein said organic acid is citric acid.
19. The multiple buffered phosphorus fertilizer according to claim 16, wherein said phosphorous acid is a member selected from the group consisting of phosphorous acid, hypophosphorous acid, polyphosphorous acid, polyhypophosphorous acid and combinations thereof.
20. The multiple buffered phosphorus fertilizer according to claim 16, wherein said fertilizer has a pH of about 5.0 to about 7.0.
21. The multiple buffered phosphorus fertilizer according to claim 20, wherein said fertilizer has a pH of about 5.5 to about 6.5.
22. The multiple buffered phosphorus fertilizer according to claim 16, wherein the number of buffering systems is two.
23. A substantially fully solubilized use-dilution fertilizer having a pH acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphorus fertilizer according to claim 16; and
(ii) water.
24. The use-dilution fertilizer according to claim 23, wherein said use-dilution fertilizer comprises a ratio of said multiple buffered phosphorus fertilizer to said water of about 1:40 to about 1:600.
25. The use-dilution fertilizer according to claim 23, wherein said water has a pH of about 6.5 to about 8.5.
26. The multiple buffered phosphorus fertilizer according to claim 16, wherein said multiple buffered phosphorus fertilizer is essentially clear and devoid of precipitate.
27. The multiple buffered phosphorus fertilizer according to claim 16, further comprising a plant nutrient, wherein said plant nutrient is a member selected from the group consisting of nitrogen, potassium, sulfur, calcium, magnesium, boron, iron, manganese, molybdenum, zinc, ammonia and combinations thereof.
28. The multiple buffered phosphorus fertilizer according to claim 16, wherein said multiple buffered phosphorus fertilizer is in a liquid form.
29. The multiple buffered phosphorus fertilizer according to claim 16, wherein said multiple buffered phosphorus fertilizer is in a solid form.
30. The multiple buffered phosphorus fertilizer of claim 1, wherein phosphorus in said multiple buffered phosphorus fertilizer is present in an amount equivalent to from about 0.30 kg/L to about 0.40 kg/L P2O5.
31. The multiple buffered phosphorus fertilizer according to claim 30, wherein said organic acid is a member selected from the group consisting of dicarboxylic acids, tricarboxylic acids and combinations thereof.
32. The multiple buffered phosphorus fertilizer according to claim 31, wherein said organic acid is citric acid.
33. The multiple buffered phosphorus fertilizer according to claim 30, wherein said phosphorous acid is a member selected from the group consisting of phosphorous acid, hypophosphorous acid, polyphosphorous acid, polyhypophosphorous acid and combinations thereof.
34. The multiple buffered phosphorus fertilizer according to claim 30, wherein said multiple buffered phosphorus fertilizer has a pH of about 5.0 to about 7.0.
35. The multiple buffered phosphorus fertilizer according to claim 34, wherein said multiple buffered phosphorus fertilizer has a pH of about 5.5 to about 6.5.
36. The multiple buffered phosphorus fertilizer according to claim 30, wherein the number of buffering systems is two.
37. A substantially fully solubilized use-dilution fertilizer having a pH acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphorus fertilizer according to claim 30; and
(ii) water.
38. The use-dilution fertilizer according to claim 37, wherein said use-dilution fertilizer comprises a ratio of said multiple buffered phosphorus fertilizer to said water of about 1:40 to about 1:600.
39. The use-dilution fertilizer according to claim 37, wherein said water has a pH of about 6.5 to about 8.5.
40. The multiple buffered phosphorus fertilizer according to claim 30, wherein said multiple buffered phosphorus fertilizer is essentially clear and devoid of precipitate.
41. The multiple buffered phosphorus fertilizer according to claim 30, further comprising a plant nutrient, wherein said plant nutrient is a member selected from the group consisting of nitrogen, potassium, sulfur, calcium, magnesium, boron, iron, manganese, molybdenum, zinc, ammonia and combinations thereof.
42. The multiple buffered phosphorus fertilizer according to claim 30, wherein said multiple buffered phosphorus fertilizer is in a liquid form.
43. The multiple buffered phosphorus fertilizer according to claim 30, wherein said multiple buffered phosphorus fertilizer is in a solid form.
44. A multiple buffered phosphite fertilizer comprising:
(i) a first buffer system comprising a phosphite; and
(ii) a second buffer system comprising an organic acid and a salt of an organic acid.
45. The multiple buffered phosphite fertilizer according to claim 44, wherein phosphorus in said multiple buffered phosphite fertilizer is present in an amount equivalent to about 0.30 kg/L or greater P2O5.
46. The multiple buffered phosphite fertilizer according to claim 44, wherein said organic acid is a member selected from the group consisting of dicarboxylic acids, tricarboxylic acids and combinations thereof.
47. The multiple buffered phosphite fertilizer according to claim 46, wherein said organic acid is citric acid.
48. The multiple buffered phosphite fertilizer according to claim 44, wherein said phosphite is a salt of a phosphorous acid, wherein said phosphorous acid is a member selected from the group consisting of phosphorous acid, hypophosphorous acid, polyphosphorous acid, polyhypophosphorous acid and combinations thereof.
49. The multiple buffered phosphite fertilizer according to claim 44, wherein said multiple buffered phosphite fertilizer has a pH of about 5.0 to about 7.0.
50. The multiple buffered phosphite fertilizer according to claim 49, wherein said multiple buffered phosphite fertilizer has a pH of about 5.5 to about 6.5.
51. The multiple buffered phosphite fertilizer according to claim 44, wherein the number of buffering systems is two.
52. A substantially fully solubilized use-dilution fertilizer having a pH acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphite fertilizer according to claim 44; and
(ii) water.
53. The use-dilution fertilizer according to claim 52, wherein said use-dilution fertilizer comprises a ratio of said multiple buffered phosphite fertilizer to said water of about 1:40 to about 1:600.
54. The use-dilution fertilizer according to claim 52, wherein said water has a pH of about 6.5 to about 8.5.
55. The multiple buffered phosphite fertilizer according to claim 44, wherein said multiple buffered phosphite fertilizer is essentially clear and devoid of precipitate.
56. The multiple buffered phosphite fertilizer according to claim 44, further comprising a plant nutrient, wherein said plant nutrient is a member selected from the group consisting of nitrogen, potassium, sulfur, calcium, magnesium, boron, iron, manganese, molybdenum, zinc, ammonia and combinations thereof.
57. The multiple buffered phosphite fertilizer according to claim 44, wherein said multiple buffered phosphite fertilizer is in a liquid form.
58. The multiple buffered phosphite fertilizer according to claim 44, wherein said multiple buffered phosphite fertilizer is in a solid form.
59. The multiple buffered phosphite fertilizer of claim 44, wherein phosphorus in said multiple buffered phosphite fertilizer is present in an amount equivalent to from about 0.30 kg/L to about 0.40 kg/L P2O5.
60. The multiple buffered phosphite fertilizer according to claim 59, wherein said organic acid is a member selected from the group consisting of dicarboxylic acids, tricarboxylic acids and combinations thereof.
61. The multiple buffered phosphite fertilizer according to claim 60, wherein said organic acid is citric acid.
62. The multiple buffered phosphite fertilizer according to claim 59, wherein said phosphite is a salt of a phosphorous acid, wherein said phosphorous acid is a member selected from the group consisting of phosphorous acid, hypophosphorous acid, polyphosphorous acid, polyhypophosphorous acid and combinations thereof.
63. The multiple buffered phosphite fertilizer according to claim 59, wherein said multiple buffered phosphite fertilizer has a pH of about 5.0 to about 7.0.
64. The multiple buffered phosphite fertilizer according to claim 63, wherein said multiple buffered phosphite fertilizer has a pH of about 5.5 to about 6.5.
65. The multiple buffered phosphite fertilizer according to claim 59, wherein the number of buffering systems is two.
66. A substantially fully solubilized use-dilution fertilizer having a pH acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphite fertilizer according to claim 59; and
(ii) water.
67. The use-dilution fertilizer according to claim 66, wherein said use-dilution fertilizer comprises a ratio of said multiple buffered phosphite fertilizer to said water of about 1:40 to about 1:600.
68. The use-dilution fertilizer according to claim 66, wherein said water has a pH of about 6.5 to about 8.5.
69. The multiple buffered phosphite fertilizer according to claim 59, wherein said multiple buffered phosphite fertilizer is essentially clear and devoid of precipitate.
70. The multiple buffered phosphite fertilizer according to claim 59, further comprising a plant nutrient, wherein said plant nutrient is a member selected from the group consisting of nitrogen, potassium, sulfur, calcium, magnesium, boron, iron, manganese, molybdenum, zinc, ammonia and combinations thereof.
71. The multiple buffered phosphite fertilizer according to claim 59, wherein said multiple buffered phosphite fertilizer is in a liquid form.
72. The multiple buffered phosphite fertilizer according to claim 59, wherein said multiple buffered phosphite fertilizer is in a solid form.
73. The multiple buffered phosphite fertilizer of claim 44, wherein phosphorus in said multiple buffered phosphite fertilizer is present in an amount equivalent to from about 0.30 kg/L to about 0.40 kg/L P2O5.
74. The multiple buffered phosphite fertilizer according to claim 73, wherein said organic acid is a member selected from the group consisting of dicarboxylic acids, tricarboxylic acids and combinations thereof.
75. The multiple buffered phosphite fertilizer according to claim 74, wherein said organic acid is citric acid.
76. The multiple buffered phosphite fertilizer according to claim 73, wherein said phosphite is a salt of a phosphorous acid, wherein said phosphorous acid is a member selected from the group consisting of phosphorous acid, hypophosphorous acid, polyphosphorous acid, polyhypophosphorous acid and combinations thereof.
77. The multiple buffered phosphite fertilizer according to claim 73, wherein said multiple buffered phosphite fertilizer has a pH of about 5.0 to about 7.0.
78. The multiple buffered phosphite fertilizer according to claim 77, wherein said multiple buffered phosphite fertilizer has a pH of about 5.5 to about 6.5.
79. The multiple buffered phosphite fertilizer according to claim 73, wherein the number of buffering systems is two.
80. A substantially fully solubilized use-dilution fertilizer having a pH acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphite fertilizer according to claim 73; and
(ii) water.
81. The use-dilution fertilizer according to claim 80, wherein said use-dilution fertilizer comprises a ratio of said multiple buffered phosphite fertilizer to said water of about 1:40 to about 1:600.
82. The use-dilution fertilizer according to claim 80, wherein said water has a pH of about 6.5 to about 8.5.
83. The multiple buffered phosphite fertilizer according to claim 73, wherein said multiple buffered phosphite fertilizer is essentially clear and devoid of precipitate.
84. The multiple buffered phosphite fertilizer according to claim 73, further comprising a plant nutrient, wherein said plant nutrient is a member selected from the group consisting of nitrogen, potassium, sulfur, calcium, magnesium, boron, iron, manganese, molybdenum, zinc, ammonia and combinations thereof.
85. The multiple buffered phosphite fertilizer according to claim 73, wherein said multiple buffered phosphite fertilizer is in a liquid form.
86. The multiple buffered phosphite fertilizer according to claim 73, wherein said multiple buffered phosphite fertilizer is in a solid form.
87. A substantially fully solubilized use-dilution fertilizer comprising a concentrate comprising a first buffer system, wherein said first buffer system is derived from a phosphorous acid and salt of a phosphorous acid, wherein phosphorus is present in said first buffer system in an amount equivalent to at least about 0.30 kg/L P2O5, such that when said concentrate is diluted with water having a pH as low as about 6.5 at a ratio as high as about 1 part concentrate to about 40 parts water, there is formed a substantially fully solubilized use-dilution fertilizer having a foliage acceptable pH for phosphorus uptake.
88. The use-dilution fertilizer of claim 87, wherein said phosphorus is present in said first buffer system in an amount equivalent to between about 0.30 kg/L P2O5and about 0.40 kg/L P2O5.
89. The use-dilution fertilizer of claim 87, wherein said substantially fully solubilized use-dilution fertilizer further comprises a second buffer system comprising an organic acid and a salt of an organic acid.
90. The use-dilution fertilizer of claim 89, wherein said first buffer system contains phosphorus in an amount equivalent to between about 0.30 kg/L P2O5and about 0.40 kg/L P2O5.
91. A method of making a substantially fully solubilized use-dilution fertilizer, said method comprising:
mixing water with a pH as low as about 6.5 and a concentrate comprising a first buffer system comprising a phosphorous acid and a salt of a phosphorous acid, thus forming said use-dilution fertilizer, wherein said use-dilution fertilizerconcentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable pH for phosphorus uptake.
92. The method of claim 91, further comprising adding a plant nutrient to said use-dilution fertilizer.
93. The method of claim 92, wherein said plant nutrient is a member selected from the group consisting of nitrogen, calcium, magnesium, potassium, molybdenum, boron, and sulfur.
94. The method of claim 92, wherein said plant nutrient is potassium.
95. The method of claim 91, wherein said mixinguse-dilution fertilizer further comprises a second buffer system comprising an organic acid and a salt of an organic acid.
96. A method of applying phosphorus to a plant, said method comprising:
(a) mixing water with a pH as low as about 6.5 and a concentrate comprising a first buffer system comprising a phosphorous acid and a salt of a phosphorous acid, thus forming a substantially fully solubilized use-dilution fertilizer, wherein said use-dilution fertilizerconcentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable pH for phosphorus uptake; and
(b) applying said substantially fully solubilized use-dilution fertilizer to the foliage of said plant, thus applying said phosphorus to said plant.
97. The method of claim 96, further comprising adding a plant nutrient to said use-dilution fertilizer.
98. The method of claim 97, wherein said plant nutrient is a member selected from the group consisting of nitrogen, calcium, magnesium, potassium, molybdenum, boron, and sulfur.
99. The method of claim 97, wherein said plant nutrient is potassium.
100. The method of claim 96, wherein said mixinguse-dilution fertilizer further comprises a second buffer system comprising an organic acid and a salt of an organic acid.
101. A substantially fully solubilized use-dilution fertilizer having a foliage acceptable pH for phosphorus uptake, produced by a process comprising:
mixing water with a pH as low as about 6.5 and a concentrate comprising a first buffer system consisting of a phosphorous-containing acid and salt thereof, thus forming said use-dilution fertilizer, wherein said use-dilution fertilizerconcentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable pH for phosphorus uptake.
102. The use-dilution fertilizer of claim 101, further comprising adding a plant nutrient to said use-dilution fertilizer.
103. The use-dilution fertilizer of claim 102, wherein said plant nutrient is a member selected from the group consisting of nitrogen, calcium, magnesium, potassium, molybdenum, boron, and sulfur.
104. The use-dilution fertilizer of claim 102, wherein said plant nutrient is potassium.
105. The use-dilution fertilizer of claim 101, wherein said mixinguse-dilution fertilizer further comprises a second buffer system comprising an organic acid and a salt of an organic acid.
106. A substantially fully solubilized use-dilution fertilizer having a foliage acceptable pH for phosphorus uptake, produced by a process comprising:
mixing water with a pH as low as about 6.5 and a concentrate comprising a first buffer system comprising phosphite, thus forming said use-dilution fertilizer, wherein said use-dilution fertilizerconcentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable pH for phosphorus uptake.
107. The use-dilution fertilizer of claim 106, further comprising adding a plant nutrient to said use-dilution fertilizer.
108. The use-dilution fertilizer of claim 107, wherein said plant nutrient is a member selected from the group consisting of nitrogen, calcium, magnesium, potassium, molybdenum, boron, and sulfur.
109. The use-dilution fertilizer of claim 107, wherein said plant nutrient is potassium.
110. The use-dilution fertilizer of claim 106, wherein said mixinguse-dilution fertilizer further comprises a second buffer system comprising an organic acid and a salt of an organic acid.
Description

This is a continuation of U.S. application Ser. No. 10/686,411, filed Oct. 14, 2003, now U.S. Pat. No. 6,896,714, which issued May 25, 2005, which is a continuation of U.S. Application No. 10/341,966, filed Jan. 13, 2003, now U.S. Pat. No. 6,645,268 B2, which is a continuation of U.S. application Ser. No. 09/637,621, filed Aug. 11, 2000, now U.S. Pat. No. 6,929,673, which issued Aug. 16, 2005, which is a continuation of U.S. application Ser. No. 09/126,233, filed Jul. 30, 1998, now U.S. Pat. No. 6,113,665, which is a continuation of U.S. application Ser. No. 08/642,574, filed May 3, 1996, now U.S. Pat. No. 5,830,255, which issued Nov. 3, 1998, which application was re-examined as B1 5,830,255 (certificate issued Jul. 11, 2000), which is a continuation of U.S. application Ser. No. 08/192,508, filed Feb. 7, 1994, now U.S. Pat. No. 5,514,200, which issued May 7, 1996

BACKGROUND OF THE INVENTION

Fertilizers are added to the soil of crops or in some cases they can be applied directly to crop foliage to supply elements needed for plant nutrition. Seventeen elements are known to be essential to the health and growth of plants. Typically, nitrogen, phosphorus, and potassium are provided in the greatest quantity. With increasing knowledge of the role of each of the nutrients essential to plants, there is a better understanding of the importance of providing a given nutrient at the appropriate stage of phenology. To accomplish this, rapid changes in fertilizer formulations and methods of application have been necessary.

Another factor changing fertilization formulations and methods is due tothe pressure from federal, state and local regulatory agencies and citizen groups to reduce the total amount of fertilizer in general, and of specific nutrients in particular, being applied to the soil. Additionally, the loss of registration of existing synthetic plant growth regulators and organic pesticides and the prohibitively high costs involved in the successful registration of new ones, also plays a roleplay roles in the changing arena of crop fertilization.

The principal source of phosphorus for the fertilizer industry is derived from the ores of phosphorus-containing minerals found in the Earth's crust, termed phosphate rock. Elemental phosphorus does not exist in nature; plants utilize phosphorus as the dihydrogen phosphate ion (H2PO4 ). While untreated phosphate rock has been used for fertilizer, it is most commonly acidulated with dilute solutions of strong mineral acids to form phosphoric acid, which is more readily absorbed by crops.

Until recently, phosphate and polyphosphate compounds were considered the only forms in which phosphorus could be supplied to plants to meet the plant's nutritional need for phosphorus. Indeed, the only phosphite compound cited for use as a fertilizer in the Merck Index (M. Windhols, ed., 1983, 10th edition, p. 1678) is calcium phosphite (CaHPO3). No phosphite fertilizer formulations are listed in The Farm Chemical Handbook (Meister Publishing Co., 1993, Willoughby, Ohio 834 p.) or Western Fertilizer Handbook (The Interstate, Danville, Ill. 288 p.) Historically, calcium phosphite was formed as a putative contaminant in the synthesis of calcium superphosphate fertilizers [McIntyre et al., Agron. J. 42:543-549 (1950)] and in one case, was demonstrated to cause injury to corn [Lucas et al., Agron. J. 71:1063-1065 (1979)]. Consequently, phosphite was relegated for use only as a fungicide (Alliete®; U.S. Pat. No. 4,075,324) and as a food preservative.

More recently, it has been shown that plants can obtain phosphorus from phosphite [Lovatt, C. J., Mar. 22, 1990, “Foliar phosphorus fertilization of citrus by foliar application of phosphite” In: Citrus Research Advisory Committee (eds) Summary of Citrus Research, University of California, Riverside, Calif, pp 25-26; Anon., May, 1990, “Foliar applications do double duty” In: L. Robison (ed) Citrograph Vol. 75, No. 7, p 161; Lovat, C. J., 1990, “A definitive test to determine whether phosphite fertilization can replace phosphate fertilization to supply P in the metabolism of ‘Hass’ on ‘Duke 7’:—A preliminary report” California Avocado Society Yearbook 74:61-64; Lovatt, C. J., 1992]. Formulations based on phosphorous acid and hypophosphorous acid, as phosphite is, generally undergo oxidation to phosphate and thus lose the benefits that could be derived from the use of phosphite fertilization applications.

The phosphate and polyphosphate fertilizers currently used have a number of properties that compromise their desirability as fertilizers. Generally, they tend to form precipitates during storage and shipping. This limits the ability to formulate concentrated solutions of fertilizers. Additionally, formulations must generally be maintained at a narrow pH range to prevent precipitation, resulting in fertilizers that are limited to particular uses.

Another drawback of phosphate fertilizers is that they are not readily taken up by the foliage of many plants and must instead be delivered to the soil for uptake by plant roots. The mobility of phosphate fertilizers in the soil is limited leading to rapid localized depletion of phosphorus in the rhizosphere and phosphorus deficiency of the plant. Frequent reapplication of phosphate fertilizers is undesirable because it leads to leaching of phosphate into the groundwater resulting in eutrophication of lakes, ponds and streams.

Phosphate and polyphosphate fertilizers have also been shown to inhibit the beneficial symbiosis between the roots of the plants and mycorrhizal fungi. They tend to support the growth of algae and promote bacterial and fungal growth in the rhizosphere, including the growth of pathogenic fungi and other soil-borne pests.

Even though phosphorus, once in the plant, is very phloem mobile (i.e. readily moving from old leaves to young tissues), phosphate is poorly absorbed through the leaves of most plant species. This is unfortunate because successful foliar phosphorus feeding would result in the application of less phosphate fertilizers to the soil and reduce phosphorus pollution of the ground water.

Accordingly, there is a need for a phosphorus fertilizer that can be utilized in irrigation systems and applied to foliage without the formation of precipitates that reduce nutrient availability and uptake by the plant and plug emitters and sprayers. There is also a need for new methods of fertilizer application that allow nutrients in a readily available form to be supplied at the exact time the plant needs them. This need includes the facility of a foliar product to be sold in a single formulation for use as a concentrated material for airplane or helicopter application or as a dilute solution for ground spray application and yet able to be maintained at a suitable pH range optimal for leaf uptake despite the need to be diluted prior to application.

Additionally, there is a demand for phosphorus fertilizers that have the facility to be used as liquids or solids (granule or powder). There is also a demand for fertilizers that do more than just supply nutrients. It is desired that the fertilizers also have demonstrated plant growth regulator activity, increase the plants' resistance to pests, promote plant health in general and root health in particular, increase the production of allelopathic compounds, increase pre- and post-harvest quality, improve stress tolerance, enhance beneficial symbioses, and improve yield over existing traditional soil or foliar fertilizers.

SUMMARY OF THE INVENTION

Given the above-mentioned deficiencies and demands of fertilizers in general, and of phosphorus fertilizers in particular, it is an object of the present invention to provide phosphorus to plants in a formulation that renders phosphorus readily available to the plants under a number of application methods such as through soil, foliar uptake, irrigation, and other methods.

It is also an object that the phosphorus fertilizer formulations be conveniently formulated in concentrated solutions that are stable during storage and shipping.

Another object of the present invention is to provide a phosphorus fertilizer that is not as inhibitory to mycorrhizal fungi as traditional phosphate fertilizers.

It is a further object of the present invention to provide a phosphorus fertilizer that does not support the growth of algae to the same degree that traditional phosphate fertilizers do.

Additional objects and features of the invention will be apparent to those skilled in the art from the following detailed description and appended claims.

The above objects and features are accomplished by a concentrated phosphorus fertilizer comprising a buffered composition comprising an organic acid and salts thereof and a phosphorous-containing acid and salts thereof. The concentrated phosphorus fertilizer can be diluted with water of pH ranging from about 6.5 to about 8.5 at ratios of concentrate to water at about 1:40 to about 1:600 to result in a fully solubilized fertilizer having a pH in a range acceptable for foliar uptake of phosphorus.

In one embodiment, the phosphorous-containing acid is selected from the group consisting of phosphorous acid, hypophosphorous acid, polyphosphorous acid, and polyhypophosphorous acid and the organic acid is preferably selected from the group consisting of dicarboxylic acids and tricarboxylic acids such as citrate.

In one embodiment, the concentrated phosphorus fertilizer is an essentially clear liquid devoid of precipitate that can be diluted at a ratio of about 1:40 to about 1:600 with water having pH of about 6.5 to about 8.5, to result in a fertilizer having a pH of about 5.0 to about 7.0, and more preferably from about 5.5 to about 6.5, to facilitate the uptake of phosphorus by a variety of plants.

A method of providing phosphorus to plants is also disclosed. The method comprises diluting a concentrated phosphorus fertilizer comprising a buffered composition comprising an organic acid and salts thereof and a phosphorous-containing acid and salts thereof with water to form a substantially fully solubilized use-dilution fertilizer having a pH in a range acceptable for foliar uptake of phosphorus, and applying the fertilizer to the plant foliage.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides phosphorus fertilizers essentially devoid of phosphate. The fertilizer comprises a double or multiple buffer system of organic acids and their salts with a phosphorous-containing acids and their salts. The formulation stabilizes the phosphorous against oxidation to phosphate. Suitable phosphorous-containing acids are phosphorous acid and polyphosphorous acid, based generally on the formula H3PO3, and hypophosphorous acid and polyhypophosphorous acid, based generally on the formula H3PO2. Phosphite, the salt of phosphorous acid, has properties that are known to be beneficial to crop production. It is taken up through the foliage of avocado and citrus, two species which classically do not take up phosphate through their foliage. Phosphite has fungicidal properties with regard to some species of pathogenic fungi: Rhizoctonia solani, Botrytis cinerea, Piricularia oryzae, Plasmopora viticola, Phytophthora cinnamomi, and Phytophthora parasitica. Recently, it has been demonstrated that phosphite also serves as a source of metabolically active phosphorus in plants. The properties of phosphite that make it desirable as a fertilizer are enhanced when it is formulated according to the present invention as a double or multiple buffer with phosphorous acid, hypophosphorous acid, polyphosphorous acid and/or polyhypophosphorous acid and their respective salts and organic acids and their salts per this invention.

Suitable organic acids have the formula R—COOH or R—COOwhere R is hydrogen or a carbon-containing molecule or group of molecules. Suitable organic acids are those that maintain the phosphite ion in a substantially fully solubilized form upon dilution with water at pH varying from about 6.5 to about 8.5 and that result in a use dilution fertilizer having a foliage acceptable pH for phosphorus uptake. Preferred organic acids are dicarboxylic and tricarboxylic acids.

By the term “substantially fully solubilized” it is meant that upon dilution, the phosphite does not precipitate, or at least not appreciably, so as to affect administration of the liquid product to the plant foliage, and thus is in a form available to the plant. With present phosphite fertilizers, there is a tendency for phosphite to precipitate if diluted with alkaline water, thereby rendering the phosphite in a form that is unavailable to the plant for uptake.

By the term “foliage-acceptable pH for phosphorus uptake”, it is meant a pH that allows phosphorus to be absorbed by the plant without causing damage to the foliage. A foliage-acceptable pH for phosphorus uptake usually ranges between about 5.0 to about 7.0, and preferably between about 5.5 to about 6.5. Phosphorus is most readily taken up by foliage at pH 6.0. Depending on the plant species, a pH below 5.0 can cause damage to leaves and/or the flowers and/or fruit. At higher pH, between about 7.0 to about 7.5, there is reduced uptake of nutrients, although generally there is no plant damage. A pH between about 7.5 and 8.0, depending on the plant species, plant damage may result. A pH greater than 8.0, generally causes damage to the plant in addition to reducing uptake of the nutrients. Accordingly, suitable organic acids are those that help provide a “buffered composition” having the desired pH range. This means that a “use-dilution fertilizer” having an acidic to neutral pH (pH 5.0 to 7.0) can be achieved upon high dilutions (up to about 1/600) of the concentrated fertilizer with highly alkaline water (up to a pH of about 8.5).

Organic acids that meet thisthese criteria include but are not limited to intermediates in the Kreb's Tricarboxylic Acid Cycle, amino acids such as glutamic acid and aspartic acid, vitamin acids such as ascorbic acid and folic acid, and their respective salts. Particularly preferred organic acids are dicarboxylic and tricarboxylic acids selected from the group consisting of citrate, pyruvate, succinate, fumarate, malate, formate, oxaloacetate, citrate, cis-aconitate, isocitrate, and α-ketoglutarate. Citrate is a particularly preferred organic acid because of it is relatively inexpensive and readily available.

These formulations allow the maintenance of continued solubility, and thus availability for uptake by plants, of phosphorus, with or without other nutrients, over a significantly wide range of concentrations and pHs. The increased solubility of these formulationformulations over that of phosphate or phosphite fertilizers makes it possible to prepare fertilizers with a greater concentration of phosphorus per unit volume than traditional phosphate or polyphosphate fertilizers or the simple unbuffered salts of phosphorous acid recently being marketed as fertilizers for foliar application which are available as super saturated solutions with only about 16% phosphite, and which are diluted approximately 1:100 to about 1:300. The resulting pH of these fertilizers varies significantly depending upon the pH of the water used, thus affecting the availability of the nutrients for foliar uptake. In contrast, the highly concentrated fertilizers of the present invention, which can be diluted with water at a ratio of about 1:600, allow for more cost effective shipping, handling, and application. They result in greater uptake of phosphorus by the canopy of plants than traditional phosphate or recent phosphite fertilizers not formulated in this manner.

The formulations provided herein also make it possible to formulate various combinations of other essential plant nutrients or other inorganic or organic compounds as desired and maintain their solubility when used over a wide range of concentrations and pHs, which is not possible for present phosphate or phosphite fertilizers. For example, boron, manganese, calcium; iron and other elements can be provided at relatively high concentrations in these formulations. Thus, these phosphorus fertilizers also enhance the canopy uptake of other mineral nutrients essential to plants. They can be used as a canopy application to improve pre- and post-harvest crop quality.

Formulations can also be prepared with copper. However, when high concentrations of copper are used; the copperused, the copper is not-fullynot fully solubilized. In this situation, the insoluble copper is desirable as it prevents rapid uptake of the copper and thus minimizes the potential for copper toxicity. As the insoluble copper is rewetted over nightovernight by dew, dissolution occurs so that additional copper is taken up. The buffering capacity of the formulation maintains the pH at a foliage-acceptable pH when the insoluble copper is rewetted so that conditions are optimal for uptake and are benign to the plant tissues. While copper is an element essential to plants, it is required in only small amounts. In relation to nitrogen, plants require, in general, 10,000- to 75,000-fold less copper. Provided to the foliage of the plant at the rate provided by this formulation, copper is a very effective fungicide, in addition to being a plant nutrient and fertilizer.

In addition to the above-mentioned advantages, the formulations disclosed have a direct benefit to the environment. Because the formulations allow successful foliar feeding of phosphorus to a number of plants that do not effectively take up phosphorus when supplied in phosphate or polyphosphate forms, and because these formulations enhance the uptake of other nutrients, they are cost-effective and can replace less efficient, traditional soil-feeding methods. This results in reducing phosphate pollution of the groundwater and eutrophication of freshwater ponds, lakes and streams.

The phosphorus fertilizers disclosed herein can also be advantageously applied through the soil or by irrigation systems as solid (granular) or liquid formulations. These formulations can be used at pHs sufficiently low to clean irrigation lines and alter the pH of the soil to solve alkalinity problems while supplying essential nutrients to plants. Example 2, below discloses a suitable formulation for irrigation application. With irrigation application, the fertilizer flowing through the irrigation system will typically have a pH lower than about 2.5, usually less than about pH 1.5. The low pH is designed to supply phosphorus while killing bacteria and algae (slime) which plug irrigation lines, thus cleaning the lines. The low pH also dissolves calcium carbonate deposits at and around the emitters, and solubilizes the calcium carbonate so Ca2+ is available to the plant. Once delivered to the soil near the plant, sufficient water is applied to achieve a pH suitable for phosphorus uptake by the plant. The form in which the phosphorus is supplied in these formulations is more mobile than phosphate fertilizers or than the simple salts of phosphorous acid recently being sold as fertilizers, and thus more available and more readily taken up by the roots of plants. An advantage of these formulations is that the form in which phosphorus is supplied does not inhibit the development of mycorrhizal fungi to the same degree that traditional phosphate fertilizers do. The present compositions can also be formulated with certain nutrients in addition to phosphorus that are readily absorbed through soil applications at pH of about 5.5 to about 7.0. Such nutrients include nitrogen, calcium, magnesium, potassium, molybdenum, boron, and sulfur.

Another advantage with the phosphorus fertilizers disclosed herein is that they do not support the growth of green algae to the same degree that traditional phosphate fertilizers do. This is of significant importance to agriculture, commercial nurseries, the ornamental and cut flower industry, and the home and garden industry, as it will prevent the growth of green algae which typically proliferate and plug irrigation emitters, foul pots and benches, and provide a niche for the growth of pathogenic bacteria and fungi. These formulations also endow the phosphorus fertilizer with anti-viral, anti-bacterial and anti-fungal activity. This bacterialcidalbactericidal activity in a phosphorus fertilizer makes it possible to use this fertilizer to inhibit ice-nucleating bacteria to thus protect plants from frost damage.

Methods of Preparation

The phosphorus fertilizers are prepared by first forming solutions of the phosphorous and organic acids. Other desired nutrients can then be added with constant stirring. The amount of phosphorous relative to organic acid is not critical, as long as appropriate buffering and solubility are achieved. Generally the amount of organic acid that is added will depend upon the form in which the nutrient elements are added. For example, if calcium is to be added in the form of calcium hydroxide (a base), then the acid form of the organic acid, for example citric acid, would be used rather than its salt, citrate. In addition to the desired nutrients, other additives, that are known in the fertilizer industry, can be added. These include, for example, wetting-agents, surfactants, spreaders, stickers etc., and are described in The Farm Chemical Handbook, supra (incorporated herein by reference). The fertilizer compositions can also be prepared as solid formulations, identical to the liquid ones by simply leaving out all of the water. The properties are the same as the liquid formulations but have the additional advantage of weighing less for the same amount of nutrient.

Methods of Application

The fertilizer is applied according to crop-specific recommendations which will depend upon the application method (foliar, soil, irrigation, etc.), time of application, rate of application, and product formulation. Crops that will benefit from the fertilizer include, but are not limited to, avocado, citrus, mango, coffee, deciduous tree crops, grapes and other berry crops, soybean and other commercial beans, corn, tomato, cucurbits and cucumis species, lettuce, potato, sugar beets, peppers, sugarcane, hops, tobacco, pineapple, coconut palm and other commercial and ornamental palms, hevea rubber, and ornamental plants.

In addition to the foliar, soil, and irrigation application methods mentioned above, the present fertilizer may prove beneficial to certain crops through other application methods. For example, trunk paints or other methodologies may provide for a continuous low supply of fertilizers, such as, for example, “intravenous” feeding as practiced in the boron nutrition of soybeans.

In order that the invention described herein may be more fully understood, the following examples are set forth. All chemicals used were of analytical reagent quality and approximately 100% by weight unless otherwise specified. All formulations are expressed in terms of weight to volume. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention in any manner.

EXAMPLE 1

A formulation was prepared of 1 gallon of 0-40-0 fertilizer with 3.86 lbs H3PO3, 1.34 lbs tripotassium citrate, 1.34 lbs of trisodium citrate, and 4.0 lbs of 58% ammonium hydroxide. The components were dissolved in water with constant stirring. This single formulation can be used at a rate of 2 quarts in as little as 20 gallons of water of pH 6.5 to 8.5 up to 300 gallons of water of pH 6.5 to 8.5 and maintain a pH between 5.5 to 6.5 without the formation of any precipitate.

EXAMPLE 2

A formulation was prepared of 1 gallon of 0-40-0 fertilizer with 3.86 lbs H3PO3 and 0.5 lbs citric acid. This formulation is stable at pH 1.0 or less and is designed for application through the irrigation system. It is stable against oxidation and precipitation when supplied through the irrigation water.

EXAMPLE 3

A formulation was prepared of 1 gallon of 0-30-0 fertilizer with 74.89% elemental boron with 2.89 lbs H3PO3, 28.67 lbs borax (Na2B4O7.10 H2O), 17.16 lbs boric acid (H3BO3), 1.54 lbs H2SO4 and 2.67 lbs citric acid. A solution of the phosphorous and citric acid was first prepared, then the other elements were added with constant stirring. This formulation can be used at the rate of 2 quarts in as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH 6.5 to 8.5 and maintain a pH between 5.5 to 6.5 without the formation of any precipitate.

EXAMPLE 4

A formulation was prepared of 1 gallon of 0-30-0 fertilizer with 21.57% Znzinc and 23.22% Mnmanganese with 2.89 lbs of H3PO3, 7.92 lbs ZnSO4, 7.16 lbs Mn(H2PO2)2.H2O, 0.61 lbs citric acid and 0.87 lbs 58% NH4OH. This formulation can be used at the rate of two quarts in as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH between 6.5 to 8.5 and maintain a pH between 5.5 to 6.5 without the formation of any precipitate.

EXAMPLE 5

A formulation was prepared of 1 gallon of 0-30-0 fertilizer with 5.4% Cacalcium. It was packaged in a two-container system where 1 gallon of solution A contained 2.89 lbs H3PO3, 0.68 lbs Ca(OH)2, and 0.28 lbs citric acid, and 1 gallon of solution B contained 0.16 lbs Ca(OH)2, 0.60 lbs KOH, 3.34 lbs 58% NH4OH, 0.28 lbs citric acid, and 0.67 lbs EDTA (ethylenediaminetetraacetic acid). Two quarts of solution A can be added to as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH between 6.5 to 8.5 followed by the addition of two quarts of solution B. The final solution is between pH 5.5 to 6.5 and without precipitation.

A formulation of 1 gallon of 0-30-0 fertilizer with 4.32% Cacalcium can be made without requiring EDTA. This formulation is also packaged in a two-container system where 1 gallon of solution A contains 2.89 lbs H3PO3, 0.67 lbs Ca(OH)2 and 0.28 lbs of citric acid, while 1 gallon of solution B contains 2.67 lbs of 58% NH4OH, 0.6 lbs KOH. Two quarts of solution A can be added to as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH between 6.5 and 8.5 followed by the addition of two quarts of solution B. The final pH of the solution is between 5.5 and 6.5 and without precipitation.

EXAMPLE 6

A formulation was prepared of 1 gallon of 0-30-30 fertilizer with 2.89 lbs H3PO3, 2.99 lbs KOH, and 0.84 lbs citric acid. Two quarts can be added to as little as 20 gallons of water of pH between 6.5 to 8.5 and up to 300 gallons of water of pH between 6.5 and 8.5. The pH of the final solution is between 5.5 and 6.5 without precipitation.

EXAMPLE 7

A formulation was prepared of 1 gallon of 0-30-0 fertilizer having 4.8% iron with 2.89 H3PO3, 1.75 lbs iron-citrate, 0.74 lbs KOH, 0.62 lbs NaOH, and 2.00 lbs of 58% NH4OH. Two quarts of the formulation can be added to as little as 20 gallons of water pH 6.5 to 8.5 and up to 300 gallons of water of pH 6.5 to 8.5. The pH of the final solution is between 5.5 to 6.7 without precipitation.

EXAMPLE 8

A formulation was prepared of 1 gallon of 0-30-0 fertilizer having 23.22% manganese with 2.89 H3PO3, 7.16 lbs. Mn(H2PO2)2, and 0.133 lbs. sodium citrate. Two quarts of the formulation can be added to as little as 20 gallons of water pH 6.5 to 8.5 and up to 300 gallons of water of pH 6.5 to 8.5. The pH of the final solution is between 5.5 to 6.5 without precipitation.

EXAMPLE 9

A formulation was prepared of 1 gallon of 0-30-0 fertilizer having 57% copper with 2.89 H3PO3, 7.3 lbs Cu(OH)2 (57% Cu), and 1.34 lbs of 58% NH4OH. Two quarts can be added to as little as 20 gallons of water of pH 6.5 to 8.5 up to 300 gallons of water of pH 6.5 to 8.5. The pH of the final solution is between 5.5 to 6.5. The copper is not fully soluble, however this is desirable in that it prevents the rapid uptake of copper when applied to plant foliage.

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62Lovatt, Carol J., "A Definitive Test to determine Whether Phosphite Fertilization Can Replace Phosphate Fertilization to Supply P in the Metabolism of 'Hass' on 'Duke 7.' A Preliminary Report," 4 pages (1992)., no month.
63Lovatt, Carol J., "A Definitive Test to Determine Whether Phosphite Fertilization Can Replace Phosphate Fertilization to Supply P in the Metabolism of 'Hass' on 'Duke 7.' A Preliminary Report," California Avocado Society 1990 Yearbook, 74, pp. 61-64 (1990)., no month.
64Lovatt, Carol J., "A Definitive Test to Determine Whether Phosphite Fertilization Can Replace Phosphate Fertilization to Supply P in the Metabolism of 'Hass' on Duke 7.-a Preliminary Report," Proc. of Second World Avocado Congress (1992), Unknown Citrograph (1990) vol. 75(7), p. 161.
65Lovatt, Carol J., "Foliar Phosphorous Fertilization of Citrus by Foliar Application of Phosphite" Summary of Citrus Research (1990), pp. 25-26.
66Lovatt, Carol J., "A Definitive Test to determine Whether Phosphite Fertilization Can Replace Phosphate Fertilization to Supply P in the Metabolism of ‘Hass’ on ‘Duke 7.’ A Preliminary Report," 4 pages (1992)., no month.
67Lovatt, Carol J., "A Definitive Test to Determine Whether Phosphite Fertilization Can Replace Phosphate Fertilization to Supply P in the Metabolism of ‘Hass’ on ‘Duke 7.’ A Preliminary Report," California Avocado Society 1990 Yearbook, 74, pp. 61-64 (1990)., no month.
68Lovatt, Carol J., "A Definitive Test to Determine Whether Phosphite Fertilization Can Replace Phosphate Fertilization to Supply P in the Metabolism of ‘Hass’ on Duke 7.—a Preliminary Report," Proc. of Second World Avocado Congress (1992), Unknown Citrograph (1990) vol. 75(7), p. 161.
69Lucas et al., "Phosphite Injury to Corn," Agronomy Journal, 71, pp. 1063-1065, 1979., no month.
70Mac Intire, et al. "Fertilizer Evaluation of Certain Phosphorus, and Phosphoric Materials by Means of Pot Cultures" Agronomy Journal (Nov. 1950), vol. 42(11), p. 543-549.
71Mahadevamurthy, et al. "Effect of Fertilizer Amendment of Soil and Antagonist Treatment on Sclerotial Germination on Claviceps Fusiformis" Plant Disease Research (1990) vol. 5(2), pp. 212-215.
72Malacinski and Konetzka, "Bacterial Oxidation of Orthophosphite," Journal of Bacteriology, vol. 91, 578-582, (1966).
73Mattingly, et al. "Progress in the Chemistry of Fertilizer and Soil Phosphorus" Topics in Phosphorus Chemistry (1967) vol. 4, pp. 157-290.
74Maxicrop product sheet: Seaweed Products for Agriculture and Horticulture (5 pgs.), no date.
75Mc Lean, Ben, "The Effects of Nitrogen, Phosphorous, and Potassium Fertilization on Citrus Fruit Quality" (Apr. 1991) found in Reports for HOS 6412 Nutrition of Horticulture Crops'' Vegetable Crops Department Institute of Food and Agriculture Sciences, University of Florida: Review Papers (Spring 1991) by Locascio, Dr. S. J.
76Mc Lean, Ben, "The Effects of Nitrogen, Phosphorous, and Potassium Fertilization on Citrus Fruit Quality" (Apr. 1991) found in Reports for HOS 6412 Nutrition of Horticulture Crops″ Vegetable Crops Department Institute of Food and Agriculture Sciences, University of Florida: Review Papers (Spring 1991) by Locascio, Dr. S. J.
77Miyake, et al. "Phosphate Response of Rice in Indonesian Paddy Fields" Technical Bulletin of the Tropical Agriculture Research Center (1984) No. 17, pp. 1-78.
78Mohit-Singh, et al. "Effect of Interaction of Nitrogen, Phosphorus and Potash on Alternaria Leaf Sport and Fruit Rot of Brinjal" Farm Science Journal (1988) vol. 3(1), pp. 21-23. CAB Abstract.
79Mucharromah, et al. "Oxalate and Phosphates Induce Systemic Resistance Against Diseases Caused by Fungi, Bacteria and Viruses in Cucumber" Kentucky Agricultural Experiment Station journal paper (Jul. 1990), 6 pages.
80Muchovej et al., "Effect of Exchangeable Soil Aluminum and Alkaline Calcium Salts on the Pathogenicity and Growth of Phytophthora capsici from Green Pepper," Phytopathology, 70, pp. 1212-1214, 1980., no month.
81Mustika, et al. "Control of Pepper Yellow Disease with Fertilizer and Pesticides" Pemberitaan, Penelitian Tanaman Industri Indonesia (1984) vol. 9(50), pp. 37-43.
82Nayudu, et al. "Bacterial Spot of Tomato as Influenced by Temperature and by Age and Nutrition of the Host" Phytopathology (May 1960) vol. 50, pp. 360-363.
83Neilsen, et al. "Response of Fruit Trees to Phosphorus Fertilization" Acta Horticulturae (1990) No. 274, pp. 347-359.
84Obreza, et al. "Citrus Fertilizer Management on Calcareous Soils" Circular 1127, a series of the Soil and Water Science Department; Florida Cooperative Extension Service (Dec. 1993), pp. 1-9.
85Ortho Books, "Definition of Phosphorus" All About Fertilizers, Soils and Water, Ortho Books, p. 53., no date.
86Ouimette, et al. "Comparative Antifungal Activity of Four Phosphonate Compounds Against Isolates of Nine Phytophthora Species" Phytopathology (Feb. 1989) vol. 79(7), pp. 761-767.
87PhilomBios DowElanco, "Provide: " Product Information Brochure published by PhilomBios DowElanco, Winnipeg, Canada, 8 pages., no date.
88Potash & Phosphate Institute, "Phosphorus . . . for the People and the Environment" Published by Potash & Phosphate Institute; Atlanta, Georgia (no date) 12 pages.
89Potash & Phosphate Institute, "Phosphorus the Energizer: Improving Plant Production for Human Health and Environment Quality" Published by Potash & Phosphate Institute; Atlanta, Georgia (no date) 12 pages.
90Product catalog of Biagro (Bioestimulantes Agricolas, S.A.), a Spanish company, undated but believed to be before Feb. 7, 1993, (with one English translation of the entire fifth page (the page containing Metalosate-F product) and another English translation of only the three Metalosate product on the fifth page).
91Product Data Sheet for "Corn Steep Liquor," published by Grain Processing Corporation, 1 page., no date.
92Prusky and Keen, "Involvement of Preformed Antifungal Compounds in the Resistance of Su87btropical Fruits to Fungal Decay" Plant Disease (1993) vol. 77(2), pp. 114-119.
93Rashid, et al. "Effects of Nitrogen, Phosphorus and Sulfur Fertilizer Combinations on the Severity of Alternaria, Drechslera and Bacterial Leaf Blights of Wheat" Bangladesh Journal of Plant Pathology (1985) vol. 1(1) pp. 33-39. CAB Abstract, no month.
94Reis, et al. "Effects of Mineral Nutrition on Take-all of Wheat" Ecology and Epidemiology: Phytopathology (1982) vol. 72(2), pp. 224-229., no month.
95Rhone-Poulenc Agrochime, S.A. v. Biagro Western Sales Inc., 1994 U.S. Dist. Lexis 20754; 35 U.S. P.Q.2D (BNA) 1203; no month.
96Robertson and Boyer, "The Biological Inactivity of Glucose 6-Phosphite, Inorganic Phosphites and Other Phosphites," Archives of Biochemistry and Biophysics, vol. 62, 380-395, 1956., no month.
97Robertson, et al. "Orthophosphite as a Buffer for Biological Studies" Archives of Biochemistry and Biophysics (1956), vol. 62, pp. 396-401., no month.
98Rothbaum and Baillie, "The Use of Red Phosphorus as a Fertiliser. Part 4. Phosphite and Phosphate Retention in Soil," New Zealand Journal of Science, 7, pp. 446-451, 1964., no month.
99Rothbaum and Kitt, "The Use of Red Phosphorus as a Fertiliser. Part 2. Extended Studies on Oxidation Rates of Red Phosphorus," New Zealand Journal of Science, 7, pp. 67-74, 1964., no month.
100Rothbaum et al., "The Use of Red Phosphorus as a Fertilizer. Part 1. Rates of Oxidation of Red Phosphorus in Soil," New Zealand Journal of Science, 7, pp. 51-66, 1964., no month.
101Rothbaum, H.P., "The Use of Red Phosphorus as a Fertiliser. Part 5. The Effect of Copper on the Oxidation Reaction of Red Phosphorus," New Zealand Journal of Science, 8, pp. 388-397, 1965., no month.
102Simpson, Ken "Fertilizers and Manures" Published by Harlow, Essex, England: Longman Scientific & Technical; New York: J. Wiley & Sons (1991).
103Smilke, et al. "The Mode of Action of Phosphite: Evidence for Both Direct and Indirect Modes of Action on Three Phytophthora spp. in Plants" Phytopathology (1989) vol. 79(9), pp. 921-926.
104Sparks, "Growth of Nutrition of Pecan Seedling from Potassium Phosphate Foliar Sprays" Hort-Science, (1986) vol. 21, pp. 451-453.
105Sugar, et al. "Management of Nitrogen and Calcium in Pear Trees for Enhancement of Fruit Resistance to Postharvest Decay" Hort Technology (Jul-Sep. 1992) vol. 2(3), pp. 382-387.
106Sukarno et al., "The Effect of Fungicides on Vesicular-Arbuscular Mycorrhizal Symbiosis," New Phytologist (1993) vol. (25), pp. 139-147.
107The Regents of the University of California and Biagro Western Sales, Inc. v. Actagro, LLC, 2004 U.S. App. Lexis 15663, no month.
108Thompson, et al. "Liming and Southern Crops: A Working Partnership" Better Crops with Plant Food: Published by the Potash & Phosphate Institute (PPI) Norcross, Georgia (1993/1994), pp. 18-19.
109Toerlen and Slabbert, "Phosphorous Nutrition of Avocados Through Truck Injection," Avocado Grower, p. 10, Jan. 1985.
110Tsubota, Goro, "Phosphate Reduction the Paddy Field I, Soil and Plant Food," (1959) vol. 5(1), pp. 10-15.
111Unknown, "Don't Back Away from a Phosphite Confrontation," (unknown publication), p. 5, Apr. 21, 1992.
112Unknown, "Foliar Applications Do Double Duty" Citograph (May 1990) vol. 75(7), p. 161.
113Unknown, Abstract entitled "Agricola (1970-1978)," (unknown publication), 1 page, 1992.
114W.B. McLean & Sons of Clermont Florida, Correspondence to Mr. Bill Paul; (Dec. 28, 1993), 2 pages.
115W.B. McLean & Sons of Clermont Florida, Correspondence to Mr. Bill Paul; (Feb. 4, 1994), 2 pages.
116W.B. McLean & Sons of Clermont Florida, Correspondence to Mr. Lex; 2 pages., no date.
117W.B. McLean & Sons of Clermont Florida, Facsimile Correspondence to Mr. Gurney; 2 pages., no date.
118Walters, et al. "Induction of Systemic Resistance to rust in Vicia faba by Phosphate and EDTA: Effects of Calcium" Plant Pathology (1992) vol. 4 pp. 444-448.
119Ward, B. W., "Assessing Phosphorus Buildup in Crop Acreage—The Upper Vermilion Watershed Project", Better Crops with Plant Food: Published by the Potash & Phosphate Institute (PPI) Norcross, Georgia (1993/1994), pp. 16-17.
120Watt, H.V.H. van der, et al. "Amelioration of Subsoil Acidity by Application of a Coal-derived Calcium Fulvate to the Soil Surface" Nature (1991) vol. 350(6314), pp. 146-148.
121Widdowson (and Rothbaum) et al., "The Use of Red Phosphorus as a Fertiliser. Part 3. Spot Trials with Perennial Ryegrass and White Clover," New Zealand Journal of Science, 7, pp. 427-455, 1964., no month.
122Wild, Brian, "Enhanced Natural Decay Control in Citrus Fruit" Published by Gosford Horticulture Posttharvest Laboratory Gosford, NSW, 7 pages., no date.
123Windhols, M. (editor) "Definition of Calcium Phosphate (CAHPO3)" Merck Index, 11th ed. (1994) p. 256.
124Yuda et al, "Search for Efficient Phosphorus Fertilization," Proc. Intern'l Soc. Citriculture, 1981., no month.
Classifications
U.S. Classification71/11, 71/32, 71/41, 71/64.1, 71/27
International ClassificationC05B7/00, C05G5/00, C05G3/00, C01B15/00
Cooperative ClassificationC05B7/00, C05G3/0076
European ClassificationC05B7/00, C05G3/00B10F
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