1

Adsorption of Methomyl pesticide on HDL (layered double

hydroxides for environmental protection

N. BOUDAOUD
(1),(2)
, A.E.K TAYEB
(2)
, H. MILLOUDI
(2)
.

(1)
Research unit in renewable energy (EPST CDER).
(2)
Oran University Department of Chemistry chemistry laboratory materials and environment
31000 Oran Algrie
E-Mail: boudaoud_2007@yahoo.fr


Abstract:

Anionic clay (layered double
hydroxides )was utilized as adsorbent to
remove insecticide Methomyl (mthylthio-
1thylidne-amine) , from aqueous
solutions by adsorption. Batch experiments
were conducted to study the effects of pH
(0310) ,the Mg
+2
/Al
+3
ratio the anion
exchange capacity, the nature Of
intercalated anion X (CO
3
,NO
3
,Cl
-
) and the
effect of layer charge on insecticide
Methomyl adsorption. the adsorption
isotherme ,described by freundlich model,
are of S-type with tendency to L type for
high Methomyl equilibrium concentration
.the lamellar structure, exchange capacities
among the highest in ion exchangers, and a
hydroxylated surface very reactive
promoting chemisorption anionic clays are
very interesting materials for adsorption
and intercalation of anions or molecules
environmentally undesirable.

1. Introduction
The extended contamination of soils and
ground water from the widespread use of
pesticides in modern agriculture is a
current concern that is impelling research
looking forremedies.The interest of anionic
clays in this field steams for their exchange
properties that make them promising
materials for the elimnation of pollutants.
On the other hand, anionic clays may be
used as soil models for predicting the
behavior of pollutants in soils. Anionic
clays (also called Layered Double
Hydroxides or LDHs) are rare in nature but
simple to prepare; hydrotalcite [Mg-Al],
hydrocalumite [Ca-Al] and the green rust
are LDHs that occur in nature. Their
structure is derived from that of brucite
Mg(OH)
2
[1]. A wide range of composition
can be obtained for these materials by
changing the nature of the metal cations
and the ratio M
II
/M
III
as well as the type of
the intercalated anion Xm- in the general
formula : [M
2+
1-x
M
3+
x
(OH)
2
]
x+
[X
m-
x/m
.nH
2
O] abbreviated as [M
2+
M
3+
X] [2,3].
Hence, their chemical and physical
properties can be varied and this has led to
intensive search for uses of LDHs in
catalysis and sorption processes. Their
highion exchange capacities make them
promising materials for the elimination of
ecologically undesirable inorganic and
organic anions. Indeed, the removal of
chromate [4,5], nitrate, phosphate, arsenate
or vanadate anions [6,7] from
contaminated water by LDHs have already
beendemonstrated. An other objective
would be the use of LDHs and modified
LDH materials as recyclable sorbents and
heterogeneous catalysts for the treatment
of contaminated waste waters. The aim of
the preon magnesium-aluminium
hydrotalcites in order to establish their
sorption capacity and mechanism. The
adsorption experiments being conducted at
pH = 7, sent work is to study the sorption
capacity of de pestecide Methomyl
(mthylthio1thylidne-amine).




2

HDL are lamellar mixed hydroxides and
trivalent metals. The structure can be
described by the stack of sheets of
composition M (OH)
2
similar to those of
brucite. The presence of trivalent metal
leads to positively charged sheets. The
electro neutrality is guaranteed by the
species anionic solvated by water
molecules present in the space interlayer
[8]. Such as mineral phases are:
Hydrotalcites [Mg-Al] hydro calumite [Ca-
Al], the "green rust" [Fe
2 +
- Fe
3 +
].
However, these minerals are never
abundant, in nature, materials clay are
mainly cationic clays (phyllosilicates).
Work of Miyata in the 70s [9], including
the synthesis "Soft chemistry" HDL,
helped their development. Given the
multiple possible combinations of the
constituent metals sheets and interlamellar
species and the many variables of
preparation, it is possible to vary the
chemical and physical properties of HDL
where the interest growing these materials
in particular in the field of catalysis [10].
On the other hand, with exchange
capacities among the strongest ion
exchangers 3-4 meq /g and a hydroxylated
surface highly reactive to promote
chemisorptions, HDLs also provide
opportunities for trapping chemical
pollutants. The efficacy of HDL in the
treatment of polluted waters anions
nitrates, phosphates or chromates has
already been demonstrated [6,11]. Many
studies also focus on the use HDL as
carrier or catalyst for the degradation of
chemical pollutants [12]. The present work
focuses first on the study of the trapping
phase [Mg
1-x
Al
x
(OH)
2
] [X.nH
2
O]
pesticide.


2. Experimental

A. Synthesis

All compounds HDL was prepared by the
co precipitation method at constant pH [9].
It consists in the controlled precipitation
carried by a base with a



solution containing salts of the two cations
in suitable proportions. Thus, the phase
[Mg
2
AlCO
3
] was synthesized at 25 C by
gradual addition of a solution of Mg and M
1 NO
3
6H
2
O AlNO
3
, 6H
2
O 0.5 M in a
reactor containing 100 ml of pre-ionized
water and stirring magnetic. The pH is kept
constant at the value of 10 0.1 by
simultaneous addition of a solution of 2M
sodium hydroxide. After a ripening period
of 24 hours at 85 C, the solid is recovered
by three cycles of washing / centrifugation
and then allowed to dry at a temperature 80
C.

Table.1. Anionic Exchange Capacity
(AEC) for different ratios of metal cations
hydrotalcites [Mg
1-x
(AI
x
(OH)
2
] [CO
3
]
0.5x nH
2
O, [13].

M
II
/M
III

x = M
III
/
(M
II
+M
III
)
C.E.A
(meq/100g)
2/1 0.33 401
3/1 0.25 325
4/1 0.20 273


B. Samples characterization:

All samples were examined by XRD; this
technique allows getting information on
the sheet and the space between the sheets.
Measures X-ray diffraction was performed
on a SIEMENS D501 powder diffract
meter equipped with a copper anticathode
tube and a monochromatic of graphite
blade. The sample is spread on a glass slide
sprinkled by sieving to limit the
phenomena of preferred orientations of the
crystallites.
Spectroscopy infrarouge IR, This
technique allows to highlight the presence
of the anion in the interlamellar space [14]
as well as the interactions that may exist
with the matrix. In addition, this technique
is very powerful to detect the presence of
carbonate anions side via the characteristic
vibration band of carbonates at around
1360cm
-1
. In this study the infrared spectra
were obtained in 4000-400 cm
-1
on a


3
Perkin Elmer SPECTRUM. Materials are
dispersed in the powder of potassium
bromide (KBr), oven-dried, and are then
analyzed. Morphological Characterization,
The scanning electron microscopy (SEM)
is another technique commonly used
enough. It provides information on the
texture of the grains, the latter being
important for application of the materials
in catalysis [14].















3. Results and Discussion

Figure 1 shows the RX patterns of the most
representative LDHs synthesized by direct
co-precipitation of materials [Mg-Al-CO
3
],
[Mg -Al-NO
3
], [[Mg-Al-SDS].
They are typical of a pure layered double
hydroxide structure with sharp and
symmetric reflections for (003), (006),
(110)and (113) planes and broad
asymmetric for (012),(015) and (018).
The diffract grams X precursors [Mg2-Al-
CO3], [Mg2-Al-NO3], [Mg2-Al-SDS],
[Mg2-Al-500] are shown in Figure 1.
Materials crystallize in a trigonal P3 with a
stack of oxygen atoms. Indexing of X-ray
spectra can be performed with a hexagonal
lattice, containing three copies per cell.
The distance between the line of lattice
003, is connected to the sheet spacing
(distance between the sheet), and allows an
approximate calculation of the lattice
parameter c by the following equation: c /
3 = d003. The line (110) in the vicinity of
60 in 2 determines the interatomic
distance of the metal-metal sheet and the
lattice parameter a: a / 2 = d110 [13,14].
The lattice parameters of the compounds
HDL are summarized in Table 2. These
results are consistent with those in the
literature [11], for the same material
MgAlCO
3
(R=2) synthesized by the same
method, have found a value of a equal to
3.02 and a value of 21.69 A .[15] when
to them, for the material found Mg
2
AlNO
3

has a value of 3.018A and a value of c
23.7 A .

Table.2. Parameters mesh anionic clays.

compounds a (A) c (A)
d
003

(A)
Mg
2
AlCO3 3.021 21.695 7.690
Zn
2
AlNO3 3.018 23.700 7.900








20 40 60 80
MgAl-500
Mg-Almethomyl
Mg-AlCO
3
2theta
Fig.1. Schmatique reprsentation of
HDL
Fig.2.XRD patterns of [MgAl-CO3],[[MgAl-methomyl],
[MgAl-500].
Fig.3. show the FT-IR includes the infrared
spectra of HDL phases [Mg
2
AlCO3], [Zn
2
Al CO3],
[Mg
2
Al500]and patterns of the most representative.


4


This technique allows highlighting the
presence of the anion in the interlamellar
space [14] as well as the interactions that
may exist with the matrix. In addition, this
technique is very powerful to detect the
presence of carbonate anions side via the
characteristic vibration band of carbonates
at around 1360cm-1. In this study the
infrared spectra were obtained in 4000-400
cm
-1
on a Perkin Elmer SPECTRUM.
Materials are dispersed in the powder of
potassium bromide (KBr), oven-dried, and
are then analyzed.
Infrared spectra of HDL phases show three
characteristic domains: From 3400 to 3600
cm-1, bands of vibration of the hydroxyl
groups of the sheet (
OH
) and water
molecules sorbed physical and interleaved.
The intensity and position of the band
depend on the hydration rate respectively,
of the charge density of the layers and the
nature of the metal cations. From 2500 to
1000 cm-1 bands are bending vibration (
H2O) molecules intercalated and adsorbed
water and the characteristic bands of the
anion present in inter leaf, we note the
bands between 1350 and 1480 cm-1
corresponding to the vibration (CO
3
2-
)
highlighting sample contamination by
carbonates despite the precautions taken
experimental.
Several studies [16,17] Nagy showed that
HDL contamination by carbonates cannot
be avoided, even if you are working under
an inert atmosphere. For low frequencies,
that is to say <1000 cm-1, the vibrations
are attributed to the observed network. We
distinguish vibrations (
M-O
valence
between the metal and oxygen atoms, and
the bending vibrations of the metal-oxygen
bonds, oxygen (
O-M-O
). Strips are strips of
a signature HDL [14].

A. Methomyl adsorption on [Mg
2
-
AlCO
3
],[Zn
2
-Al- CO
3
]

The dye adsorption isotherms of
pesticide Methomyl were recorded at 25
C in a closed reactor with magnetic
stirring. Typically, a mass of 10 mg of clay
is dispersed in 25 ml of a solution of
colorant concentration variable C
i
(2-
6mmole/l); After a contact time of 24
hours, the suspensions were centrifuged.
Herbicide concentration in the supernatant
solution this in equilibrium with the
adsorbed by clay Cs is determined by UV
4000 3500 3000 2500 2000 1500 1000 500
0,0
0,2
0,4
0,6
0,8
1,0
1,2
*
*
*
*
*
%

t
r
a
n
s
m
i
t
a
n
c
e
Wavelength(cm
-1
Mg
2
AlCO
3
Mg
2
Almethomyl
methomyl
Fig.4.influence of the pH


5
spectrometry (Methomyl: = 254nm.
Isotherms relate the amount of pollutant Cs
adsorbed on clay (expressed per gram of
clay: C
s
(mol / g) = (C
i
- C
e
). V / m) that in
equilibrium in solution C
e
. This adsorption
is well described by the Freundlich
equation: C
s
= K.Ce1 / n. The linear
transform (log C
s
= log K 1 / n.log C
e
)
allows the calculation of the constants K
and 1 / n that provide information on
respectively the adsorption capacity of the
clay and the affinity adsorbate / adsorbent
(or the degree of linearity between C
s
and
C
e
). Giles et al. thus distinguish several
types of isotherms that relate to different
types d'interactions adsorb ate-adsorbent
[18].

The influence of pH on the adsorption of
Methomyl by phase [Mg
2
-Al-CO
3
]was
initially examined. Thus, an acidic pH <5
causes partial dissolution when in a basic
medium de clay pH> 7, competition with
anions carbonates is very likely given the
high affinity of HDL for these anions. The
pH also changes the solubility of the
insecticide and the surface charge clay.
The measurements show an adsorption
maximum at pH between 6- 7 which
corresponds to natural waters as indicated
by the effect of pH presented fig.4





Preliminary adsorption experiments were
conducted in order to determine the
optimal conditions for adsorption of
methomyl on LDH
S
regarding the contact
time The kinetic study (fig.1)shows that
the adsorption equilibrium state is reached
after contact time 100min. adsorption on
LDHS is very fast .it is also the case for
2.4D on HDL
S
[13]and monobutyltin in
clays minerals [19]. Here, the shape of the
Kinetic curve indicates that we are dealing
with only one adsorption phenomenon
which must be a surface process related to
the slow diffusion of the organic
molecules. To be sure that the equilibrium
state is reached, Methomyl -HDL
S
contacte
time of 24 h was applied in the adsorption
experiments






Fig.6 displays the Methomyl adsorption
isotherms on [Mg-AlCO
3
], [Zn-
AlCO
3
],[Mg-Al500]and [Mg-Aledta]
phases for a sample mass of 10 mg. one
can distinguish three different parts on the
adsorption isotherms of [Mg-AlCO
3
], [Zn-
AlCO
3
]. Curves phase are S-type and L-
type tend towards a higher concentration
for. Type S isotherm indicates interaction
competitive adsorbate / adsorbent and
adsorbate / adsorbat.la matrix [Mg-
AlCO
3
], [Zn-AlCO3] and [Mg-Aledta],
Significant, not adsorbed at the 1.10
mmole / l. curve tends to L-type change in

S L in a same isotherm can be explained by
the passage of a saturation of external sites
has a surface adsorption process with
internal retention gap feuillets.les
interaction internal tanteaucoup stronger
than surface. At low equilibrium
concentration C
e
This for> 1.5 mmol,
adsorb ate-adsorbent interactions are
necessary and isotherms resemble S type
,according to the classification [18].This
2 3 4 5 6 7 8 9 10 11
9,30
9,32
9,34
9,36
9,38
9,40
9,42
a
d
s
o
r
b
e
d

p
e
s
t
e
c
id
e
(
m
m
o
l
e
/
L
)
pH
0 200 400 600 800 1000 1200 1400 1600
0
20
40
60
80
100
120
a
d
s
o
r
b
e
d

c
o
n
c
e
n
t
r
a
t
io
n

(
m
m
o
le
/
l
)
time(min)
Fig.5. Kinetic study of adsorption of Methomyl (Ci=
1.2mmole/l)
on 10mg of at 25C [Mg
2
AlCO
3
]



6
isotherm assignment is supported by
Freundlihe 1/n values [20].the maximum
of Methomyl is reahed at the plateau( for
C
e
=1.10mmole/l) at curve tends to L-type .
Isotherm of the S-type Indicates
competitive interactions adsorbate /
adsorbent and adsorbate / adsorbate, with
the Possibility for the solute to be adsorbed
gold horizontally to the area of the
adsorbent or vertically reflecting a minimal
competition entre le adsorbate and the
solvent for the adsorption sites. The shape
of the adsorption curve is characteristic of
a process of chemisorption isotherm is then
Modeled by the Langmuir equation.












The scanning electron microscopy (SEM)
is another technique commonly used
enough. it provides information on the
texture of the grains, it is important for the
application of material sin catalysis[14].

Fig.6. contains snapshots of scanning
electron microscopy obtained for anionic
clays studied. Textures of phases HDLs
[Mg
2
AlCO
3
] presents a mixture of
dispersed particles from large blocks and
spherical particles. Similar results were
observed [13] our material [Mg
2
AlCO
3
].
For cons, the crystallites of the matrix
[Zn
2
AlCO
3
] are compact, large and much
more swollen than those observed in the
snapshots [Mg
2
A CO
3
] and [Zn
2
AlCO
3
]. It
justified the change in shape of the
crystallites by the moisture level of nitrate
compared to other stage phases.
The fig.6 some [Mg
2
-Al-CO
3
], [Zn
2
-Al-
CO
3
] micrographs are shown. In general,
the solid materials morphology analyzed
by SEM presents particles with irregular
grains. A texture of phases [Mg2AlCO3],
[MgAlNO3] presents a mixture of poly-
dispersed particles in the form of large
blocks and of small spherical particles and
highly aggregated. The plate formed on the
[Mg
2
AlCO
3
] indicates particles with
angular lines similar results were observed
by [13].

4. Conclusion

With high anion exchange capacities and
highly reactive hydroxyl surfaces, the
layered double hydroxides are interesting
materials for trapping molecules
environmentally undesirable Through their
exchange properties, the anionic clays
provide opportunities for trapping anionic
organic pollutants. we initiated the study
of absorption properties of a series of
materials HDL, HDL EDTA , the pesticide
over looked Methomyl. For this purpose,
we used materials crystalline type anionic
clay chlorinated [Mg
R
AlCO
3
], prepared by
the co precipitation method in basic
medium (pH = 9) constant. The products
obtained were characterized by X-ray
diffraction, infrared spectroscopy, thermal
analysis, and scanning electron
microscope. The results of these analyzes
have confirmed the structure of the
precursor. The adsorption isotherms of
Methomyl on difference synthesized
materials, type S, indicate moderate
interactions between organic pollutants and
clay. Adsorption proceeds in exchange for
first and then the entire surface of the solid.
It depends on many factors such as pH, the
charge density of the layers, the
morphology of the clay and the ratio of
solid / liquid phases.
1,00 1,05 1,10 1,15 1,20 1,25
0
2
4
6
8
10
d
c
b
a
q
e
(
m
m
o
l
e
/
g
)
ce(mmole/l)
Fig.6.SEM micrographs from (a) [Mg
2
AlCO
3
],
(b)[Mg
2
AlNO
3
].
Fig.6. Methomyl adsorption isotherms for (a)
[Mg
2
AlCO
3
]
, (b) [Zn
2
AlCO
3
],(c)[Mg
2
Al500], (d)[Mg
2
Aledta].




7
By their composition rich HDLs can also
be considered as relatively simple soil
models. The study of complex clay /
pesticide shows the influence of properties
hydrophilic / hydrophobic and surface
charge of the various components the
transfer of pesticides.


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