SIFT DESK Abderahim Ahmadou et al.

Journal of Food Science & Technology (ISSN: 2472-6419)

Effect of pyrolysis temperature on ochratoxin A

adsorption mechanisms and kinetics by cashew nut shell biochars

DOI: 10.25177/JFST.4.7.RA.565
Research
Received Date: 22nd Aug 2019 Copy rights: © This is an Open access article distributed
Accepted Date: 05th Sep 2019 under the terms of International License.
Published Date:10th Sep 2019

Abderahim Ahmadou 1,2,4, Nicolas Brun 5, Alfredo Napoli 3, Noel Durand 1,2, Didier Montet1,2
1. Centre de Coopération Internationale en Recherche Agronomique pour le Développement (CIRAD), UMR
QualiSud, 73 rue Jean-François Breton, 34398 Montpellier Cedex 5, France
2. Qualisud, Université de Montpellier, CIRAD, Montpellier SupAgro, Université d'Avignon, Université de
La Réunion, Montpellier, France.
3. Centre de Coopération Internationale en Recherche Agronomique pour le Développement (CIRAD), UR
Biowoeb, 73 rue Jean-François Breton, 34398 Montpellier Cedex 5, France
4. Institut Polytechnique Rural de Formation et Recherche Appliquée (IPR/IFRA) de Katibougou, 45 Route
de Koulouba, Annexe de Dar-Salam Bamako, Mali
5. Institut Charles Gerhardt, ENSCM, 34296 Montpellier Cedex 5, France

CORRESPONDENCE AUTHOR
Abderahim Ahmadou
E-mail: abderahim.ahmadou@cirad.fr ; ORCID of the author: 0000-0002-9130-0767

CITATION
Abderahim Ahmadou, Nicolas Brun, Alfredo Napoli, Noel Durand, Didier Montet, Effect of pyrolysis temper-
ature on ochratoxin A adsorption mechanisms and kinetics by cashew nut shell biochars (2019)Journal of Food
Science & Technology 4(7) p:877-888

ABSTRACT
Biochars were produced from cashew nut shell at 400, 600 and 800°C. Production temperature significantly
affected biochar properties and consequently the adsorption mechanisms of ochratoxin A. Biochars produced
at higher temperatures had significantly higher specific surface areas, resulting in higher OTA adsorption ca-
pacities.

The isotherms and kinetics of the adsorption were used to identify the adsorption mechanisms. For the kinetics
study, experiments were carried out after adjustment of the parameters influencing the system, such as pH,
biochar quantity and OTA initial concentration. Experimental results were modelled according to isotherm
equations representing Langmuir model and Freundlich model. Langmuir model matched best with the experi-
mental data. The chemical surface reaction was fitted to a pseudo-second order equation, with very high re-
gression coefficients.

Keywords: Biochar, Adsorption, Ochratoxin A, Isotherms, Kinetics

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1. INTRODUCTION applied way of protecting animals against the harmful

Mycotoxins are low molecular weight secondary me- effects of mycotoxins present in animal feed. Most
tabolites produced by filamentous fungi that have studies related to the prevention of mycotoxicosis by
adverse effects at low levels on humans and animals. the utilization of adsorbents are focused on alumino-
They have a significant impact on economies and silicates, mainly zeolites (clinoptilolite) and benton-
international trade. Fungi producing mycotoxins are ites (montmorillonite) [9], [10].
known as mycotoxigenic. Some of them are capable
of producing more than one mycotoxin and some my- Different strategies, including preventive pre- and
cotoxins are produced by more than one fungal spe- postharvest measures, have been developed to neu-
cies. [1] tralize mycotoxins in animal feed such as good agri-
cultural practices (GAP) and good storage practices
They appear in the feed chain because of fungal in- (GSP). These actions are considered the best way of
fection of crops, and due to the use of mouldy grains controlling mycotoxin contamination; however, even
and forage as components of animal feed. Fungi can exercising of good practices might not completely
invade and produce mycotoxins on the growing avoid or eliminate mycotoxins in the feed chain [11].
plants before harvesting (pre-harvest toxins) or pro- Moreover, the use of physical and chemical methods
duce toxins after harvest and during crop storage and for the detoxification of agricultural commodities
transportation (postharvest toxins). In general, envi- contaminated with mycotoxins is restricted due to the
ronmental conditions, such as high temperatures, high problems associated with safety issues, possible loss-
moisture levels, and insect damage, cause stress and es in nutritional quality coupled with limited efficacy
predispose plants in the field to mould growth and and cost implications [12].
mycotoxin contamination [2]. Moreover, poor har-
vesting practices, improper drying, handling, packag- As mycotoxins cause serious diseases in farm ani-
ing, and transport conditions contribute to increase mals, the EU approved the use of mycotoxin-
the risk of mycotoxin production [3]. detoxifying agents, by including a new group of feed
additives defined as ‘substances that can suppress or
In recent years, mycotoxin contamination of cereal reduce the absorption, promote the excretion of my-
grains and animal feeds has evoked global concern cotoxins or modify their mode of action’ [11]. At the
for potential health risk on humans and animals. So same time, the EFSA reported a review of mycotoxin
far, more than 300 mycotoxins have been identified -detoxifying agents used as feed additives that cov-
worldwide. [4]. Ochratoxin A (OCHRA) is produced ered aspects such as mode of action, efficacy and
by several fungi of Penicillium and Aspergillus gene- feed/food safety. Since then, numerous studies have
ra, primarily by P. verrucosum, A. ochraceus and A. been published on the efficacy of the adsorbing
carbonarius. It is a potent nephrotoxin and has been agents [11], [13], [14], [15], [16], [17].
associated with fatal human kidney disease. This
compound is also genotoxic and teratogenic and has However, most studies still focus on the efficacy of
been classified as a possible human carcinogen [5]. adsorption of a specific compound as well as to clas-
sify mycotoxin adsorbing agents (minerals, organic
The economic consequences of mycotoxin contami- and synthetic) for feed decontamination, focusing on
nation are very significant, and often crops with large adsorbents with the ability to bind to multiple myco-
amounts of mycotoxin have to be destroyed. The toxins, which are in great demand of animal feed pro-
most susceptible crops to contamination with myco- ducers, but are still little studied in scientific litera-
toxins are cereals such as wheat, maize, barley, rye ture.
and oat [6], [7], [8]
The goal of adding adsorbents to the feed of livestock
Utilization of adsorbents in animal diets is the most and poultry is to alleviate harmful effects of mycotox-

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ins by preventing their passage into the animal’s scribed by Bordoloi et al. (2015) [26]. Twenty g of
blood and organs via complex formation between biomass samples were placed into the reactor at ambi-
adsorbents and mycotoxins [18]. ent temperature. The heating rate of the reactor was
5°C per min to rise the selected peak pyrolysis tem-
Biochar is a carbon-rich substance produced by sub- perature of 400, 600, 800°C, under constant flow rate
jecting biomass to pyrolysis (i.e., in the absence of of nitrogen at 30 L/min. Residence time into the reac-
oxygen) [19], playing an important role in controlling tor was fixed at 1 h after reaching the peak tempera-
transport and bioavailability of organic contaminants. ture. The cooling step of biochar was done by natural
Recently, biochar has drawn substantial attention as a convection.
promising adsorbent and an effective means of se-
questering pesticide residues in soil [20], [21], [22] Mass yield of biochar was calculated using the fol-
and thus biochar may help to reduce human risk to lowing equation [27]:
environmental pollutants [19]. However, the effec- X 100
Mass yield (%) =
tiveness of biochar for sequestering pesticides from
contaminated soil varied in many aspects, e.g., de- Where, Wf is the mass (g) of the dry biochars and Wo
pending on biochar properties, soil properties, and is the mass (g) of the dry biomass.
environmental factors [23]. Biochar properties can
vary dramatically depending on both the temperature 2.3. Biochar characterization
and biomass source used for its production, and the Before any analysis and tests, the different biochars
properties can substantially impact the capacity to were ground and sieved at 200 µm.
absorb pesticides [24], [25]. Moisture and ash contents analysis were done by
heating the samples in oven air at 105°C for 24 h and
The objective of this research was to study the effect to 710 ± 10°C for 2 h, respectively, and weighing the
of production temperature on ochratoxin A adsorption residue.
capacity by various biochars obtained from cashew
nut shell produced in three pyrolysis conditions. Cor- Volatiles analyses were done by heating the samples
relations between pyrolysis temperature on biochar without air to 900°C for 7 min using Nabertherm ov-
properties and its OTA adsorption capacity were esti- en.
mated.
The total content of C, N and H were determined us-
2. MATERIALS AND METHODS ing a dry combustion method using Variomacrocube
2.1. Biomass CHN analyzer. The O + S content was determined by
The cashew nut shell is a co-product resulting from subtracting the ash and C, N and H contents from the
kernel extraction activity. It was purchased from total mass of the sample.
"Agribusiness Mali" located in Bamako, Mali and
conditioned in a room at 20°C and at a hygrometry of The pH of biochar was determined according to No-
66 % HR for more than 72 h in order to have a homo- vak et al. (2009) [28] and Cheng and Lehmann (2009)
geneous biomass; its moisture and elemental compo- [29]. Two grams of biochar (ground and sieved at 200
sition was measured before pyrolysis. Biomass µm) were shaken with 40 mL distilled water for 30
(cashew nut shell) was pyrolyzed without prior grind- min. This suspension was allowed to stand for 10 min
ing. before measuring the pH with a pH electrode pH Lab
(Mettler Toledo).
2.2. Biochar production technology
Pyrolysis experiments were conducted in a horizontal The Hitachi-S4800 was used for scanning electron
fixed-bed tubular reactor (Fig. 1) in which the tem- microscope (SEM) to evaluate the morphology of the
perature was controlled using a PID controller as de- different biochars.
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chased from R-Biopharm France.

Carbon dioxide adsorption isotherms were recorded
on a 3FLEX Physisorption instrument 2.4.2 Effect of biochar production temperature on
(Micromeritics) at 273 K between 0 and 1 atm (i.e. OTA adsorption
relative pressure between 0 and 0.028). The mi- The pyrolysis temperature is an important parameter
croporous specific surface areas of biochars were that plays on biochars physicochemical properties.
determined by applying the Langmuir model. Mi- Biochar production temperature effect on OTA ad-
croporous volumes were determined at a relative sorption was carried out by stirring 1000 mg of each
pressure of c.a. 0.028. biochar (400, 600 and 800°C) with 5 mL of the
water/methanol solution (w/w) containing OTA at 38
2.4. Ochratoxin A adsorption ng / mL in a 50 mL falcon tube . The whole solution
OTA adsorption onto the different biochars depended was stirred at 500 vibrations per min for 45 min.
on biochar intrinsic properties, modalities, and con- After, 2 mL of each filtrate was collected and filtered
tact duration between biochar and OTA. In this sense, with a syringe and then analyzed by HPLC to deter-
different conditions have been studied (pH, mass ef- mine OTA residual concentrations.
fect, pyrolysis temperature effect) and contact time
have been considered. 2.4.3. Study of biochar mass effect on OTA adsorp-
tion
The three biochars produced at 400, 600 and 800°C The tests were carried out by stirring 5 mL of the wa-
were previously ground and sieved at 200 µm. The ter-methanol solution (w/w) containing OTA at 38
different conditions used are described below. Each ng / mL, with different masses (25, 100,175, 250, 500
test was performed in triplicate. and 1000 mg) of the three different biochars in a 50
mL falcon, under constant stirring of 500 vibrations /
2.4.1. Preparation of water-methanol mixture con- min, for 45 min at pH 6.54. After 2 mL of each fil-
taining mycotoxins trate was collected and filtered with a syringe and
Generally, pH plays an important role during myco- then analyzed by HPLC to determine OTA residual
toxins adsorption because animal feed additives first- concentrations.
ly gather in stomach where the pH value is below 3.5
and then pass through the intestine where the pH val- 2.4.4. Study of pH effect on OTA adsorption
ue is 6.5. pH has also an important effect on soil The pH of the water-methanol solution containing
quality and crops yield. pH of the soils varied accord- OTA at 38 ng / mL was adjusted to 4.15, 6.54 and
ing to the zones and range from acidic pH (5) to an 9.05 by using solutions of 1 M HCl or NaOH.
alkaline pH (8.5). Soil pH can change the surface 250 mg of each biochar was added in 5 mL water-
chemistry of the biochar in soil and thus affect the methanol solution (w/w) containing 38 ng / mL OTA
biochar adsorption capacity. Three different pH solu- at pH 4.15, 6.54 and 9.54 in a 50 mL falcon, under
tions were tested to measure the effect of pH on the constant agitation of 500 vibrations / min, for 45 min,
adsorption of OTA by biochars. then 2 mL of each filtrate was collected and filtered
for HPLC analysis.
To get an acidic pH, the pH of the water was de-
creased to 4.15 by using 1 M HCl solution. To get a 2.4.5. Study of contact-time effect on OTA adsorp-
basic pH, pH of water was increased to 9.05 by using tion
1 M NaOH solution. The contact-time effect on OTA adsorption by the
different biochars tests were carried out by adding
A 50/50 water-methanol solution (w/w) was prepared 250 mg of each biochar (400, 600 and 800°C.) in 5
to solubilize OTA standard until to obtain a concen- mL of water-methanol solution (w/w) containing
tration of 38ng/mL. The OTA standard was pur- OTA at 38 ng / mL at pH 6.54 with constant stirring

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of 500 vibrations / min during 45 min. Samples were (1 µg/mL; ref PD 226 R. Biopharm Rhône Ltd, Glas-
taken at different intervals time and final OTA con- gow, UK).
centration was determined by HPLC after filtration.
3. RESULTS AND DISCUSSION
2.4.6. Study of OTA concentration effect on bio- 3.1. Biochar characterization
chars The moisture content of the cashew nut shell after
In order to build a sorption isotherm for each biochar, stabilization in climatic room was 5.35% at 20°C and
250 mg of biochar was added to 5 mL water- the standard deviation was 0.28. Its Carbon, Hydro-
methanol solution (w/w) containing different OTA gen and Nitrogen contents were respectively 50.04,
concentrations (25, 35, 55, 75 and 100 ng/ mL) at pH 3.89, and 0.42%.
6.54 under constant stirring of 500 vibrations / min
during 45 min. Samples were taken at different inter- As shown in Table 1, biochar yield decreased logical-
vals time and after filtration the final OTA concentra- ly with increasing pyrolysis temperature. It may be
tion was determined by HPLC. due to the conversion of compounds such as cellu-
lose, hemicellulose and lignin into carboneous prod-
Pseudo first order, pseudo second order are two of the ucts, water and CO2.
most commonly used kinetics models to reveal the
time-dependence of adsorption [30]. They were used Biochar yield decreased from 25.02 % for the biochar
to simulate the kinetics data: produced at 400°C to 21.54 % for the biochar pro-
qt = qe (1-e-k1t) (1) duced at 800°C (Table 1).
2
qt = (k2 qe t ) / (1 + k2qet) (2)
Ash content increased with the increase of tempera-
−1
Where k1 (min ) is the constant rate of pseudo first tures from 8.85% at 400°C to 12.65% at 800°C
order adsorption, k2 (g/mg/min) is the pseudo second (Table 1). This was due to the increase in the relative
order constant rate. abundance of the minerals that were stable during
In Eq. (2), qe (mg/g) is the equilibrium adsorption carbonization [32].
capacity, and qt (mg/g) in each equation is the ad-
sorbed ochratoxin A at time t. The results of the proximate, ultimate analyses of the
biochars are summarized in Table 1. They revealed
The equations were linearized to facilitate constants that carbon content increased with pyrolysis tempera-
determination and the application results of these dif- ture. The biochar produced at 800°C had a highest
ferent models allowed us to identify the main step carbon content of 87.42% and Biochar produced at
that leads OTA global adsorption mechanism of the 400°C had the lowest carbon content (70.04%).
different biochars.
In contrast to carbon content, the volatile matters log-
2.5 Ochratoxin A analysis ically decreased with increasing pyrolysis tempera-
OTA was quantified by HPLC using a fluorescence tures from 400 to 800°C. Recovered volatiles were
detector (Shimadzu RF 20A, Japan) [31]. The operat- highest with 21.90% in biochar produced at 400°C
ing conditions were as follows: injection volume of and 10.22% for biochar produced at 800°C.
100 µL; C18 reverse-phase HPLC column, Upti- Biochar solution pH varied from pH 10.61 (400°C) to
sphere type, ODS, 5 µm particle size, 5 ODB, 250 x pH 9.81 (800°C). Our biochars were thus strongly
4.6 mm, with identical pre-column, thermostatically alkaline. Previous literature reported biochar pH val-
controlled at 35°C; isocratic flow rate of 1 mL/min ues (without further processing of biochars) between
(mobile phase: methanol/water/acetic acid, 69/30/1); pH 4 and pH 12, with typical values being above pH
excitation wavelength of 333 nm and emission wave- 7. Zhao et al. (2013) found biochar pH levels between
length of 460 nm. The contents were calculated from 8.8 and 10.8, depending of biomass feedstock type.
a calibration curve established from an OTA standard
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Table 1. Properties of biochar at different temperatures

Sample Pyrolysis Elemental composition VM (%) FC Ash (%) pH Biochar
tempera- yield (%)
ture
(°C) C (%) H (%) N (%)

Cashew 400 70.04 3.65 0.61 21.90 69.85 8.25 10.61 25.02
Nut Shell
Cashew 400 83.51 2.06 0.59 14.08 77.39 8.53 9.83 23.13
Nut Shell
Cashew 400 87.42 0.85 0.89 10.22 77.13 12.65 9.81 21.54
Nut Shell
VM: Volatile Matters
FC: Fixed Carbon

Fig.2. Influence of pyrolysis temperature on CO2 ad-

sorption by different biochars
Fig.1. Scanning electron microscopy (SEM) images
of biochars prepared from cashew nut shell at differ- The Langmuir surface area of cashew nut shell bio-
ent magnification chars was strongly affected by production tempera-
(a)Raw cashew nut shell; (b) Biochar 400°C; (c) Bio- ture. The specific surface area of biochar pyrolyzed
char 600°C; (d) Biochar 800°C at 400°C reaches 151 m2/g, climbs to 250 m2/g at
600°C and dramatically increases to 306 m2/g for the
The morphology of raw cashew nut shell and its bio- biochar produced at 800°C. The increased surface
char (after pyrolysis) are shown in Fig. 1. Scanning area suggests that micropores in biochar gradually
electron microscopy observation shows some differ- developed with increased production temperature in
ences in size and shape of the particles. 400–800°C, which was also observed in previous
studies [33].
On the raw cashew nut shell is observed a coating
which corresponds to the cashew nut shell liquid For the three biochars produced at 400, 600 and 800°
(CNSL) which is a major compound among the con- C the micropore volumes are respectively 0.05, 0.09
stituents of the cashew nut shell; but after pyrolysis, and 0.11cm3/g (table 2).
the images (b,c and d) show an absence of the CNSL, The dramatic increase in surface area from 400°C to
which is due to its thermal decomposition under heat 800°C was due to the decomposition of lignin and
effect. All biochars have different shapes and sizes quick release of H2 and CH4, which generates signifi-
with the presence of porosity and the particles have cant densities of micropores [34].
quite varied dimensions.

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Table 2. Porous characteristics of biochars

Biochar 800°C Biochar 600°C Biochar 400°C
BET surface area (m2/g) # 306 250 151
Micropore volume (cm3/g) § 0,11 0,09 0,05
#
Langmuir theory; §Micropore volume determined at p/p0 0,028

3.2. OTA adsorption results To avoid an ineffective overdose, it is therefore use-

3.2.1. Biochar production temperature effect on ful to work with biochar mass ≤ 500 mg.
OTA adsorption To determine the adsorption capacities by saturating
With 1000 mg of each biochar in 5 mL of water- all the probable sites, we chose to work with 250 mg
methanol solution (w/w) containing OTA at 38 ng / of biochar.
mL; we observed a difference in OTA adsorption
rates which was mainly related to the increase in the
pyrolysis temperature. The adsorption rates for the
biochars produced at 400, 600 and 800°C were re-
spectively as follows; 66.21%, 78.98% and 92.35%.
The increase of biochar production temperature al-
lowed an increase in the OTA adsorption rate.
Among the effects of the increase of pyrolysis tem-
perature on biochar properties; as mentioned above,
we also obtained an increase of porosity; and the in-
crease of the porosity can be a favorable parameter
for molecules adsorption. Fig.4. Biochar mass effect on OTA adsorption

3.2.3 pH effect on OTA adsorption

The tests were carried out at pH 4.15, 6.54 and 9.05
and the results showed a slight effect of the pH on
OTA adsorption by the different biochars. The effect
was mainly related to the biochar production temper-
atures. Biochars produced at 400 and 600°C appeared
to be the most affected by the pH change. In general,
the best adsorption rates for all biochars were ob-
tained at pH 4.15 and pH 6.54.

Fig.3. Production temperature effect on OTA adsorp-

tion on biochars

3.2.2. Biochar mass effect on OTA adsorption

The adsorption rates varied according biochar mass
used; an increase in OTA adsorption rate was ob-
served with the increase of biochar mass.
The adsorption rates vary with the type of biochar
used (400,600 and 800°C). For the biochars produced
at 400 and 800°C, the best adsorption rates are ob-
tained with 500 mg, so it’s not necessary to add more Fig.5. pH effect on OTA adsorption
biochar.

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3.2.4. Effect of contact-time on OTA adsorption

The observation of contact-time effect showed two
different forms. The first was fast and was in the first
15 min, while the second was slow. They could ex-
press the equilibrium between biochar and OTA. The
adsorption rates varied depending on the type of bio-
char used (400, 600 and 800°C).
Most of the OTA was adsorbed by the different bio-
chars in the first 20 min and equilibrium was reached
after 30 min of contact.

Fig.7. adsorption isotherms of OTA on cashew nut

shell biochars (250 mg biochar in 5 mL solution of
water-methanol solution (w/w))

On the other hand, the Freundlich model is an empiri-

cal expression, which assumed that a multilayer ad-
sorption occurs on the heterogeneous surface or sur-
face supporting sites of various affinities [35]. The
equation is described as follows:

Fig.6. Effect of contact-time on OTA adsorption Where KF and 1/n are the Freundlich constants which
represent the adsorption capacity and adsorption
3.3.5. Adsorption isotherms and kinetics strength, respectively. The magnitude of 1/n quanti-
OTA adsorption at different concentrations (35, 55, fies the degree of heterogeneity of the adsorbent sur-
75 and 100 ng / mL) experimental data was fitted face and the favorability of adsorption [36]. KF and n
with the Langmuir and Freundlich isotherm models. can be obtained from the intercept and slope of the
It is assumed by Langmuir isotherm model that the linear plot of ln qe versus ln ce.
adsorption process is monolayer, which means that
no further adsorption occurred once adsorption took Table 3 presents the values of Langmuir and Freun-
place on specific sites of the adsorbent. The relation- dlich constants, extrapolated from the equations of
ship is expressed as follows: these two models. By adjusting the experimental
points on both models, and based on the values of the
(1) R2 coefficient, it appears that the Langmuir one ex-
presses better the adsorption type for all three bio-
Where qe is the equilibrium adsorption capacity (mg/ chars (R2 = 0.98). Thus, the OTA molecules could be
g), Ce represents the equilibrium concentration in so- adsorbed in monolayers, without interactions be-
lution (mg/L), KL is the Langmuir constant (L/mg) tween them.
and qm represents the maximum adsorption capacity
of the adsorbent (mg/g). Experimental values of qm
and KL are calculated from the slope and intercept of
the linear plot of Ce/qe against Ce.

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Table 3 Isotherm parameters for OTA adsorption on biochars issued from cashew nut shell
Adsorbent Langmuir model Freundlich model
Qmax (ng/mg) KL R2 K 1/n R2

Biochar 400°C 0.15 0.41 0.9826 0.75 0.042 0.8027

Biochar 600°C 0.27 0.31 0.9883 0.75 0.028 0.5900

Biochar 800°C 1.08 0.31 0.9868 0.60 0.10 0.2348

The favorable nature of the adsorption can be ex- the adsorbed quantities qe, the pseudo-first order con-
pressed in terms of a dimensionless constant called stants k1 and the regression coefficients R2 for the
the separation factor or equilibrium parameter (RL), three biochars are given in Table 5. The values of R2
which is defined by: were found relatively low and between 0.5079 and 0,
9007. The calculation of qe for the three biochars
shows that the amounts of OTA adsorbed are rather
small compared to the experimental quantities. These
The RL values indicate the isothermal type as being observations lead us to say that the adsorption of the
irreversible (RL = 0), favorable (0 <RL <1), linear (RL OTA did not follow the pseudo first order equation.
= 1) or unfavorable (RL> 1) The application of the pseudo-second-order kinetics
The RL values are shown in Table 4: model to the results obtained for the OTA adsorption
allowed us to calculate the values of the adsorbed
Table 4. Values of the dimensionless separation fac- quantities qe, the pseudo-second-order constants k2
tor or the equilibrium parameter and the regression coefficients R2 for the three bio-
chars used and the results are given in Table 5. In
Initial concentration RL- B400 RL- B600 RL- B800
(ng / mL) view of these results, it appears that the equilibrium
35 0.063 0.083 0.084
adsorbed quantity increased with the increase of bio-
55 0.041 0.054 0.041 char production temperature. On the other hand, the
75 0.030 0.040 0.031 R2 values are very high and far exceed those obtained
100 0.023 0.030 0.031 with the pseudo-first order model. The amounts fixed
at equilibrium qe are 0.15, 0.23, 0.82 ng / mg respec-
B400 = Biochar 400°C, B600 = Biochar 600°C, B800 = Biochar 800°C tively for the three biochars produced at 400, 600 and
800°C and are very close to the values found experi-
The values of RL for OTA adsorption on the three mentally (Fig. 7).
biochars (400,600 and 800°C) are less than 1 and
very close to 0, which indicates a favorable adsorp- These last two observations lead us to assume that
tion (also the desorption tests have shown that OTA the adsorption process follows the pseudo-second-
adsorption on biochars is irreversible). order model. The plot of t/qt vs. t, for the three bio-
chars, allowed to determine, by extrapolation, the
Pseudo-first-order constants were determined by ex- constants of the pseudo-second order, at different
trapolation of the Log (qe-qt) vs plot. t. The values of contact times.

Table 5. Kinetics parameters for OTA adsorption by cashew nut shell biochars (250 mg of each biochar in 5 mL
of water-methanol solution (w/w)) with OTA at different concentrations
Biochar Pseudo first order Pseudo second order
2
qe (ng/mg) K1 R qe (ng/mg) K1 R2
400°C 0.06 0.1425 0.9007 0.15 1.225 0.9544
600°C 0.06 0.0414 0.5079 0.23 1.237 0.9697
800°C 0.03 0.0138 0.6777 0.82 1.446 0.9712

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 SIFT DESK Abderahim Ahmadou et al.

Desorption tests In vivo application or field-scale applications of

The desorption study permitted to observe the de- cashew nut shell biochars for ochratoxin A adsorp-
tachment of OTA adsorbed on biochars. In order to tion in soil or animal feed is suggested for future re-
evaluate the strength of OTA-Biochar bond, we ap- search, to verify the laboratory findings of the present
plied two desorption tests. study.

For the first test we used 5 mL of water/methanol REFERENCES

solution (w/w) in a 50 mL flask containing 250 mg of [1] Marin, S., Ramos, A.J., Cano-Sancho, C.,
dried biochar having been in contact with OTA at 35 Sanchis, V. " Mycotoxins: occur-
rence,toxicology, and assessment.," Food Chem.
ng/mL under stirring for 45 min, then after 20 min of
Toxicol , pp. 60, 218-237., 2013. View Arti-
ultrasonic agitation the solution was filtered and ana- cle
lyzed by HPLC. In the second desorption test, the [2] Medina, A., Rodríguez, A., Sultan, Y., Magan,
water-methanol solution was replaced by a 5 mL so- N. "Climate change factors and and Aspergillus
flavus: effects on gene expression, growth and
lution of 10 mM TRIS-EDTA with 20% methanol,
aflatoxin production.," World Mycotoxin J, pp. 8,
which is a fairly well-known OTA elution buffer and 171-179., 2015. View Article
after stirring for 45 min, followed by 20 min of ultra- [3] Bhat, R., Rai, R.V., Karim, A.A "Mycotoxins in
sonic agitation the solution was filtered and analyzed food and feed: present status and future con-
cerns," Compr. Rev. Food Sci. Food Saf, pp. 9,
by HPLC.
57-81., 2010. View Article
[4] Zhao, Z., Liu, N., Yang, L., Wang, J., Song, S.,
The results obtained for all three biochars showed a Nie, D., Yang, X., Hou, J., Wu, A " Crosslinked
desorption rate of 1% using water-methanol solution chitosan polymers as generic adsorbents for sim-
ultaneous adsorption of multiple mycotoxins,"
and a desorption rate of 4% with TRIS-EDTA, which
Food Control, pp. 57, 362-369., 2015. View Arti-
shows the strength of OTA-biochar binding; after cle
OTA adsorption on biochar it was not possible to [5] Golge, O., Kabak, B. "First report: exposure esti-
separate it under the experimental conditions that mates to ochratoxin A through wheat bread and
rice intake in Turkey," J. Cereal Sci., pp. 69, 213-
were applied.
217., 2016. View Article
[6] Cano-Sancho, G., Marin, S., Ramos, A.J.,
4. CONCLUSION Sanchis, V. "Biomonitoring of Fusarium spp.
Biochars were produced from cashew nut shell at mycotoxins: perspectives for an individual expo-
sure assessment tool," Food Sci.Technol. , pp.
400, 600 and 800°C. The influence of pyrolysis tem-
16, 266-276, 2010. View Article
peratures on the adsorption characteristics and mech- [7] Rodríguez-Carrasco, Y., Ruiz, M.J., Font, G.,
anisms of ochratoxin A on cashew nut shell biochars Berrada, H., "Exposure estimates to Fusarium
were investigated. Biochars produced at higher tem- mycotoxins through cereals intake," Chemo-
sphere , pp. 93, 2297-2303., 2013. View Arti-
peratures have higher specific surface areas, resulting
cle
in higher OTA adsorption capacities and faster ad- [8] Vidal, A., Marín, S., Ramos, A.J., Cano-Sancho,
sorption kinetics. G., Sanchis, V "Determination of aflatoxins, de-
oxynivalenol, ochratoxin A and zearalenone in
wheat and oat based bran supplements sold in the
The Langmuir model better expresses the type of ad-
Spanish market," Food Chem. Toxicol., pp. 53,
sorption; OTA molecules are then adsorbed in mono- 133-138., 2013. View Article
layers on the biochar and the study of the influence of [9] Shawna, L., Lemke, S., Patrick, G., Grant, T.,
initial concentration on the kinetics has shown that Timothy D., Phillips, J "Adsorption of Zeara-
lenone by Organophilic Montmorillonite Clay,"
the adsorption process follows the pseudo-second
J. Agric. Food Chem., 1998, 46 (9), pp 3789-
order model. The adsorption capacity of biochar mass 3796, pp. 46 (9), 3789-3796, 1998. View Arti-
increased with the increase of OTA initial concentra- cle
tion in the solution. [10]Li, Z., Bowman.S.R "Sorption of Perchloroeth-
ylene by Surfactant-Modified Zeolite as Con-

——————————————————————————————————————————————————–
WWW.SIFTDESK.ORG 886 Vol-4 Issue-7
 SIFT DESK Abderahim Ahmadou et al.

trolled by Surfactant Loading," Environ. Sci. [20]Zhang, X., Wang, H., He, L., Lu, K., Sarmah, A.,
Technol., pp. 32 (15), 2278-2282, 1998. View J. Li, J "Using biochar for remediation of soils
Article contaminated with heavy metals and organic pol-
[11]Di Gregorio, M.C., de Neeff, D.V., Jager, A.V., lutants," Environ. Sci. Pollut. Res., pp. 20-12,
Corassin, C.H., de Pinho Carão, A.C., de Albu- 8472-8483, 2013. View Article
querque, R., de Azevedo, A.C., Fernandes [21]Beesley, L., Marmiroli, M "The immobilisation
Oliveira, C.A "Mineral adsorbent for prevention and retention of soluble arsenic, cadmium and
mycotoxins in animal feed. Toxin Rev. 33, 125- zinc by biochar," Environ. Pollut., , pp. 159, 474-
135.," Toxin Rev., pp. 33, 125-135., 2014. View 480, 2011. View Article
Article [22]Safaei, K.M., Zhang, Q., Lin, D., Zheng, Y.,
[12]Kolosova, A., Stroka, J "Substances for reduction Fang, H., Yu, Y "Biochar: a Review of Its Impact
of the contamination of feed by mycotoxins.," on Pesticide Behavior in Soil Environments and
World Mycotoxin J., pp. 4, 225-256., 2011. View Its Potential Applications," J. Envir. Sci, pp. 44,
Article 269-279, 2016. View Article
[13]Magnoli, A.P., Monge, M.P., Miazzo, R.D., [23]Qiu, Y., Xiao, X., Cheng, H., Zhou, Z., Sheng,
Cavaglieri, L.R., Magnoli, C.E., Merkis, G.D "Influence of environmental factors on pes-
C.I.,Cristofolini, A.L., Dalcero, A.M., Chiacchi- ticide adsorption by black carbon: pH and model
era, S.M "Effect of low levels ofaflatoxin B-1 on dissolved organic matter," Environ. Sci.Technol.
performance, biochemical parameters, and afla- 43 (13) (2009), pp. 4973-4978, pp. 43, 4973-
toxin B1 in broiler liver tissues in the presence of 4978, 2009. View Article
monensin and sodium bentonite.," Poultry Sci. , [24]Wang, Z., Han, L., Sun, K., Jin, J., Ro, K.S., Li-
pp. 90,48-58., 2011. View Article bra, J.A "Sorption of four hydrophobic organic
[14]Neeff, D.V., Ledoux, D.R., Rottinghaus, G.E., contaminants by biochars derived from maize
Bermudez, A.J., Dakovic, A., Murarolli, R.A., straw, wood dust and swine manure at different
Oliveira, C.A.F "In vitro and in vivo efficacy of a pyrolytic temperatures," Chemosphere, pp. 144,
hydrated sodium calcium aluminosilicate to bind 285-291, 2016. View Article
and reduce aflatoxin residues in tissues of broiler [25]Zhang, G.X., Zhang, Q., Sun, K., Liu, X.T.,
chicks fed aflatoxin B1.," Poultry Sci., pp. 92, Zheng, W.J., Zhao.Y "Sorption of simazine to
131-137., 2013. View Article corn straw biochars prepared at different pyrolyt-
[15]Nesic, K., Resanovic, R., Nesic, V., Sinovec, Z ic temperatures," Environ. Pollut., pp. 10, 159,
"Efficacy of mineral and organic adsorbent in 2011. View Article
alleviating harmful effects of zearalenone on pigs [26]Bordoloi, N., Narzari, R., Chutia, R.S., Bhaskar,
performance and health.," Acta Vet. Beograd. , T., Kataki, R "Pyrolysis of Mesua and Pongamia
pp. 58, 211-219., 2008. View Article glabraseed cover: characterization of bio-oil and
[16]Santos, R.R., Vermeulen, S., Haritova, A., Fink- its subfractions," Bioresour. Technol, p. 83-89,
Gremmels, J "Isotherm modeling of organic acti- 2015. View Article
vated bentonite and humic acid polymer used as [27]Niandou, M.A.S, Novak, J.M, Bansode, R.R, Yu
mycotoxin adsorbents.," Food Addit. Contam. , J, Rehrah D, Ahmedna, M "Selection of pecan
pp. 28, 1578-1589., 2011. View Article shell based activated carbons for removal of or-
[17]Wang, J.P., Chi, F., Kim, I.H "Effects of mont- ganic and inorganic impurities from water," J.
morillonite clay on growth performance, nutrient Environ. Qual, p. 902-911, 2012. View Arti-
digestibility, vulva size, faecal microflora, and cle
oxidative stress in weaning gilts challenged with [28]Novak, J.F, Busscher, W.J, Laird, D.L, Ahmed-
zearalenone," Anim. Feed Sci. Technol. , pp. na, M, Watts, D.W, Niandou, M.A.S "Impact of
178, 158-166., 2012. View Article biochar amendment on fertility of a Southeastern
[18]Jard, G., Liboz, T., Mathieu, F., Guyonvarc, A., coastal plain soil," Soil Science , pp. 174, 105-
Lebrihi, A "Review of mycotoxin reduction in 112., 2009. View Article
food and feed: from prevention in the field to [29]Cheng C.H., Lehmann, J "Ageing of black car-
detoxification by adsorption or transformation," bon along a temperature gradient," Chemosphere,
Food Addit. Contam., pp. 28, 1590-1609., 2011. pp. 75, 1021-1027, 2009. View Article
View Article [30]Inyang, M.I., Gao, B., Yao, Y., Xue, Y., Zim-
[19]Ahmad, M., Rajapaksha, A.U., Lim, J.E., Zhang, merman, A., Mosa, A., Pullammanappallil, P.,
M., Bolan, N., Mohan, D., Vithanage, M., Lee, Ok, Y.S., Cao, X "A review of biochar as a low-
S.S., Ok, Y.S "Biochar as a sorbent for contami- cost adsorbent for aqueous heavymetal remov-
nant management in soil and water: a review," al.," Crit. Rev. Environ. Sci. Technol., pp. 46,
Chemosphere, pp. 3, 19-33, 2014. View Arti- 1950-1956, 2015. View Article
cle [31]Nakajima, M., Tsubouchi, H., Miyabe, M., Ueno,

———————————————————————————————————————————————————
WWW.SIFTDESK.ORG 887 Vol-4 Issue-7
 SIFT DESK Abderahim Ahmadou et al.

Y "Survey of aflatoxin B-1 and ochratoxin A in tion and environmental application of or-
commercial green coffee beans by high- ganoclays for the removal of phenolic com-
performance liquid chromatography linked with pounds," J. Colloid Interface Sci.,, pp. 393, 319-
immunoaffinity chromatography," Food and 334, 2013. View Article
agricultural immunology, pp. 9:77-83, 1997. [36]Xu, J., Wang, L., Zhu, Y "Decontamination of
View Article bisphenol A from aqueous solution by graphene
[32]Bordoloi, N., Narzari, R., Chutia, R.S., Bhaskar, adsorption," Langmuir, pp. 28, 8418-8425,
T., Kataki, R "Pyrolysis of Mesua and 2012. View Article
Pongamia glabraseed cover: characterization of [37]Cano-Sancho, G., Marin, S., Ramos, A.J.,
bio-oil and its subfractions," Bioresour. Tech- Sanchis, V "Biomonitoring of Fusarium spp.
nol, p. 83-89, 2015. View Article mycotoxins: perspectives for an individual ex-
[33]Yang, G.B., Wang, Z., Xian, Q., Shen, F., Sun, posure assessment tool," Food Sci., 2010. View
C., Zhang, Y., Wu, J "Effects of pyrolysis tem- Article
perature on the physicochemical properties of [38]Pfohl-Leszkowicz, A., Hadjeba-Medjdoub, K.,
biochar derived from vermicompost and its po- Ballet, N., Schrickx, J., Fink-Gremmels, J
tential use as an environmental amendment," "Assessment and characterisation of yeast-based
RSC Adv., pp. 5, 40117-40125., 2015. View products intended to mitigate ochratoxin expo-
Article sure using in vitro and in vivo models.," Food
[34]Zhao, B., O'Connor, D., Zhang, J., Peng, T., Addit. Contam., pp. 32, 604-616, 2015. View
Shen, Z., Tsang, D.C.W., Hou, D "Effect of py- Article
rolysis temperature, heating rate, and residence [39]Wang, Z., Han, L., Sun, K., Jin, J., Ro, K.S.,
time on rapeseed stem derived biochar.," J. Libra, J.A «Sorption of four hydrophobic organ-
Clean. Prod. , pp. 174, 977-987, 2017a. View ic contaminants by biochars derived from maize
Article straw, wood dust and swine manure at different
[35]Park, Y., Ayoko, G.A., Horváth, E., Kurdi, R., pyrolytic temperatures .» Chemosphere, 2016:
Kristof, J., Frost, R.L "Structural characterisa- 144, 285-291. View Article

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