Ecological Engineering 84 (2015) 370–374

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Ecological Engineering
journal homepage: www.elsevier.com/locate/ecoleng

Short communication

Conversion of spent mushroom substrate into micronutrient fertilizer

via biosorption in a pilot plant
Łukasz Tuhy a,∗ , Mateusz Samoraj a , Zuzanna Witkowska a , Piotr Rusek b ,
Katarzyna Chojnacka a
a
Department of Advanced Material Technologies, Faculty of Chemistry, Wrocław University of Technology, Smoluchowskiego 25, 50-372 Wrocław, Poland
b ˛
New Chemical Syntheses Institute, Al. Tysiaclecia Państwa Polskiego 13a, 24-110 Puławy, Poland

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

Article history: The paper presents a pilot-plant for the biosorption and the technology of the production of micronutrient
Received 9 January 2015 fertilizer components that are based on spent mushroom substrate with a qualitative and a quantitative
Received in revised form 16 July 2015 description as well as an economic analysis thereof. The biomass was enriched with zinc and manganese
Accepted 7 September 2015
ions, which resulted in good biosorption capacities: −15.84 and 11.81 mg/g for Zn(II) and Mn(II), respec-
tively. Material losses were/material loss was relatively low (about 10%). The efficiency of the system was
Keywords:
over 100 kg of micronutrient component per day and the price of the new preparation was estimated at
Biosorption
$4.76 per kg including labor costs and depreciation of the installation.
Pilot-plant
Spent mushroom substrate The pilot-plant for biosorption was shown to be an efficient method for the production of new prepa-
Kinetic models rations based on waste biomass and constituting an alternative to conventional micronutrient fertilizers.
Economic analysis The economic analysis of the system and the production of new preparations shows that it is also a
technology which does not require high investment and operation costs.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction The use of biomass in wastewater treatment provided many

Biosorption is defined as the property of biomass (or
biomolecule) to bind and concentrate ions or other molecules from
aqueous solution on its surface (Volesky, 2007). It is a phenomenon
based on the passive binding of molecules to the metabolically
inactive (non-living) biomass (Naja and Volesky, 2011).
Biosorption was widely examined on a laboratory scale where
the influence of the biomass and of its different physical param-
eters on the effectiveness of the process was taken into account
(Das et al., 2014). On a laboratory scale, biosorption was carried
out in batch (Khouni et al., 2012) or column reactors (Rubilar
et al., 2012). In both cases, pH, temperature, contact time and
biomass concentration have been reported as main factors affect-
ing biosorption efficiency (Netzahuatl-Munoz et al., 2012). In the
case of column reactors, it was reactor dimensions and flow rate
that were proved to be important for biosorption (Chauhan and
Sankararamakrishnan, 2011).
Abbreviation: SMS, spent mushroom substrate.
∗ Corresponding author.
E-mail address: lukasz.tuhy@pwr.edu.pl (Ł. Tuhy).
advantages over traditional methods. Low cost and easy availability
of biosorbents, easy recovery and hence a possibility of the reuse
seems to be the most important (Gupta et al., 2010).
The conducted studies and described applications of biosorption
mainly focus on wastewater treatment (Şener et al., 2014) while the
data describing the application of biosorption in other branches
of industry is poor. There are also some reports describing the
use of biosorption in the production of micronutrient dietary bio-
components for animals (Witkowska et al., 2014) or micronutrient
fertilizers (Tuhy et al., 2014).
Among many different types of biomass, spent mushroom sub-
strate (SMS) constitutes currently a point of interest due to its
sorption properties and potential for the application in industry
(Chang and Ren, 2015).
Every year UE produces more than 3.5 million tons of mush-
rooms (Gea et al., 2014). Spent mushroom substrate (SMS)
constitutes a waste from mushroom farms. Poland generates
1.5 million tons of spent mushroom substrate per year and the
amount is growing (Majchrowska-Safaryan and Tkaczuk, 2013).
SMS belongs to the group of agricultural waste materials, the uti-
lization of which is a subject of interest of many researchers. The
effective conversion route of the waste would enable cost reduction
of its disposal (Yan et al., 2014). SMS like other agricultural wastes

http://dx.doi.org/10.1016/j.ecoleng.2015.09.032
0925-8574/© 2015 Elsevier B.V. All rights reserved.
 Ł. Tuhy et al. / Ecological Engineering 84 (2015) 370–374 371

Fig. 1. Flow sheet of the experimental plant for biosorption (1 – water tank, 2 – pump, 3 – micronutrient solution tank, 4 – helical agitator container, 5 – feeding pump, 6 –
sorption reactors, 7 – spray nozzle, 8 – sorption basket, 9 – perforated bottom, 10 – biomass grinder, 11 – water treatment plant, 12 – impeller pump, 13 – peristaltic pump,
14 – filter press, 15 – dryer, 16 – liquid fertilizer tank, MS – micronutrient salts, BI – biomass, RB – enriched biomass, LF – liquid fertilizer, W – water, A – eluent stream, B –
enriched bio-mass stream, C – press filtrate, D – eluent).

has been shown to contain a number of organic compounds and 5

functional groups, which makes it a good biosorbent (Putra et al., y = 0.0084x - 0.25
4
2014) with promising properties to be used in agriculture (Tuhy R² = 0.8989
ln (Ct\(Co-Ct)

et al., 2014). 3
The aim of the present work was the production of micronutri-
2 Mn
ent fertilizer bio-components based on spent mushroom substrate y = 0.0019x - 0.0006
in a new pilot plant installation. The qualitative and quantitative R² = 0.9042 Zn
1
description as well as economic analysis was performed.
0
0 100 200 300 400 500 600
2. Materials and methods -1
t, min
2.1. Experimental plant for biosorption processes
Fig. 2. Linear plot of Yoon–Nelson model with experimental data for SMS enrich-
ment with Zn(II) and Mn(II).
The pilot plant for the biosorption process is presented in Fig. 1.

2.2. Biosorption process
As a biosorbent, spent mushroom substrate (SMS) delivered
by the mushroom farm “Hajduk” (Poland) was used. The biosorp-
tion of Zn(II) and Mn(II) by biological material was conducted in
the Experimental Plant for Biosorption (200 L column reactor) sepa-
rately for each micronutrient for 10 h. The concentration of zinc(II)
(ZnSO4 ·7H2 O, POCH, Poland) and manganese(II) (MnSO4 ·1H2 O,
POCH, Poland) in the solutions was about 500 mg/L for each process.
pH was regulated by pH regulator at 5. Biosorption was conducted
at 25 ◦ C. In each process, 20 kg of biosorbent was used. After each
batch, the suspension was transferred to the filter press (MONTECH
PKF 500) for biomass recovery. The final product was dried in an
industrial dryer (Hajnowka, Poland) at 50 ◦ C for 24 h. The content of
elements in the enriched biomass was examined by ICP-OES after
mineralization.
2.3. Multielemental ICP-OES analysis
The concentration of elements in digested biomass was deter-
mined by ICP-OES Varian-Vista MPX, Australia. Samples were
supplied with ultrasonic nebulizer CETAC U5000AT+. The analyses
were carried out in the Laboratory Accredited by the Polish Cen-
ter of Accreditation (PCA) according to PN-EN ISO/IEC 17025:2005.
All samples were analyzed in three repeats (results of analy-
ses were an arithmetic mean, the relative standard deviation
was <5%).
3. Results and discussion
3.1. Continuous flow studies
The comparisons of Yoon–Nelson, Thomas, Adams–Bohart, Wol-
borska model parameters, with the use of linear regression analysis
for Zn(II) and Mn(II) biosorption by SMS are shown in Table 1. The
linear plot of the Yoon–Nelson model with experimental data for
SMS with Zn(II) and Mn(II) are shown in Fig. 2.
Experiments showed that for all micronutrient ions, the
Yoon–Nelson and Thomas models gave a good fit for the biosorp-
tion of particular ions to SMS (R2 = 0.9181 and 0.9012 for Zn(II)
and Mn(II), respectively). The linearization of experimental data
according to the Adams–Bohart and Walborska models were char-
acterized by a worse fitting (Table 1). The Yoon–Nelson model
(Fig. 2) seems to be the best for the description of the biosorp-
tion process carried out in the pilot-plant presented here because
it requires the definition of a smaller number of process parameters,
and hence it is more universal and can fit description of biosorption
of other types of biomass undergoing biosorption in the pilot-plant.
372 Ł. Tuhy et al. / Ecological Engineering 84 (2015) 370–374

3.2. Economic analysis

0.8989

0.8989

0.6958

0.6958
0.9042

0.9042

0.8480

0.8480
R2
In Poland, 250–300,000 tons of mushrooms are produced every
year, which poses problems with storing, disposing, and utilization
of SMS (Kalembasa and Becher, 2012).
The biosorption in which spent mushroom substrate was
enriched with micronutrient ions essential in plant cultivation

kAB = 0.00728 [mL/min mg]

kAB = 0.00308 [mL/min mg]

kTh = 0.00924 [mL/min mg]
kTh = 0.0407 [mL/min mg]
(Zn(II), Mn(II)) was conducted. The enrichment of the biomass with
micronutrient ions in the pilot plant allowed for carrying out a
kYN = 0.0084 [1/min]

kYN = 0.0021 [1/min]

␤a = 0.0220 [1/min]
ˇa = 0.0200 [1/min]
preliminary economical analysis of the process. The number of fer-

q = 2.746 [mg/ml]

q = 7.143 [mg/ml]
qe = 15.71 [mg/g]

N0 = 2747 [mg/L]

N0 = 7214 [mg/L]
qe = 11.7 [mg/g]

tilizer components produced by the biosorption in the pilot plant

 = 29.8 [min]

 = 28.6 [min]
Parameters

and the degree of the enrichement of the biomass with micronu-

trient ions are shown in Table 2.
The cost of the disposal of spent mushroom substrate ranges
from $55 to $400. Some mushroom farms make SMS available for
free to farmers and the only cost of the acquisition is connected
with providing transport.
The material loss in the process was about 10%. The estimated
cost of the utilization of SMS to micronutrient fertilizer components
SMS + Mn

SMS + Mn

SMS + Mn

SMS + Mn
SMS + Zn

SMS + Zn

SMS + Zn

SMS + Zn
Material

by biosorption on a pilot plant scale was estimated at (1055$/tons).

The highest cost was generated by drying of the biomass, which
constitutes about 40% of the total cost. One of the methods to reduce
costs is to replace the tray dryer i.e. with a more efficient fluid bed
dryer.
(2)

(4)

(6)

(8)

The cost of the pilot-plant installation was estimated at $77,650.

Yoon–Nelson, Thomas, Adams–Bohart, Wolborska model parameters using linear regression analysis for Zn(II) and Mn(II) biosorption by SMS.

the time of total depreciation of the installation was assumed to

− kTh C0 t

amount to 5 years, thus yielding a 20% annual depreciation or $42.5.

U0
z
= kAB C0 t − kAB N0

It was assumed that the duration of one biosorption cycle was

ˇa H
v
= kYN t − kYN

8 h (6 h for biosorption and 2 h for additional works such as conser-

kTh qe x

−
Q

vation, biomass pretreatment, etc.), which gives 3 cycles per day.

ˇa c0 t

Due to process automation, one person is needed to conduct the

q
=


process during each cycle. To recap, the overall process requires

=
−1
Linear form

 

720 man-h per month (four people employed as full-time workers

 
C0 − Ct

C0

C0
Ct

Ct

Ct

c0
c

and one as a half-time employee). Assuming that the average salary



for a manual worker in Poland is $800 per month, the total monthly
ln

ln

ln

ln

labor cost ot the installation is $3600 ($120 per day).

The productivity of the pilot-plant is 108 kg of micronutrient
fertilizer component based on spent mushroom substrate per day.
(1)

(3)

(5)

(7)

The total cost of the production of the new preparation is $2.57.

The estimated market price was assumed to be 150% higher than


the production costs due to additional managing costs and the pro-
− kTh C0 t

ducer’s margin, all of which should amount to approximately $3.86,

∂ cb
∂H 2
U0
z

2
= exp(kYN t − kYN )

kAB C0 t − kAB N0

with a further possibilty of being reduced to about $3.25 if apply-

= Dax
 kTh1qe x 

ing an alternative way of drying of the final product. The proposed

Q

dosage of the new preparation is about 0.1–0.5% when mixed with

∂cb ∂q
∂t

NPK fertilizer, the price seems to be economically feasible.

Model equation

+
1 + exp

The production of fertilizer components derived from biosorp-

∂H

= exp

tion in a column reactor in a pilot plant constitutes an efficient and

+v
C0 − Ct

economically attractive process. The cost of the production of one

=

∂cb
Ct

∂t
C0

C0
Ct

Ct

batch of the new preparation (ca. 18 kg) is less than $70 wherein
∂

drying of the biomass constitutes the most expensive process

(about 40% of production costs). For this reason the improvement
of drying seems to be the most crucial step in the biosorption pilot
plant development.
Yoon–Nelson (Yoon and Nelson (1984))

Adams–Bohart (Loderio et al. (2006))

3.3. Perspectives
Wolborska (Trgo et al. (2011))
Thomas (Saadi et al. (2013))

The biosorption carried out in the pilot-plant was shown to

be efficient process with low material losses (7–10%). Conducting
biosorption in the pilot-plant made it possible to point out advan-
tages and disadvantages of the installation. Furthermore, as it was
shown, the costs of the installation and the total cost of the pro-
duction of micronutrient components produced in the pilot-plant
Model
Table 1

is relatively low. Among disadvantages, high energy consumption

of the drying chamber has to be pointed out. It can be overcome
 Ł. Tuhy et al. / Ecological Engineering 84 (2015) 370–374 373

by the application of a fluidal dryer enabling an approximately 40%

Amount [kg]
reduction in drying costs.
The technology described above can be applied in the pro-

18.2
18.0
duction of biological components with micronutrients (zinc and
manganese) and can be used in plant cultivation for enrichment
of edible parts of plants with essential microelements. Produced

3574 ± 464
4873 ± 633
micronutrient components can be delivered to plants with a typical
NPK fertilizer or separately. One of the advantages of this technol-
ogy is that fertilizer components can be produced without leaking

Fe
them into groundwater (in contrast to inorganic salts). In the use
The multielement content and the amount of materials produced in biosorption process in pilot plant (the content of micronutrients, which the biomass was enriched with, was marked in bold).

of the proposed technology causes micronutrients to be bound to

the surface of the biological material which is fully biodegrad-
91.35 ± 12
91.50 ± 12
able. Micronutrients delivered to plants as bio-preparations are
characterized by comparable bioavailability while their release is
controlled by the equilibrium constant of groups located on the sur-
Cu

face of the biomass and participating in biosorption, which enables

a release of micronutrients in a controlled manner (Michalak et al.,
11,810 ± 1535

2013). Additionally, the biomass of SMS which is converted to the

488.5 ± 64

micronutrient components was shown to be a rich source of ele-

ments such as K, P, S, Ca in assimilable forms. It was proved that
Mn

through the application of the proposed technology, there is a

Micronutrients [mg/kg]

possibility to cultivate plants biofortified with an increased con-

tent of microelements (from 8 to 31%) without tampering with
15,840 ± 2059

the genotype (data not published). The proposed technology of

591.8 ± 77

the production of micronutrient components with the use of SMS

was examined on a laboratory scale and its effectiveness con-
firmed in the pilot plant system. Furthermore, the positive effect
Zn

of the application of SMS biocomponents with micronutrients on

plant quality and plant yield was proved in seed testing on a
595.8 ± 119
536.9 ± 107

laboratory scale and in environmental conditions in field tests car-

ried out on maize. Taking into account all aspects pointed above,
the described technology achieved Technology Readiness Level
Na

(TRL) 5.
A further search for new biological material drying methods and
for new types of the biomass which can potentially be used for the
3558 ± 712
3619 ± 724

production of micronutrient fertilizer components can both lead to

an increase in the portfolio of new micronutrient fertilizer products
Mg

and significantly reduce production costs.

88,160 ± 17,632
101,900 ± 20,380

4. Conclusions

The pilot-plant installation for biosorption as proposed here

was used for the production of micronutrient fertilizer compo-
nents derived from the biomass of spent mushroom substrate.
Ca

The enrichment of SMS with micronutrients can be described by

the Yoon–Nelson and Thomas models. The technology advanced
36,940 ± 7388
42,600 ± 8520

here made it possible to efficiently produce large amounts of

biomass enriched with micronutrients. The economic analysis of
the installation and the production of new preparations show
that it is also a technology which does not require high financial
S

outlays.
2261 ± 452
1991 ± 398

Acknowledgments
Macronutrients [mg/kg]

The work was supported by the Polish National Center for

K

Research and Development, under Grant no. N R05 0014 10

and the Polish National Science Center, under Grant no. UMO-
12,190 ± 2438
12,490 ± 2498

2012/05/E/ST8/03055.

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