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Abstract: Nano-porous keratin fiber is effective in removing heavy metals from solutions. The biosorption
of heavy metals from solutions is dependent upon the solution pH, the contact time, surface area and
temperature. The intrinsic properties of the keratin fiber, ie stability over a wide range of pH, structural
toughness and high surface area, are the positive factors. Alkaline ultrasonic treatment of the keratin
fiber resulted in a multi-fold increase in metal uptake. Adsorption of heavy metals using both batch and
column operations was conducted. Multiple elution and adsorption tests indicated that it is possible to
reuse keratin fiber as a biosorbent for a number of cycles.
2004 Society of Chemical Industry
∗ Correspondence to: P Kar, Department of Metallurgical and Materials Engineering/MS388, University of Nevada Reno, Reno, NV 89557,
USA
E-mail: pkar@unr.edu
Contract/grant sponsor: MaXim LLC, Pasadena, CA, USA
(Received 31 March 2004; revised version received 29 June 2004; accepted 6 July 2004)
Published online 7 September 2004
2004 Society of Chemical Industry. J Chem Technol Biotechnol 0268–2575/2004/$30.00 1313
P Kar, M Misra
800
600
400
X 200.000
Z 4.648
200
Keratin Protein Fiber
numbers obtained analytically some of the experi- to claim that both wool and avian keratin bind metal
ments were repeated in their entirety. Blank samples cations at the same sites (ie the carboxylic group).
containing deionized water were used intermittently However, the exact mechanism of chemiosorption
as internal checks to test the dependability of AA cal- of metal cations onto avian keratin fiber is not
ibration. For each sample the AA took three readings fully understood for all metals (cations and anionic
and gave the final result, which was the average of all complexes) at very acidic and alkaline pH values.
three readings. It may also be added that removal of metals like
mercury and chromium at very acidic pH values may
be occurring by binding of anionic mercury complexes
RESULTS AND DISCUSSION to disulfide bonds.
Batch test results
Removal of heavy metal by batch mode Removal of heavy metals from a mixed-metal solution
Copper, lead, chromium, mercury and uranium are Tests were performed on two different combinations
among the heavy metals removed from solutions using of mixed metals as follows: (1) three-metal solution,
the keratin fiber. Table 1 shows the different metals, and (2) five-metal solution.
corresponding pH and the metal loading. Cations
like copper and lead were removed from solutions
Three-metal solution. Solutions (100 cm3 ) containing
most effectively between pH 5 and 6. Chromium and
about 2 ppm of Cu, Pb, and Hg at three different pH
mercury were removed better at relatively lower pH
values, ie 1.9, 5.5, and 5.9, were conditioned with
values. Uranium removal was observed at relatively
0.3 g of keratin fiber. The filtrate was analyzed for Cu,
alkaline pH values. The rate of removal was rapid
Pb, and Hg. As shown in Table 2, the removal was of
and the adsorption process was close to completion in
the following order: Pb > Hg > Cu at pH 5.5 and 5.9.
30 min. It was interesting to observe that the increase
The result subscribes to the belief that biosorption of
in the amount of adsorbate (or the keratin fiber) did
metal cations onto keratin protein fiber is better when
not affect the metal uptake markedly in the batch tests;
the metal cation is higher in atomic weight, thus lead is
this may be due to the presence of hydrophobic groups
adsorbed better than copper because its atomic weight
in the surface of fiber which make mixing difficult in
is greater. At the same time mercury, though highest in
water solutions.
atomic weight, is believed to form an anionic complex
Metal removal by keratin occurs by a combination
in solution and thus showed better adsorption at the
of physiosorption and chemiosorption. Physiosorption
lower pH, unlike Pb and Cu.
occurs by trapping of metal ions in the nano-porous
network in the fiber. Chemiosorption is believed to
occur at the carboxylic binding sites of wool keratin Five-metal solution. Solutions (100 cm3 ) containing
in the pH range of 2–6.17,18 In this pH range about 2 ppm of Cu, Pb, Zn, Cd, and Ni at three
metal cations compete with protons for the available different pH values, 4.2, 5.0, 5.6, were conditioned
carboxylic binding sites. Therefore after the removal with 0.2 g of keratin fiber. As shown in Table 2, the
of heavy metals from solutions, protons are released highest metal removal occurred at pH 5.6 and the
into the solution, decreasing its pH. Reconfirming the removal was in the following order: Pb > Cu > Cd >
above mechanism it has been observed that the pH Zn > Ni. The higher removal of lead compared with
decreases as a result of the removal of heavy metal copper can be explained by the same reasoning as
cations from solutions by keratin fiber. Moreover, given in the previous paragraph, ie the greater the
since wool keratin and avian keratin fiber both belong
to same class of material (ie keratin), it may be safe Table 2. Metal removal from mixed metal solutions, ie three-metal
and five-metal solutions
Table 1. Different heavy metals, the corresponding pH range for
Three-metal solution
removal by keratin fiber and the maximum loading onto keratin fiber
Removal (%)
Loading (milligrams of heavy
Metals pH range metal per gram of keratin)
pH Cu Pb Hg
Pb 5 or above 3.83 (batch tests)
1.9 0 0 97.6
5.33 (ultra-fine)
4.5 56.2 100 92.3
9 (alkaline-ultrasonically
5.6 62.1 100 89.6
processed and batch mode)
12 (alkaline-ultrasonically Five-metal solution
processed and column mode)
Removal (%)
Cu 4 or above 3.25
Zn 4 or above Very small
pH Cu Pb Zn Cd Ni
Ni 5 or above Very small
Hg 2–6 4.36 4.2 38.20 69.70 0.00 9.70 10.90
U 5–8 Not verified 5.0 45.65 78.60 2.10 14.50 7.00
Cr 1.5–6 3.50 5.6 48.80 83.50 3.80 17.00 10.10
atomic weight the better the metal cation uptake-by concentration of 10 ppm, could be purified, meeting
the keratin fiber. Also, it can be inferred from these the United States Environmental Protection Agency
results that the keratin fiber removes very low amounts (USEPA) standard (ie 20 ppb). In the second cycle
of Zn, Cd and Ni. Why Zn, Cd and Ni did not show 40 dm3 of the same solution were purified (meeting
substantial adsorption is still not clear, but the results the EPA standard). Subsequent cycles could have
demonstrate the cation selectivity of the keratin fiber. resulted in the purification of larger volumes of the
solution. The results are shown in Fig 6. Desorption
Column test results tests confirmed that 99% of the lead can be removed
Biosorption of uranium—column adsorption of uranium from the keratin by washing with hydrochloric acid.
from Gerlach water The amount of lead uptake during column experi-
Drinking water in Gerlach (a town in the state of ments was 12 mg per gram of keratin as compared
Nevada, USA) contains 150 parts per billion (ppb) of with 9 mg per gram (on average) in the batch tests
(discussed in the next section) using alkaline ultra-
uranium, it is naturally occurring. However, it violates
sonically processed material. The higher uptake in the
the drinking water standard for uranium, which is
column mode is attributed to better contact between
20 ppb. The keratin fiber was successfully tested for
adsorbate and adsorbent.
uranium removal from this water. The pH of the
water was 7.8. The results of uranium removal from
the Gerlach water, conducted in the packed column Effect of alkaline ultrasonically processing
using 100 g of the keratin fiber, are given in Fig 5. Ultrasonic waves have been used for many practical
As can be seen, the column-packed keratin fiber is applications because these affect the surface properties
capable of purifying the uranium to meet the drinking by increasing the surface area and altering the surface
water standard of 20 ppb; 30 dm3 of the water was chemistry of a material. Ultrasound was used to
successfully purified by the column. process keratin fiber after mixing it in an alkaline water
solution. The treatment modified the keratin fiber
surface by increasing the surface area (by the cavitation
Continuous column adsorption of lead using the alkaline effect) and by embedding hydroxyl ions in it. These
ultrasonically processed keratin fiber hydroxyl ions brought about surface precipitation of
A column adsorption test was conducted using alkaline heavy metals. The treatment, as described earlier
ultrasonically processed keratin fiber (see ‘Materials in the Materials and Methods section, was carried
and Methods’ section for description of the process- out by mixing keratin fiber (as-received) in alkaline
ing). Ultrasonically processed keratin fiber (135 g) was solution (pH between 11 and 12) and exposing
packed into a column (schematic as shown in Fig 4); the solution to ultrasound at different frequencies.
105 dm3 of the solution having 10 ppm lead were Treatment was done in the continuous mode using an
successfully purified using the column. In the first col- ultrasonic frequency of 16 or 20 kHz or combination
umn cycle 65 dm3 of lead solution, having an initial of the two and also in a batch mode using an
ultrasonic frequency of 24 kHz. The uptake of lead
using ultrasonically-treated keratin fiber is given in
180 Table 3. As can be seen, the continuous mode of
treatment yielded better lead removal than the batch
150 45
40
Final Concentration (ppb).
Cycle-I
Effluent Lead Concentration (ppb).
120 35 Cycle-II
30 EPA Standard for Lead
90 25
20
60 15
10
30
EPA standard 5
0
0 0 10 20 30 40 50 60 70 80
0 10 20 30 40 50 Volume Passed (liters)
Volume of Gerlach Water Passed (litres)
Figure 6. Plot of Effluent Lead Concentration vs Volume Passed,
Figure 5. Plot of Uranium Uptake from Gerlach Water (containing results from the continuous column test using the alkaline
150 ppb Uranium) using keratin fiber. Nearly 30 liters of water ultrasonically processed fiber. The fiber filtered almost 50 liters of lead
contaminated with low concentration of uranium was filtered using in the first pass and about 40 liters of lead after washing and
the as-received keratin fiber. regeneration.
Removal (%)
Effect of size reduction
It is difficult to grind the keratin fiber, however size 30
reduction could be achieved by grinding in a ball-mill
having the brand name ‘SPEX Mill’. The Particles
size, decreased as a function of grinding time and the 20
four different particle sizes so obtained are given in
Table 4. Tests performed with ground keratin fiber Initial Conc. - 10ppm
show a marked increase in the heavy metal uptake Initial Conc. - 20ppm
10
(shown in Table 4). This may be due to increase in Initial Conc. - 30ppm
the surface area and exposure of the functional groups Initial Conc. - 40ppm
responsible for metal binding. However, size reduction
0
is a difficult and an energy-intensive process and not 0 5 10 15 20 25 30
feasible commercially. Time (hours)
16 (continuous) 91
20 (continuous) 85 20
16 and 20 (continuous) 89
24 (continuous) 80
10
Table 4. The loading to keratin fibers of different sizes (please note
that sizes here do not refer to that of a single fiber but to a single unit
which is a cluster of numerous single fibers) 0
0 5 10 15 20 25 30
Loading Time (hours)
(milligram
Figure 8. Removal of Copper at 35 ◦ C, removal improved from the
of lead
25 ◦ C case although the same trend of low removal (%) at high
Product Approximate per gram
concentration was observed.
identification Product obtained size (µm) of keratin)
Coarse Supplied by Maxim in 1000–5000 3.83 capacity of the keratin fiber was believed to be almost
October 2000 reached for the degree of contact between metal
Medium Supplied by Maxim in 300–1000 4.39 cations and keratin fiber for limitations attributed
December 2000 to improper mixing (ie the adsorbate–adsorbent
Fine 7.5min grinding in 200–500 4.41 contact) in the batch test experimental mode, etc.
SPEX Mill
Temperatures higher than 45 ◦ C were not considered
Ultra Fine 20min grinding in 15 5.33
because the fiber material is believed to be destabilized
SPEX Mill
at the higher temperatures. Though tests for the
70
ACKNOWLEDGMENT
60
We thank MaXim LLC, Pasadena, CA, USA, for
Initial Conc. - 10ppm
Initial Conc. - 20ppm
supporting this work.
Removal (%)