Laurenţiu FilipescuDepartment of Technology of Inorganic Substances and Environmental Protection, Faculty of Applied Chemistry and Material Science, University Politehnica of Bucharest, Phone: (021)4023885, e-mail: [email protected]
A NEW CONCEPT CONCERNING THE FOLIAR
FLUID FORMULATIONS
International Conference On Chemistry And Chemical Engineering, Timisoara, 2008
1.1. FOLIAR FLUIDSFOLIAR FLUIDS
Composition Composition
Foliar nutritive products are concentrated fluids containing particular components of the following classes of
chemical compounds:
• macronutrients (N+P+K),
• mezonutrients (Ca+Mg),
• micronutrients (B+Mo+Zn+Cu+Fe+Mn),
• biostimulants (organic substances promoting growth in crop size and quality)
• Fungicides (inorganic and organic substances providing protection against fungi and other fruit
diseases both during vegetative growth and post harvesting storage).
Required properties
1. complete solubility and chemical stability at higher concentrations as commercial product,
2. compatible in mixture with diluting hard waters as sprinkling solutions,
3. hiding power,
4. adherence,
5. penetration power through waxy cuticles, cell walls and plasma cell membrane,
6. moderate pH,
7. low saline and contact stress,
8. environmental friendliness.
DestinationDestination
Complementary nutrient sources associated with growth enhancers or pesticides available
and used in the most simple and efficient ways to handle crop control during any vegetative
development stage.
Formulation pitfalls Formulation pitfalls
Refining quality of foliar products according to the plant transient demands is confined to
restrictive limits due to objectionable changes in physical properties required for foliar application.
Most of the researches in the field of foliar fertilizers/foliar growth enhancers and pesticide were
focusing on active formulas in term of nutrient ratios and concentrations or biological active
components availability and phytotoxicity. The problems of foliar product penetration and uptake
yields, or formula efficiency were chiefly treated in terms of adjuvant adding to improve foliage
distribution or to ease application.
2. NEW FORMULATION APPROACH2. NEW FORMULATION APPROACH
This paper brings about a new concept for approaching foliar nutrition, taking the leaf cuticle
penetration mechanism as a keystone in formula design and product properties assessment. According
to this concept the new foliar fluids are concentrated emulsions containing two distinctive phases:
•an organic phase which is the carrier of growth enhancing and fungicide functions,
•an aqueous phase yielding all the mineral constituents of usual NPK liquid/foliar fertilizers with or
without micronutrients.
Both phases after dilution and hydrolysis are dispatching all the mineral/organic plant
nutritive/enhancing entities at a prerequisite level.
Original approach of the hydrolyzing emulsion application and leaf born nutritive species was
fulfilled with high regard to the permeation of the biological active entities through cuticle by both lipophilic
and polar paths of diffusion.
Consequently, the emulsion components selection has been made in good agreement with the
mass transport mechanism of lipophilic species through cutin wax domains (Buchholz and Schonherr
2000), as well as with high humidity/hydrolysis promotion at leaf surface in order to activate the cuticular
permeability to water and non lipophilic species (Schreiber 2005).
Reliable correlations composition – property were searched for finding adequate balances in
chemical formulation and foliar products required properties.
3. 3. CUTICULAR PENETRATION OF THE NUTRIENTCUTICULAR PENETRATION OF THE NUTRIENT
The foliar fluids applied on the aerial organs of plants have to penetrate three barriers:
a) waxy cuticle covering the epidermal cells or stomata walls;
b) epidermal cell walls; and
c) the epidermal cells plasma membrane.
Permeation of the active entities through cuticle occurs by the lipophilic and polar paths of
diffusion.
Permeation through the cell wall and plasma membrane occurs by active enzyme transport
and takes place only if cuticle resistance is subdued.
Both processes are highly dependent on fluid composition and on particular properties of the
properly applied diluted solutions (Schreiber 2005).
4. PENETRATION MECHANISM
The plant cuticle membrane has a composite structure made of (Stark and Tian 2006):
a) cutan, a non-saponifiable non-depolymerizable hydrocarbon polymer;
b) cutin, an easy solvent depolymerizable biopolymer;
c) waxes which are soluble lipids predominantly linear with different functionalities
(alkanes, alcohols, aldehydes, acids, etc.).
Figures 1 and 2 show the a leaf crossing section and respectively the the fine structure of
cuticle.
Figure 1. Leaf section Figure 2. Fine structure of the cuticle (Koch et al., 2006)
Figure 3. Schematic drawing of a solubility membrane traversed by an aqueous pore(Schonherr, J. 2006)
There are 3 criteria to match emulsified foliar nutritive fluid formula to cuticle pentration mechanism
First criterionFirst criterion
Due to their lipophilicity and mobility, organic compounds can easily cross the lipophilic
pathways opened in liphophilic domains which cover randomly the waxy cuticle surface. This
process is strongly depending on the size of diffusing molecules and the presence of liphophilic
accelerators. Accordingly, the first criterion in the formulation of emulsified foliar nutritive fluids is
the low molecular mass of the selected lipophilic organic carrier phase or lipophilic species of
growth enhancers and fungicides.
Second criterionSecond criterion
Polar and not charged water molecules can diffuse under high mobility conditions across the plant
cuticle using lipophilic cutin and wax domains as transport pathway. Actually, the water molecules are
absorbed into lipophilic cuticle producing swelling and promoting cuticular transpiration, and giving birth
of polar islands inside the lipophylic domains. Significant increase in the cuticular permeability of the
non lipophilic/ionic species was observed when larger amounts of water are absorbed in these newly
substantiated polar domains. This process is rather affected by relative humidity than the molecular
mass of transported ionic or charged molecules. Hence, the second criterion in the formulation of
emulsified foliar nutritive fluids is the relative humidity inside the mass transport limiting layer, which can
be hold at highest values by promoting hydrolysis of the organic components in the thinly layer
dispersed on the foliage surface.
Third criterionThird criterion
Stomatal penetration and foliar uptake yield of the ionic components is governed by three
parameters: relative humidity, stomatal area and number of wetting cycles. In addition, some applied
fluid properties as the surface tension, viscosity, contact angle as well as the use of additives
stimulating the stomatal opening are certainly factors of leverage in upsurging foliar absorption of the
ionic species. Therefore the third criterion in the formulation of emulsified foliar nutritive fluids is linked
to the development of reliable correlations composition – property and the matching applied fluid
properties to the compulsory terms of the stomata opening and foliar uptake mechanism.
5. SELECTION OF THE PARTICULAR COMPONENTS OF 5. SELECTION OF THE PARTICULAR COMPONENTS OF FOLIAR NUTRITIVE FLUIDSFOLIAR NUTRITIVE FLUIDS
From the above overview on foliar absorption mechanism and the presumed matching properties
of emulsified nutritive fluids, we figure out the following mandatory features for both aqueous and
organic phase of these fluids: Organic phase:
- low molecular mass organic acids and appropriate overbasic salts which may hydrolyze
over pH interval 7.0 - 9.0 by dilution with hard waters and prone to quick reaction with atmospheric
carbon dioxide and calcium/magnesium ions from hard waters,
- generation of stabile hydrolizates emulsions with high solubility and mobility through waxy
cuticle barrier,
- capacity to dissolve growth enhancers and fungicide;
Aqueous phase:
-high soluble saline components carrying macro and micronutrients,
-additives promoting the stomata opening,
-low density, viscosity and surface tension,
-capacity of wetting and spreading as thinly layers over the leaves.
All these properties must be associated with typical NPK formulas in foliar nutritive fluids
containing growth enhancers and fungicide components.
The best choice for the main components of emulsified nutritive fluids are:The best choice for the main components of emulsified nutritive fluids are:
- Low molecular organic carrier or growth enhancers and fungicide: naphthenic and oleic acids
option due to the following reasons: stability of their emulsions with saline solutions, solubility of their neutral and
overbasic ammonium/potassium salts (as mineral nutrients) in aqueous solutions, fast reaction of their overbasic
ammonium/potassium salts with carbon dioxide, miscibility with many classes of organic compounds, low
surface tension of their emulsions or aqueous salt solutions. Also, the naphthenic ammonium and potassium
salts, as well as naphthenic acids copper, zinc and manganese overbasic salts act as plant growth enhancers
(Wort et all. 1973, Wort 1976, Shulian Zhou et al. 1991, Hoque et al. 1992, Begum et al. 2002,), and oleic acid
overbasic salts exhibit antimicrobial and fungistatic action (Lack and Heiden 2006, Harry and Rajamannan 2006,
Colleman 2004). Naphthenic and oleic overbasic salts diluted solutions are hydrolyzing by air carbonation. Both
naphthenic and oleic acids are environmentally safe products completely biodegradable aerobic and anaerobic
in soils and waters (Biryukova and all. 2007, Scott 2005, Clemente 2004).
- Macronutrients:
* potassium option as the overbasic salts of both naphthenic and oleic acids is based on two factual
observations: stomata opening stimulation by potassium ions (Willmer et all.1983) and fungicide performances
of the potassium bicarbonates (Zitter and Drennan 1995, Ziv and Zitter TA 1992), coupled with its contribution as
macronutrient in any common fertilizer;
* nitrogen option as urea, due to this compound contribution to stability of the overbasic sals in saline
solutions (Calogrea and al. 2003, Chitu and al. 2004)
* phosphorus option as monohydrogen and dihydrogen orthophosphates, due to their buffering capacity in
diluted emulsified nutritive fluids (Cirjaliu-Murgea and al. 2005);
* micronutrients option for any soluble salt which do not interfere with organic acid overbasic salts.
6. FOLIAR NUTRITIVE FLUIDS DISTINGUISHED 6. FOLIAR NUTRITIVE FLUIDS DISTINGUISHED
PROPERTIESPROPERTIES
- Composition – property diagrams. - Composition – property diagrams.
Overbasic potassium salts of the naphthenic and oleic acids, picked up as intermediaries
bearing the physical and chemical properties matching the above selection criterion, are non-
crystalline materials with poor solubility in water. Meaningful overbasicity and additives choice may
produce aqueous emulsions/solutions of these salts bearing mandatory properties for foliar applied
fluids.
The use of ethanol as the third component in the pseudoternary system overbasic salts of
the naphthenic and oleic acids – water - ethanol is a good replacement for the random and mostly
insecure choice of other compatibility additives, because the miscibility water – ethanol and
ethanol – organic acids provides a convenient weight in handling the mixture properties and
shifting them to worthwhile values.
Pseudoternary liquid – liquid diagrams in systems overbasic naphthenate/oleate – water –
ethanol isotherms subsuming overbasicities from 2/1 to 6/1 are providing valuable information
about the balanced compositions which may carry demanded properties in both concentrated
emulsified fluids and diluted hydrolyzing solutions (figure 4).
Figure 4. Pseudo ternary systems overbasic potassium naphthenate – water – ethanol (a) and overbasic potassium oleate – water – ethanol (b) at 30ºC; Overbasicity 2/1, 4/1 and
6/1; Composition – surface tension diagrams.
Composition - property diagrams like these from figures 4 yield new data and leverage prospects due to
ethanol share in properties adjustment and control. Some other properties linked to fluids foliar
application may be disclosed by similar composition-properties diagrams as those presented in figure 4.
Intermediaries hydrolysis. Intermediaries hydrolysis.
The initial assumptions on hydrolysis process originate from the workable step by step reaction
of carbonation with free air carbon dioxide, able to push the pH beyond a certain hydrolyzing point
and help adherent layers precipitation, while other species of nutritive compounds are nucleated from
diluted emulsion over hydrolyzing mass and grew as amorphous or poor crystallized phases.
The figures 5(a) and 5(a) illustrate the hydrolysis onset process going on at a pH dependent
dilution ratio of the overbasic naphthenate (molar ratio 4/1 and 1M), respectively potassium overbasic
oleate (molar ratio 4/1 and 1M) emulsions.
a b
Figure 5. Hydrolysis of potassium overbasic naphthenate (4/1) 1M(K) non pre-carbonated (a) and pre-carbonated up to pH 10 (b) during dilution with deionized water
Figure 6. Hydrolysis of potassium overbasic oleate (4/1) 1M(K) non pre-carbonated (a) and pre-
carbonated up to pH 10 (b) during dilution with deionized water
a b
Working on overbasiciy, carbonation degree and ethanol concentration seems to be a fair
reasonable way for control diluted spaying fluid pH.
Hydrolysate layer precipitation.Hydrolysate layer precipitation.
Hydrolysate layer precipitation process was monitored through pH measurements over the entire duration
of applied liquid layer carbonation process accompanied by a partial water evaporation.
It was assumed that immediately after application the emulsified overbasic salts, hydrolysis advances due
to air free carbon dioxide absorption and the liquid film breaks out in a discontinuous micelle structured
fluid leaving on the leaf surface an adherent layer of organic hydrolysates.
While the hydrolysis and carbonation progress in extent, there is expected a significant decline in liquid
phase pH, because more and more hydroxyl ions are bound into hydrolysate complexes. Minimum value
of pH is reached when full hydrolysis is achieved and organic layer building up ceased.
Figure 7. a) Layered matrix precipitation in non pre-carbonatated naphthenate K4R(OH)3 1M. Diluted solutions 1/25 (▲), 1/50 (∆), 1/100 (●), 1/200 (○); b) Layered matrix precipitation in pre-carbonatated K4R(OH)3 1M, diluted 1/100 (●); K4R(CO3)3/2 , diluted 1/100 (▲) 1M; K4R(OH)3 1M +
urea, diluted 1/100 (○);K4R(CO3)3/2 1 M + urea, diluted 1/100 (∆)
Hydrolysates particle size distributionHydrolysates particle size distribution..
Hydrolysate particles have a relative mobility on the leaf surface within applied fluid layer, from where
they canpenetrate liphophilic or polar pathways inside cuticle. Sooner or lather, due to liquid phase
evaporation, hydrolysate particles are entrapped into semisolid matrix layer and released during daily
rewetting and transpiration. Both spontaneous freshly hydrolyzed and terminating released size particle
are critical facing the depth cross through cuticle. In other words as small is the hydrolysate particle size
as large is its probability to penetrate either liphophilic or polar pathways. We assume the unexpected
magnitude in stimulative performances of these hydrolysable products is originating from the hydrolysate
capacity to use both liphophilic and polar pathways through cuticle.
0
20
40
60
80
100
120
140
160
180
0 10 20 30 40 50
Time, minutes
Mo
de,
nm K Naphthenate, dilution 1/25
K Naphthenate, dilution 1/200
K Oleate, dilution 1/25
K Oleate, dilution 1/200
Figure 5 shows that the one of the ranking feature of the
overbasic sold hydrolysates is the particle dominant dimension
(expressed by the mode of particle size distribution), which is
placed between 10 nm and 200 nm. Dominant particle size in
1/25 diluted overbasic oleate lays in the same interval as
dominant size in concentrated emulsions. For other dilutions this
significant parameters is displaced to higher dimensions and
eventually on higher dilutions hydrolysis products are flocculated.
Figure 8. Hydrolysate particle size in layered matrix
ExpectationsExpectations
The new class biological activities are extending over:
- dormant buds stimulation;
- ratio fruitlets/flowers;
- growth enhancing both in fruits and shoots;
- boosting crop and quality;
-promotion against fungi and other fruit diseases;
-extended protection against fungi and fruit diseases during the
long term storage.
CONCLUSIONSCONCLUSIONS
There was demonstrated the viability of a new way to formulated emulsified foliar fluids
on the grounds of prominent attributes originating from the mechanism and kinetics of
foliar absorption. The two liquid phase emulsions enable the implementation of
multifunctional biological performances and best control of the foliar properties. Also, a
new mechanics in the waxy cuticle penetration was provided through reactive
components hydrolysis, pH control and particle size distribution.
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Acknowledgment
The work was carried out with the financial support of CNCIS, Program Idei, project
1035/2007.