Fertasa Symposium - 2015

A Practical Approach Review of

Humic and Fulvic acids.
Christo Malan. P hD (Plant Physiology)
Fertasa Symposium - 2015

Aim of the Talk

o a general oversight of what humic and fulvic acids are;
o a comparison of the 2 compounds
o where they come from
o what their benefits are
o Exaggerations and pitfalls
oRegulation and registration
oHow to choose the right product
Fertasa Symposium - 2015

What are humic and fulvic acids?

Active soil organic matter that forms the key

component of sustainable agricultural practices.
Consist of C, H, O, N and S.
Fertasa Symposium - 2015

Activity mainly determined by Functional chemical

groups:
carboxylic acid (COOH), hydroxyl (-OH), carbonyl (C=O),

Functional groups allows humic and fulvic acids to form

complexes/chelates with cations such as Mg2+, Ca2+, Fe2+ etc. to keep
them available for crop utilization.
Important aspect is the role of these molecules in regulating
bioavailability of nutrient ions and its effect on crop performance.
Fertasa Symposium - 2015

Non-Humic Substances with the same active functional groups that often
part of HA and FA aggregate structures:

amino acids, sugars

organic acids like citric acid.

HCOOH – Formic acid,
CH3COOH – Acetic acid
Fertasa Symposium - 2015 Comparison between Humic and fulvic acid
Humic
• Relatively large molecules >35 Kdalton
weight and 150 – 300 nM size
• Lower chemical reactivity – less
functional groups or ionic charges
• A solution at a pH above 10, alkaline
• Precipitate in productive agricultural
soils, with the pH between 5 and 7
• Precipitate when reacted with divalent 2+
cations
• Cannot be absorbed by plant roots or
leaves.
• Cannot shuttle complexed nutrients into
the plant.
Fulvic
• Relatively small molecules <35 Kdalton weight
and 80 -100 nM size
• Higher chemical reactivity – higher number of
functional groups or ionic charges
• Water soluble at any pH
• No precipitation at any pH. Always in solution,
especially in productive agricultural soils
• No precipitation when reacted with divalent 2+
cations
• Can be absorbed by plant roots and leaves
• Fulvic acid complexed nutrients shuttled into
the plant.
Fertasa Symposium - 2015
Comparison between Humic and fulvic acid
Humic Fulvic

• enhance utilization of nutrients via • Enhance utilization of mineral nutrient

ion exchange sites and prevent
reaction with phosphate anions
which will form insoluble
phosphate compounds.
• at sufficient concentrations
contribute towards cation
exchange capacity (CEC) of soil.
• Humic acids CEC: 400-870
meq/100g
fulvate complexes which are in solution
can be taken up by plant roots and
therefore utilized by the plant – serve as
a shuttle to carry nutrients into the plant.
• contribute towards CEC of the soil at
sufficient concentrations.
• Fulvic acids CEC: 900-1400 meq/100g
Fertasa Symposium - 2015 Proposed molecular structures: molecular aggregates

Humic acid structure

Fulvic acid structure

Fertasa Symposium - 2015

HS are practically classified based on solubility at an acid and alkaline pH.

Humins consist of plant and animal material resistant to
decomposition (solid material not soluble in water at any pH);

Humic acids are substances in the process of decomposition (large

molecules that are alkaline extractable) but not soluble at productive
soil pH;

Fulvic acids are a complex mixture of smaller size organic molecules

resulting from humic acid decomposition through microbial action and
soluble in water at any pH.
 Chemical characteristics Fulvic vs Humic Chemical characteristics Fulvic vs
1.2 5 1.4 Humic
1.15
1.2 200 350
1
180 Mol size Nm
300

0.8
1
160 Mol weight KDalton
140 Humic, 300 250
0.8

0.6 0.635 120

200
0.6 100
0.57
150
80
0.4 0.47
0.4
COO−meq OH/g) 4.4
60 100

0.2 40
0.2
50
CEC eq/100g Molar O/C Molar H/C 20 Fulvic, 2
0 0 0 0

Fulvic Humic Fulvic Humic

Summarized chemical characteristics of humic and fulvic acids (Stevenson, 1982 and Helal,2007).

C and O contents, acidity and degree of polymerization all change with

increasing molecu lar weight.

Fertasa Symposium - 2015 Chemical characterization of humic fractions (Helal, 2007).

Molar H/C ratio Molar O/C ratio COO−(meq OH/g)

FA 1.17 (+22%) 0.57(+21%) 5(+14%)

HA 0.96 0.47 4.4

Fulvic acids contain more functional groups of an acidic nature,

particularly COOH more reactivity towards reacting with cations .
Fertasa Symposium - 2015 Extraction of humic and fulvic acids.

KOH, NH3OH,
NaOH

Precipitate

To pH 1 - 2
Use alkali again to make a
solution of a Humate
mineral salt complex Solution
e.g. K-humate with
K content 4 – 4.5 %
Fertasa Symposium - 2015 Electron microscope photographs below shows the
polymeric or aggregate structures of HS

Saturated Low H+
Negative charges
with H+ repel
Fertasa Symposium - 2015 Chemical characteristics

Functional Once the

hydrogen ions Two anions can
carboxyl (COOH) + Reaction
are bind to positive
hydroxyl (OH)
dissociated a divalent metal ( 2COO- + Fe++
groups (on the
negatively cations, (Fe++), 2COOFe +
outside of the
charged anion (Cu++), (Zn++), 2H+) binds
polymers)
(Ca++), (Mn++),
dissociate (expel) (COO- or CO-) (Mg++).
two anions.
hydrogen ion. results
 Chemical characteristics
Humic
and
Fulvic
acids
neutralize
cations
Insoluble
Ca2+ + Ca3(PO4)2 0.0002g/100mℓ
Mg2+ + MgPO4 0.00026
Zn2+ + ZnPO4 0
Fe2+ +
PO42- FePO4 0
Cu2+ + CuPO4 0
Mn2+ + MnPO4 0
Fertasa Symposium - 2015 Physical characteristics

HS profoundly influences the structure of soils.

Important – concentration related
Intensive tillage of soils results in loss of humus that leads to:
• hard and compact soils,
• poorly aerated soils
• poor water-permeability
• Poor water holding capacity.
Fertasa Symposium - 2015 Physical characteristics
Effect of high Fig 3: Water infiltraton tempo as indicator of soil structure
improvement when treated with ByoCarb 50 applied @ 20, 40 and 60
concentration (20%) l/ha
renewable resource 90%
Water puddled soil NaOH puddled soil
83%

Aver % Water infiltration

extract FA on water 80%
64%
permeability in soil 70%

improvement
60% 51%
where structure was 49%
50%
destroyed by 40% 31%
puddling with water 30%
18%
and more severely 20%
10% 0% 0%
with NaOH. 0%
Water ByoCarb 20 ByoCarb 40 ByoCarb 60
Fertasa Symposium - 2015 Physical characteristics

Humic Substance physical benefits:

• bind soil particles into structural aggregates that plays a
major role in managing soil erosion.
• Estimated that up to 70% of the exchange capacity of soils
is the result of the colloidal HS aggregates.
• Aggregates help maintain a loose, open, granular condition
of soils with improved aeration and water holding capacity.
Fertasa Symposium - 2015

Humic substance biological benefits- impact on plant metabolism

Direct effects:
o HS can contain auxin or auxin-like molecules – Growth stimulation.
Indirect effect:
o Hormone production enhancement - improved uptake of Zn that catalysis
natural auxin formation.
o hormone production by improved growth and multiplication of Rhizosphere
synergistic bacteria.
o Improved nutrient uptake SUPPORT total metabolism stimulation.
All stimulatory effects like the increase CO2 uptake, ATP synthesis, mitochondrial
respiration and enhanced photosynthesis can be an indirect consequence of the all
of the above.
Fertasa Symposium - 2015 Biological characteristics

Take note that crop growth improvement claims made for

commercial HA and FA products should be questioned because,
The effect of the equivalent nutrient portion (e.g. K in K-humate,
4,5 – 5% K) must be tested separately from the humic or fulvic
acids.

Such a product used in a soil deficient in K, the K in the product

will have an effect on crop performance.

Combined use should show synergism.

Fertasa Symposium - 2015 1. Nutrient vs Fulvic acid synergistic effect:

Differential effect on 4.6 % 2.1 % 2.8 % 3.1 %

30.0
chlorophyll in maize 29.7
29.5 29.5

Chlorophyll - SPAD units

29.5 29.2

grown under 29.0

28.6
28.7 28.7
28.4
controlled conditions 28.5
28.0
and treated with the
27.5
equivalent amount of 27.0
27.1

nutrient alone (LC-F) 26.5

compared to nutrient 26.0

25.5
plus Fulvic acid (LC+F) Control LC - F LC - F LC - F LC - F LC + F LC + F LC + F LC + F
(15ℓ/ha) (20ℓ/ha) (30ℓ/ha) (40ℓ/ha) (15ℓ/ha) (20ℓ/ha) (30ℓ/ha) (40ℓ/ha)
Fertasa Symposium - 2015 1. Nutrient vs Fulvic acid synergistic effect:
Fig 15: % Increase in root and top growth mass: nutrients plus
Fulvic acid compared to nutrients alone (0%)

40% 37%
36%
Likewise much more 32%
33%

30%
drastic synergistic 27%

% Increase
23%
22%
20%
differential effect on 20%

root and top growth 10%

mass 0%
15ℓ/ha 20ℓ/ha 30ℓ/ha 40ℓ/ha

Plant Mass Root Mass

Fertasa Symposium - 2015 2. Bacterial hormonal effect:
80

a a
Effect of a high concentration FA 70 a
ab b
(ByoCarb50) treatment on the nr of 60 b b
b

Colony forming units/g soil

b
fungi, bacteria and yeasts retrieved 50
c
c

from soil. c 0 kg/ha

2.5 kg/ha
40 c c c
No significant growth promoting a a
5 kg/ha
10 kg/ha

effect on fungi within a 96 hour 30

b
20 kg/ha

b b
incubation period. 20

Bacterial and yeast growth 10 a a

a
a a
a a a a
a
stimulation occurred from 48 hours 0

after incubation, specifically at the 48 h 96 h 48 h 96 h 48 h 96 h

10 and 20 kg /ha equivalent

Fungi Bacteria Yeast
dosages.
[Mean of three replicate plates of two dilution series ]
University of Pretoria, 2007
Fertasa Symposium - 2015 Claims and facts
Common exaggerated HA and FA product claims that often are
the reason for failure of these products:
• Overstated active ingredient content of products
• Soil chemical, physical and biological activity properties at
application rates and product content that are too low to
have any effect and without any valid experimental results
to prove it,
• Claims that humic acids are more bio-active than fulvic acid
as a soil application.
Fertasa Symposium - 2015

Reasons for using either Humic or Fulvic acids or both must be clear:
Change CEC or Neutralize charges
Stimulate
physical structure of of nutrient ions to
soil microbial action
improve uptake
long term at
sufficient dosages Depends on
dependent what the
can be expensive
and has to be on concentration
compared to using concentration active
compost or ai and
manure at a lower ingredient is
cost and will application and how it is
achieve the same method applied
goal
Fertasa Symposium - 2015 Claims and facts

Note:
Not all black or dark brown liquids/suspensions/powders are
humic or fulvic acids.
For example, black coal dust sold to uninformed farmers as
“slow release humic acid” is not oxidized at all and therefore
are totally insoluble and inactive.
Fertasa Symposium - 2015 Sources and characteristics of products from different sources.

Humic acid sources as K, Na, Ammonium, Mg humate powder, granules

or liquid.
Leonardite/lignite, peat, pecan nut shells, compost, manure , wood or fermented
fresh plant material extracts. The higher the oxidation state the more active it is.

Fulvic acid sources.

Due to solubility of fulvic acids it easily leaches out of source material,
• present in low concentrations (0.2 – 1% w/v) in leonardite, peat, compost
sources.
• In South Africa, novel high concentration fulvic acid extracted from a
sustainable renewable resource has shown to have high ion charge neutralizing
and biological activities.
Fertasa Symposium - 2015 Analysis of humic and fulvic acids.

BemLab implemented an internationally accepted chemical analysis

procedure to analyse commercially available humic and fulvic acid products
in South Africa in order to assist to better control and regulate the chemical
quality of HS products and also to assist in the registration of such products.

HA concentration is determined gravimetrically, while the FA that

remained in solution is determined spectrophotometrically.

The method was developed using the procedure described in two publications, namely,
GAN, D., KOTOB, S.I. & WALIA, D.S., 2007. Evaluation of a Spectrophotometric Method for Practical
and Cost Effective Quantification of Fulvic Acid. Annals of Environmental Science. 1, 11-15.
THURMAN, E.M & MALCOLM, R.I., 1981. Preparative isolation of aquatic HS. Environ. Sci. Technol. 15,
463-466.
Fertasa Symposium - 2015 Analysis of humic and fulvic acids.
All HA and FA products made up of an organic portion and an
inorganic mineral portion.
What must be analyzed?
• Total macro- and micronutrients including S.
• Humic and fulvic acid concentration (%) using standardized
internationally accepted methodology.
• % Carbon
• Moisture %
• Specific density - kg/l
Fertasa Symposium - 2015 Proof of activity: Dosage response and optimal dosages
Fulvic acid (20%) (ByoCarb 50) Dosage Response - Average % Results of field trials done on
Yield increase, 12 Trials, WA
30% R 4.50 wheat in Western Australia,
% Yield
Increase R 4.13 28% 27% R 4.00
repeated on 12 farms, was
25% Rand for R1 combined and the dosage
R 3.50
response curve was plotted
% Yield Increase

23%

ROI for R1 spent

20%
19%
R 3.00
to establish the in situ
R 2.59 R 2.50 concentration range where
15%

13% R 2.00
the highest yields were
obtained.
10% R 1.50
R 1.38

R 1.00
A high concentration
5%
R 0.84
renewable resource fulvic
R 0.50
R 0.27 acid (55 – 55% dry matter, 18
0%
1
0
0% 2
5 3
7 4
15 5
21 6
60
R 0.00
– 22% pure fulvic acid) used.
ByoCarb 50 Dosage (ℓ/ha)
Fertasa Symposium - 2015
Dosage response and optimal dosages

I. Data analysis by Rose et al (2014), where 89 papers (700 analysis points)

relevant to the question of, to what extent Humic substances will result in
plant growth responses, showed an optimum growth response at a
dosage of approximately 20 kg/ha.

II. The WA field trials shows that the optimum application dosage is
between 15 and 21 liters/ha based on yield alone but based on ROI, it was
between 5 and 7 liters/ha.

III. Chen et al. (2004) used the data of a number of studies to calculate the
optimum dosage of HS and arrived at a figure of approx. 22.5 kg/ha as a
soil application.
 Humic and fulvic acids (HS) as synergists – farm benefits
Improved nutrient use efficiency with the use of FA was observed on wine grapes
in the Western Cape .
The 20% FA product at 30 ℓ/ha (3x10 ℓ split over a 2 month period) was used on 4 vineyard
cultivars (8 blocks, separate adjacent control and treatment blocks).

Vineyard blocks % Increase relative to control

Cabernet 6.1%
Chardonnay 13.5%
Shiraz 12.0%
Viognier 1.2 %
Fertasa Symposium - 2015 Humic and fulvic acids (HS) as synergists – farm benefits

1:2 Water extract soil analysis Average wine mineral content

Average results for 4 cultivars: % Increase in % relative to control for 4 cultivars
water soluble nutrient concentration relative to indicating the higher mineral
control. 140%
153% nutrition value.

98% 98%
79% 75%
57%
38% 46%
24% 18% 15% 23% 17%
18% 15% 9%
-31% 8% 5% -2% 7%

EC P K Ca Mg Na S Zn Cu Mn Fe P K Ca Mg S Na Zn Cu Mn Fe B

These results show the direct synergistic benefit in using FA in conjunction

with nutrients in the soil.
 How to choose between different Humic and fulvic acid products =
Information required for registration purposes.
Active ingredient of the product? Humic or fulvic or both?
Concentration as per analysis of the active ingredient/s?
 Source of the humic and /or fulvic acid extraction?
Which mineral nutrients are in the product and at what
concentrations as per analysis? Products oxidized Nitric acid will
contain a high concentration of N but comparible low amounts of
humic and/or fulvic acid. This is an expensive N product instead of
supplying N as conventional fertilizers and the small amount organic
material in these products does not contribute to the intended goal.
 How to choose between different Humic and fulvic acid products =
Information required for registration purposes..
What is the pH of the product? Water soluble: humates pH>10 and fulvic
below 6.
What is the specific density of the product? Generally a good
quality product with high organic active content will have a density higher than
approximately 1.2 kg/ℓ.
What is the carbon content of the product, can be a good
indication of concentration and potential activity.
Fulvic acid products: Does it have water dispersing (water
surface breaking), wetting and re-wetting
(hygroscopic) characteristics that both for soil and foliar applications,
beneficial enhanced infiltration, uptake and utilization of nutrients.
Fertasa Symposium - 2015 Conclusions
The compounding benefits for using Humic Substances to
ensure sustainability in crop production are:
 improvement of soil chemistry and structure
 improvement of biological status of soils
 improved utilization of nutrients supplied and obvious cost
savings
 improved water utilization and possible cost savings
 improved yield – higher income/ha
 improved quality – higher income/ha
Fertasa Symposium - 2015 Conclusions
The amount of research data that proves its significant positive
impact on a broad spectrum of agricultural situations, should be
proof enough to consider these products for their intended use,
provided attention is given to the quality of products,
correct dosages and how being used,
otherwise poor results will make the name “snake oil” stick and
the true on-farm benefits will not be realized.
Fertasa Symposium - 2015

Thank you
Fertasa Symposium - 2015 What are the intended benefits required?
List of Intended benefits of organic amendments from Bünemann et al (2006), amended.
Reasons for organic amendment
(a) Supply bulk nutrients for plant production
(b) Increase availability of existing soil nutrients
(c) Increase the availability of applied fertilizers
(d) Fix N from air
(e) Improve soil chemical fertility
(f) Improve soil physical condition
(g) Improve soil biology
(h) Plant growth promoters
(i) Direct suppression of plant disease
(j) Indirect suppression of plant disease
(k)Decontamination of polluted soils.
(l) Break down crop residues and other compostable materials