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Quick Release Nitrogenous Fertilizer from Human Hair

Article · January 2016

DOI: 10.9734/BJAST/2016/23454

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 British Journal of Applied Science & Technology
14(2): 1-11, 2016, Article no.BJAST.23454
ISSN: 2231-0843, NLM ID: 101664541

SCIENCEDOMAIN international
www.sciencedomain.org

Quick Release Nitrogenous Fertilizer from

Human Hair
Md. Mominur Rahman1*, Kazi Bayzid Kabir1, Md. Masudur Rahman1
and Zannatul Ferdous1
1
Department of Chemical Engineering, Bangladesh University of Engineering and Technology
(BUET), Dhaka-1000, Bangladesh.

Authors’ contributions

This work was carried out in collaboration between all authors. Author Md. Mominur Rahman
designed the study, performed the statistical analysis, wrote the protocol, and wrote the first draft of
the manuscript and managed literature searches. Authors KBK, MMR, ZF managed the analyses of
the study and literature searches. All authors read and approved the final manuscript.

Article Information

DOI: 10.9734/BJAST/2016/23454
Editor(s):
(1) Verlicchi Paola, Department of Engineering, University of Ferrara, Via Saragat 1, Ferrara,
Italy.
Reviewers:
(1) Yongchun Zhu, Shenyang Normal University, China.
(2) A. Veerareddy, Defence Research Development Laboratory, Hyderabad, India.
Complete Peer review History: http://sciencedomain.org/review-history/12917

st
Received 1 December 2015
Accepted 29th December 2015
Original Research Article th
Published 7 January 2016

ABSTRACT

Liquid nitrogenous fertilizer was synthesized using waste human hair as the raw material.
Potassium hydroxide (KOH) and Tetramethylammonium hydroxide (TMAH) were used as the non-
recoverable solvents for diffusion controlled reductive cleavage of hair protein. Performance of
these solvents was analyzed and compared both individually and for different combinations.
Experiments showed that KOH was better for dissolving hair and extraction of nitrogen in the forms
of ammonium and nitrate ions compared to TMAH. Thereafter a vegetation pot experiment was
established to investigate the performance of the produced liquid fertilizers compared to the
commercial Nitrogen-Phosphorus-Potassium, NPK (15-15-15), fertilizer on the growth and yield of
a short cycle crop, spinach (Spinacia oleracea L). The study design consisted of four treatments
viz. no fertilization (T1), KOH based liquid fertilizer from human hair (T2), TMAH based liquid
fertilizer from human hair (T3) and commercial NPK (T4). Each treatment had four replicate pots
and was also done in parallel. The different treatments were added to the pot based on the total
nitrogen requirement of 50 kg/ha for the spinach following broadcasting method. Plant physiology
_____________________________________________________________________________________________________

*Corresponding author: E-mail: [email protected];

 Rahman et al.; BJAST, 14(2): 1-11, 2016; Article no.BJAST.23454

including plant height, number of the leaves, fresh and dry weight of the edible part of the
harvested plant after 28 days suggested that the performance of the synthesized fertilizers as a
nitrogen source were better than the commercial NPK fertilizer. These outcomes encourage such
novel use of waste human hair.

Keywords: Human hair; liquid nitrogenous fertilizer; saolvent; Spinacia oleracea L; treatment.

1. INTRODUCTION potassium (K), a macro element essential for

plant life. Sodium hydroxide, although less
Human hair is a complex tissue consisting of expensive, is not particularly beneficial as the
+
several morphological components, each plant requirement for Na is low and an excess of
+
consisting of several different chemical species. Na ions has an adverse effect on plant
The presence of trace elements in hair is the physiology [13].
reason behind its forensic importance in
replacing blood and urine analyses [1-3], skin The use of aqueous solutions of TMAH to
disease diagnostics, drug identification and dissolve hair and other biological materials for
tracking human migration patterns by isotopic analytical purposes has been reported [14,3,15].
correlation [4]. The physical properties of hair TMAH could also be a potential nitrogen source,
have interested researchers for different contributing to the total nitrogen content of the
applications such as adsorption for utilisation in liquid fertilizer, and is therefore included in this
effluent treatment [5,6] and arsenic removal from study for comparison.
drinking water [7]. Hair, a potential human waste,
contains up to 17% nitrogen by weight within the This paper reports the synthesis of nitrogenous
complex protein structure [8,9] which, if fertilizers from human hair using aqueous
transferable, could be used as a nitrogen source. solutions of KOH and TMAH as solvents. The
Several attempts have been made to use hair as scope of this study also included demonstration
a slow-release source of nitrogen, assuming of the effect of the synthesized fertilizers on
disintegration and mineralization within a spinach (Spinacia oleracea L) in comparison with
timescale of months [10,11]. To the authors’ that of a commercial NPK (15-15-15) fertilizer.
knowledge, preparation of a quick-release The synthesized fertilizers using KOH and TMAH
nitrogenous fertilizer from human hair has never as the solvent were found to enhance plant
been reported in open literature. growth and yield in comparison to the
commercial product.
The main problem with synthesizing a quick-
release nitrogenous fertilizer from human hair is 2. MATERIALS AND METHODS
disintegrating the hair. Human hair has a high
cystine content (1400-1500 micromoles/g hair) 2.1 Fertilizer Synthesis
[9] accounting for the inertness of the material.
Cystine is an amino acid characterised by a Potassium hydroxide pellets and TMAH 25%
disulphide bond, which provides strong (w/v in water) were used to prepare solvent
intramolecular and intermolecular cross-links solutions of different concentrations. A single
[12]. bulk sample of collected hair was used for all
tests.
Cleavage of the disulphide bond is extremely pH
dependent. High and low pH enhances The composition of the collected human hair
decomposition by different mechanisms [9]. At a sample was determined using a Perkin Elmer
pH above 10, moving boundary kinetics or 2400 Series II CHNS/O analyser.
diffusion of alkaline substances into the hair
control the reaction rate. In addition, the bond- To prepare the fertilizer, a measured amount of
strengthening effects of macro and micro dry, water-washed human hair was placed in a
molecules present in the soil are enhanced under solvent solution. The mixture was stirred for 5
alkaline conditions. minutes and then rested for 5 minutes to avoid
excessive foaming. The cycle was continued until
When selecting the hair solvent, other potentially the hair was completely dissolved. The resultant
advantageous properties should be considered in solution was passed through a 200–mesh Tyler
conjunction with pH. For instance, KOH contains series sieve to remove any undissolved hair. This

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 Rahman et al.; BJAST, 14(2): 1-11, 2016; Article no.BJAST.23454

process was repeated for increased amount of determined by adding Total Kjeldahl nitrogen
hair up to the saturation point of the hair solution. (TKN) [19] and available nitrogen in the form of
This process was then repeated for the various nitrate-nitrogen (NO3-N). NO3-N was measured
solvent solutions of interest. in 1:10 2 M potassium chloride (KCl) extract
[20,21] using ultraviolet visible (UV)
The prepared liquid fertilizer samples were then spectrophotometer (Cadmium reduction method
analysed for pH, density, viscosity and ion and measured at a wavelength 400 nm). Bray-P1
concentration of nitrate and ammonium. pH was test protocol was followed in determining
measured using a HACH pH meter and density extractable phosphorus (P) in soil [22]. Soil
was measured using a Mettler Toledo DA-100M sample was extracted by Bray-1 solution and
density meter. A model 35 FANN viscometer was filtered. The filtrate was then analyzed for
used to measure the dynamic viscosity and ion extractable P using UV Spectrophotometer at a
concentrations were measured using a HACH wavelength 890 nm (Ascorbic Acid Method).
DR/4000 spectrophotometer (USA). Potassium was extracted from the soil by mixing
1N ammonium acetate solution at pH 7 [23]. The
2.2 Vegetation Pot Experiment available K was then measured by analyzing the
filtered extract on an atomic absorption
The main objective of the pot experiment was to spectrometer (AAS). Cation exchange capacity
identify the performance of synthesized (CEC) of the soil was determined by the barium
nitrogenous fertilizers from human hair compared chloride (BaCl2) compulsive exchange method
to the commercial synthetic fertilizer. Four [24]. Water holding capacity of the soil was
treatments were included in the experiment, viz. examined by water saturation method [25].
no fertilization (T1), synthesized fertilizer from
human hair with KOH (T2), synthesized fertilizer The pot trials were carried out in 2-litre capacity
from human hair with TMAH (T3) and pots with 20.32 cm opening diameter. All the pots
commercial NPK 15-15-15 (T4). A short cycle were filled with experimental soil and fitted with a
crop, spinach (Spinacia oleracea L) was selected tray placed at the bottom of the pots to capture
for this study. The study design was set up such any excess water escaping from the pots. The
that it was a randomized trial with a total of four water was added to all the pots until they comply
different treatments and each treatment had four with the field capacity levels and was allowed to
replicate pots and was also done in parallel, settle for 48 hours. Different treatments were
amounting to eight pots per treatment. This gives applied to the pots on January 12, 2015 using
a total of 32 pots. broadcasting method according to the
recommended dose 50 kg N/ha for spinach [26].
The soil was selected based on the most Then the pots were allowed to stand for 5 days
common soil present in the agricultural areas of before seedling transplantation.
the particular region in which the selected crop is
grown. The top layer of the soil, (i.e., the first 0– The seedlings were grown from seeds in the
10 cm) was excavated from the identified site same greenhouse in which the pot trials were
and any unwanted objects such as vegetation, conducted using the same soil. Seeds were
stones, debris were discarded during excavation. sown on December 27, 2014. After 14 days of
After transporting to the laboratory, any soil clogs seed germination, the seedlings were
remaining were separated or broken down using transplanted into the experimental pots with a
a wooden mallet. The soil was then dried at room single plant per pot on January 17, 2015. The
temperature, after which it was passed through a pots were regularly watered to maintain their
6mm sieve. A composite soil sample from each water content within the field capacity levels
treatment was mixed thoroughly and crushed throughout the duration of the experiment to
gently to allow it to pass through a 4 mm sieve. A ensure maximum growth of the crop. Any water
sub-sample was then ground again and passed that percolated through the pot and into the tray
through a 2 mm sieve. The resulting sample was collected and used to water the same pot in
(< 2 mm) was then analyzed for different order to minimize the nutrient loss via leaching.
properties of the soil. Soil texture was The pots were moved around once in a week in a
determined following sedimentation method [16]. randomized manner to minimize any climate
Moisture content was determined using oven dry effects.
method at 105°C up to constant weight [17]. Soil
to water ratio 1:2.5 was maintained to measure The number of leaves and stem height of each of
the soil pH [18]. Total nitrogen (N) was the plants grown using all the treatments were

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 Rahman et al.; BJAST, 14(2): 1-11, 2016;; Article no.BJAST.23454
no.

recorded at 0, 1, 2, 3, 4 weeks after solvents in any proportion reduced their

transplantation. The spinach plants were effectiveness, with minimum dissolution of hair at
harvested after 28 days (4 weeks) and after ~70% TMAH solution in KOH solution.
harvesting a number of parameters were
measured: Fresh and dry weight and moisture Additional experiments were performed in which
content of the edible part of the plant (dried at the hair was added to the solvent gradually. The
105°C to constant weight). results show that this method decreases the
maximum dissolved amount (Fig. 3). This is
3. RESULTS AND DISCUSSION
SSION consistent with the fact that the reaction of hair
proteins with bases is strongly dependent on pH
3.1 Preparation of the Fertilizer and each subsequent addition of hair results in a
decrease in solution pH.
The hair sample contained 46.3% carbon, 6.7%
hydrogen, 14.8% nitrogen and 3.1% sulphur. Large scale dissolution experiments were carried
out for both solutions. The linear relationships
Two potential solvent solutions were between the volume of solvent and mass of the
investigated; KOH and TMAH. Unlike KOH, hair dissolved are shown in Fig. 4. KOH
TMAH can contribute to the total nitrogen content dissolves more hair compared to TMAH. The
of the resultant liquid fertilizer. KOH and TMAH quantity of hair dissolved can be expressed as
dissolved hair at concentrations as low as 2%
w/v. The time required to complete the W KOH = 0.9985VKOH
dissolution process is inversely related to the W TMAH = 0.7557VTMAH
concentration. The dissolution performance of
KOH was invariably superior to that of TMAH, as
shown in Fig. 1. For 10% KOH and 10% TMAH where W is the weight (kg) of hair and V is the
the dissolution process was complete after 1 and volume (L) of the solvent.
1.5 hrs respectively.
The densities of the prepared fertilizer solutions
3
Combined use of solvents was also considered. (KOH and TMAH based) were 2097-2115
2097 kg/m
3
The dissolution results show that the solubility of and 1739-1748 kg/m respectively. The dynamic
hair in the 10% KOH solution decreased on viscosity was determined as 6.2--6.4 mPa.s for
addition of TMAH (Fig. 2). The concave shape in the KOH solution and 6.7-6.86.8 mPa.s for the
the plot was the result of reaction between TMAH solution. The pH of the final solution in
solvents before reacting with hair. Mixing the both cases was found to be between 7.5 and 8.

Fig. 1. Time required for dissolving hair in aqueous solvent of KOH/TMAH

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 Rahman et al.; BJAST, 14(2): 1-11, 2016;; Article no.
no.BJAST.23454

Ammonium (NH4+) ion and Nitrate (NO3-) ion contribution of hair to NH4+ and NO3- ions could
concentrations of the synthesized fertilizers were not be determined since the solvent solution itself
determined and are shown in Table 1. With 10% contains nitrogen. However, the total nitrogen
KOH as the solvent, approximately 79% of N was content was lower than n that for KOH due to the
extracted from hair as NH4+ and 18% as NO3-. lower dissolution of hair in TMAH 6.
6
For the equivalent TMAH solution, the

Fig. 2. Variation of hair solubility in solvent mixtures ((quantity of TMAH is shown in x-axis;
x the
rest is KOH)

Fig. 3. Variation in solubility due to gradual addition of hair to KOH (upper curve) and TMAH
solvents

Table 1. Nitrogen content in the synthesized liquid fertilizer

Solvent g NH4 / L g NH4-N / L g NO3/ L g NO3-N / L

10% KOH 150.17 116.80 117.82 26.60
10% TMAH 101.79 89.07 89.40 20.19

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 Rahman et al.; BJAST, 14(2): 1-11, 2016;; Article no.
no.BJAST.23454

Fig. 4. Relationship between volume of solvent and mass of hair dissolved

Considering the quantity of hair dissolved, synthesized fertilizers as they are slightly basic in
concentrations of the ions in the product fertilizer nature. Physico-chemical
chemical properties of the soil
and cost of the solvents 10% KOH is preferable are shown in Table 2.
compared to the 10% TMAH. However, the
performances of the synthesized fertilizers were Leaves count on each of the plants of different
then compared with commercial rcial NPK (15-15-15)
(15 treatments at 0, 1, 2, 3, and 4 weeks revealed
fertilizer through pot trial on spinach. that there appeared to be no significant
differences in number of leaves on the plant
3.2 Performance of Synthesized grown using different treatments till the end of
Fertilizers first week. However, there appeared a significant
difference in leaf count at the end of the pot trial
Sedimentation result shows that the soil for pot session. Plants grown using no fertilizer (T1) and
experiment contains 65% sand, 15% silt and KOH based fertilizer from om human hair (T2)
20% clay which categorize the soil texture as showed the least (13±1.19) and the highest
Sandy Loam. The soil was slightly acidic in (17±2.07) number of leaves respectively at the
nature with a pH of 6.8 which was suitable for the end of fourth week (Fig. 5).

Table 2. Physico-chemical
chemical properties of the soil for vegetation pot experiment

Parameters Value Methods

Moisture (%) 8.85 Oven dry method at 105°CC up to constant weight [17]
pH (Soil:Water :: 1:2.5) 6.80 Glass electrode pH meter [18]
Total N (% dw*) 0.12 Kjeldahl and NO3-N
N by Cadmium reduction method using UV
spectrophotometer [21,19,20]
NO3-N (mg/Kg dw*) 7.70 Cadmium reduction method using UV spectrophotometer
Available P (mg/Kg dw*) 12.6 Bray-P1 and Ascorbic acid method using UV
spectrophotometer [22]
Available K (mg/Kg dw*) 13.3 Ammonium acetate method using Atomic Absorption
Spectrophotometer [23]
CEC (meq/100 g) 10.74 BaCl2 compulsive exchange method [24]
Field Capacity (% dw*) 16.91 Water saturation method [25]
*Dry Weight Basis (dw)

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 Rahman et al.; BJAST, 14(2): 1-11, 2016; Article no.BJAST.23454

Treatment T2 contributed the highest positive of plants grown using different treatments
change in leaf count (565%) whereas this was (Fig. 7), overall changes in stem height manifest
the lowest for treatment T1 (346%) during the it quickly (Fig. 8). The highest overall changes in
vegetation pot experiment (Fig. 6). stem heights were observed for treatment T1 and
the lowest overall changes were for treatment
An inverse relationship between the leaf count T2. The higher change in stem height of spinach
and stem height of grown spinach was observed might be related with the nutrient deficiency of
using different treatments. Though this result is the soil.
not vivid from the weekly changes in stem height

20
18 T1
Average number of leaves/plant

16 T2
14
T3
12
T4
10
8
6
4
2
0
0 1 2 3 4 5
Weeks

Fig. 5. Weekly average leaf count of the grown spinach using different treatments

900
Overall change in leaf count (%)

800
700
600
500
400
300
200
100
0
T1 T2 T3 T4
Treatments

Fig. 6. Overall changes in leaf count for different treatments

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 Rahman et al.; BJAST, 14(2): 1-11, 2016; Article no.BJAST.23454

1.00

Average stem height (cm)

0.80 T1
T2
0.60
T3
0.40 T4

0.20

0.00
0 1 2 3 4 5
-0.20
Weeks
-0.40

Fig. 7. Weekly average stem height of the grown spinch using different treatments

600.00
Overall change in stem height (%)

500.00

400.00

300.00

200.00

100.00

0.00
T1 T2 T3 T4
Treatments

Fig. 8. Overall changes in stem height for different treatments

However comparison of the dry weight of the g/plant for the commercial NPK (T4). Improved
edible part of the plants after harvesting (Fig. 9) performances were seen with T2 and T3
there appears to be a significant difference compared to control T1 and T4 which was due to
between different treatments. The lowest readily available nitrogen in the synthesized
average weight (<2 g/plant) was seen for the fertilizers T2 and T3 (Table 1). It was further
plants grown without any additional nutrients (T1) manifested that the T2 (KOH based synthesized
which is what it would be expected. The results fertilizer from human hair) showed the best
for the TMAH based liquid fertilizer from human performance on the dry mass basis of the grown
hair (T3) and KOH based liquid fertilizer from spinach.
human hair (T2) showed remarkable differences
compared to the commercial NPK (T4). The Fig. 10 shows the average NO3 concentrations in
average dry masses of the edible part of the the edible part of the harvested spinach using
grown spinach were 5.12 g/plant for T3 and 5.79 different treatments. The concentrations of nitrate
g/plant for T2 which were much higher than 3.83 varied between treatments. As expected the

8
 Rahman et al.; BJAST, 14(2): 1-11, 2016; Article no.BJAST.23454

concentrations in the edible part of the plant for Since the only nitrogen source was the synthetic
those grown without addition of fertilizer (T1) was fertilizer added to the soil during the vegetation
very low. There was a significant difference in pot trial, the physical growth and enhanced
nitrate concentrations in the plants grown on nitrate content in the grown spinach can be
NPK (T4) and TMAH based fertilizer (T3) attributed to the effect of this synthesized
compared to KOH based fertilizer (T2) as the fertilizer. These results and observations are
nitrogen concentration in the form of nitrate was direct consequences of the presence of nitrogen.
in the highest amount in T2 (Table 2). Though The results of some other studies showed that
the nitrate concentration in the edible part of the high levels of readily available nitrogen increased
grown spinach using T2 was the highest (2289 leaf number and vegetative growth of plants thus
mg/kg green mass) among the treatments, it was increasing the photosynthetic capacity which
below the upper limit of the nitrate concentration resulted higher dry matter in the grown plants
(2500-3000 mg/kg) in green spinach set by [28].
European Union [27].

60
Average green and dry mass(g)/plant

Green mass
Dry mass
50

40

30

20

10

0
T1 T2 T3 T4
Treatments

Fig. 9. Average green and dry mass of the hearvested spinach using different treatments

3000
Average NO3 content (mg/kg GW)

2500

2000

1500

1000

500

0
T1 T2 T3 T4
Treatments

Fig. 10. Average nitrate concentrations in the grown spinach using different treatments

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 Rahman et al.; BJAST, 14(2): 1-11, 2016; Article no.BJAST.23454

3.3 Practical Considerations and 3. Ribeiro AS, Curtius AJ, Pozebon D.

Implications Determination of As, Cd, Ni and Pb in
human hair by electrothermal atomic
A survey was conducted by the authors to absorption spectrometry after sample
estimate the amount of hair available from treatment with tetramethylammonium
barbers’ shops around Dhaka city. The hydroxide. Microchem J. 2000;64(1):105-
calculations showed that a total of approximately 10.
20 tonnes of waste human hair can be collected 4. Ehleringer JR, Bowen GJ, Chesson LA,
per month from the city, containing approximately West AG, Podlesak DW, Cerling TE.
3 tonnes of nitrogen. Development of a feasible Hydrogen and oxygen isotope ratios in
collection strategy for will therefore be the next human hair are related to geography.
big challenge. Proceedings of the National Academy of
Sciences. 2008;105(8):2788-93.
The synthetic fertilizer analysis showed that the 5. Krishnan S, Cancilla A, Jervis R. Industrial
nitrogen is available in suitable forms for plant wastewater treatment for toxic heavy
uptake. The final pH of the solution was slightly metals using natural materials as
basic, implying that the liquid fertilizer can be adsorbants. J Radioan Nucl Ch. 1987;
effectively used for acidic soils. The soil pH 110(2):373-8.
levels in 45 districts of Bangladesh are acidic, 6. Krishnan S, Cancilla A, Jervis R. Waste
while in the other 19 districts the soil pH ranges water treatment for heavy metal toxins
from acidic to slightly basic (Mia et al. 2005). using plant and hair as adsorbents. Sci
Therefore, the synthesized fertilizer could be Total Environ. 1988;68:267-73.
used throughout the country. 7. Wasiuddin N, Tango M, Islam M. A novel
method for arsenic removal at low
4. CONCLUSION concentrations. Energ Source. 2002;
24(11):1031-41.
8. Mitu AM. Damage assessment of human
The synthesis of a quick-release nitrogenous
hair by electrophoretical analysis of hair
fertilizer from waste human hair incorporating
proteins (PhD Thesis): Bibliothek der
such simple methodology either remains
RWTH Aachen; 2004.
unexplored or has not yet been reported. The
9. Robbins CR. Chemical and Physical
synthesized fertilizers were found to be an
Behavior of Human Hair. Springer Berlin
effective nitrogen source for plant growth
Heidelberg; 2012.
enhancement. Hence this study forms the basis
10. Zheljazkov VD. Assessment of wool waste
for further work on the effects of such fertilizer on
and hair waste as soil amendment and
plant physiology. Future commercialization of this
nutrient source. J Environ Qual. 2005;
process would largely depend on the
34(6):2310-7.
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11. Zheljazkov VD, Silva JL, Patel M,
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COMPETING INTERESTS HortTechnology. 2008;18(4):592-6.
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Authors have declared that no competing the chemistry of human hair. 1. Analyses
interests exist. of cystine, cysteine and cystine oxides in
untreated human hair. Int J Cosmet Sci.
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© 2016 Rahman et al.; This is an Open Access article distributed under the terms of the Creative Commons Attribution License
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provided the original work is properly cited.

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