Maleic hydrazide interaction with soil clay surfaces

Chemosphere, Voi.23, No.4, Printed in G r e a t B r i t a i n

D~

473-483, 1991

0045-6535/91 $3.00 Perga~ion P r e s s plc

+ 0.00

MALEIC HYDRAZIDE INTERACTION WITH SOIL CLAY SURFACES.

M.C. Hermosfn,

l.Rold~n and J. Cornejo.

Instituto de Recursos Naturales y Agrobiologia Apartado

1052. Sevilla 41080.

de Sevilla C.S.I.C.

SPAIN.

ABSTRACT The binding mechanism

of

the

herbicide maleic hydrazide

has been studied by adsorption Transform Infrared the such

surface as

whereas

characteristics

for

penetred

in

the

complexes

the minerals.

sepiolite, of

sepiolite and to exchangeable

the

that

hydroxylated

permanent

spaces,

MH

For

adsorption

negative

interlamellar showed

(XRD) and Fourier

(FT-IR). The results showed different mechanisms of

phyllosilicates

also

MH-mineral

and

soil clay surfaces

isotherms at different pH, X-ray diffraction

spectroscopy

lepidocrocite

(MH) to mineral

was

as

charge)

surfaces

of MH occurred at external

surfaces

charge,

shown

(variable

depending of

such

as montmorillonite,

by XRD results.

bonded to surface hydroxyl

cation, directly or through water-bridge,

FT-IR

MH

spectra of

on lepidocrocite on montmorillonite

and by

C=0 groups of the herbicide molecule. INTRODUCTION The increase of concerns knowledge of the ultimate the environment. hydrazide minerals level

with of

process affecting the herbicide or other

(HERMOSlN et al., 1987;

constituting

evidences

different

strength

irreversible

minerals.

evidence

for

Although that

were

some

1988; McCONNELL

on

CORNEJO,

reported.

phyllosilicates

mechanism

behaviour in

in the retention of maleic 1987) I'2 and the diverse

These last authors brought

minerals

of

adsorption

HERMOSIN and 1987;

and

and fibrous

were suggested no direct

has been shown to be an extremely

of the interaction between pesticides 1979;

(montmorillonite)

such as iron oxihydroxides

Infrared spectroscopy

MARTIN and SANCHEZ-CAMAZANO, and HOSSNER,

ai.,31991).

surface minerals

posible

level (SHOVAL and YARIV,

al., 1982, 1985;

and

(HERMOSIN et

adsorption

useful tool for the investigation a molecular

HERMOSIN

pollutants

the basic

the clay fraction of soils have been reported to adsorb MH at different

reversible adsorption on hydroxilated clay

quality have made necessary

The soil colloids has been shown to be important

in soils

and

about the environmental

and soil

PEREZ-RODRIGUEZ,

AOCHI and FARMER,

minerals

1980; HERMOSIN

1988;

to et

MICERA et al.,

1989)~ -11

The aim of this work was to assess the interaction or binding 473

mechanism of MH with soil

t~74

clay minerals

occurring

the enviromental diverse soil

through the adsorption process.

These interactions

impact of this compound or others similar

chemicals.

minerals was measured at three different pH and

may be implied in

The sorption of MR on

saturated MH-mineral

complexes

were prepared and examined by FT-IR spectroscopy. .MATERIALS AND METHODS The clay minerals used in this study were two montmorillonites SAz-I and SWy-I Sepiolite

(VAN OLPHEN

from

HERMOSIN 1988) 13.

Vallecas,

and FRIPIAT, Spain

layer charge

1979) 12 from the Clay Minerals Repository

(Tolsa,

The surface properties

of different

S.A.) and a synthetic

of these clays are

Lepidocroclte

(CMS), a

(CORNEJO and

summarized on Table I.

TABLE i Surfaces properties Mineral

of minerals CEC

SBE T

Mineral

meq/100g

m2/g

SAz

120.0

97.4

L

116.0

SWy

76.4

31.8

S

283.0

CEC = cation exchange

capacity;

m2/g

SBE T = specific surface area by BET method

The sorption isotherms were carried out as described earlier adjusting

the initial desired pH of the MB-solid

The satured MH-mineral (0.32g) with 3mM complex

complexes were

MH solution

was washed

adsorbed.

SBE T

(20ml) for

rapidly with

20ml

(HERMOSlN et al., 1991)3but

suspension with diluted HCI or NaOH.

prepared by successive 24h. After six

of distilled

or seven

treatments treatments

water to eliminate

the

of the mineral the resulting MH excess not

The complexes were air-dried and gently hand-ground.

The FT-IR spectra of the mineral and herbicide-mineral -supporting

film prepared from a 2% suspension dried on

on KBr disk for Lepidocrocite

complexes were obtained on self-

Mylar paper for montmorillonite

and

and pure MR, and recorded on a Nicolet 5PC.

RESULTS The

adsorption

are shown on Figure adsorption

isotherms I.

of MH on the minerals

All minerals

showed low

curve lowered considerably SAz
at pH=7.4.

studied at three pH (4.0, 5.4 and 7.4)

variations From

Figure

1 the pH effect on MH sorption

increased

from

isotherms.

For SWy the sorption curves were of "L ~ type for pH 4.0 and 5.4 and changed to "C"

type for pH 7.4 whereas

showing in the last two

with pH except sepiollte whose MH

instances

for sepiolite was the contrary,

changes

in

the shape of the

"L" type for pH 7.4 and "C" type for

475

90-

90

SAz

8o-

E .:t

60

~, 6o

50=

o E

/ t O"

e 30

.

20 ~

..q#'"

"""

2 (e. mm0L/l

90

/I

80

! / /I :

,

3

1

90" 80

50

,, ,"

30

10

~ !e "

~

O

E 50 m,

i

2O

P

0

g0

50

u

3

100'

70

4O

2. Ce, m m o l / I

110

/Io

70

E

Q

20

"0

oO~ . ~ U 100

3O

.-°

t

50

40

o

.,

70

70

c~ o

,o

SWy

B0

P.II

®

......• ..... '

.........

2

r

30

~/

"

20

3

o

I0

0 1

40

t

t= '

Ce. m m o t / i

i

Ce, mm0~ll

Figure I. MH adsorption isotherms on soil minerals at three different pH: @--------0,4,0----

--'0

,5.4,0

.......

®,7.4

4.0 and 5.4. From the adsorption curves on Figure i, it is shown that pH effect on the amount of M~ adsorbed changed with equilibrium concentration,

except for sepiolite and lepidocrocite

The sorption data were fitted to the Freundlich equation: Cs = Kf Ce nf (i) were

Cs

is

the

concentration.

The

capacity (HERMOSIN VAN BLADEL,

amount

of

specific and

1980) 14 were

herbicide

adsorbed

constant Kf,

CORNEJO,

which

and

Ce

is

is a measure

the

of the relative

1987) 2 and nf, known as adsorption

calculated.

These

values

are

repoted

herbicide

intensity on

correlation coefficient found for the logarithmic form of equation (I).

Table 2

equilibrium adsorption (MOREALE and besides

the

476

TABLE 2 MH adsorption parameters

Mineral

pH

Kf ~mol/g

nf

and correlation

coefficients

r

Mineral

from Freundlich equation

pH

Kf ~mol/g

nf

SAz

4.0 5.4 7.4

5.9 12.4 12.4

0.55 0.73 0.68

0.81" 0.98** 0.96**

S

4.0 5.4 7.4

48.2 41.2 7.6

1.21 1.17 0.64

0.99** 0.99** 0.99**

SWy

4.0 5.4 7.4

26.4 41.7 32.9

0.68 1.03 1.01

0.98** 0.99** 0.99**

L

4.0 5.4 7.4

59.7 69.3 61.26

0.40 0.52 0.42

0.96** 0.95** 0.93**

* P<5% and ** P
300

300

SAz

250

"" 200 -

200 -6 E

SWy

250 o 150"

15O

ul" 100

Ioo f

5O 1

2

3

N

4

5

50

6

2

i

3

5

4

6

number of freQtmenf 350 l

350"

I

30o-[

3oo~

150 1

150

L

= g

,

N

100 i

100

I

50 -~

f

50

T 0

~

2

3

4

5

6

number of t r e a t m e n t

Figure 2. C u r v e s of sucessive saturation with MH for soil minerals studied.

The

sucessive

saturation of the

increased by this treatment. different Figure 2

mineral

Figure 2

studied and the

the values of

reported for all minerals

surface

mineral shows

the

final sorbate coverage

showed curves

of

the

sorption

sucessive

concentration

(0, ~mol/m)

and SWy sample showed

that

the maximum

saturation

increased:

for the different

capacity can be for the

SAz
value indicating

On

are also

probably the

477

access of MB molecules to the incerlamellar spaces of this mineral.

The complexes obtained as

above were assayed by IR spectroscopy. The FT-IR sample

are

spectra of

shown on

montmorillonite

the organo-mineral

Figure 3

complexes

for lepidocrocite,

besides

the respective

Figure 4 for sepiolite and

(SWy). The main bands in the IR spectrum of MH pure compound

adsorbed montmorillonite

and sepiolite

are summarized on table 4. For

(KBr disk)

(Figure 2A).

(KBr disk)

The MH bands

were assigned

18

/ 15

V

10

5 J

0-

I

1

l

I

I

3000

T

I

2000

1000

WAVENUMBERS Figure 3. FT-IR spectra of lepidocrocite

(---) and MH-lepidocrocite c o m p ] e x (

/

M8

/

40 / 30

" .............

ii

" "i

10

I

I

I

~

I

and

complex on KBr disk no appreciable bands attributable

to MH were observed due to its low amount adsorbed according to BELLAMY (1980a)! 5

Figure 5 for

(self-supporting film) and on lepidocrocite

MH-SAz

untreated

I

4000

1

w 3000

I

/

/

/

"

~ 1800

1

I

l

i 1000

4800 WAVENUMBERS

Figuce 4. FT-IR spectra of sepiolite

(---) and MH-sepiolite complex (

).

).

478

44

//.,

-

40--

,,/

'I

t ""

,i

30-

20.

10-

I

I

4800

I 4100

i

i

r

3000

i

/ /

,

1800

i

I

I

I

I000

WAVENUMBERS

Figure 5. FT-IR spectra of montmorillonite,SWy,(---) and MH-SWy complex (--).

TABLE 3 Infrared frecuencies of pure MH and MH-mineral complexes in cm

Assignment

MH

~0-H

1200

C-N Amide ~N-H III

1274

L

-1

S

1292 1322

1327

C-O ~C=C

1411

~ N - H Amide C-N II

1550

1462

1470

~C=C

1579

1586

1600

9C-0 Amide I

1665

1654

1650

c~N

1417

SWy-i

1292 1318

1333 1406 1420 1437

1640 1654 (1650) 1

QC-N

2969

2891 3010

(3390) 2 ~N-H

3457

I~O_M of clay water and 220_H of clay water.

3221

479

The spectra of MB-mineral some cases,

complexes

splitted as compared

with

showed bands corresponding the pure herbicide,

chemical bonding that disturbed

the energy of some

were different

mlneral

for the diverse

Amide I, II and III bands

and PN-H,

studied.

bonds of MH molecule.

although in some

associated

as indicative of certain

The most important

PC=C (L and S). Also with respect to the adsorbent stretching modes of water molecules

to Mll but shifted and, in

cases

These

surface

band changes

feature were observed on

changes

were also observed in

changes were observed on water bending and

to exchangeable

cation of montmorillonite

and

sepiolite. The most relevant

change observed for all

the Amide I band, which is fundamentally a weakness

of C=O bond,

(BELLAMY 1980b)

16

as corresponds

. This Amide I band

III band, which is a combination

PC-N modes,

to the stretching

of the two modes

vC-N and 6N-H,

and for

MH-SWy

changes

for water vibrations.

For SWy complexes

and 1635 cm-lindicated

some replacement

frequency of these bands of from 3420 to 3390 cm water-bridge

(BELLAMY,

was observed,

MH-SWy

and from

complex.

increased

The Amide

in frequency and

a combination

almost dissappeared.

as shown in

of the 6N-H and

Similar changes were

by TAHOUN AND MORTLAND

1980b) 16. For

as indicating

were observed

(1966)!7Also

a

only on MH-SWy,

and MH-S complexes

a great decrease of intensity of water bands at 3420 of H20 by MH molecules.

complexes were observed:

1635 to 1650 cm MH-S

the substitution

From the IR spectra results the lepidocrocite

MH-SWy

H-bridge

in the frequency of vN-H was observed for MH-SWy complexes.

With regard to the adsorbent,

-1

implied in

range was enlarged)

which is also

obserbed for diverse amides adsorbed on montmorillonite decrease and broadening

mode when is

(showed when frequency

The Amide II band,

lowered in frequency

in frequency of

due to vC=O, from 1664 to 1660-1640 cm -I indicating

splitted in the case of the

splitted for MH-SWy and MH-S complexes Figures 3-5 and on Table 4.

complexes was the decreasing

-1

Also some displacement

POH decreased

, respectively,

indicating

complex a small decrease

and ~OH increased the formation of

in ~OH of zeolitic water

of some of these molecules

MH-mineral

of the

by MH.

complex can be considered

in two groups:

i)

and sepiolite and 2) SWy.

DISCUSSION Taking into

account the

(GREENLAND AND MOTT, above, the

the external

1978) 18 , the polar

mechanism of

oxides, hydroxides

nature of the mineral

surfaces,

studied in

nature of the MH molecule

MH adsorption on soil

and phyllosilicates

surfaces

mineral

but montmorillonite

and the results

surfaces are

can adsorb polar molecules

the present

discussed

on their hydroxyl

and sepiolite has also an interlamelar

work

described below. The groups of or channel

z~80

internal

surfaces

that

can be

accesible

to polar

molecules

(MORTLAND, 1970;

SERNA e t a l . ,

1979)! 9 ' 2 0 The

polar

hydroxilated

character

surfaces

Mtt

implication

lepidocrocite

of t h i s

bands

:he d o u b l e

bond c h a r a c t e r

that

c h a n n e l s of the

and s e p i o l i t e ,

on s e p i o l i t e

and s p l i t t e d

o f C-N

(increase

forms as i n c r y s t a l l y n e

explained

the changes

adsorption

occurred

18

and minimum

~hould be

replace

For t h a t

a t pH=5.4

close to

pH

For sepiolite

a d e c r e a s e of

1979) 20 was

sorption

for

charged and

repelled the

capacity

behaviour was observed

for sepiolite,

due to the

of the

lower zpc

o f MH a d s o r p t i o n

lepidocrocite.

Mtt m o l e c u l e

lepidocrocite curves.

The MH bands

a r e as p h e n o e n o l i c

(zero point

and s e p i o l i t e

For l e p i d o c r o c i t e

charge,

group of the MH

but the adsorption decreasing

silanol

of

above showed some a l t e r a t i o n . on

C=O

also in the

also maximum

GREENLAND and MOTT,

adsorption was found at pH=7.4, when part of the surface hydroxyl

negatively

the

and a d e c r e a s e o f i n t r a

reason the

that

sorption zpc

of

t h e Amide I I and

and t h e r e v e r s i b i l i t y

sorption

its

indicative

some o f t h e s e w a t e r p o s i t i o n

very

seems t o i n d i c a t e

observed at different

is

(SERNA e t a l . ,

1991) 3 l o w e r t h a n

of Mtt

(HERMOSIN e t a l . ,

t o 1654 and 1650 c m - l f o r

frequency)

water

than for lepidocroclte

mechanism

with

3 and 4 and T a b l e 3) showed

which

frequency).

MH, o n l y t h e s e b a n d s d e s c r i b e d

proposed

bond

f r e q u e n c y as a c o n s e q u e n c e o f i n c r e a s e

o f Amide I I I

surface.

was f o u n d (HERMOSIN e t a l . ,

above

their

some Mtl m o l e c u l e s c o u l d

sepiolite

hydrogen

h y d r o x y l . As a c o n s e c u e n c e

band o f z e o l i t i c

o b s e r v e d f o r MH-L and Mtt-S c o m p l e x e s

1978)

form

1973) 21 and s e p i o l i t e

respectively,

altered

was f o u n d h e r e h i g h e r

The

to

two MIt-mineral c o m p l e x e s ( F i g u r e s

o f 1620 em -1 d e f o r m a t i o n

sepiolite

(WATSON e t a l . ,

H-bond o f Mtt ( d e c r e a s e o f Amide I I

observed indicating open

is suitable

g r o u p i n H-bond t o s u r f a c e

are also

and i n t e r m o l e c u l a r intensity

of these

o f MIt

i n t h e f r e q u e n c y o f vC=O from 1665 c m - l f o r p u r e h e r b i c i d e

a d s o r b e d on

?anide I I I

C--O bond

s u c h as o x i d e s

1980)~ 2 The I R - s p e c t r a a decrease

of

(BSi-OH) groups

molecules.

The

groups same

at pH=7.4 was much higher

(GREENLAND and MOTT,

1978)

18

which at

that pH could be fully dissociated. As shown on Figure 5 and on Table 4 the considered

above and thus will be discussed

SWy showed a decrease indicating shiftings

complex spectrum was different

separately.

in the amount of water molecules

their substitution to higher

MH-SWy

by polar MH molecules.

frequency ~OH and lower

remaining

water

molecules

1980b) 16.

This type of

were H-bonded to

bond has

been

The

FT-IR

associated

spectra of MH complex of

to the

The absorption

exchangeable

shown by

other

that some of the

making a water-bridge

authors

cation

bands of water underwent

frequency vOH which suggested MH molecules

of those

for other

(BELLAMY,

polar molecules

481

(SERRATOSA, 1968; SANCHEZ-CAMAZANO and SANCHEZ-MARTIN, SANCHEZ-MARTIN and SANCHEZ-CAMAEANO,

1983)'' 24(TAHOUN

frequency.

the exchangeable cation

lowering is indicative

on SWy

sample

that this group of MH molecule is bound to

directly (coordinated) or through water bridge (TAHOUN and MORTLAND,

1966)I~ In these complexes both binding

water-bridge

adsorption

were on Amide I, II and llI bands. The vC=O was splitted and lowered in

The frequency

1654 cm -I band had

1966;

1987; McCONNELL and HOSSNER, 1989) 17'8'11.

The most important features observed for IR bands of MH upon (Figure 5, Table 4)

and MORTLAND,

three

components:

bound to exchangeable

mechanisms

seemed to occur. Effectively the complex

1640 and 1654

cm -I corresponding to vC--O directly and

cation and 1650 cm

-l

•

is the water

bending mode of those

water molecules. The amide III band increased and splitted in frequencing by the increase the double bond character to the

C-N

bond (TAHOUN and MORTLAND,

1966)

17

and the great intensity

of 1292 cm-lband could be due to the coupling of amide III band with 6OH, of phenoenollc form of MH,

bonded

to the

oxygens of the

basal plane

of silicate

almost dissappeared most probably because of NH group as suggested

also by

the decrease

of MH molecules to the exchangeable also the

behavlour of MH

but the sorption layer

can be hydrolyzed

UYTERHOEVEN,

1973;

II

band

are H-bonded to the basal oxygen atoms

cations of interlamellar

spaces of SWy sample explained

pH. At pH 5.4 and 7.4 was almost the same

pH 4.0 because at this pH part the aluminium of thes silicate

and removed

HERMOSIN

amide

in frequency of vNH (Figure 5, Table 3). The association

adsorption at different

decreased at

layer. The

and

but remaining

PEREZ RODRIGUEZ,

at interlamellar 1980) 25,26

spaces

blocking

the

(VANSANT and access to MH

molecules. From adsorption and IR results soil

surfaces

by H-bond

through carbonyl

observed for the complexes, agrees with

the results

reported here I~ molecules

the strength of

reported elsewhere

groups.

seem to be bonded to mineral

From the shifting of the PC=O (Table 3)

MH-mineral

bond increased: L
(HERMOSIN et al., 1991) 3 on desorption of MH in

those minerals. CONCLUSIONS The herbicide

maleic hydrazide

interacts

with

soil clay

minerals through

different

mechanisms depending on the characteristics of their surfaces: I) For highly hydroxylated surfaces, such as lepidocrocite and sepiolite, MH is adsorbed by H-bonding between C=O group of the herbicide molecule and surface hydroxyl of minerals. On these surfaces MH seems to be adsorbed as phenoenolic form. 2) For expandable phyllosilicates of permanent

charge

(montmorillonite)

interlamellar

482

adsorption occurred

when the layer charge was not too large.

This interlamellar

occurred by MH binding to exchangeable cation directly (coordinated)

adsorption

and through water bridge

by the carbonyl group of the herbicide molecule which was as phenoenolic

form, bonded also by

NH and OH groups to the basal oxygens of the silicate layer. REFERENCES i) HERMOSIN, M.C.; CORNEJO, J. and PEREZ-RODRIGUEZ,

J.L., Soil Sci. 144, 250-256 (1987).

2) HERMOSIN, M.C. and CORNEJO, J., Soll Scl. 144, 453-457 (1987). 3) HERMOSIN, M.C.; ROLDAN, I. and CORNEJO, J, J. Environ. Sci. Health B (in the press)(1991). 4) SHOVAL, S. and YARIV, S., Clays and Clay Minerals 27, 19-28 (1979). 5) HERMOSIN, M.C. and PEREZ-RODRIGUEZ,

J.L., Clays and Clay Minerals 29, 143-147 (1980).

6) HERMOSIN, M.C.; CORNEJO, J.; WHITE, J.L. and HESS, F.D., J. Agric. Food Chem. 7) HERMOSIN, M.C.; CORNEJO, J. and PEREZ-RODRIGUEZ, 8) SANCHEZ-MARTIN,

M.J. and SANCHEZ-CAMAZANO,

(1982).

J.L., Clay Minerals 20, 153-159 (1985).

M., Chemosphere

16, 937-944 (1987).

9) AOCHI, Y. and FARMER, W.J., Soil Sci. Soc. Am. J. 52, 1265-1270 (1988). i0) MICERA, G.; PUSINO, A.;

GESSA, C. and

PETRETTO, S., Clays and Clay Minerals 36, 354-358

(1988). 11) McCONNELL,

J.S. and HOSSNER,

L.R., J. Agric. Food Chem. 37, 555-560 (1989).

]2) VAN OLPHEN, H. and FRIPIAT, J., Minerals.

Pergamon Press, Oxford.

Data Handbook

for Clay Materials and

others Nonmetalli

(1979).

13) CORNEJO, J. and HERMOSIN, M.C., J. Soil Sci. 39, 265-274 (1988). 14) MOREALE, A. and VAN BLADEL, R., J. Environ. Qual. 9, 627-633 15) BELLAMY, L.J.,

The Infrared

Spectra of Complex

(1980).

Molecules.

Vol. One. Chapman and Hall,

London (1980a). 16) BELLAMY, L.J., The Infrared Group Frequencies.

Spectra of Complex

Chapman and H a l l ,

and MOTT, C . J . B . ,

Vol Two: Advances

in Infrared

London (1980b).

17) TAHOUN, S.A. and MORTLAND, M.M., S o i l S c i . 18) GREENLAND, D . J .

Molecules.

102, 248-254 and 314-321 ( 1 9 6 6 ) .

I n "The C h e m i s t r y of S o i l C o n s t i t u e n t s "

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