Some Humifulvate® Science

The inventor of HUMET®, Dr. Elek Csucska, once said: "Creation takes care of those who need care. Creation holds the materials that Nature had preserved for the ages when civilised man, losing control, would harm himself and need help... We need to discover and study these materials."

Who could deny the relevance of these sentences written decades ago! Perhaps not known generally, but it is a fact that more than half of the precious stock of human medicines today are of natural origin or are made up of close analogues of natural molecules. Sometimes a new 'breakthrough' in therapy can originate from the discovery of a completely new natural substance. Just think of the bright success of the very efficient anticancer agent, Taxol. People today turn 'back' to nature in increasing numbers: we can observe a renaissance of natural products, health preparations and food supplements. It is a new discovery - recognised as a modern thought by the scientific community also - that complexity is one of the major benefits of natural health products: their demonstrated effects may not always be traced back to a single, simple and easily describable active ingredient. They are rather complex mixtures of close or distant analogue substances, where the overall effect of the mixture is more beneficial than the sum of the effects of the individual components; in other words, a synergistic action takes place.

Complexity, however, carries certain risks with it: because of the unbelievable variety of nature, it is difficult - although not impossible - to guarantee absolutely identical effect for natural materials reproduced many times in sequence. Just one example: the chemical profile of extracts from individual plants collected from the same camomile field varies - although just slightly - with individual plants and differs by the period of day. Nevertheless it is not impossible to guarantee a permanent and standardised composition: it requires strict manufacturing circumstances, adequate analytical methods and dozens of biological and human studies.

The purpose of this paper is to provide a comprehensive, chemical and biological description - reflecting all that we know today - of a new active ingredient that demonstrates a series of beneficial effects and is made of a special kind of peat, known as Humifulvate, as well as its most common product formulation that contains added essential trace elements. As you will see, Humifulvate is essentially a unique blend of natural humic and fulvic acids. For this reason we had to include a short description of humin substances as found in nature, based on scientific literature. Since Humifulvate is most commonly used as a formula supplemented with essential elements, it seemed reasonable to give a brief summary of the biological activity of these elements also.

In addition, this paper has been compiled for yet another purpose: in the tail of the popularity of natural substances, general 'magical preparations', all-curative 'wonder mixtures' healing every ailment seem to appear from time to time and unfortunately in increasing number, taking advantage of people's naiveté. It must be made clear that Humifulvate itself and the products derived from it do not fall in this category. We would like to demonstrate that our claims are based on dozens of - very expensive - trials designed and carried out with definite aims in mind as well as experience of more than eight years of human consumption rather than on gossip, beliefs, or anecdotal evidence.

I. HUMIC SUBSTANCES

(In the Hungarian language the English expression "humic substances" refers to both humus and humin substances.)

1.1. General description of humic substances

Humic substances are the most common forms of organic carbon in the natural environment. These organic key components of the soil and sediments are extremely widespread on the surface of the earth. Most humic substances are chemically attached to inorganic components (clay and oxides), and a smaller part gets dissolved in the solutions of the soil, particularly under alkaline conditions. An important feature of humic substances is that they can combine with metal ions, oxides and clay minerals to form water soluble or insoluble complexes and can interact with organic compounds such as alkanes, fatty acids, capillary-active substances and pesticides.

The humic compounds occurring in the soil and peat deposits play a vital role in the terrestrial and aquatic ecosystems [2]. Farmers use humates to accelerate seed germination and improve rhizome growth [1]. These materials are able to stimulate oxygen transport, accelerate respiration and promote efficient utilisation of nutrient by plants [1,3,4]. Livestock food fortified with humic compounds has brought about improvements in the animals' reproduction cycles, resistance to diseases and growth rate [5]. These observations prompted scientists to study the specific properties of humates and their possible benefits in improving the health and well-being of humans.

Humic substances do not correspond to a unique chemical entity in structural and chemical terms and their characterisation is difficult.

Aiken and colleagues [6] have defined these substances as follows: "Humic substances are a category of naturally occurring heterogeneous organic substances of high molecular weight that can be isolated from the environment and operationally defined in terms of their solubility."

Several different humic substances have been identified:

Humus: This is the fraction of humic substances that is not soluble in water at any pH value. These substances have the greatest molecular sizes, as their molecular weights can be around 300,000 dalton. The oxygen content in this substance is the lowest and falls in the range of 32-34%, while the nitrogen content is the highest, being around 4%. Because of the high molecular weight, the negative surplus charge on their surfaces is insufficient for peptising the macromolecules even at strongly alkaline pH, and so their mobility in the soil is insignificant when in a coagulated state.

Humic acid: This is the fraction of humic substances that is not soluble in water under acid conditions (below pH 2), but becomes soluble at a greater pH. Humic acids are soluble in dilute alkaline solutions and precipitate as soon as the solution becomes slightly acidic. These substances have medium molecular size and their molecular weight is around 5,000-100,000 dalton. Oxygen represents 33-36%, while nitrogen represents 4% in this substance. Because of their medium molecular size, sufficient negative surplus charge on their surfaces for peptising the macromolecules will occur only in a more alkaline medium with a pH over 8 and thus their mobility in the soil is limited in neutral acidic-alkaline conditions.

Fulvic acid: This is the name of the fraction of humic substances that is soluble under all pH conditions. Fulvic acids dissolve in dilute alkaline solution and will not precipitate even if the solution turns slightly acidic. These substances have the lowest molecular size, as their molecular weight is around 2000 dalton. This is the material with the highest oxygen content (around 45-48%) and the lowest nitrogen content (less than 4%). Because of their low molecular weight their surface negative surplus charge is sufficient to peptise the macromolecules even at neutral or slightly alkaline conditions resulting in significant mobility in the soil.

Phenolic acid: This substance is not defined based on solubility but it is identified as a component of humic substances.

The two most important groups of potentially therapeutic humic substances are humic and fulvic acids [1]. Scientific literature has documented two potential therapeutic benefits of these substances: (A) their ability to positively influence mineral and trace element absorption, and (B) their capacity to bind heavy metals and thereby decrease potential metal toxicity. These activities are attributed to their ability to chelate and facilitate the utilisation of metal ions. Phenolic acids have also been widely studied for their potential therapeutic properties, specifically their metal chelating ability. However their therapeutic role compared to humic substances still needs further investigation.

1.2. The balance in the formation and degradation of humic substances

The origin of humic substances

The easily disintegrating organic matter that gets into the soil transforms quickly - in optimal circumstances - into water, carbon dioxide and elemental nitrogen or inorganic nitrogen compounds. The non-decomposing organic complexes polymerise and transform into humic substances by adsorption to the nitrogen-containing materials.

Humus is clearly the product of the activities of microorganisms in the soil (bacteria, fungi, ray fungi). Therefore the structure and elemental composition and the number of functional groups of humic substances depends greatly on the circumstances of their formation, moreover the place is also determinant, because the process is greatly influenced by the microbial flora of the given location. Since the natural formation of humic substances is a polymerisation process, the age of various humic fractions probably corresponds directly to the size of the molecules. The microbes digest the more easily decomposing organic materials, and burn them, while producing humic substances as end products from the fractions that degrade more slowly.

Humic substances originate from degrading plant residues in the soil. In scientific literature, based on molecular similarity, the lignin content of the plants is considered to be the source of humus, but in fact all organic building blocks of the vegetation, including carbohydrates, proteins, fats, waxes and resins play their roles in the formation of humus.

Degradation of humic substances

The microbes of the soil are primarily responsible for degradation. Many aerobic microorganisms that live in the soil use the humic substances as their nutritional source, as they obtain energy for life activities from the oxidation of these substances. Degradation takes place in a reverse order compared to the build-up of vegetation, in other words the materials with the lowest molecular weights will disintegrate the most speedily. This is mainly due to the solubility characteristics of humin molecules and the speed of their transport to microorganisms or their cell membranes. The fact that the decomposing enzymes working inside the microbes or at their cell membranes can less easily access the sites catalysed by the given enzyme as the size of the molecule decreases, also reinforces this tendency.

Balance in the formation and degradation of humic substances

Approximately 3% of the humic content of the soil is renewed every year. This means that in a balanced situation, that is when circumstances remain unchanged, this is the portion of the soil that disintegrates and gets newly formed. However, this statement applies to the easily degrading humic substances of the soil only. The more stable humic substances of large molecular weights can remain the same through very long periods, i.e. centuries.

The physical and chemical properties, water regulatory conditions, vegetation and microbial fauna of a given soil determine directly the nature of humification, i.e. the quality and quantity of the humic substances in the soil.

Generally, oxidation, in other words the higher air content of the soil creates an imbalance toward reducing the quantity of humic substances. The humin content of steadily and intensively cultivated soils that have been continually stirred up and are thereby penetrated by air, is significantly lower than that of rested soils. The rate, puffer capacity against reduction and average molecular weight of oxidative functional groups (that is carboxyl and phenolic groups) of the soil increase when the soil is cultivated.

While reduction increases the amount of humic substances, the average molecular weight and the levels of oxygen-containing functional groups are lower. Under extreme reductive circumstances the plant residues decompose and humify rather slowly.

Change in the vegetation has a significant impact on the humin content of the soil. It is interesting and thought provoking however, that reduction of humus content was found to be prevalent in experiments in which forest areas were brought under agricultural cultivation. In the United States the humin content of the soil decreased by 64% in 30 years in corn monocultures.

The impact of reverse change was found to be much lighter and statistically less manifest. This phenomenon highlights the difference in the speed of humic substance formation and degradation. Therefore, the balance of formation and degradation cannot be controlled by using simply a chemical approach.

1.3 Methods for describing the humic substances

In order to be analytically characterised, humic substances first need to be isolated from their sources. Taking into consideration the complexity and sensitivity of the components, this is a rather difficult task. The International Humic Substance Society (IHSS) recently approved a complex methodology suitable for obtaining the various components of humic substances. This methodology, although absolutely precise, is rather time-consuming and expensive.

The most common methods used to characterise the humic substances in the sixties were the so-called destructive testing methods (oxidation, reduction, pyrolysis). A number of non-destructive methods have been developed since then. These include elementary analysis, the assay of oxygen-containing functional groups or nitrogen-containing components. The properties of humic substances can also be described with the help of instrumental analytical methods. These include potentiometric and conductometric titration, and within the category of spectral methods, UV and visual, fluorescent, infrared, NMR and ESR spectroscopy. But other methods may also be used, including for instance X-ray diffraction, surface stress measuring, determination of molecular weight, steam pressure and membrane osmometry, size excluded chromatography (SEC), electrophoresis, ultracentrifuge, viscometry and mass spectrometry. Other methods worth mentioning include light dispersion, X-ray dispersion, electron microscope and ultrafiltration.

1.4. General chemical properties of humic compounds

Structure of humic molecules

The skeleton of humic molecules is made up of a carbon chain of complex space formula containing a high amount of aromatic rings attached directly to one another or through oxygen and nitrogen as bridge units. The etheric, ester, keto, imine and imido groups occurring at the points where hydrocarbon particles are connected, render some parts of the molecule slightly hydrophilic, while the molecular parts consisting mainly of carbon and hydrogen are considered hydrophobic.

Functional groups

The characteristic properties of humic substances are due to the functional groups situated on the carbon chain. They could be acidic (e.g. carboxylic acid and phenol), alkaline (e.g. amine, imine) or neutral groups (alcohol, aldehyde, ketone, ether, ester and amide). The common feature of these functional groups detectable in most parts of the molecule is that they can render certain parts of the molecules hydrophilic, while other lyphophilic parts are capable of binding materials that are immiscible in water. This soap-like property of humic molecules permits the binding of water-insoluble materials that do not get attached to the inorganic solid particles of the soil (fats, oils and the organic molecules soluble in them) as well as their transport in a colloidal solution through the soil, thereby facilitating their passage to plant roots and absorption to the plant. The functional groups that contain oxygen are prevalent in the humus molecules, and of all these, the carboxylic acid and phenolic groups are responsible for rendering the slightly acidic properties of humic substances. The groups that contain nitrogen primarily render certain parts of the molecule alkaline.

Colloid-chemical properties

Since relatively strong acidic and alkaline groups may occur within the humic molecule, this results in a dipolar ionic structure similar to that of proteins. This structure plays a major role in the electrostatic interactions among the various ions and the humic substances. A typical characteristic of humic substances is the isoelectric point (Point of Zero Charge, PZC), where positive and negative charges neutralise each other within the molecule. It refers to the pH value where the molecule is the least soluble, and this is where hydratation is the lowest and where the hydrophobic characteristic manifests itself the most expressively. Furthermore, the macromolecule in the soil and the root zone of the plant has the lowest mobility at this pH value. However, due to the dipolar ionic nature of the molecule, the zero charge applies only to the gross charge of the entire molecule, as there are a lot of positive and negative charges in various local sites of the molecule. If the pH value is lower, the gross charge of the molecule is positive, while if the pH is higher, it is negative. Because of the prevalence of oxygen-containing, acidic groups, the isoelectric point is in the pH = 3 - 5 range. As the set of molecules under discussion is not standard, only a pH range can be given.

Similarly to other macromolecules, the humic molecules also are capable of forming colloidal solutions only. This is important as these molecules can provide a surface for various surface-related processes, primarily adsorption in a diluted, mobilised condition. They resemble large molecular proteins in the living organisms in this respect also. Because of their extensively varied (almost random) molecular structure and continually changing spatial structure a lot of functional group combinations can be found on the surface of the humic substances that are positioned in such a way so that they are able to establish chemical bonds on the given molecules or create electrostatic interactions. Thus these groups may weaken the internal linkages of the molecule or the ionic substance and are capable of catalysing chemical reactions, although with much lower efficiency than certain specific proteins.

Complex-chemical properties

On the same account, the humic molecules can function as ligands of complexes, similarly to chelated structures carrying appropriate central atoms. This effect is particularly important as the randomly coiling molecules can be fixed by a polyligand dative bond to stabilise the formed complex. This stabilised complex however may break up if the number of oxidation or the pH at the root of the plant changes, and so the humic molecule will deliver its central atom it had transported and make it available for absorption by the plant functioning therefore as an excellent carrier molecule.