Abstract
Lithovit®, an excellent foliar fertilizer, consists of (Ca,Mg)CO3 supplemented by numerous of important micro-nutrients. It is produced by milling natural limestone in special mills down to particle diameter < 10 μ. Spraying the aqueous solution (0.5%) of this very fine, tribodynamic activated powder, on the foliage, the lithovit particles penetrate partly directly through the stomata of the leaves into the intercellular compartment. The rest remains as a film on the leaves surface. The Mechanism of Lithovit action as fertilizer is still not totally clear. Very probably it is due to supplying the plants with CO2 in much higher concentration than that in the atmosphere and so enabling the photosynthesis to take place with much higher degree leading to stronger natural growth and increasing yield. Furthermore, the supplements of the different trace elements increasing the enzymatic activity should play also a role in this process.
The release of CO2 in the intercellular compartment is probably due to the docking of the Lithovit particles having a negatively charged surface (as a result of the tribodynamic activation) on the cell membrane forming a negative electrostatic potential which attracts the protons formed inside the cell due to the water splitting in the first light reaction of the photosynthesis. The protons pass the membrane, dock on the negative charged CO3 – groups of the Lithovit forming intermediary H2CO3 which decomposes to CO2 and H2O.
The release of CO2 from the Lithovit remaining on the leaves surface is probably due to its transformation to (Ca,Mg)(HCO3)2 during the night by means of CO2 (produced by the plants in addition to that in the atmosphere) and H2O (which covers the leaves as dew in addition to that produced by the plants). During the day the temperature rises gradually, water evaporation occurs and the (Ca,Mg)(HCO3)2 is back, transformed to Lithovit giving CO2 on high concentration directly in the leaves surface. In that way Lithovitacts as a quasi-permanent catalytic depot.
The observation that perennial plants treated with Lithovitonly in the first growth period grow much better and give higher yield also in the second growth period without further treating with Lithovit leads to the assumption that further mechanism such as epigenetic effects could also be responsible for the Lithovit action.
Lithovit consists of Calcium-, Magnesium- Carbonate (Ca,Mg)CO3, supplemented by numerous important micro-nutrients. It is produced by milling natural limestone in special mills down to particle diameter < 10μ. Spraying the aqueous suspension (0.5%) of this very fine, tribodynamic activated2) powder on the foliage, the Lithovit particles penetrate in part directly through the stomata of the leaves into the intercellular compartments. The rest remains on the leaves as a film. However, Lithovitacts as an excellent fertilizer. The mechanism of this action is still not totally clear. Very probably it is due to supplying the plants with Carbon dioxide (CO2) in much higher concentration than that in the atmosphere and so enabling the Photosynthesis to take place with higher degree leading to stronger natural growth and increasing yield. Furthermore, the supplements of micro-nutrients increasing the enzymatic activity should play also role in this process.
The following mechanisms are discussed for releasing CO2 from the Lithovit:
1) Release of CO2 from the Lithovit in the intercellular compartment:
In the photosynthesis (a lot of reactions are for simplicity not mentioned here) light energy is converted to chemical energy by means of the light-sensitive chlorophyll. Finally, CO2 + Water are converted to carbon hydrates + oxygen. The initial light reaction is the decomposition of Water, where electrons (negative elementary charges) are taken away from water molecules converting them to Oxygen and protons (positively charged hydrogen atoms). The Lithovit particles dock with their negative charged surface on the cell membrane producing a negative electric potential which attracts the protons, that pass the cell membrane and dock on the negative charged Carbonate groups building intermediary carbonic acid which decomposes to CO2 and H2O. The equivalent amount of Ca2+ and Mg2+ ions partially migrate through the cell membrane and participate into the metabolism, partially react with water giving (Ca,Mg)(OH)2 and Protons which react again with Carbonate giving CO2 and so on.
2) Release of CO2 from the Lithovit particles remaining on the leaves surface:
The pH of the 0.5 % aqueous Lithovit suspension is 9.8 at 20oC. At this pH value Carbonate (CO3 2-) and Hydrogencarbonate (HCO3 -) as well as (theoretically) Carbonic acid (H2CO3) exist in equilibrium. Taking the corresponding equilibrium constants K1 = 1.92x1010 of reaction (1) and K2 = 2x103 of reaction (2)
CO3 2- + H+ « HCO3 - (1)
HCO3 - + H+ « H2CO3 (2)
H2CO3 « CO2 + H2O (3)
into account, the ratios [HCO3-] / [CO3 2-] = 3.05 and [H2CO3] / [HCO3 -] = 2x10-6.8 are obtained. That means H2CO3 is practically not existing in the suspension. The question is: How CO2 develops from the Lithovitremaining on the leaves surface?
At night the leaves are covered with dew water. At the same time, the plants burn in darkness carbon hydrates to cover their energy need and produce CO2 + H2O. This Carbon dioxide (in addition to that in the atmosphere) + H2O (from the dew additionally to that produced) converts the carbonate in Lithovit into Hydrogencarbonate according to:
(Ca,Mg)CO3 + H2O + CO2 « (Ca,Mg)(HCO3)2 (4)
During the day the temperature rises gradually and the equilibrium reaction (4) is shifted to the left-hand side (due to evaporation of water) developing CO2 from the Hydrogencarbonat. In that way, Lithovit is acting as quasi catalytic depot supplying permanently CO2 at high concentration right at the leaves surface.
Because of the observation that perennial plants treated with Lithovit only in the first growth period grow much better and give higher yield also in the second growth period without further treating with Lithovit, Munzinger3), therefore, assumes that further mechanisms such as epigenetic effects could also responsible for the action of Lithovit. In such a case, the trace elements contained in Lithovitas micronutrients could play an important role.
Considering the mechanism 2), which role plays the tribodynamic activation of Lithovit particles?
This should be probably that the highly activated Lithovit particles changes the structure of water and increases its dissociation: In pure water, the water dipoles normally exist as units of 9 molecules bound in tetrahedral structure by means of hydrogen bridge bonds. These dipoles dock with their positive Hydrogen ends on the negatively charged oxygen atoms of the carbonate groups laying at the surface of Lithovit particles. The hydrogen bonds break down due to the resulted electrostatic interaction. The energy needed for that should be supplied by means of energy fluctuation within the highly active Lithovitparticles. The electron density inside the O – H bonds of the water dipoles is shifted toward the O- atoms, so that dissociation of water molecules takes increasingly place. The H+ Ions then, dock on the negative charged carbonate groups of the Lithovitforming HCO3 - , The OH- ions react with CO2 forming HCO3 - as well. Of course the formation of HCO3 - is thermodynamically controlled by means of the equilibrium constant. However, the barrier of the formation energy is much easier overcome by means of this mechanism, which could be regarded as a catalytic reaction of the Lithovit.
This assumption of increasing dissociation of Water by means of Lithovit is based on the following observation:
At 20oC the pH value of 0.5% aqueous suspension of Lithovit is 9.84), while that of 10% suspension is 9.54). The amount of CaCO3 as well as of MgCO3 in the suspension is in both cases much higher than the solubility values of the two compounds. In pure water, the solubility values are only dependent on temperature and pressure and should, therefore, be equal in both suspensions, if the material should have not been activated before. In such cases the same total concentration of CO3 2- would have been obtained in the suspension. Since the equilibrium constants of reactions (1) and (2) are (at constant ionic strength) also only dependent of temperature and pressure, the same pH value should have been obtained in the two suspensions. The higher [H+] concentration in the 10% suspension indicates clearly the higher dissociation of water due to its higher degree of electrostatic interaction with the bigger amount of Lithovit.
1) It is the intention of the author to explain this question in such a simple way also easily understandable to non-scientific readers.
2) The tribodynamic activation is easily understood when we bear in mind that energy is never created nor destroyed (first law of thermodynamic). Energy can only be converted from one form (e.g. light energy, chemical energy, heat energy, electrical energy, magnetic energy, kinetic energy, potential energy, mechanical energy) to another. If a system transforms from one state in which its components have high kinetic energy (system of higher internal energy) to another state in which the components have less kinetic energy (system of lower internal energy), so the difference between the internal energies of the two systems will be set free as heat energy That is, for example, the case when Water vapour is condensed to liquid water (heat of condensation), respectively when liquid water is frozen to ice (heat of freezing). Conversely one has to supply the same amount of heat (heat of melting) in order to melt ice to liquid water and further the heat of evaporation in order to transform liquid water to vapour. (Of course, the entropy terms which describe the degree of disorder in the system must also be considered here. To simplify the text, these are let away). It is very similar in case of crystallisation where the moveable particles in a solution (system of higher internal energy) get bound in a lattice where they are only vibrating with very small amplitude (System of lower internal energy). Again the difference between the internal energies of the systems is released as crystallisation energy in form of heat. If the particles have an electric charge (ions) the difference of the electrostatic and potential energies of the two systems participates to the crystallisation energy too. A crystal growth to a big solid body with a great number of lattice units (e.g. natural limestone) results in a correspondingly high value of crystallisation energy. Conversely, when such macro materials are crushed to much smaller units, for instance by milling, only a part of the mechanical energy is converted to heat due to the friction, whereby a considerable part is transformed to the obtained particles as activation energy. The stronger the cracked bonds between the lattice units in the crushed material, the higher is the activation energy. In case the components building lattice are electrically charged (ion lattice, e.g. limestone) a corresponding higher activation energy is obtained due to energy further needed for the separation of the electric charges. Of course, the particles in the whole are electrically neutral, the centres of the positive charges and that of the negative ones, however, are not located at the same point, but at different sites. In case of lithovit the oxygen atoms of the carbonate groups show to the surface of the lattice units and so to the surface of the particles. Due to the high affinity of the oxygen to electrons, the surface of the Lithovit particles is negatively charged. The strong increase of the surface energy, the separation of the electric charges and the deformation of the lattice units laying directly under the surface result the high reactivity of Lithovit.
3) Stefan Munzinger, Broschüre Lithovit Grundlagen: 06106, Version 1.0 * 30. September 2006, Zeovita GmbH, Breite Str. 54, D-37154 Notheim
4) Taken from the analysis sheet dated June 11, 2006 of the Institute of Fertilizers and Seeds LUFA, Finkenborner Weg 18, D- 31787 Hameln