阅读说明：本技术 针对果实生理病症和害虫的永久性生态肥料 (Permanent ecological fertilizer for fruit physiological diseases and pests ) 是由 A·普列托吉戈 于 2019-12-30 设计创作，主要内容包括：本发明涉及适用于针对果实生理病症和害虫的永久性固体钙肥料,其特征在于它包含大于98.5重量%的碳酸钙。本发明的目的还在于该肥料用于保护农作物抵抗害虫的用途,并优选用于保护梨和/或苹果作物。(The present invention relates to a permanent solid calcium fertilizer suitable for use against physiological conditions of fruits and pests, characterized in that it comprises more than 98.5% by weight of calcium carbonate. The invention also relates to the use of said fertilizer for protecting crops against pests, and preferably for protecting pear and/or apple crops.)

1. Solid calcium fertilizer suitable for use against physiological conditions of fruits and pests, characterized in that it comprises more than 98.5% by weight of calcium carbonate.

2. Use of a fertilizer according to claim 1 for protecting crops against pests.

3. Use of a fertilizer according to claim 2 wherein the crop plant is a pear and/or apple crop plant.

4. Use of a fertilizer according to claim 2 or 3, wherein the use comprises applying to the crop between 1% and 12% by weight of the fertilizer dispersed in an aqueous suspension.

5. Use of a fertilizer according to claim 4 wherein the application of the fertilizer is by micro-comminution at a pressure between 7-10 bar, producing a spray of droplets having a diameter equal to or less than 80 μm.

6. Use of a fertilizer according to any one of claims 2-5 wherein the fertilizer is applied during the entire agricultural cycle.

7. Use of a fertilizer according to claim 6 wherein the application comprises:

a) a first treatment in january consisting of applying to said crop an aqueous suspension of said fertilizer in an amount of 50 kg/Ha of 5% w/w;

b) a second treatment from the end of april until the beginning of the May consisting of applying to the crop an aqueous suspension of 6% w/w of the fertilizer in an amount of 60 kg/Ha;

c) a third treatment in June consisting of applying to the crop an aqueous suspension of the fertilizer at 2% w/w in an amount of 20 kg/Ha, and a further application in July consisting of applying to the crop an aqueous suspension of the fertilizer at 1% w/w in an amount of 10 kg/Ha;

d) a fourth treatment from october to november consisting of applying to the crop an aqueous suspension of 1% w/w of the fertilizer in an amount of 10 kg/Ha.

Technical Field

The present invention relates to the field of chemistry and in particular to a novel calcium fertilizer suitable for use against physiological conditions of fruits and pests.

Background

Chemical pesticides play an important role in plant protection and pest control over the past few decades. However, these chemical pesticides are known to have risks and effects associated with their use in human health and the environment. To reduce these risks, a common legal framework (directive 2009/128/EC) was established to achieve sustainable use of pesticides. This directive minimizes or prohibits the use of chemical pesticides in certain areas.

The instructions 2009/128/EC encourage the development of alternative methods or techniques to reduce the dependence on the use of pesticides. Accordingly, a need has arisen to develop new natural products suitable for controlling agricultural pests as alternatives to synthetic pesticides that have played an important role during the past decades.

In this context, the present invention relates to novel natural fertilizers having protective activity against crop pests. It has surprisingly been found that this new product has remarkable fertilizing properties, in addition to controlling pests, and the ability to avoid physiological disorders of the fruit.

Despite the important growth in the development of new insecticidal treatments in recent years, no effective solution has been found to date for products having the ability to protect crops against pests and at the same time being able to achieve foliar nutrition of plants, including diffusion of nutrients in plants.

The present invention relates to novel formulations based on calcium carbonate which have a surprising synergistic effect both as a protective agent against pests and as a calcium fertilizer.

In the prior art, different inventions have been disclosed relating to the use of calcium carbonate as a plant fertilizer and as a protective agent against pests.

US6069112 discloses a method for preventing sunburn and other physiological conditions such as water heart disease, spotting (cockking) and acne without diminishing photosynthesis comprising applying to at least a portion of the surface of the plant an effective amount of a finely divided heat treated particulate material which may comprise calcined calcium carbonate.

NZ280358 discloses a fertilizer comprising fine particles of substantially pure calcium carbonate in precipitated form.

AU7601491 relates to liquid fertiliser compositions comprising sedimented lime consisting of shells, corals etc. and which are found on cliffs, along rivers and creeks or elsewhere where such lime may have sedimented. The amount of calcium carbonate disclosed in the examples was 84.30%, 83.75%, or 81.8%.

DE10021029 discloses a process for preparing agents for improving plant growth and/or for reducing pesticide residues, which is obtained by stirring limestone powder with at least one binder and optionally further additives.

JP2013087091 relates to a control agent for controlling codling moth safely and economically. The control agent is applied to the surface of the fruit to prevent codling moth from oviposition. The product comprises calcium or magnesium carbonate and a fixing agent for fixing the agent to the surface of the fruit. The average particle size of the inorganic powder is in the range of 0.1 to 3 μm.

EP3033944 discloses the use of calcium carbonate as a plant protection agent against pests during plant growth. The calcium carbonate is used in the form of particles having a particle size of between 0.1 and 200 μm.

WO9838867 discloses a method for protecting a surface from arthropod infestation comprising treating the surface with an effective amount of finely divided calcined kaolin, hydrophobic calcined kaolin, hydrous kaolin, hydrophobic calcium carbonate, calcium carbonate or mixtures thereof.

Finally, JPH0680511 relates to products against insect pests comprising powdered calcium carbonate.

Based on the inventions disclosed in the prior art, it can be concluded that even if calcium carbonate is described as an effective fertilizer, known and currently available fertilisation products have different drawbacks, such as their short persistence in the crop or the risks associated with their method of application. Short durability is an important disadvantage because it means that the composition is lost whenever there are severe weather conditions (e.g. high winds, dew or rain). This has important economic consequences, requiring the composition to be applied each time it is lost, with consequent costs. The product object of the present invention solves this problem and avoids the need to apply the composition to the crop in multiple applications. The invention provides the advantage that the composition can remain in the crop even under severe weather conditions with only one application.

Furthermore, the alternatives known in the prior art have the disadvantage of affecting the physical appearance of the fruit, remaining white after harvesting. The present invention solves this problem because it controls pests that affect crops without adversely affecting the appearance of the fruit.

More particularly, the novel product solves the following problems:

the permanence of the product, avoiding the need to apply it in multiple applications, and in particular after severe weather conditions;

its application does not affect the physical appearance of the fruit, avoiding any remaining residues in the form of white spots;

fertilizing ability, nourishing crops while protecting them against pests. In particular, it is even more common than liquid fertilizers (calcium chloride, CaCl)₂) More efficiently, calcium is provided in a continuous manner under humid conditions. The product object of the invention thus allows to reduce the number of applications required to achieve fertilizing activity.

Disclosure of Invention

In order to solve the above problems and avoid the drawbacks associated with the fertilizers known in the prior art, the present invention relates to a new solid calcium fertilizer suitable for use against fruit physiological disorders and pests, characterized in that it comprises more than 98.5% by weight of calcium carbonate.

The main advantage of the product object of the present invention is that it is an effective solid ecological fertilizer suitable for the nutrition of crops at foliar level of calcium and, in the case of fruit crops, with calcium crossing the fruit cuticle. It is also characterized by long persistence in the crop due to the solid condition of the fertilizer. This is an important advantage compared to other fertilizers of the prior art where fertilization is achieved by the roots of plants or trees.

The invention also relates to the use of said fertilizer for protecting crops against agricultural pests. To achieve this, the product is applied during all phases of the agricultural cycle.

In a preferred embodiment of the invention, the fertilizer will be used in eco-friendly agriculture, and more preferably for controlling pests and diseases affecting pear and apple crops.

The application method is characterized in that it comprises applying between 1% and 12% by weight, and more preferably between 2% and 6% by weight of a fertilizer dispersed in an aqueous suspension. In particular, the amount of bioavailable calcium in a 12% aqueous suspension of the fertilizer may range between 62 ppm and 132 ppm, and more preferably, the amount may be 92 ppm.

The novel fertilizer has been shown to achieve a reduction of more than 80% of the pests affecting fruit trees.

In a preferred embodiment of the invention, the fertilizer will be used to protect pear crops against stem miners.

In another preferred embodiment of the invention, the fertilizer will be used to protect apple crops against codling moth (codling moth: (codling moth)Cydia pomonella))。

The main advantages of the fertilizer object of the present invention are the following:

its persistence, allowing continuous fertilization and protection during the whole agricultural cycle. This reduces costs associated with the treatment of the crop, reduces the number of applications required, and the consumption of phytochemical products;

its location in the crop: it penetrates inside the stomata of the leaves and it is also distributed along the entire fruit epidermis. It is therefore an effective alternative to calcium agrochemicals (e.g. calcium chloride) and allows to reduce the costs associated with the amount of fertilizer and protective agents against pests required per hectare;

surface activity of fertilizer granules: it allows to provide calcium in a continuous manner and in a solid state. It also has a high ionic surface activity during humid conditions (dew, rain) and allows to increase the bioavailability of calcium at the fruit flesh; and

it allows a dual action, both as a permanent foliar calcium fertilizer and as a protective agent against pests.

Drawings

Figure 1 shows the distribution of fertilizer in the crop. In particular, it shows how calcium particles are distributed inside the stomata of the leaf on which the fertilizer is applied. This is an important advantage of the claimed fertilizer compared to other fertilizers known in the art (which, due to their size, cannot penetrate inside the stomata of the plant);

FIG. 2 shows the distribution of calcium particles in guard cells of the stomata of the leaf;

FIG. 3 shows the distribution of calcium particles on the stratum corneum and epidermis of Golden apple;

FIG. 4 is a detailed view of calcium particles infiltrating the inside of the epidermis of a Golden apple;

FIG. 5 shows a detailed view of calcium particles distributed on the stratum corneum of Conference pears.

Detailed Description

One of the main advantages of the fertilizer object of the present invention compared to other calcium fertilizers known in the prior art is the high persistence in the crop under all weather conditions and during the whole agricultural cycle. Thus, one of its major benefits is that it functions as a continuous calcium pump. This avoids the need to apply calcium in multiple foliar applications, as is required when using calcium liquid fertilisers (e.g. calcium chloride).

This advantageous effect of the novel fertilizer is due to the surface chemical composition of the fertilizer, which is in addition to Ca²⁺Or CO₃ ^2-In addition to other ionic species (e.g. CaOH)⁺、CO₃H^-Or CO₃CaOH^-(confirmed by XPS or TOF-SIMS measurements)). They are all in humid conditions (rain, and rain, and rain, and rain, and rain, and rain, or rain, and rain,Dew) and allows for increased calcium bioavailability. In particular, it has surprisingly been found that the effective amount of calcium provided by the fertilizer object of the present invention is much higher than that provided by other fertilizers of the prior art. Surprisingly, surprisingly high synergistic fertilization was indeed achieved, achieving calcium bioavailability in the range of 62 ppm to 132 ppm.

The chemical mechanism involved in the continuous supply of calcium to the claimed fertilizer is as follows:

a) first, the ionic species Ca on the surface of the solid calcium compound²⁺And CO₃ ^2-Activated and released in aqueous suspension:

fertilizer + H₂O ↔ Ca²⁺ + CO₃ ^2- + H₂O

b) CO released thereafter₃ ^2-Hydrolysis and conversion to CO₃H^-：

CO₃ ^2-+ H₂O ↔ CO₃H^- + OH^- + H₂O

c) Finally, the bicarbonate anion CO₃H^-Conversion to CO in aqueous media₂：

CO₃H^- + H₂O ↔ CO₂ + OH^- + H₂O

The high surface activity of the claimed fertilizer allows Ca to be obtained²⁺And CO₂Because these ionic species are released under humid conditions (rain or dew) and they are transported through the xylem of the crop until reaching the flesh of the fruit. Crop pair CO₂Absorption of (2) makes the equilibrium towards higher CO₃H^-Shifting the yield with simultaneous conversion to Ca²⁺And CO₂。

Thus, the application of the fertilizer to the surface of the crop (stem, leaves and fruit) and the action of rain or dew increases the production of calcium bicarbonate, which then decomposes into Ca in aqueous solution²⁺And CO₂：

Fertilizer + H₂O + CO₂(g) ↔ Fertilizer + CO₃H₂ ↔ Ca (HCO₃)₂ ↔ Ca²⁺ + CO₂ + H₂O + CO₃ ^2-

The invention also relates to the use of the claimed fertilizer for protecting against pests in crops. The distribution of the fertilizer on the surface of the leaves/fruits is essential for the subsequent activity as a calcium fertilizer: its deposition forming a thin monolayer structure maximizes the covering effect of the fertilizer.

Furthermore, this allows to increase the contact surface area of the fertilizer granules in the stem, leaf or fruit of the plant treated with the fertilizer. In this way, the durability of the fertilizer is guaranteed under all weather conditions (rain, dew or wind).

In addition to fertilizing activity, the fertilizer is also suitable for combating agricultural pests. In particular, the novel fertilizer protects both trees and fruits against sunburn and pests. The novel fertilizer has been shown to reduce pests affecting trees by more than 80%. This is due to the way the fertilizer is distributed over the surface of the trees and its long persistence.

It is therefore also an object of the present invention to apply fertilizers to crops during the entire agricultural cycle. The deposition of the fertilizer is achieved by micro-comminuting an aqueous suspension of the fertilizer under high pressure, preferably between 7 bar and 10 bar, resulting in a spray of droplets preferably equal to or less than 80 μm in diameter. The water contained in the granules is then evaporated, distributing them, forming a uniform layer on the surface of the fruit or leaf on which the fertilizer is applied, maximizing the covering effect of the fertilizer.

Experiment of

To demonstrate the effectiveness of the claimed product, various experiments were performed, including treatment of pear and apple crops.

The fertilization treatment was carried out in the last week of April, using a suspension of 6% by weight of fertilizer in water (60 kg fertilizer/Ha) and crushing it under a pressure of 8 bar.

Fig. 1 and 2 show the distribution of fertilizer over the leaves. In particular, the figure shows how the fertilizer can penetrate inside the leaf stomata (fig. 1) or distribute it around the stomata on guard cells located in the leaf epidermis (fig. 2).

Figures 3 to 5 show the distribution of fertilizer over the fruit.

Figure 3 shows how fertilizer granules are distributed over the cuticle and epidermis of Golden apple.

Figure 4 shows how some fertilizer particles penetrate the interior of the polygonal cells of the epidermis of Golden apple. Similar experiments were performed using Conference pears having a thicker cuticle layer than the cuticle layer of Golden apples. The cells of Conference pear are not polygonal. They have a circular shape and a more disordered distribution than apple cells.

FIG. 5 shows how other fertilizer particles are distributed in a disordered multilayer structure along the entire cuticle surface of the pear, close to the cuticle pores connecting the cells of Conference pear with the epidermal cells. Subcutis is the pericarp, and pericarp is the pulp formed by the parenchyma cells.

Under humid conditions (dew or rain), the fertilizer can release more Ca²⁺It can be applied to fruits and accumulated in the flesh. Thus, under humid conditions, the fertilizer favors Ca²⁺And CO₂"in situ" feed into the epidermis and from the epidermis to the pulp.

The experiments carried out also demonstrate the synergistic effect due to the properties of the claimed fertilizer. In particular, due to Ca supplied to the fruit²⁺The fertilizer allows to reduce physiological disorders of the fruit, such as bitter pocks (bitter pit) or lentigo (lenticul patch pit), while maintaining the firmness of the fruit.

An additional advantage of the claimed fertilizer is that it is easy to remove from the fruit after harvesting. Thus, it does not adversely affect the physical appearance of the fruit as compared to other known fertilizers (e.g., calcined kaolin).

The application of the novel fertilizer can be carried out during the entire agricultural cycle and it allows both the nutrition of the crop and the protection of the crop against agricultural pests with an effective amount of calcium. Depending on weather conditions, treatments may be performed at different times during the agricultural cycle.

In a preferred embodiment of the invention, the treatment may be carried out as follows:

dormancy process (winter):

pre-harvest protection of fruit trees: a first treatment in january consisting of an aqueous suspension of fertilizer applied in an amount of 5% (w/w) in 50 kg/Ha;

spring, summer and fall treatments:

with Ca and CO₂Foliar fertilization of fruits including protection of fruits against sunburn and pests in a second treatment from the bottom of april up to the beginning of the five months, consisting of applying an aqueous suspension of a 6% (w/w) fertilizer in an amount of 60 kg/Ha;

with Ca and CO₂Comprises protecting the fruit against sunburn and pests in a third treatment of june consisting of an aqueous suspension of 2% (w/w) of the fertilizer applied in an amount of 20 kg/Ha, and a further application in july consisting of an aqueous suspension of 1% (w/w) of the fertilizer applied in an amount of 10 kg/Ha;

post-harvest protection of fruit trees against pests in the fourth treatment from october to november, consisting of applying an aqueous suspension of a fertilizer in an amount of 1% (w/w) in an amount of 10 kg/Ha.

Although this is a preferred embodiment, the time of year when the fertilizer is applied to the crop may vary depending on the weather conditions at the locus of the crop.

However, since calcium is more easily absorbed in a continuous manner, consistent with fruit cell division (a period of 6-8 weeks after flowering), it is preferred to perform a first foliar treatment of the flesh of the fruit during this period.

Furthermore, there is a strong competition between leaves and fruits for the available calcium in the crop. Thus, in a preferred embodiment of the invention, the novel fertilizer claimed is applied in a plurality of foliar applications, so that calcium penetrates directly into the interior of the pulp, passing through the cuticle and epidermis of the plant or tree.

When the fruit grows to a diameter of about 6-8 cm, in a preferred embodiment of the invention, the method will comprise reapplying the fertilizer at a lower concentration of 10 kg/Ha-30 kg/Ha to enhance the supply of calcium (both foliar and cuticle) to the flesh of the fruit.

The fertilizer object of the present invention also has the advantage of providing fertilizing activity without the side effects associated with an increased salt index when applying liquid fertilizers available in the prior art (such as the most commonly used CaCl)₂) This is common. The novel fertilizer has low salinity and thus avoids the increase in pH of the soil associated with the use of calcium salts (e.g., calcium chloride). Thus, while the "salt index" of calcium chloride is 87, the "salt index" of the novel fertilizer is 0.8. This is an important advantage as it avoids an increase in the osmotic pressure of the soil.

Experiment 1 foliar fertilization of pulp from Golden apple

A first experiment was performed to measure foliar fertilization of Golden apples.

The treatment was carried out in the last week of April, using a suspension of 3% by weight of the claimed fertilizer in water (30 kg/1000 l water/Ha). The reference treatment (blank) was 3% CaCl₂Solution (30 kg/1000 l water/Ha).

With CaCl₂The calcium supply to the pulp proved to be 50% more effective with the claimed fertilizer than with the calcium supply achieved with the treatment.

The results of this first experiment are shown in table 1 below:

TABLE 1

Sample (I)	Treatment of	Drying material	Calcium carbonate
				Golden apple pulp	CaCl2 (30kg/Ha)	14.3%	24 ppm
Golden apple pulp	Fertilizer as claimed (30kg/Ha)	15.2%	36 ppm

This experiment demonstrates that the novel fertilizer claimed compares to the most commonly used fertilizer (CaCl)₂) Is more effective. In particular, it has been demonstrated that when the claimed fertilizer is applied to Golden apple at a concentration of 3% in water (30kg fertilizer/1000 l water/Ha), with CaCl₂The calcium supply to the pulp was 50% higher than that achieved by the treatment.

Experiment 2 foliar application of Conference Pear pulp

A second experiment was performed to measure foliar fertilization of Conference pears.

The treatment was carried out in the last week of April, using a suspension of 3% by weight of fertilizer in water (30 kg/1000 l water/Ha). Blank is untreated fruit.

The claimed fertilizer proved to be 24% more effective in calcium supply to the pulp compared to the blank (untreated fruit).

The results of this second experiment are shown in table 2 below:

TABLE 2

Sample (I)	Treatment of	Drying material	Calcium carbonate
				Conference pear pulp	Untreated	18.4%	76 ppm
Conference pear pulp	Fertilizer as claimed (30kg/Ha)	19.3%	94 ppm

Additional experiments were performed to demonstrate the effectiveness of the fertilizer in protecting crops against pests.

Pear trees treated with the novel fertilizer were subjected to comparative tests for resistance to stem miners. The percentage of leaf miner occupancy was calculated by visually inspecting 200 tree chucks sampled from 1 Ha of total crop area. These trees had only 5% stalk sneak impact compared to untreated trees with 45% stalk sneak impact.

Additional comparative tests were performed on pear trees treated with the novel fertilizer against green aphids. The percentage of green aphid occupancy was calculated by visual inspection of 200 tree suckers sampled from 1 Ha of total crop area. These trees were not infected compared to untreated trees with an infection percentage of 60%.