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Thermal degradation of keratin waste

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DOI: 10.1016/j.jaap.2011.03.003

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 Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Thermal degradation of keratin waste

Mihai Brebu ∗ , Iuliana Spiridon
“Petru Poni” Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Thermal degradation of sheep wool, human hair and chicken feathers was studied by TG-MSD/FTIR
Received 10 November 2010 and by pyrolysis followed by GC-MSD analysis in order to identify the degradation compounds and the
Accepted 5 March 2011 temperature range in which they are formed. Only small differences were found between the studied
Available online 12 April 2011
keratin samples. They consist mainly in shift of characteristic temperatures of degradation and in rela-
tive amounts of compounds in degradation products, especially in aqueous phase. Degradation started
Keywords:
with formation of ammonia and CO2 (from 167 and 197 ◦ C respectively and with maximum evolution at
Keratin
273 and 287 ◦ C respectively), continues with formation of sulphur-containing inorganic compounds (SCS,
Wool
Hair
SCO, H2 S and SO2 at 240, 248, 255 and 253–260 ◦ C respectively) and of water (255 ◦ C). Thiols are formed
Feathers in two stages (257 and 320 ◦ C) while the evolution of nitriles is maximum around 340 ◦ C and continues
TG-MSD/FTIR up to about 480 ◦ C. Phenol and 4-methylphenol are the most important degradation compounds, for-
Pyrolysis med at 370 and 400 ◦ C respectively. Nitrogen was present mainly in aliphatic/aromatic nitriles, pyrroles,
GC-MSD pyridines and amides while sulphur was found mainly as sulphides, thiols, thiazoles and thiophenes.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Keratins are extremely strong, structural proteins, with high sta-
bility and low solubility, which are major components of some
tissues found in birds, reptiles and mammals (e.g. horns, hooves,
hair, feathers and nails or in outer layer of skin). Their special pro-
perties come mainly from permanent, thermally stable disulphide
cross-linking bridges between cysteine amino acid residues.
Estimations consider that about 5 000 000 tone/year of keratin
remain as waste by-product of various industries that could lead
to environmental pollution. Poultry feather is the most abundant
keratinous waste material. Feathers contain more than 90 wt% ␤-
keratin and represent 5–7% of the total weight of mature chickens.
Feather waste at poultry processing plants has high protein con-
tent and hence it is used for feed stuff (e.g. chicken poultry, swine,
rainbow trout and salmon). This involves harsh treatments that
decrease the nutritional quality and reduce the digestibility [1]. The
EU regulation limits the use of feather waste for animal feed, due
to the concerns on mad cow disease and avian flu, therefore new
treatment methods should be found. The waste feathers are also
used on a limited basis as nitrogen fertiliser but this could create
environmental problem due to their difficult degradation. Incine-
ration is not a suitable treatment method because it can lead to
environmental pollution [2,3].
Keratin also represents more than 90 wt% of the dry weight of
hair. The ␣-keratin in mammalian hair is less tough that the plea-
∗ Corresponding author. Tel.: +40 232 217454; fax: +40 232 211299.
E-mail addresses: bmihai@icmpp.ro, iahim b@yahoo.com (M. Brebu).
ted sheets of ␤-keratin in feather. Cysteine and sulphur level varies
among different parts of wool/hair and feathers leading to harder or
softer materials with [4,5]. For example the outer layer of wool/hair
fibre is rich in cystine and highly cross-linked while the cortex
contains microfibrils of low-sulphur proteins dispersed within a
matrix of high-sulphur proteins and glycine/tyrosine-rich proteins
[6,7]. Human hair contains about 3.3–4.3 wt% sulphur [8]. The cattle
hair contains about 12.4–14.4 wt% nitrogen; 1.6–11.8 wt% melanin;
1.4–2.4 wt% ash [9,10]. Human hair contains about 50 wt% carbon,
7 wt% hydrogen, 22 wt% oxygen, 16 wt% nitrogen, 5 wt% sulphur,
with slight differences according to the source of the hair; the ash
content is of about 0.3–1 wt% [11].
Melanin has highest variation, this being affected by season,
environment, genotype or area of body. Melanin almost totally dis-
sipates as heat the absorbed UV radiation hence it has an important
protective role against photodegradation [12,13].
Recent studies considered the keratin waste as possible rene-
wable source for production of sustainable materials [14]. Waste
feather could be used to obtain biodegradable polymers for modern
packaging [15], adhesives for wood board, or as reinforcement
agent for commodity thermoplastics [16]. Possible applications of
wool keratin were found for cell cultivation in cosmetics and tissue
engineering [17,18] or for nano polymer blends [19].
Whatever reuse method for keratin waste or its derivatives,
the new-produced materials eventually reach the end-of-life and
become waste. Pyrolysis could be a suitable treatment method of
polymer waste as it allows both energy and material recovery.
While the pyrolysis of commodity plastics was largely studied, few
data are available on the thermal behavior and the degradation
products of keratin waste.

0165-2370/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2011.03.003
 M. Brebu, I. Spiridon / Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295 289

This paper deals with thermal degradation of keratin waste 100

from different sources in order to determine the nature of degrada- TG
DTG
tion compounds and the temperature domains for their formation.
These data might be of good value when thermal methods are con- 80
sidered for treatment of composite materials that contain natural
polymers such as keratin waste. It is interesting to compare the Wool
pyrolysis behavior of feathers with that of wool and hair because 60 Hair
Feathers

Tg , %
of differences in chemical composition, solubility and molecular
configuration.
40

2. Materials and methods

20
Waste sheep wool (old, not-dyed fabric), human hair (cosmeti-
cally untreated) and chicken feathers (from barb and rachis) were
collected and used after grinding in agate ball mill for 60 min at 0
100 200 300 400 500
700 rpm.
The TG-FTIR/MS analyses were performed on a Jupiter STA 449 Temperature , oC
F1 (Netzsch) simultaneous TGA/DSC instrument coupled with and
Fig. 1. Tg curves of studied keratin waste.
Vertex-70 (Bruker) FTIR spectrophotometer and a QMS 403C Aëo-
los (Netzsch) MSD mass spectrometer. Amounts of about 10 mg
sample were heated by 10 ◦ C/min up to 600 ◦ C in open Al2 O3 cru-
The DTG curves showed that the main degradation step of
cible, under 50 ml/min He flow. The practice of thermal analysis
hairs and feathers consists of several successive, overlapped sta-
of heterogeneous materials such as keratin ones usually requires
ges. For example the degradation started slowly for human hair up
performing of several measurements. Homogeneity of our samples
to about 224 ◦ C when the rate strongly increases (sharp decrease
was increased by milling and no significant difference was found
of DTG curve)—Fig. 1. Two main stages partially separated at about
after repeating the TG analysis; therefore the results from single
300 ◦ C follows, with maximum degradation rates at about 276 and
tests are presented. Some small differences were expected for the
311–326 ◦ C respectively. The mass loss was of 23 wt% (excluding
characteristic temperatures of degradation determined from TG,
sample humidity) below 300 ◦ C and of 42 wt% above 300 ◦ C.
FTIR and MS data due to transportation of the volatile products
The TG-FTIR analysis showed similar results for the studied
from the TG furnace to the detectors through the 1.5 m transfer
keratin samples, considering both the IR bands and the temperature
lines (heated at 190 ◦ C) and also due to different data sampling by
range of their evolution—Fig. 2. Therefore discussions were made
each instrument. Interpretation of FTIR spectra was made according
for the human hair that gave the best separation of the degradation
to freely available NIST spectra database [20].
stages at 300 ◦ C.
Pyrolysis was performed on 10 g samples in a semi-batch glass
The FT-IR analysis of evolved gases from TG analysis of human
reactor previously described [21] that was heated by 10 ◦ C/min up
hair showed several bands with similar evolution in same tempera-
to the final degradation temperature of 500 ◦ C. The volatile pro-
ture ranges—Fig. 2b. Sample humidity appeared in FT-IR spectra as
ducts passed through a water-cooled condenser and the condensed
small bands at 1508 cm−1 and in the region above 3400 cm−1 (not
products were collected in a graduate cylinder. The liquid pyrolysis
shown in Fig. 2b) that have maximum intensities at 80 ◦ C. The band
product consisted of an organic fraction and of a water fraction. The
at 1508 cm−1 had another evolution step between 220 and 300 ◦ C,
organic compounds in aqueous fraction were extracted with ethyl
with maximum value around 247–254 ◦ C. Two degradation sta-
acetate then the extracted solution was concentrated in vacuum
ges occur between 220 and about 450 ◦ C with maxims at 250–290
before analysis.
and around 326 ◦ C respectively. These are partially separated at
GC-MSD analysis was performed on a 6890N Agilent
300 ◦ C (also shown by DTG curve) and are followed by another
gas chromatograph coupled with a 5975 inert XL Agilent
stage, at higher temperatures. The first and second degradation sta-
mass selective detector working at 70 eV, over a HP5-MS
ges are dominated by formation of inorganic gases that started to
(30 m × 0.25 mm × 0.25 ␮m) column packed with (5%-phenyl)-
appear as early as 167 ◦ C for ammonia (960/929 cm−1 accompanied
methylpolysiloxane. The following parameters were used: injector
by smaller bands with similar evolution in 750–1150 cm−1 range,
– 280 ◦ C; split ratio – 100:1; flow rate – 1 ml/min; temperature
1624 and 3328 cm−1 ) and 197 ◦ C for carbon dioxide (2356/2310 and
program – 45 ◦ C, 5 ◦ C/min up to 200 ◦ C, 20 ◦ C/min up to 300 ◦ C
667/629 cm−1 ). The maximum evolution rates in the first degrada-
(2 min).
tion step were at 273 ◦ C for NH3 and at 287 ◦ C for CO2 . In the second
degradation stage ammonia and carbon dioxide have maximum
3. Results and discussions evolution around 326 ◦ C.
The band at 1539 cm−1 had a rapid evolution with a sharp
3.1. TG-FTIR/MSD analysis increase from 220 ◦ C to 244 ◦ C and a tail up to 300 ◦ C. The bands
at 2071/2048 cm−1 that could be correlated to C O double bond
The studied keratin waste had similar degradation behavior also have sharp increase up to 251 ◦ C followed by a tail but this band
during thermogravimetric measurements, with two distinct steps have a second evolution stage with maximum around 326 ◦ C similar
of mass loss—Fig. 1. The first one occurred below 120 ◦ C and corres- to NH3 and CO2 . The peaks of the FT-IR bands in the first degrada-
ponds to loose of adsorbed water. The main structure of keratin tion stage explain the inflexions of DTG curve in the 230–300 ◦ C
materials decomposed in the second step, from about 150 ◦ C up to temperature range. The bands at 2870–2970 cm−1 corresponding
about 600 ◦ C. The TG curves were almost parallel for human hair to saturate aliphatic group frequencies had main evolution starting
and sheep wool. However our wool sample started to degrade at above 300 ◦ C, with maximum around 475 ◦ C. The bands at 3014,
higher temperatures (∼180 ◦ C) compared to the hair one (∼150 ◦ C). 1718 and 1302 cm−1 corresponding to olefin groups became signi-
Feathers started to decompose at about 155 ◦ C and the process ficant above 450 ◦ C and have maximum intensities around 530 ◦ C
occurred faster than for hair and wool (more rapid fall of TG curve). showing the advanced degradation of structure at higher tempera-
290 M. Brebu, I. Spiridon / Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295

Fig. 2. The FT-IR spectra of the evolved gases from TG analysis of sheep wool (a), human hair (b) and chicken feathers (c).

tures. It was difficult to obtain clear assignments of the IR bands in the spectra of both water and ammonia but the relative ratio bet-
corresponding to classes of organic compounds due to the high ween them is different in these two compounds. m/z is the main
complexity of the spectra. However the MSD analysis could help ion fragment in the spectra of water, followed by m/z 17, while
to elucidate the degradation stages. the latter one is the main one and the former one is very small in
The detailed analysis of the variation of m/z mass numbers with
1000 1000
temperature during TG analysis offers valuable information on the 18
m/z 18 17
H2O NH 3
volatile compounds formed during thermal degradation of sam- 0.8 750 750 16 0.8
m/z 15,16,17,18 ion current , A(*1exp8)

ples. The release of sample humidity during heating is shown by 500 500

the peak at 80 ◦ C of m/z numbers 18, 17 and 16 that are characte- 250 17 250
ristic for the MS spectra of water—Fig. 3. The evolution of these mass 0
16
0
18
0.6 10 12 14 16 18 20 22 10 12 14 16 18 20 22 0.6
m/z 17 / m/z 18 ratio

numbers continues during TG analysis but the shape of the curves

is different. The m/z 17 and m/z 16 showed two peaks between
220 and 450 ◦ C, that have almost similar heights and are separated m/z 17 / m/z 18
m/z 17
at 300 ◦ C. The evolution of the m/z 18 curve is characterised by a 0.4 0.4
strong peak between 220 and 300 ◦ C that is followed by a small,
long tail. The m/z 17 versus m/z 18 ratio had constant value (∼0.27) m/z 16
from room temperature up to 200 ◦ C. This is explained by the fixed 0.2 0.2
ratio (0.212) between the intensities of these mass numbers in the
MS spectra of water which is the only compound evolved from the
hair in this temperature range (release of humidity). However this m/z 15
ratio increases above 200 ◦ C showing that the evolution of m/z 17 0.0
50 100 150 200 250 300 350 400 450 500 550
0.0

became faster than that of m/z 18. Therefore m/z 17 and m/z 18 Temperature , C
o
start to appear from different sources that means different degra-
dation compounds. Indeed m/z 17 and m/z 18 are mass fragments Fig. 3. The evolution of water and ammonia during TG analysis of human hair.
 M. Brebu, I. Spiridon / Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295 291

the spectra of ammonia. Therefore we can say that water is formed a

between 220 and 300 ◦ C and ammonia is released in two stages in 2.5
1000
76
220–450 ◦ C temperature range. This is supported by the variation m/z 60 750 SCS

m/z 60,62,76,78 ion current , A(*1exp10)

of the signal for m/z 15 whose evolution is similar to that of m/z 16
500
and is in good correlation with the evolution of IR bands for water 2.0
250 32 44
and ammonia in Fig. 2. The m/z 15 and 16 had another evolution
peaks above 450 ◦ C (with maximum values around 530 ◦ C) that are 0
10 20 30 40 50 60 70 80
1000
not accompanied by evolution of m/z 17 or 18. This shows the for- 1.5 60
750 SCO
mation of alkyl-containing organic compounds, in good agreement
with observations from FT-IR analysis. 500 32

Inorganic sulphur compounds are formed in the 200–300 ◦ C 1.0 m/z 76 250
28 44
temperature range—Fig. 4. The sharp evolution of m/z 76 and 78 0
10 20 30 40 50 60 70 80
with maximum value at 240 ◦ C and of m/z 60 and 62 with maxi-
mum value at 248 ◦ C (Fig. 4a) showed the formation of SCS and 0.5
SCO and explain the FT-IR bands at 1539 and 2071/2048 cm−1 res-
m/z 62
pectively. H2 S is formed with maximum rate at 255 ◦ C, as proved m/z 78
by the m/z 32–36 (Fig. 4b) while maximum evolution of SO2 occurs
0.0
at 253–260 ◦ C (Fig. 4c). The evolution of m/z 47 cluster (CH2 SH+) 150 200 250 300 350 400 450 500 550
showed the formation of thiols in two stages, around 257 and Temperature , oC
320 ◦ C (Fig. 5a). Formation of nitriles started above 250 ◦ C and con-
tinues up to about 480 ◦ C, with a visible peak of m/z 27 (HCN+), 41 b 1.5 1000
1.5

m/z 32 34
(CH3 CN+) and 54 (C2 H4 CN+) clusters around 340 ◦ C (Fig. 5b). H 2S
750

m/z 33,34,35,36 ion current , A(*1exp9)

The aromatic compounds are formed in the main degradation

m/z 32 ion current , A(*1exp9)

stage, in 300–500 ◦ C temperature range. This is shown by the evolu-
tion of m/z 51, 65, 77 clusters that are typical for the fragmentation 500 32 33
1.0
spectrum of benzene ring, and are accompanied by m/z 91 and
250
107 clusters for methyl- and ethyl-groups attached to aromatic 1.0
ring—Fig. 6. It is interesting to note that some clusters have maxi-
0
mum evolution at different temperatures suggesting that several 30 32 34 36 38 40
compounds might not be formed simultaneously. For example it m/z 34 0.5
appeared that phenol is formed with maximum rate at about 370 ◦ C
(m/z 94 and 66) while methylphenol is formed at about 400 ◦ C (m/z m/z 33
107 and 77). 0.5
m/z 36
3.2. Pyrolysis m/z 35
0.0
150 200 250 300 350 400 450 500 550
Pyrolysis of feathers, wool and hair gave 13–15 wt% gaseous pro- o
Temperature , C
ducts, 12.5–15.5% oils and 20–26% aqueous fraction, the residue
being of 37–43%—Fig. 7. Hair gave the highest amount of aqueous
c
0.8
1000
fraction while wool left the highest amount of solid residue. A pow- m/z 64 64
SO2
m/z 48,50,60,66 ion current , A(*1exp10)

der condensed at the cold outlet of the reactor (6.4, 10.2 and 14 wt% 750
for wool, hair and feathers, respectively). The Q-TOF MS analysis
(direct injection of aqueous solution in the electrospray ion source m/z 48
500 48
0.6
of an Agilent 6500 Series Accurate-Mass Quadrupole Time-of-Flight
Q-TOF LC/MS, positive ion mode) revealed that the powder consis- 250
ted of a mixture of amino acids from keratin materials: cysteine 32
(Cys), glutamic acid (Glu), threonine (Thr), leucine (Leu), valine 16
0.4 0
(Val), and aspartic acid (Asp)—Fig. 8. 20 30 40 50 60 70
The GC-MSD chromatograms were similar for aqueous pha-
ses and oils of wool, hair and feathers—Fig. 9. Pyrolysis of wool,
hair and feathers produces many N- and S-containing compounds, 0.2
coming from the amino acids in the protein composition of these
m/z 66
keratin waste as well as from the disulphide bridges in keratin
structure. Nitrogen was present mainly in aliphatic/aromatic nitri- m/z 50
les, pyrroles, pyridines and amides while sulphur was found mainly 0.0
as sulphides, thiols, thiazoles and thiophenes. Molecular S8 sulphur 150 200 250 300 350 400 450 500 550
was also found, both in aqueous phase and in pyrolysis oils. Phe- Temperature , oC
nol and 4-methylphenol coming from degradation of tyrosine units
Fig. 4. Evolution of SCS, SCO (a), H2 S (b) and SO2 (c) during TG analysis of human
were the main compounds, which were free of N or S. Tyrosine has
hair.
higher thermal stability compared to other amino acids such as
aspartic acid, histidine, glutaminic acid that are among the cons-
tituents of proteins in wool/hair and also in feathers [22] and this aromatics: aqueous phase: benzene (2.56); toluene (3.65);
explains the formation of phenol and 4-methyl phenol at higher ethylbenzene (5.33); styrene (5.95); oils: benzene; toluene; ethyl-
temperatures, as determined above from the Tg-MSD analysis. benzene; xylene (5.46); styrene;
The main compounds identified in pyrolysis fractions of wool alcohols: aqueous phase: ethanol (1.75); 2-furanmethanol (5.17);
were as following (retention time given in brackets): benzenemethanol (9.71); oils:—;
292 M. Brebu, I. Spiridon / Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295

a 1000

m/z 51,66,77,91,94,107 ion current , A(*1exp11)

94
1000 PhOH
47 48 750 m/z 91
0.6 750 CH3SH 5
m/z 45,47,48,62 ion current , A(*1exp10)

500 45 500
66
m/z 45 250 250 39
15 33 50 55 63
0 0
m/z 48 10 20 30 40 50 4
40 50 60 70 80 90 100
1000 1000
29 C H SH 62 107
750 2 5
0.4 27 47 750 CH3PhOH
500
3
m/z 51
250 34 500
0 250 77 79
10 20 30 40 50 60 39 51 53 90
2 0
40 50 60 70 80 90100110 m/z 94
m/z 47
0.2 m/z 66

m/z 107
m/z 62 m/z 77
0
150 200 250 300 350 400 450 500 550
0.0
150 200 250 300 350 400
o
450 500 550 Temperature ,oC
Temperature , C
b 1000
41
1000
28 54
Fig. 6. Evolution of aromatic compounds during TG analysis of human hair.

750 CH3CN 750 C2H5CN

m/z 27,39,41,54 ion current , A(*1exp10)

6 500 500
250 39 250 26 52
14 28 15 40
0 0
10 20 30 40 10 20 30 40 50 60

m/z 27
4

m/z 41
2

m/z 39
m/z 54
0
150 200 250 300 350 400 450 500 550
Temperature , oC Fig. 7. Product yield from pyrolysis of feathers, wool and hair.

Fig. 5. Evolution of C1 –C4 thiols (a) and nitriles (b) during TG analysis of human
hair. nitriles: aqueous phase: acetonitrile (1.83); propanenitrile
(2.15); 2-methylpropanenitrile (2.37); butanenitrile (2.63); 4-
phenols: aqueous phase: phenol (8.27); 2- and 4- methylpentanenitrile (4.91); hexanenitrile (5.68); pentanedini-
methylphenol (10.33 and 10.93); 2,4-dimethylphenol (13.00); trile (10.68); 2-methylpentanedinitrile (11.17); benzeneacetoni-
4-ethylphenol (13.56); oils: phenol; 2- and 4-methylphenol; trile (12.69); benzenepropanenitrile (15.56); oils: acetonitrile;
2,4-dimethylphenol; 4-ethylphenol; propanenitrile; 2-methylpropanenitrile; 3- and 2- buteneni-

x10 2
Asp

1 119.16
Thr

133.17
0.9
Leu

0.8

0.7 131.16
Val

0.6
Cys

0.5 117.14
121.17
Glu

0.4
[L e u+H] +

[ Met+H] +
[ Val+H]+

[ Asp+H] +
[ Thr+H] +

0.3
[ Cys+H] +

147.19
[Glu+H]+

124.13 135.19
114.14
Met

0.2

0.1
149.21
0
2 114 116 118 120 122 124 126 128 130 132 134 136 138 140 142 144 146 148 150
Counts (%) vs. Mass-to-Charge (m/z)

Fig. 8. Q-TOF MS spectra of the powder condensed on the cold parts of the reactor.
and feathers (c).
b
a

0
0
0
0

2e+6
4e+6
2e+6
4e+6
2e+6
4e+6
2e+6
4e+6

6e+6
6e+6

Time , min
Time , min

Abundance
Abundance

acetonitrile

2
2
propanenitrile propanenitrile
butanenitrile

C5 C6 C 7
C5 C6 C 7
pentanenitrile acetal
pyrrolye toluene
toluene pyrrole

4
4
acetamide

C8
C8
3-methyl-1-H-pyrrole 2-methylpyridine
4-methylpentanenitrile 3-methyl-1-H-pyrrole
ethylbenzene 4-methylpentanenitrile
propanamide

6
6
styrene

C9
C9
2,5-dimethyl- & 2-ethyl- 1-H-pyrrole 2,5-dimethyl - & 2-ethyl- 1-H-pyrrole

8
8
dimethyltrisulfide
phenol phenol

C10
C10
4-ethyl-2-methylpyrrole 3-methylbutanamide
2-aminopyridine

10
10
2-methylphenol
2-amino-4-methylpyrimidine
4-methylphenol 4-methylphenol

C11
C11
3-methyl-2-pyridinamine

12
12
4-methylpentanamide
4-methylpentanamide
benzeneacetonitrile benzeneacetonitrile
2,4-dimethylphenol
3-methyl-2,5-pyrrolidinedione
ethylphenol

14
14

2-ethyl-3-methylpyrazine

C12
C12

benzenepropanenitrile benzenepropanenitrile
M. Brebu, I. Spiridon / Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295

16
16

indole indole

C13
C13

hair, pyrolysis oil

wool, pyrolysis oil

5,5-dimethylhydantoin

18
18

hair, aqueous fraction - ethylacetate extract

wool, aqueous fraction - ethylacetate extract

3-methyl-1-H-indole 3-methyl-1-H-indole

20
20

C14
C14

5-ethyl-5-methylhydantoin

Fig. 9. Details of GC-MSD chromatograms (n-C5 –n-C14 range of NP-gram) with the main identified compounds in aqueous fraction and in pyrolysis oils of wool (a), hair (b)
293
294 M. Brebu, I. Spiridon / Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295
c
Abundance
4e+6
2e+6
0
4e+6
2e+6
0
Time , min2 4 6 8 10
C5 C6 C7 C8 C9
trile (2.43 and 2.67); butanenitrile; pentanenitrile (3.75);
4-methylpentanenitrile; hexanenitrile; benzonitrile (8.32); 4-
methylbenzonitrile (11.67); benzenepropanenitrile;
pyrroles: aqueous phase: pyrrole (3.50); 3- and 2-methyl-1H-
pyrrole (4.85 and 5.03); 2,5- and 2,3-dimethyl-1H-pyrrole (6.76
and 7.06); 2- and 3-ethyl-1H-pyrrole (6.78 and 7.27); 2-ethyl-
4-methyl-1H-pyrrole (7.95); 4-ethyl-2-methylpyrrole (8.97);
2,3,5-trimethyl-1H-pyrrole (9.23); 2-acetlypyrrole (10.58); 2-
pyrrolidinone (11.11); 1- and 3-methyl-2,5-pyrrolidinedione
(11.36 and 13.30); 1-ethyl-2,5-pyrrolidinedione (12.61); 2,5-
pyrrolidinedione (15.69); oils: pyrrole; 3- and 2-methyl-
1H-pyrrole; 2,5-dimethyl-1H-pyrrole; 2-ethyl-1H-pyrrole; 2,5-
and 2,3-dimethyl-1H-pyrrole; 2-ethyl-1H-pyrrole; 2-ethyl-4-
methyl-1H-pyrrole; 4-ethyl-2-methylpyrrole; 2,3,5-trimethyl-
1H-pyrrole; 2,5-pyrrolidinedione;
pyridines: aqueous phase: tetrahydropyridine (3.10); pyri-
dine (3.4); 2-, 3- and 4-methylpyridine (4.50, 5.40 and
5.46); 2,6-, 3,5- and 2,3-dimethylpyridine (5.90, 7.02 and
7.40); 2-ethylpyridine (6.36); 2-aminopyridine (9.08); 3-, 5-
and 4-methyl-2-pyridinamine (11.57, 12.03 and 12.16); 2,6-
dimethyl-4-pyridinamine (14.58); oils: 3- and 4-methylpyridine;
ethylpyridine; dimethylpyridine; 2-aminopyridine;
pyrimidines: aqueous phase: 2-pyrimidinamine (8.38); 2-amino-
4-methylpyrimidine (10.51); oils: 2-amino-4-methylpyrimidine
pyrazines: aqueous phase: 2-ethyl-3-methylpyrazine (14.08);
oils:—;
amides: aqueous phase: acetamide (3.90); propanamide
(5.53); 2-methylpropanamide (6.67); butanamide (7.76);
3-methylbutanamide (9.02); methacrylamide (10.49); 4-
methylpentanamide (12.35); picolinamide (16.07); oils:
acetamide; 4-methylpentanamide;
others: aqueous phase: aniline (8.13); acetal (3.16); 3,3-
dimethyloxetane (6.16); 2-methylbenzenamine (10.78); indole
feathers, aqueous fraction - ethylacetate extract
fetahers, pyrolysis oil
12 14 16 18 20
C10 C11 C12 C13 C14
Fig. 9. (Continued ).
(17.02); 5,5-dimethylhydantoin (17.85); 3-methyl-1H-indole
(19.46); 5-ethyl-5-methylhydantoin (19.96); oils: indole; 3-
methyl-1H-indole;
sulphides: aqueous phase: hydrogen sulphide (1.62); carbon
disulphide (1.93); methylethyldisulphide (2.56); dimethyldisulp-
hide (3.37); dimethyltrisulphide (7.92); dimethyltetrasulphide
(14.87); oils: hydrogen sulphide; carbon disulphide;
thiols: aqueous phase:—; oils: methanethiol (1.71); ethanethiol
(1.83); propanethiol (2.18); butanethiol (2.62);
thiazoles: aqueous phase: thiazole (3.25); 2- and 4-methylthiazole
(4.28 and 4.46); 3-, 4- and 5-methylisothiazole (4.97, 5.09
and 5.12); 2,4-dimethylthiazole (5.87); 2-ethylthiazole (6.10), 2-
ethyl-4-methylthiazole (8.04); oils: thiazole; 2-methylthiazole;
2,4-dimethylthiazole; 2-ethyl-4-methylthiazole;
thiophenes: aqueous phase:—; oils: thiophene (2.56); 3-
methylthiophene (3.69); dimethylthiophene (5.6);
other S compounds: aqueous phase: methylthiocyanate
(3.00); bis(methylthio)methane (4.79); dimethyl- and methyl-
thioformamide (9.39 and 9.91); 2-thienylamide (18.52); S8
sulphur (32.91); oils: 4-methylthiobutanenitrile (11.13); S8
sulphur.
The details of GC-MSD chromatograms showed that the main
compounds in pyrolysis oil from wool were pyrrole and toluene
at n-C8 in NP-gram, phenol at n-C10 , methylphenol at n-C11 ,
benzeneacetonitrile and phenol derivatives at n-C12 and benze-
nepropanenitrile and indole at n-C13 . Humps of the baseline are
observed at retention times greater than 10 min due to presence of
numerous decomposition compounds with similar structure that
were difficult to separate by the GC column. Clear identification
of structure was difficult to obtain for most compounds in this
range due to these humps that became noise for the peak signals,
as reported by other authors, too [23].
 M. Brebu, I. Spiridon / Journal of Analytical and Applied Pyrolysis 91 (2011) 288–295
The pyrolysis oils of wool contains aliphatic and aromatic nitri-
les (homologue series from acetonitrile to hexanenitrile and from
benzonitrile to benzenepropanenitrile), pyrole, pyridine and phe-
nol accompanied by their derivatives and also small amounts of
hydrocarbons such as benzene and aromatic derivatives and some
paraffins. Compounds with amine and amide functional groups
were also identified.
Many sulphur compounds were identified in pyrolysis oils but
their amount was very small. These compounds were thiols, thiop-
henes and thiazoles. 4-methylthiobutanenitrile was identified and
this might be an intermediary structure that could lead to isothia-
zole by cyclisation. Inorganic hydrogen sulphide and sulphur were
also found dissolved in pyrolysis oils.
The main organic compounds in aqueous fractions were ace-
tonitrile at n-C5 , acetal and pyrrole at n-C8 , phenol at n-C10 and
methylphenol at n-C11 . The number of compounds is much higher
in aqueous fraction compared to pyrolysis oils and clear identifi-
cation of heavier compounds was difficult to achieve due to poor
separation, similar to pyrolysis oils. Most of polar compounds parti-
tioned between aqueous fraction and pyrolysis oils thus they were
found in both fractions. Strongly polar compounds preferentially
shifted to the aqueous phase and they were not found in pyroly-
sis oils. This is the case of light aliphatic alcohols that were found
only in aqueous phase. Other classes of compounds found only in
aqueous phase were the homologue series of light aliphatic amides
and the pyrazine derivatives. Contrary, thiols and thiophenes were
found only in oil. Organic sulphides were found only in aqueous
phase while H2 S and CS2 were also found in oil. Acetonitrile went
mainly to the aqueous phase and explain the peak at n-C5 . Acetal
was found only in aqueous phase and this is the compound that
increased the size of NP-gram peak at n-C8 . Pyrrole and toluene
have different partition coefficients; therefore most part of pyrrole
went to the aqueous phase while toluene remained mainly in the
oil. Ethylbenzene, xylene and styrene were other aromatic hydro-
carbons that remained mainly in the oil. Ishizawa and Misawa
found that benzene, toluene and styrene were the pyrolysis com-
pounds from human hair whose amounts significantly differ among
individuals due to presence of particular amino acids in the hair
[24].
Only few differences were observed between pyrolysis products
of wool, hair and feathers, and these were mainly in the distribu-
tion of compounds in aqueous phases. Wool contained more phenol
at n-C10 as well as more 3-methylbutanamide, 2-aminopyridine
and 4-methylphenol at n-C11 that explained higher amounts of
medium compounds in n-C10 –n-C12 region of NP-grams—Fig. 8a.
Feathers contained more acetonitrile at n-C5 , acetamide at n-C8 ,
5,5-dimethylhydantoin at n-C14 (coming from condensation of two
alanine units) and 5-ethyl-5-methylhydantoin at n-C15 , that explai-
ned the peaks at the corresponding positions in the NP-grams. The
5-substituted derivatives of 2,4-imidazolidinediones (hydantoin)
resulted from lactam ring formation [25]. A complex peak was
found in the 18.9–19.4 min range of GC-chromatogram of aqueous
fraction from feathers that corresponds to the peak at n-C14 in NP-
gram. However a clear identification of the compounds was difficult
to achieve.
4. Conclusions
Keratin materials such as waste sheep wool, human hair and
chicken feathers thermally decompose in two main steps, each
one consisting of several overlapped stages. The degradation step
occurs in 170–300 ◦ C temperature range, and is dominated by the
evolution of inorganic gases (NH3 , CO2 , SCS, SCO, H2 S, and SO2 )
and of thiols. Nitriles and aromatics (from which phenol and 4-
methylphenol are the most important degradation compounds)
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are formed in the second step, above 300 ◦ C. The main classes of
heteroatom-containing compounds were nitriles, pyrroles, pyridi-
nes, amides, sulphides, thiols, thiazoles and thiophenes and they
originate from the initial amino acids in the composition of keratin.
Acknowledgements
Many thanks to Dr. Cornelia Vasile for valuable discussions,
to Ph.Dc. Oana Paduraru and Ph.Dc. Manuela Pintilie for TG-
MSD/FTIR analysis and to Dr. Mihaela Silion for Q-TOF MS
analysis. Support for Dr. Mihai Brebu from European Social
Fund—“Cristofor I. Simionescu” Postdoctoral Fellowship Program
(ID POSDRU/89/1.5/S/55216) is acknowledged.
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