Fertilizer compositions for administering ionic metal microelements to plant roots

Abstract: Metal ions selected from the group consisting of Fe⁺³, Mn⁺², Cu⁺² and Zn⁺² are administered to plant roots in a composition comprising citric acid, whereas the molar ratio of citric acid to metal ions in this composition is about 0.8 to 2.5.

Description: The present invention is in the field of plant nutrition and is concerned with the administration of ionic metal microelements to plants. In particular, the present invention provides the use of compositions for administering iron, manganese, copper and zinc ions to the roots of plants. Various metal ions are essential elements in plant nutrition and soil deficiency thereof is very often the cause of poor plant growth. Of particular importance for plant growth are iron, manganese, copper and zinc ions, iron being especially important. The following description of the prior art will focus in particular on the problems associated with the iron administration, but it should be understood that similar problems are associated also with the administration of the other three metals mentioned before. Iron ions in the soil are present either in their di - (Fe⁺²) or trivalent (Fe⁺³) form, neutral or alkaline conditions favouring the latter. In their trivalent form iron ions hydrolyse water to form highly stable precipitates, the solubility coefficient being in the order of 10³⁸. Thus, in soils having a neutral or basic pH, such as calcareous soils in which the calcium carbonate acts as a buffer maintaining a high pH, iron precipitates rapidly becoming unavailable to plants' roots. It has been hitherto proposed to administer iron in a divalent ionic salt form. However, this method did not prove to be sufficiently efficient. The most widely accepted method for the administration of iron is in the form of a complex of a synthetic chelate, in particular FeEDDHA or FeEDDHMA (Chen and Barak, 1982, Advances in Agronomy, 35:217-239 ). The main disadvantage of these synthetic chelates is in their high price (see, for example, Barak and Chen, 1987, Soil Sci.Soc.Am. J. 51:893-896 ) but, as noted by Barak and Chen and others, the use of FeEDDHA to the administration of iron to the soil was nevertheless the method of choice. The high efficiency of using the synthetic chelate EDDHA for the administration of iron has also been shown by Bell, 1977 (Principles and Application of Metal Chelation, Clarendon Press, Oxford). The use of organic acids, such as citrate, as chelating agents of metal ions has been proposed but as has been shown (e.g. Bell, 1977, supra), citrate was found to be far inferior in its properties than the above synthetic chelating agents at pH below 11 (see page 133, fourth paragraph of Bell, 1977, supra). As shown by Cline et al., 1982 ( Soil Sci. Soc. Am. J. 46:1158-1164 ), ion chelates comprising citrate as the chelating agent were unstable at pH above 7. A composition comprising citric acid and metal ions has been described in SU-886874. The composition according to this patent is probably a pesticidal composition intended for topical application onto plant leaves and comprises various other ingredients including an adherent substance and sulfur which latter is probably the pesticidally active agent. A compositon comprising ferric ions and citric acid has been described in CA-1,152,769. The composition according to this latter patent comprises also a nitrogen source which is an essential ingredient, and is used for the topical administration of ferric ions to plants, via their leaves. None of these patents discloses or even suggests that citric acid may be used as a chelating agent in composition for administering metal ions to plant roots. US-A-4 265 653 describes an aqueous plant nutrient solution consisting essentially of a soluble ferrous compound in an amount sufficient to provide between 0.1 and 2.0 wt% of ferrous ion, a soluble manganous compound in an amount sufficient to provide about 5 wt% of manganous ion, between 1 and 1.5 moles of citric acid anion per mole of manganous ion, ammonia in an amount sufficient to maintain said solution at a pH between 7.5 and 12, and water. CA-A-1 152 769 discloses an aqueous fertilizer solution containing ferric iron, an iron complexing agent, water-soluble nitrogen nutrient and water, characterized by the weight ratio of water-soluble nitrogen nutrient to iron being at least about 3:1 and the iron complexing agent being citrate. GB-A-1 364 464 describes a composition in solid form comprising one or more alkaline-earth metal; heavy metal or boron salts in admixture with citric acid and/or a water-soluble salt thereof as the sole or major sequestrant for said salt. It also provides an aqueous solution comprising a fertilizer material and said composition. Chem. Abs. 113 (1990), July 2, no. 1, 5231n describes that a mixture of water, citric acid, CuSO₄ and ZnSO₄, optionally containing MgSO₄ and/or MnSO₄ and/or FeSO₄ and/or FeCl₃ is neutralized with NH₃ to give a trace element fertilizer. FR-A-2 244 402 provides compositions for the treatment of iron deficiency-induced chlorosis in calcareous soils comprising citric acid in combination with other chelating agents to form mixed chelates with iron ions. The prior art thus taught away from using organic acids in general, and citrate in particular, as chelating agents for the administration of metal ions to the soil in a form available to plant roots. The entire research was concentrated on finding more efficient ways of using synthetic chelates to this end. The present invention is based on the surprising discovery that metal ions selected from the group consisting of Fe⁺³, Mn⁺², Cu⁺² and Zn⁺² can effectively be supplemented to soils in a composition comprising these metal ions (to be referred to hereinafter at times as "said metal ions") together with citrate in a molar ratio of citrate to said metal ions of about 0.5-2.5. Administration of such a composition to soils was found to render said metal ions available to plant roots even in neutral or alkaline soils, as evidenced by positive effect on plants' health and growth rate. The present invention thus provides the use of a plant fertiliser composition comprising one or more metal ions selected from the group consisting of Fe⁺³, Mn⁺², Cu⁺² and zn⁺² and citric acid, the molar ratio of citric acid to said metal ions being about 0.5 to about 2.5. Preferably the molar ratio of citric acid to said metal ions is about 0.8 to 2.0, the ratio of about 1.0 to about 1.5 being particularly preferred. The composition used in the present invention may be provided as a dry particulate solid (to be referred to hereinafter at times as the "dry composition of the invention"), e.g. in the form of powder or granulates, which may be administered to the soil as such or after its dissolution in water. Compositions used in accordance with the present invention may also be provided in the form of an aqueous solution (to be referred to hereinafter at times as the "liquid composition of the invention"), either ready for administration or as a concentrate which is diluted prior to use. The use of said composition is useful in a method for providing one or more metal ions selected from the group consisting of Fe⁺³, Mn⁺², Cu⁺² and Zn⁺² to plant roots, which method comprises administering said ions to the soil in which the plants grow in a composition comprising citric acid and said one or more metal ions, in a molar ratio of citric acid to metal ions of about 0.5 to 2.5, preferably about 0.8 to 2.0, and most preferably about 1.0 to 1.5. Said metal ions may be administered by various means known per se. A dry composition used in the invention may be administered by spreading granulates or powder of such a composition on the soil or by introducing same to the soil during tilling thereof. A liquid composition used in accordance with the invention may be administered by direct spraying or by introducing same through the irrigation system. The use of above compositions are particularly useful for administering said ions to calcareous soils. Furthermore, the composition used in the present invention are useful in the treatment of plant chlorosis. In the following, the invention will be illustrated with reference to some non-limiting Examples: Example 1 Annona sp. plants were grown on a shallow mountainous rendzina soil, having a high lime content. The entire plantation was irrigated with sprinklers and had a fertilization system forming part of the irrigation system. The plantation was divided into two plots (each having an area of 2,000 m²): plot A received three consecutive weekly treatments of 1 kg FeEDDHA each, administered through the irrigation system; plot B , which had a separate irrigation system, received three consecutive weekly treatments each consisting of 1 l of an aqueous composition used in accordance with the invention comprising (mole/litre): FeCl₃ - 0.98, MnSO₄ - 0.17, ZnSO₄ - 0.057, CuSO₄ - 0.04, citric acid - 1.8. The treatment of plot A started during the month of May and the treatment of plot B commenced 10 days later. Prior to the treatment, the plants in both plots showed signs of chlorosis. A week after the beginning of the treatment in plot A , a greening of most of the plants was observed. When the treatment commenced in plot B , most of the plants of plot A were already entirely green and in a rapid growth phase. A week following the onset of treatment, most of the plants in plot B started to green, the greening becoming evident in all plants after about two weeks. One month after the onset of treatment, the plants of both plots had a similar green colour and the plants in both plots had a similar growth rate. In both plots several plants, in about equal propor-tions in both, remained chlorotic even after the treatment. Notably, however, the chlorosis was much more pronounced in the respective plants in Plot A as compared to Plot B . Adding the composition used in accordance with the invention to those plants in Plot A improved their condition considerably. Example 2 Plum trees ( Prunus sp. ) were grown on a similar soil as in Example 1. Irrigation and fertilization were central. The trees sprouted in the spring (during the month of April). The trees were not treated with ionic metal microelements. Some of the trees showed a certain degree of chlorosis evidenced by yellow leaves relative to other trees, which had dark or light green leaves. Some of the chlorotic trees were treated with 40 ml of a composition used in accordance with the invention, which was administered by infusing same directly into the ground below a dripper of the irrigation system. The administered composition consisted of the following ingredients (moles/litres): FeCl₃ - 0.23, MnSO₄ - 0.425, ZnSO₄ - 0.17, CuSO₄ - 0.115, citric acid - 1.09. After about two weeks, the treated trees greened and the leaves started to grow, in contrast to untreated chlorotic trees which remained yellow and did not show signs of leaf growth. After an additional period of several days, the treated trees could not be distinguished from the healthy trees. Example 3 Pepper ( Capsicum sp. ) was grown on a loessial soil having a lime content of about 20%. The entire plot had a central irrigation and fertilization system, the water supplied to the plants by drippers. The plants in the plot were chlorotic which was evidenced by their light green colour. The plot was divided into three sub-plots, each receiving a different treatment: plot A was treated with a fertilizer composition used in accordance with the invention, consisting (moles/litres) of: FeCl₃ - 0.98, MnSO₄ - 0.17, ZnSO₄ - 0.057, CuSO₄ - 0.04, citric acid - 1.8, dissolved in 1 litre of water; plot B was treated in the same manner with 1 kg. per 1,000 m² of FeEDDHMA; plot C received no treatment at all. After two weeks, the plants in plot A were greener and larger than both the plants in plot B and in plot C . Example 4 Vines ( Vitis cv. Sultanina ) were grown in a vineyard having a total area of 6,000 m² on a shallow mountainous rendzina soil. Water was administered by drip irrigation and the vineyard had a central fertilization system. The entire vineyard was treated with a commercial FeEDDHA in an amount of 1 kg. per 1,000 m². Notwithstanding this iron treatment, about half of the plants remained yellow and their growth was inhibited. After about four weeks, the unhealthy plants were treated with a composition used in accordance with the invention consisting (moles/litre) of: FeCl₃ - 0.74, MnSO₄ - 0.51, ZnSO₄ - 0.057, CuSO₄- 0.04, citric acid - 1.75. The treatment consisted of the administration of 2 litres of this composition per 3,000 m². The effect of the treatment was evident after about one week, by growth and greening of the treated plants. After about two weeks following the onset of treatment, the so-treated plants were greener and showed more pronounced growth than the non-treated plants which had a priori a better condition. All the above examples show that the fertilizer compositions used in accordance with the present invention are highly effective in administering metal ions to plant roots. Furthermore, it may be appreciated that the use of the composition has a big advantage over prior art compositions such as FeEDDHA, as they have a much lower cost than the commercially available synthetic chelates.

Claims: Use of a composition consisting of citric acid and one or more metal ions selected from the group consisting of Fe⁺³, Mn⁺², Cu⁺² and Zn⁺² as a plant fertilizer for soil administration wherein the molar ratio of citric acid to metal ions is about 0.5 to 2.5. Use according to claim 1, wherein said molar ratio is about 0.8 to 2.0. Use according to claim 2, wherein said molar ratio is about 1.0 to 1.5. Use according to any one of claims 1 to 3, wherein the composition is in the form of a dry particulate solid. Use according to any one of claims 1 to 3, wherein the composition is in the form of an aqueous solution. Use according to any one of claims 1 to 5 for the treatment of plant chlorosis.

Inventors: ZIVION YORAM, ZUSMAN AMNON, ZIVION, YORAM, ZUSMAN, AMNON
Applicants: ZIVION YORAM, ZUSMAN AMNON, LEKET BAR CHEMICALS LTD. ZIVION, YORAM
Application year: 1991
Main classification: C05D9
IPC codes: C05D9