STABILIZED UREA BASED FERTILIZERS FOR FOLIAR APPLICATION

Abstract: A solution of a divalent cationic monovalent anionic salt and urea for use as a foliar spray. The divalent cationic monovalent anionic salt is preferably a salt of magnesium, calcium or zinc and a chloride or nitrate. The amount of the divalent cationic monovalent urea salt is present in solution in an amount such that a 4:1 Urea N:Metal molar ratio is approached in which proportion the urea becomes urease resistant.

Description: Stabilized urea based fertilizers for foliar application. The present invention relates to a liquid fertiliser composition and a method of stabilising urea based fertilisers for foliar application. There are two distinct approaches which can be used to introduce nitrogen to plants. Nitrogen can either be uptaken by the absorption of nitrogen as nitrate at the plants roots or it can be absorbed as urea on the leaf surfaces. These differences give rise to either soil applications or foliar applications of nitrogen based fertilisers. For soil application the nitrogen source can be added as urea, ammonium compounds, nitrites or nitrates since in the soil the nitrogen containing compounds are broken along the path. Urea NH 1- -7>* NNOU- ~> N>'O u 3- The choice of fertiliser will depend on a variety of factors. Since urea in the most concentrated form of artificial nitrogen fertiliser available (46%N) it is commonly used for both foliar and soil application. In both cases the urea is broken down by urease to ammonia. For soil applications this is essential since -2- the nitrogen source can only be uptaken as nitrate but for foliar applications the breakdown results in the leaf surfaces being scorched, which can result in the plant being killed. Consequently dose levels are limited to 10kg Urea-N per hectar in foliar applications for any one application. In soil whilst it is necessary to have the urea converted to nitrate it is desirably to slow down the enzymic hydrolysis of urea to ammonia since when volatilisation occurs, some volatilised ammonia is lost and does not follow the path to nitrate. Manufacturers of soil based fertilisers have attempted to tackle this problem and the problem of nitrate leaching by either: 1. Dusting prills of urea with sulphur to slow bacterial induced hydrolysis of urea, or 2. Adding direct nitrifying inhibitor such as dicyandiamide and 2-chloro-6-(trichloromethyl)pyridine to fertilisers to slow the reaction in the soil of NH 3 — N0 2 _->N0 3 . Furthermore, Fenn and Co. Workers have suggested adding solutions of calcium chloride, magnesium chloride or magnesium sulphate to soil to reduce the volatilisation of NH 3 from the soil. These salts are claimed to alter the reactivity of the soil solution by an inter-reacting series of effects wh i ch i nc l ude : - a) Enhancing the ammonia absorbing power of the crop in the presence of enhanced levels of soluble calcium; b) Acidifying the soil solution by interchanging H + and Ca ++ in the base exchange clay complex, releasing H + short term into the soil solution thus reducing NH 3 volatilisation effects; and c) Integrating Ammonium Carbonate, formed by reaction of gaseous ammonia with Carbon Dioxide, and Calcium Chloride to produce Calcium Carbonate and Ammonium Chloride, again reducing volatilisation by fixing the ammonium ion as a salt; All these effects are described as direct action on the NH 4 ion in the soil, derived either from natural organic sources or added nitrogen fertiliser. When used for foliar application the urea is dissolved in water and sprayed. The amount of urea applied is however limited by the fact that the urea is broken down on the plant leaf to volatile ammonia which can scortch thereby damaging or killing the plant or is lost by volatilisation. Urea solutions are known and GB 1561136 concerns itself with maximizing the amount of urea which can be dissolved in water. The patent discloses adding calcium chloride to urea and water to increase the proportion of urea which can be dissolved in a given amount of water. This specification discloses a liquid fertiliser which comprises a Urea-N:Ca molar ratio of up to 5.6:1 when the urea and calcium chloride are mixed with 58% by weight water, and no claim is made to such a solution. There is however a need for a nitrogen fertiliser which can be sprayed onto plants in a form whereby immediate breakdown to ammonia at the leaf surface is avoided. In this way volatilization and plant scortch is avoided and the nitrogen uptake levels will be increased, since the urea will remain on the leaf surface in which form it can be readily uptaken. The applicants have found that by dissolving urea in water with a sufficient amount of a divalent cationic monovalent anionic salt, the urea is made resistant to breakdown by urease. Accordingly there is provided a liquid fertiliser comprising urea, a divalent cationic monovalent anionic salt and water characterised in that the divalent cationic monovalent anionic salt is present in an amount sufficient to make the urea substantially resistant to breakdown by urease. Substantial urease resistance has been found to be achieved as the molar ratio of urea-N to the divalent -6- colbalt and nickel or phosphate. According to a further aspect of the invention there is provided a method of making the urea component of a liquid fertiliser more resistant to breakdown by urease, the method comprising mixing the urea in solution with an amount of a divalent cationic monovalent anionic salt sufficient to make the urea substantially resistant to breakdown by urease. The applicants have found that when urea is mixed with a divalent cationic monovalent anionic salt in effective proportions the hydrolysis of urea by urease, which is the main reaction on the plant leaf surface involving the formation of volatile ammonia is inhibited. Whilst not wishing to be bound by theory this phenomena is believed to be caused by the salt causing the urea to assume its Tautomer III configuration, defined in the classical organic literature. It is believed that a complex with the divalent cationic monovalent anionic salt is then formed. II III Structure II above is favoured by many as the -7- with urea of the formula Y " H + N ■ NH \ C ■ ■ 0 " X ++ 0 " - HN + H 3 Y Solutions believed to contain complexes of this type have been shown to be stable to decomposition by urease, thus slowing down dramatically the evolution of ammonia, and giving a longer period for the urea per se to be able to penetrate either the leaves or the hypercotyl direct, rather than via the route Urea - NH 3 - NO2 - N0 3 for root absorption, with the consequent losses of NH 3 by atmospheric evolution or nitrate leaching. This provides many advantages in normal agromomic practice. Preferably the effective amount of the divalent cationic monovalent anionic salt will be an amount giving rise to a ratio of 4 urea nitrogens to 1 divalent cation. In such a molar ratio, a complex is believed to be formed throughout the solution. However since ratios which approach 4:1 have been shown to be substantially urease resistant it is believed but when ratios of the urea-N to salt do not reach this theoreticl ratio a complex may still be formed in part. -8- giving rise to a ratio of 4 urea nitrogens to 1 divalent cation. In such a molar ratio, a complex is believed to be formed throughout the solution. Howe ' ver since ratios which approach 4:1 have been shown to be substantially urease resistant it is believed but when ratios of the urea-N to salt do not reach this theoreticl ratio a complex may still be formed in part. These findings are of great importance since it enables urea to be applied to crops in greater amounts by foliar application as opposed to soil applications. The reason for this is that in appropriate ratios the breakdown of urea to ammonium is inhibited. Solutions having effective ratios have been shown to slow the action of urease on the urea depending on the divalent cation/nitrogen ratios. This slowing down in the conversion of urea to ammonium means that the urea can be absorbed by the plants leaves. Without an effective ratio the urea is rapidly degraded to ammonia which can not be uptaken by the plant leaves and which furthermore can cause scorching of the plant and loss by volati1isation. It is believed for example that when a urea/calcium chloride solution having an effective ratio is applied to a leaf, the calcium will be absorbed against a -9- concentration gradient. The gradient is created by calcium accumulating in the leaves, some being built into cell wall structure, as pectate, and excess precipitated as oxalate. Calcium uptake would be slow and the stable urea complex maintained. Urea would be absorbed by the leaf as urea rather than as ammonium-N from the stable structure and will be controlled probably by the rate of calcium absorbtion. It is known that the absorbtion of nitrogen by the leaf is more efficient if absorbtion takes place as urea-N rather than ammonium-N. The presence of calcium chloride promotes this effect. The socio-economic benefit of these findings is enormous. Nitrogen may be foliar applied and taken up efficiently and sufficiently to grow high quality yields without the problems of nitrate water pollution. A variety of compositions have been tested and are used by way of example only, to illustrate the invention. Two qualative tests and one quantative test have been used to test whether urea degradation by urease occurs when the urea was mixed to various cationic/anionic salts in various proportions. These methods are described below and the results achieved are noted in the tables. - 10- A test model was prepared whereby air, which has previously been scrubbed with boric acid was bubbled over a urea solution containing.3280mg of Urea in a closed container. A standard urease tablet was added, sufficient to decompose 400mg Urea in 3 hours at 35°C and the aspired air was then scrubbed with boric acid and the evolved NH 3 analysed by one of the following three methods. 1) The pH at the beginning and end of the reaction was checked. Normal Urea with urease was shown to give a rise of pH from 7-10 whereas stabilised urea remained at pH7, even in the presence of urease. A constant pH therefore indicates stabilising activity. Qual itative. 2) NH 3 gas evolution is easily detected by inserting a piece of pH paper into the container and measuring the pH change in the atmosphere - Qualitative. 3) The method can be quantified by direct analysis of NH 3 by the Kjeldahl method - Quantitive. a) Quantitive Test Method: 10 Mis of test solution was warmed to 27° in a 50 ml beaker. One BDH urease tablet was added and crushed with a glass rod. The beaker was placed on a constant temperature tray and maintained at 27°C. It was covered -11- with a bell jar and ammonia-free air was passed across the sample for 6 hours. The air was passed through 100mls of 2% boric acid solution containing indicators. The resulting solution was analysed for pp ammonia nitrogen (NH 3 - N). The molar ratios of Urea-N to Metal (Me) can be simply calculated from the weight ratios given. For example a 14:0:0:10 solution N:P:K:Me where the divalent cationic monovalent anionic salt is calcium chloride has a N:Me/molar ratio of 4:1 No moles = wt rmm N = 14 : Ca = 10 IT Jϋ 1 : 0.25 4 : 1 In practice a 14:0:0:10 will be made from 14 x 60 urea, and τ$ 10 x 111 calcium chloride, i.e. —zπr 30 g of Urea and 27.75g Calcium chloride, The mix being made up to 100 g with water. Table 1 shows the stabilising effect that different divalent cationic monovalent anionic salts have on urea. Table 1: Ammonia evolution with time, urea/divalent cation and monovalent anion salts compared with urea alone. -13- That monovalent cationic and divalent anionic salts do not show a stabilizing effect on urea can be seen from table 2. Table 2: Ammonia evolution with time, urea/equivalent cation/ anion salts and various acids compared with urea alone and urea/CaCl 2 and urea/MgCl 2 at optimum concentrations. • - 75- Salts such as MgS0 4 and KC1 give virtually no stabilisation nor do the sulphates and phosphates of urea. Metal salts of variable valency state (i.e. Fe, Ni , Mn, Co, Cu) were found to decompose in the presence of urea to complex oxides and hydroxides. There are clearly defined ratios within which the stabilisation effect occurs which have been determined by quantitative studies with regard to the chlorides as given in Table 3 and confirmed with a series of qualitative studies for chlorides and nitrates as given in Tables 4 to 9 inclusive. Tables 4 to 9 show that significant amount of Urea- N can be maintained on the leaf surface at ratios of Urea-N:Me which require only limited amounts of Me. For example at 10:1 N:Ca little or no smell was noted after 120 hours, indicating a large proportion of the nitrogen remains as urea-N. (table 4) For example at 15:1 N:Ca only a slight smell of ammonia was noted, indicating significant Urea-N remains even after 168 hours, (table 5). From these qualative tests it can be seen that even at ratios of 23:1 N:Zn urea resistance can prove significant. - 1 6- It is clear from table 3 that more significant inhibition commences at 14-0-0-5 Ca for CaC1 » 19-0-0-7 Ca for Ca(N0 3 ) 2 , 14-0-0-4 Mg for MgC1 2 , and 19.6-0-0-4.8 Mg for Mg(N0 3 ) 2 . Table 3: Ammonia evolution with time, urea/metal chlorides at given analysis. NB Zn++ in itself tends to be toxic to urease. Formula Anion NH, evolved Comments N-P-K-Me 7 αays ppm 14-0-0 1640 1 ml aliquots of water added to p r e v e n crystallization 14-0-0-2 Ca i Cl 905 Heavy ppt of CaC0 3 14-0-0-4 Ca : Cl 272 Heavy ppt of CaCOo 14-0-0-5 Ca Cl 45.6 Slight ppt of CaCO, 14-0-0-6 Ca Cl 35.6 Slight turbidit 14-0-0-10 Ca Cl 4.6 No ppt 14-0-0-5 Ca/3 Mg < Cl 0 No ppt 14-0-0-2 Mg ' Cl 14-0-0-3 Mg Cl 14-0-0-4 Mg Cl 14-0-0-6 Mg Cl 6.2 No ppt 9-0-0 9-0-0-1 Zn Cl 9-0-0-5 Zn Cl 9-0-0-10 Zn Cl no ppt Table 4 NH evolution and pH change with time: Urea/CaC formulations , - • --- TIME HOURS • ™" 0 "" " 24 • - -- — - FORMULA N-P- -Ca pHa pH1 NH 3 Soly pHa pH1 NH 3 Soly 14-0-0 7 7 0 Clear i 11 10 +++ Clear 14-0-0-2 Ca 7 7 0 Clear 10 9 ++ ppt 20: 1 ω c m_o-0-4 Ca 7 7 0 Clear 9 8 + si 10:1 ppt ω H l4_0_0-6 Ca 7 7 0 Clear 7+ 7+ • 0/+ v.si ppt H 6.6:1 C H l4_0-0-8 Ca 7 7 0 Clear 7 7 0 Clear 5:1 0) a: 14-0-0-10 Ca 7 7 0 Clear 7 7 0 Clear PI 4 : 1 m pHa - pH of atmosphere 0 no smell above test solution + siight smell pHl - pH liquid ++ oderate sme 11 NH - ammonia de tected +++ Strong smell by smell Soly - Clarity of solution Table 4 NH o evolution and pH change with time: Urea/CaCl 2 formulations ω c oo 0) H mam H C m ω x pHa - pH of atmosphere 0 - no smell above test solution + - slight smell pHl - pH liquid ++ - moderate smell NH o - ammonia detected +++ - strong smell by smell Soly - Clarity of solution pHa - pH of atmosphere 0 no smell X PI above test solution + slight smell pHI - pH liquid ++ moderate smell =3 NH o - ammonia detected +++ strong smell by smell Soly - Clarity of solution Soly - clarity of solution Table 6 NH o evolution and pH change with time: Urea/MgC1 2 formulations Soly - Clarity of solution Table 6 NHo evolution and p H change with time: Urea MgCl2 formulations . pHa - pH of atmosphere 0 - no smell above test solution + - slight smell pHI - pH liquid ++ - moderate smell NHo - ammonia detected +++ - strong smell by smell Soly - Clarity of solution Table 7 NH o evolution and pH change with time: Urea/Mg(N0 3 ) 2 ormulations , pHa - pH of atmosphere 0 - no smell above test solution + - slight smell pHI - pH liquid ++ - moderate smell NHo - ammonia detected +++ - strong smell by smell Soly - Clarity of solution Table 7 NH o evolution and pH change with time: Urea/M (N0 3 ) 2 formulations pHa - pH of atmosphere 0 - no smell above test solution + - slight smell pHI - pH liquid ++ - moderate smell NH o - ammonia detected +++ - strong smell by smell Soly - Clarity of solution Table 8: NHo evolution and pH change with time: Urea/ZnCl 2 formulations. TIME HOURS FORMULA 26 96 N-P-K-Zn pHa pH1 NH, Soly pHa pHI H, Soly pHa pH1 NH- 0.5-0-0 7 7 Clear 10 Clear 10 10 ++ 8.5-0-0-2 Zn 7 7 Clear 7 Turbid 7 7+ 19-7:1 8.5-0-0-4 Zn Clear 6+ Clear 9.8:1 CO c 8.5-0-0-6 Zn 6- Clear 6+ Clear 00 6.5:1 I ! H 8.5-0-0-8 Zn 5+ Clear Clear j 5+ H I C 4.9:1 H m 8.5-0-0-10 Zn Clear Clear ! 3-9:1 CO x pHa - pH of atmosphere no smell n above test solution slight smell pHI - pH liquid ++ moderate smell NHo - ammonia detected +++ strong smell by smell Soly - clarity of solution Table 9 NHo evolution and pH change with time: Urea/Zn (NO ) 2 formulations, ' 6 pH1 NH. Soly 10 ++ Clear 7 Clear m a 7 Clear O -I 6 Clear c r*ι 6- Clear <0 X πi Clear Clear pHa - pH of atmosphere 0 - no smell above test solution + - slight smell pHI - pH liquid ++ - moderate smell NHo - ammonia detected +++ - strong smell by smell Soly - Clarity of solution Table 9 NH o evolution and pH change with time: Urea/Zn( 0 3 ) 2 formulations TIME.Ji0.URS_ FORMULA 24 48 N-P-K-Zn pHa pH1 NH 3 Soly pHa pH1 NH. So 9-0-0-0 11 10 +++ Clear 11 11 +++ Cl 9.9-0-0-2 7 7 0 Clear 7 7 Cl CO 23: 1 G 00 10.8-0-0-4 7 7 0 Clear 7 Cl CO 12.5:1 H 11.2-0-0-5 7 7- 0 Clear 7- Cl G 10.4: 1 ■uul PI 11.6-0-0-6 7 6 0 Clear 6+ Cl O 8.9:1 X PI 12.5-0-0-8 7 6 0 Clear Cl 7.25: 1 13.4-0-0-10 7 6- 0 Clear 6- Cl 6.2: 1 pHa - pH of atmosphere 0 - no smell above test solution + - slight smell pHI - pH liquid ++ - moderate smell NHo - ammonia detected +++ - strong smell by smell Soly - Clarity of solution -29- In the case of Zn, inhibition of hydrolysis also occurs but as Zn can easily poison the enzyme and nutritional Zn requirements of plants are of a low order, Zn is only ever considered as an additive to either Ca, Mg or mixed Ca/Mg products for practical use in agriculture. However with 8.5 to 9%N in a solution a minimum of 4% Zn is necessary to effect stability in its own right (9-0-0- 4% Zn). It has been further found that the stabilising effect on urea can be achieved by mixing the divalent cationic monovalent anionic salt so that the molar ratio approaches 4:1. Field Test Work Seven field trials have been carried out on four crops - Winter Wheat, Spring Wheat, Spring Barley, and Potatoes. The broad conclusions of this work can be summarised as follows: (a) Phytotoxicity on Cereals The phytotoxicity of urea to cereal crops caused by rapid evolution of ammonia under high temperature conditions is dramatically reduced by the presence of CaC1 at optimum ratios with an almost identical effect from Ca(N0 3 ) 2 and MgC1 2 - See Table 10 below. -30- SUBSTITUTE SHEET -31 - (b) Phytotoxicity on Potatoes In one trial on potatoes phytotoxicity was not prevented by CaC1 with urea. It is thought that the presence of C1 compromised the results. C1 is known to be highly toxic to potatoes and Ca(N0 3 ) 2 is being checked as an alternative. (c) Nutritional Responses From the nutritional stand point the following trends can be noted: i. Urea/CaC1 2 or Urea/MgC1 2 are, in general, equal or superior in nutrient uptake response when compared to urea alone. This variability would be expected as it is only when significant loss of NH 3 occurs from a urea alone spray that the inhibition effects of CaC1 2 or MgC1 2 can express themselves as a superior nutritional N response. SUBSTITUTE SHEET -32- ii. Slight to marked effects show on the improvement of the uptake of secondary nutrients such as calcium and magnesium when either Urea/CaC1 2 or Urea/MgC1 2 is applied. See Table 11 below. SUBSTITUTE SHEET Table 11: Nutrient Uptake/Offtake from foliar sprays. Timing of sprays on cereals - late season. -34- 1 1 1 Urea/CaC1 2 and Urea/MgC1 2 as foliar sprays at lower N rates approaches the nutritional value (measured as yield, specific weight, 1000 grain weight) of traditional soil applied granular fertilisers at standard rates, in some cases, but never exceeds them. There is a trend for Urea/MgC1 to be slightly better than Urea/CaC1 2 but this may be related directly to the Mg status of individual soils. See Table 12 above. I V There are strong indications that in the series of trials carried out that Urea/CaC1 2 and Urea/MgCI 2 have a greater effect on quality than on yield. This would be expected, however, from the spray timings involved. See Table 13. SUBSTITUTE SHEET Table 12: Nutritional value of Urea/CaCl 2 and Urea/MgCl ? spray treatments compared with traditional granular fertilisers soil applied. O G I U) I 21 -A G -I PI ω For summary of overall results see Table 14 Part 3 Table 13: Quality Assessment - Cereals. G »ι H c c) For summary of overall results see Table 14 Part 4. PI -37- Trials were carried out on cereals mainly as late season foliar sprays at a time when nutritional responses from nitrogen would be expected to be in crop quality rather than yield. This is the current traditional market for foliar applied urea, (d) Summary of all Trials Table 14 summarises the field trials. Results which were positive for Urea/CaC1 2 or Urea/MgC1 2 are indicated +, results which where positive for Urea alone are indicated -, results where no difference was observed or measured are indicated =, and where the characteristic was not tested is indicated x, except for Part 3 see below. SUBSTITUTE SHEET Table 14 Part 1: Comparison of phytotoxicity between trials. O 3: Table 14 Part 2. Comparison of Nutrient Uptake between trials Trial Ref: Table 11 Nutrient Uptake Table 14 Part 3: Yield comparison between soil applied traditional granular fertilizers applied at standard rates and Ure C Cl2 and Urea/MgCl j products foliar applied at lower N rates as shown. Trials Ref: Table 12 Yield Comparitive Comparison N rates kg/ha Urea/CaCl 2 - Granular Urea/MgCl 2 Fertilizer NOSCA Spring Barley .» 70 75 NOSCA Potatoes s 20 30 CO ASEPTA Spring Wheat X 20 40 c ASEPTA Potatoes «»• 20 50 SCOT AG Winter Wheat + 20 30 o LANDMARK Winter Wheat X 20 40 I H LINDEAN FM Spring Barley X 15 Not Known •fcr O I c H in Table 14 Part 4: Comparison of quality benefits between trials. CO X m Trial Ref: Table 13 Quaidty Characteristics m H røSCA Spring Barley = 1000 Grain wt. Specific weight fOSCA Potatoes X ftSEPTA Spring Wheat + 1000 Grain wt ftSEPTA Potatoes X 3C0T AG Winter Wheat + % Protein, Hagberg no. LANDMARK Winter Wheat X LINDEAN FM Spring Barley X -4 1 - The conclusion to be drawn from these trials are that foliar treatments with Urea or their stabilised forms of Urea/CaC1 2 and Urea/MgC1 2 can act as an alternative to soil applications when it comes to maintain crop quality and yields. Furthermore they have the benefits of far less risk of leaching because of the "property of direct absorbtion into the leaf. SUBSTITUTESHEET

Claims: -42- CLA I MS 1. A liquid fertiliser comprising urea, a divalent cationic monovalent anionic salt and water characterised in that the divalent cationic monovalent anionic salt is present in an amount sufficient to make the urea substantially more resistant to breakdown by urease. 2. A liquid fertiliser as claimed in claim 1 in which the divalent cationic monovalent anionic salt is one or more selected from calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, zinc chloride and zinc nitrate. 3. A liquid fertiliser as claimed in any of the preceding claims which further comprises a potassium salt. 4. A liquid fertiliser as claimed in claim 4 in which the potassium salt is potassium sulphate or potassium chloride. 5. A liquid fertiliser as claimed in any of the preceding claims which further comprises a sulphur product. 6. A liquid fertiliser as claimed in claim 6 in which the sulphur product is ammonium thiosulphate or ammonium sulphate. 7. A liquid fertiliser as claimed in any of the SUBSTITUTE SHEET -43- preceding claims which excludes trace elements selected from the group comprising manganese, copper, iron, cobalt and nickel. 8. A liquid fertiliser as claimed in any of the preceding claims which excludes phosphates. 9. A method of making the urea component of a liquid fertiliser composition more resistant to breakdown by urea, the method comprising mixing the urea in solution with an amount of a divalent cationic monovalent anionic salt sufficient to make the urea substantially resistant to breakdown by urease. 10. A method of applying urea to a crop by foliar application the urea being applied in solution with an effective amount of a divalent cationic monovalent anionic salt.

Inventors: HIGGONS DENNIS JOHN, POOL STEPHEN NEWALL, STOLLER JERRY HERMAN, HIGGONS, DENNIS, JOHN, POOL, STEPHEN, NEWALL, STOLLER, JERRY, HERMAN
Applicants: STOLLER CHEM LTD, STOLLER CHEMICAL LIMITED
Application year: 1990
Main classification: C05C9
IPC codes: C05C9, C05G3