Download as pdf or txt
Download as pdf or txt
You are on page 1of 11

Pestic. Sci.

1997, 50, 53È63

Adsorption, Desorption and Mobility of Four


Commonly Used Pesticides in Malaysian
Agricultural Soils*
Uan-Boh Cheah,a” Ralph C. Kirkwoodb and Keng-Yeang Luma
a Strategic, Environment and Natural Resources Research Centre, Malaysian Agricultural Research &
Development Institute (MARDI), PO Box 12301, 50774 Kuala Lumpur, Malaysia
b Department of Bioscience & Biotechnology, University of Strathclyde, The Todd Centre, Glasgow G4
ONR, Scotland, UK
(Received 2 August 1996 ; revised version received 10 January 1997 ; accepted 5 February 1997)

Abstract : Working with Malaysian agricultural soils, high Freundlich adsorption


distribution coefficients (K ) were observed for paraquat (28É7 and 1419) and
glyphosate (83É8 and 417) andads(f)lower values for 2,4-D (0É57 and 5É26) and lindane
(2É65 and 14É1) in a sandy loam and a muck soil, respectively. Desorption of 2,4-
D and lindane from the muck soil occurred. The adsorption of the pesticides was
not a†ected by temperature (20¡C/30¡C), pH or addition of the pesticides as a
mixture. Leaching of 2,4-D and lindane was evident under a high water inÑux
(200 mm). Comparable results in the leaching of 2,4-D were observed between
laboratory studies and a VARLEACH model prediction.

Key words : adsorption ; desorption ; mobility ; 2,4-D, paraquat, lindane ; glypho-


sate ; soil ; Malaysia

1 INTRODUCTION migratory behaviour in the various compartments of


the environment.
Glyphosate, paraquat, 2,4-D and lindane are commonly Studies on the adsorption, desorption and mobility of
used in Malaysian agriculture. The herbicides are used pesticides in soils have been conducted previously on
for the control of a wide range of broad-leaved weeds 2,4-D,3h5 lindane,6h9 paraquat10h13 and glypho-
and grasses in plantation crops such as rubber, oil palm sate.14h21 Such studies, however, have not been report-
and cocoa. Paraquat is often used in vegetable and rice ed for Malaysian soils. Publications on pesticide
agro-ecosystems for weed clearance prior to the start of leaching and mobility in the soil proÐle of this country
a new growing season. Usage of glyphosate for this are also not available. Data generated from research on
purpose has gained momentum in recent years as a these aspects is of major importance in determining the
result of a reduction in the price of the herbicide since environmental fate of these pesticides and the potential
its patent expired. The popularity of 2,4-D for the of groundwater contamination in Malaysian agro-
control of broadleaf weeds in the rice ecosystem is environments. The objectives of the present study were
reÑected in the estimated annual expenditure of RM 4 to determine the adsorption-desorption characteristics
million on the chemical.1 Lindane has been reported to and the mobility of 2,4-D, lindane, paraquat and
o†er e†ective control of the main stemborer species, glyphosate in two Malaysian agricultural soils.
Chilotraea polychrysa (Meyr.) and T ryporyza incertulas
(Walk.) in the cultivation of rice.2 Adsorption of pesti- 2 MATERIALS AND METHODS
cides by soils is an important process inÑuencing their
2.1 Adsorption/desorption
* Based on a communication presented at the COST
ACTION 66 6th International Workshop “Pesticides in the
Soil and the EnvironmentÏ held on 13È15 May 1996 at Strat- 2.1.1 Soils and Pesticides
ford on Avon UK. Soils, collected from a rice-growing area in Tanjong
” To whom correspondence should be addressed. Karang (Pasir Panjang) and a vegetable-growing area
53
Pestic. Sci. 0031-613X/97/$17.50 ( 1997 SCI. Printed in Great Britain
54 Uan-Boh Cheah, Ralph C. Kirkwood, Keng-Y eang L um

in the Cameron Highlands (Kea Farm), were air dried replaced with aqueous calcium chloride (0É01 M ; 10 ml)
and sieved through a 2-mm sieve. They were classiÐed and the tubes were then shaken for a further 4 h. The
as muck and sandy loam, respectively, through mechan- desorption equilibration time was slightly longer than
ical analysis (Table 1). The cation exchange capacity that (2 h) employed by Wahid and Sethunathan7 for
(CEC) was determined using 1 M ammonium acetate. lindane and by Piccolo et al.21 for glyphosate. This pro-
The method as described by Allison22 was employed for cedure was repeated four times, after which the soil was
determining the organic carbon content. The pH of the air dried, homogenised and samples (0É3 g) were
soils was also recorded. radioassayed using a biological oxidiser.
[Ring-U-14C] 2,4-dichlorophenoxyacetic acid, spe-
ciÐc activity 6É29 ] 105 kBq mmol~1, radiopurity [ 2.1.3 E†ects of pH, temperature and use of a pesticide
98%, [U-14C] lindane, speciÐc activity 3É40 ] 105 mixture
kBq mmol~1, radiopurity [ 98% and [methyl-14C]- A solution of the appropriate pesticide (10É0 mg litre~1)
paraquat dichloride, speciÐc activity 3É81 ] 105 kBq was added to the soil sample (2 g) and the pH adjusted
mmol~1, radiopurity [ 98%, were obtained from Sigma to 4É0 or 6É5 using dilute hydrochloric acid or dilute
Chemical Company, St. Louis, USA. [14C]Glyphosate, sodium hydroxide solution. The tubes were shaken
speciÐc activity 18É9 ] 105 kBq mmol~1, radiopurity (30¡C ; 1500 rev min~1 ; 4 h), the contents centrifuged
98É6%, was obtained from Amersham International plc, (3000 rev min~1 ; 30 min) and the supernatant was
Amersham Place, Little Chalfont, Buckinghamshire, radioassayed as above. The e†ect of temperature on
UK. adsorption was investigated at 20¡C and 30¡C. The
e†ect on adsorption of using a mixture of the pesticides
was studied using solutions containing 2,4-D, lindane,
2.1.2 Experimental procedure paraquat and glyphosate (each at 10É0 mg litre~1 in
All determinations were performed in triplicate. An 0É01 M calcium chloride). [14C]2,4-D (1É85 kBq), sup-
equilibration time was determined using 1É0 mg litre~1 plemented with non-labelled material, was used when
solutions of 2,4-D (in ethanol), lindane (in acetone), the e†ect on the adsorption of 2,4-D was investigated,
paraquat (in ethanol) and glyphosate (in water) (1É85, with non-labelled lindane, paraquat and glyphosate
0É148, 5É92 and 0É925 kBq of the 14C-labelled pesticides added to the mixture. Similar solutions containing
respectively, mixed with non-labelled analytical grade [14C]lindane (0É148 kBq), [14C]paraquat (5É92 kBq) or
materials). A period of 4 h was found sufficient for [14C]glyphosate (0É925 kBq) with the other com-
adsorption equilibration, and degradation of the chemi- ponents unlabelled, were used.
cal did not occur in this period. A statistical analysis of the above experiments was
Pesticide solutions (0É1, 0É5, 1É0, 2É0 and 5É0 mg conducted using SPSS for Windows (Statistical Soft-
litre~1) were prepared using non-labelled materials and ware published by SPSS). An analysis of variance and
14C-labelled 2,4-D, lindane, glyphosate and paraquat, in the Bonferroni (Least SigniÐcance) Test were carried
solvents and with radioactivity as described above. Soil out.
(2 g) was shaken with the pesticide solution (10 ml) on
an orbital shaker for 4 h. The contents were centrifuged 2.2 Mobility
(3000 rev min~1 for 30 min) and the supernatant (1 ml)
was radioassayed. The experiment was carried out for 2.2.1 Soil column technique
sandy loam and muck soils. Muck (120 g) and sandy loam (165 g) soils were placed
Desorption studies were performed in a similar in a glass column comprising two segments (15 cm
manner using the 1É0 mg litre~1 pesticide solutions. length ] 2É5 cm diameter) held together using clamps
After radioassay of the supernatant from centrifugation, to provide a total depth of 25 cm. The column was
the remainder of the supernatant was removed and covered with black polyethylene on the outside. Radio-
TABLE 1
Physicochemical Properties of Soils Used

Coarse Fine Organic


sand sand Silt Clay carbon
CECa
Soil type (%) pH (meq 100 g~1)

Sandy loam 54É8 31É6 22É5 10É0 1É3 6É7 7É1


(Cameron Highlands)
Muck 0É9 3É8 27É5 32É5 30É5 4É7 54É1
(Tanjong Karang)

a CEC : Cation exchange capacity.


Mobility of pesticides in Malaysian agricultural soils 55

labelled pesticides (18É5 kBq), augmented with non- the pesticides. The model was run on a personal com-
labelled materials, were introduced into the column. puter with a 486 processor.
Distilled water (98É1 ml) was then passed through the
column to simulate 200 mm rainfall. The Ñow rate was 3 RESULTS AND DISCUSSION
adjusted such that the volume of water used was eluted
within 48 h. The leachate was collected at the end of the 3.1 Adsorption/desorption
two-day period. An aliquot (5 ml) of the leachate was
radioassayed. The soil from the top 10 cm, middle
3.1.1 2,4-D
10 cm and bottom 5 cm of the two glass segments was
Adsorption of 2,4-D to both sandy loam (r2 \ 0É92) and
air dried, homogenised and three subsamples from each
muck (r2 \ 0É93) soils was found to best Ðt a Freundlich
soil layer were combusted and radioassayed. Three rep-
adsorption isotherm. Freundlich adsorption distribu-
licate columns were used for each of the pesticides
tion coefficients (K ) of 0É57 and 5É26 litre kg~1 were
investigated. ads(f)
obtained for the sandy loam (Table 2) and muck soils
(Table 3) respectively. The corresponding 1/n values
2.2.1 Modelling were 0É96 and 0É77, respectively.
The CALF model23 as modiÐed by Walker,24 Walker The results agreed with the results of several studies
and Welch25 and given the name VARLEACH by indicating a Freundlich adsorption isotherm for 2,4-
Walker and Hollis,26 was used to predict the leaching of D.3h5 Di†erent K values were reported, however, as
ads(f)

TABLE 2
Adsorption, Desorption and Organic Carbon Distribution Coefficients of Pesticides in the Sandy
Loam Soil

Pesticide

Parameter (litre kg~1)a 2,4-D L indane Paraquat Glyphosate

K 0É49 (^0É07) 3É53 (^0É81) 56É4 (^0É71) 133 (^5É2)


ads(1)
K 0É57 (^0É69) 2É65 (^1É19) 28É7 (^1É2) 83É8 (^1É4)
ads(f)
1/n 0É96 (^0É18) 0É85 (^0É11) 0É60 (^0É05) 0É85 (^0É08)
K 43É9 (^53É1) 204 (^91É5) È È
oc
K 2É57 (^0É34) 16É3 (^6É8) 1304 (^210) 103 (^4É3)
des1
K 5É34 (^0É47) 33É4 (^4É6) NAb 203 (^8É5)
des2
K 10É3 (^1É0) 31É04 (^6É7) NA 200 (^8É1)
des3
K 16É9 (^1É4) 39É7 (^7É1) NA 251 (^32)
des4
r2 0É92 0É85 0É96 0É98

a Except for 1/n.


b NAÈNot available as desorption did not occur.

TABLE 3
Adsorption, Desorption and Organic Carbon Distribution Coefficients of Pesticides in the Muck
Soil

Pesticide

Parameter (litre kg~1)a 2,4-D L indane Paraquat Glyphosate

K 6É95 (^1É72) 14É6 (^3É0) 1693 (^145) 1188 (^252)


ads(1)
K 5É26 (^1É27) 14É1 (^1É2) 1419 (^2É2) 417 (^1É4)
ads(f)
1/n 0É77 (^0É13) 0É97 (^0É08) 1É01 (^0É13) 0É78 (^0É06)
K 17É3 (^4É2) 46É2 (^3É8) È È
oc
K 28É7 (^3É8) 170 (^31) NAb 971 (^200)
des1
K 48É5 (^4É0) 317 (^113) NA 4720 (^5É9)
des2
K 51É9 (^11É1) 853 (^371) NA 4716 (^6É2)
des3
K 44É6 (^4É0) 1350 (^430) NA NA
des4
r2 0É93 0É98 0É95 0É99

a Except for 1/n.


b NAÈNot available as desorption did not occur.
56 Uan-Boh Cheah, Ralph C. Kirkwood, Keng-Y eang L um

a result of di†erences in soil constituents and pH. The has a low adsorption capacity, including negative
observed K values of 1É67 and 8É37 litre kg~1 adsorption for clays.27
ads(f)
(Tables 2 and 3) were higher than those determined by The 1/n values observed for the sandy loam and
Grove,3 who reported K values ranging from 0É09 muck soils were below unity, indicating that the relative
ads(f)
to 1É30 litre kg~1 for soils with varying amounts of adsorption decreased with increasing solution concen-
organic matter content (1É77È10É49%). The higher pH of tration.28 A similar observation was made by Grover.3
the soils used (5É9 and 7É8) may account for the lower K values of 43É9 litre kg~1 and 17É3 litre kg~1 were
oc
K values observed by Grover3 in view of the lower determined for the sandy loam (Table 2) and muck
ads(f)
proportion of 2,4-D in the molecular form. The (Table 3) soils respectively. Lower K values ranging
oc
observed values were also lower than the K of 0É09 from 16É2 to 22É5 litre kg~1 obtained from several soils
ads(f)
on a loamy sand reported by Ogram et al.4 the pH of were reported by Hamaker and Thompson,29 the lower
the sand was, however, not speciÐed. A high K values resulted from the lower adsorption coefficients.
ads(f)
value of 204 litre kg~1 was observed by Susarla et al.5 Based on the K values observed, mobility of 2,4-D in
oc
for a silty loam soil with a pH of 5É8. these soils can be classiÐed as very high (K 0È50) fol-
oc
The K value obtained from the Freundlich equa- lowing the classiÐcation of McCall et al.30 for pesticide
ads(f)
tion for the sandy loam (0É57) was slightly higher than mobility in soils.
that calculated at the 2,4-D solution concentration of The weak binding of 2,4-D to soils was indicated by
1É0 mg litre~1 (K ; 0É49), while the K value for its signiÐcant desorption from both soils, 20É3% of the
ads(l) ads(f)
the muck soil (5É26) was lower than K (6É95). The sorbed 2,4-D being desorbed from the sandy loam soil
ads(l)
di†erences, however, were not signiÐcant. after four successive desorption processes (Table 4). A
The higher K value observed for the muck soil similar desorption pattern was noted for the muck soil,
ads(f)
suggests greater adsorption of 2,4-D to that soil, which with 20É4% of the adsorbed herbicide being desorbed.
was attributed mainly to the high organic matter This suggests that, although there was preferential affin-
(52É3%) of the soil. Organic matter is an important ity of 2,4-D for muck soil, the binding was essentially
factor in the adsorption of 2,4-D to soils as a corre- weak. K values of 2É6, 5É3, 10É3 and 16É9 litre kg~1
des
lation exists between K and soil organic matter were obtained for four successive desorption processes
ads(f)
content.3 The lower pH of the soil (4É7) may enhance from the sandy loam. This contrasts with the higher
the adsorption process, as a result of the availability of values of 28É7, 48É5, 51É9 and 44É6 litre kg~1 obtained
a higher amount of undissociated 2,4-D.3 The lower for the muck soil. The observed K values were higher
des
K observed for the sandy loam was attributed to than the 0É24 litre kg~1 determined by Susarla et al.5
ads(f)
the low organic matter (2É2%) of the soil. for a sandy loam.
The high pH (6É7) of the sandy loam soil may con- The relative affinity of 2,4-D for the sandy loam and
tribute to the lower K observed. Most of the 2,4-D muck soils was reÑected in the percentage radioactivity
ads
would have been in the anionic form at this pH3 and recovered in the soils. A signiÐcant amount (50É0%) of
repulsion of 2,4-D anions to the negatively charged soil [14C]2,4-D was recovered as soil-bound residues in the
colloids would be expected. The clay content in the soil muck soil while only 5É08% was recovered for the sandy
(10É0%) had little or no e†ect on adsorption as 2,4-D loam.

TABLE 4
Desorption of Pesticides from Soils

Amount desorbed (% of applied)


Soil Desorption
type process 2,4-D L indane Paraquat Glyphosate L SDa

Sandy loam 1 11É15 (^0É12) 10É81 (^0É24) 0É42 (^0É00) 2É29 (^0É02) 3É85
2 5É02 (^0É03) 4É62 (^0É04) 0É06 (^0É00) 1É29 (^0É02) 0É45
3 2É58 (^0É02) 4É28 (^0É11) 0É00 (^0É00) 1É19 (^0É02) 0É44
4 1É54 (^0É00) 3É12 (^0É05) 0É00 (^0É00) 0É74 (^0É00) 0É07
LSDa 1É85 3É41 È 0É37
Muck 1 7É75 (^0É02) 1É78 (^0É01) 0É00 (^0É00) 0É51 (^0É01) 0É45
2 4É38 (^0É04) 1É49 (^0É02) 0É00 (^0É00) 0É13 (^0É00) 0É69
3 4É26 (^0É03) 0É52 (^0É02) 0É00 (^0É00) 0É09 (^0É00) 0É33
4 3É97 (^0É02) 0É26 (^0É01) 0É00 (^0É00) 0É00 (^0É00) 0É04
LSDa 0É42 0É42 È 0É19

a LSD : Bonferroni modiÐed least signiÐcant di†erence.


Mobility of pesticides in Malaysian agricultural soils 57

The adsorption of 2,4-D to the sandy loam and muck bound residues in the muck soil ; the corresponding
soils was not signiÐcantly (P \ 0É05) a†ected by pH (4É0 Ðgure for sandy loam was 9É42%.
and 6É7) or temperature (20¡ and 30¡C). Similarly Harris The adsorption of lindane to the sandy loam and
and Warren31 found no apparent e†ect of temperature muck soils was not signiÐcantly (P \ 0É05) a†ected by
on the adsorption of 2,4-D to peat. As pH increases, the pH (4É0 to 6É7), temperature (20¡C and 30¡C) or when
amount of 2,4-D in the molecular form decreases, applied in the pesticide mixture.
causing reduced adsorption to soil.3 This was not,
however, observed in the pH range of the present study.
There was no signiÐcant di†erence (P \ 0É05) in the 3.1.3 Paraquat
adsorption of 2,4-D to the soils in the presence of pesti- Adsorption of paraquat to the sandy loam (r2 \ 0É98)
cide mixtures. This may be attributed to di†erent and muck (r2 \ 0É95) soils was found to best Ðt a
mechanisms of binding of the pesticides to the soils, Freundlich adsorption isotherm in the concentration
resulting in little competition for adsorption sites. range of 0É1 to 5É0 mg litre~1. The observation was con-
trary to several studies which demonstrated that para-
quat adsorption to soils followed the linear form of the
3.1.2 L indane Langmuir equation.12,13 In previous studies high con-
Adsorption of lindane to the sandy loam (r2 \ 0É95) and centrations of solute were used and this may account
muck (r2 \ 0É98) soils was found to best Ðt a Freundlich for the di†erent results observed in the present work.
adsorption isotherm ; K and K were comparable Gamar and Mustafa12 used high concentrations (up to
ads(f) ads(l)
for both soils. K and K values of 2É65 and 3É53 0É01 M) in their study while Kookana and Alymore13
ads(f) ads(l)
litre kg~1 were observed for the sandy loam, and 14É1 used concentrations of 0É005 to 0É05 M. The Langmuir
and 14É6 for the muck respectively ; 1/n values for the equation is reduced to a Freundlich relation in the case
two soils were 0É85 and 0É97 respectively. The results of dilute solutions,33 such as those used in the present
were consistent with those of Wahid and Sethunathan7 study, and may account for the observed Freundlich-
who observed a Freundlich adsorption isotherm of type adsorption. High K values of 28É7 and 1419
ads(f)
lindane for four di†erent types of rice-Ðeld soils. In the litre kg~1 were observed for the sandy loam (Table 2)
present study, the K values observed were compara- and muck (Table 3) soils respectively. These indicate a
ads(f)
ble to a value of 1É4 litre kg~1 for sand reported by high adsorption of paraquat to both sandy loam and
Nordmeyer et al.32 and values of 8É91 and 31É62 litre muck soils, similar to the results of previous
kg~1 reported by Wahid and Sethunathan.7 studies.34h36 Paraquat adsorbs easily to predominantly
The higher K values observed for the muck soil negatively charged soil colloids. The mechanism of
ads(f)
were attributed to the high organic matter content of adsorption of paraquat involves ionic and charge trans-
the muck. This observation was similar to those from fer bonds33 and the K value of the herbicide may
oc
several studies conducted previously.6h8 Organic matter therefore not be applicable.
has been demonstrated as the most important factor Desorption of paraquat from the muck was not
governing the adsorption and desorption of lindane in observed, but low desorption was recorded in the sandy
soil.7 loam after the Ðrst (0É42%) and second desorption
K values of 204 and 46É2 litre kg~1 were determined (0É06%) processes. Subsequent desorption processes,
oc
from the sandy loam and muck soils. Based on these however, failed to displace the paraquat cation from
values, mobility of lindane in soils can be classiÐed either type of soils. The low desorption observed in the
between very high (K 0È50) and medium (K 150È sandy loam may have been caused by the calcium chlo-
oc oc
500) following the classiÐcation of McCall et al.30 for ride used in the experiment. At the high concentration
pesticide mobility in soils. The observed value was of 750 g litre~1, calcium chloride has been found to
lower than the K of 1081 litre kg~1 reported by Kay cause an immediate elution of 10% of paraquat from a
oc
and Elrick.6 sandy loam.36 Estimation of K was not possible in
des
Desorption of lindane occurred in both types of soils, view of the almost negligible desorption.
though a signiÐcantly higher degree of desorption Biological oxidation of the soils revealed the high
(P \ 0É01) was observed from the sandy loam. A total amounts of soil-bound paraquat residues of 60É53% and
amount of 22É83% of [14C]lindane was desorbed from 84É63% in the sandy loam and muck soils, respectively.
the soil after four successive desorption processes, while Using an aqueous solution of 10 mg litre~1, adsorp-
a low quantity (4É05%) was desorbed from the muck tion of paraquat was not a†ected by pH (4É0 to 6É7) in
soil. The same phenomenon was noted by Wahid and either soil (P \ 0É05), conÐrming the results of Akhavein
Sethunathan,7 who concluded that desorption of and Linscott.37 Temperature (20¡C and 30¡C) had no
lindane in soils decreased with increasing organic e†ect (P \ 0É05) on paraquat adsorption, conÐrming the
matter content. results of previous studies concerning the adsorption of
The affinity of lindane for organic matter was reÑec- paraquat to soils with high clay or organic matter
ted in the high amount of 62É07% recovered as soil- content.11,37
58 Uan-Boh Cheah, Ralph C. Kirkwood, Keng-Y eang L um

3.1.4 Glyphosate Application in admixture with the other pesticides


Adsorption of glyphosate to the sandy loam (r2 \ 0É98) did not inÑuence the adsorption of glyphosate to the
and muck (r2 \ 0É99) soils was found to follow a soils (P \ 0É05) under the conditions of the experiment.
Freundlich adsorption isotherm. K and K
ads(f) ads(l)
values of 83É8 and 133 litre kg~1, respectively were 3.2 Mobility
observed for the sandy loam, while the corresponding
values for muck soil were 417 and 1188 litres kg~1. 3.2.1 Soil thin-layer chromatography (T L C)
These results were consistent with those of several pre- R values of 0É36 and 0É05 were recorded for 2,4-D on
f
vious studies demonstrating a Freundlich adsorption sandy loam and muck soils, respectively (Table 5) ; there
isotherm with glyphosate ;15,18,20,21 the K values were no di†erences in the R values between top and
ads(f) f
observed in the current investigation were also compa- sub-soils. These values were lower than those reported
rable to those reported in the literature, which range by Helling and Turner40 for a sandy loam (1É00), silt
from 8 to 1835É6 litre kg~1. loam (0É50) and silty clay loam (0É69). Nevertheless the
A high adsorptive capacity of glyphosate to both R value demonstrates the mobility of 2,4-D in a sandy
f
sandy loam and muck soils was evident from the high loam soil.
K values, and agreed with the results of Sprankle et The R value of lindane for the sandy loam (0É05) was
ads(f) f
al.14 The adsorption of glyphosate involves ligand almost identical to that for the muck soil (0É04) ; again
exchange and therefore the K value, as in the case of there were no di†erences in the mobility between top
oc
paraquat, may not be applicable. and sub-soils. A soil TLC R value for lindane is not
f
Desorption of glyphosate from both the sandy loam cited in the literature, although values for DDT, diel-
and muck soils was evident (Table 4), although the drin and endrin, which have similar physicochemical
desorption was signiÐcantly higher (P \ 0É01) in the properties to lindane, were found to be zero.41
sandy loam than in the muck soil (5É51% compared to An R value of 0É04 was observed for paraquat for
f
0É73%) Piccolo et al.21 demonstrated a much higher top and sub-soils of both the sandy loam and muck soil,
desorption (15È80%) in their study, depending on the which is similar to the R value of zero reported for silt,
f
soil characteristics. In either case, it was shown that silty clay and sandy loams.40,41 The R value correlates
f
adsorption of glyphosate to soils is not permanent and well with results published for laboratory and Ðeld
that leaching through the soil proÐle may occur. studies, indicating the non-migratory behaviour of para-
The adsorption of glyphosate to the soils was not quat in soils.11
inÑuenced (P \ 0É05) by pH(4É0È6É7), in agreement with R values of 0É05 and 0É02 were observed for glypho-
f
Torstensson.19 McConnell and Hossner,18 however, sate in the sandy loam and muck soil, respectively
found that adsorption of glyphosate to clays generally (Table 5) and are comparable to the 0É04È0É14 reported
decreased as the system pH increased and noted that by Sprankle et al.14 on a sandy loam. The immobility of
there were exceptions. Glass20 observed pH- glyphosate in soil measured by this technique provides
independent adsorption of glyphosate to the clay additional evidence for its strong binding to soils.
mineral illite. By contrast, Nicholls and Evans38
3.2.2 Soil column studies
demonstrated that glyphosate adsorption to a sandy
loam increased as pH increased from 2É0 to about 4É0 ; 3.2.2.1 2,4-D. Leaching of [14C]2,4-D in the sandy
at higher pH, however, adsorption decreased with loam and muck soil columns amounted to 4É58% and
increasing pH. 0É23% respectively (Table 6), corresponding with the
Temperature (20 and 30¡C) had no e†ect on the results of several studies, indicating the mobility of 2,4-
adsorption of glyphosate to the test soils (P \ 0É05), D in sandy and low organic soils.41,42 By contrast,
contrary to the Ðndings of Freed et al.39 who reported a Bovey43 indicated little movement of the herbicide in
pronounced e†ect of temperature on glyphosate adsorp- soils and concluded that 2,4-D posed no hazard due to
tion. leaching into the subsoil or in groundwater. The detec-

TABLE 5
R Values as Determined by Soil TLC
f
Sandy loam Muck

Pesticide T op soil Subsoil T op soil Subsoil

2,4-D 0É36 0É35 0É05 0É05


Lindane 0É05 0É05 0É04 0É05
Paraquat 0É04 0É04 0É04 0É04
Glyphosate 0É05 0É03 0É02 0É05
Mobility of pesticides in Malaysian agricultural soils 59

TABLE 6
Pesticide Leaching in Soils under a Simulated 200 mm Rainfall

Radioactivity (% of applied)

L eachate Soil

Pesticide Sandy loam Muck Sandy loam Muck

2,4-D 4É58 (^1É60) 0É23 (^0É07) 80É87 (^8É00) 76É07 (^9É54)


Lindane 1É050 (^0É013) 0É012 (^0É004) 62É85 (^7É87) 70É56 (^10É01)
Paraquat 0É037 (^0É52) 0É006 (^0É014) 53É13 (^8É51) 77É01 (^6É60)
Glyphosate 0É073 (^0É013) 0É044 (^0É001) 69É1 (^12É9) 69É11 (^8É44)

tion of 2,4-D in groundwater in recent years however, of degradation of 2,4-D in the laboratory study. The
provides further evidence of its mobility in soils.44 soil used in the study was air dried and sieved before
The residues of [14C]2,4-D in the soil columns placing in the column, and these processes may have
amounted to 80É87% and 76É07% in the sandy loam resulted in a decrease of soil microbial population and
and muck soils respectively. A comparison of the results activity.
of the laboratory study and model prediction showed a Thus, reasonable agreement between the results of the
reasonably good agreement in the amounts of radioac- column study and the model prediction was observed
tivity found in the leachate of both sandy loam and only in the sandy loam column. Distribution of [14C]-
muck soils (Fig. 1). The amount of [14C]2,4-D found in 2,4-D residues in the three layers of the soil column
the leachate of the laboratory study was slightly higher were 39É41 (top 10 cm), 29É78 (middle 10 cm) and
than predicted, possibly due to a preferential Ñow down 11É68% (bottom 5 cm), compared with the predicted
the sides of the glass column. values of 44É99, 34É00 and 5É84%.
The total amount of [14C]2,4-D found in the sandy
loam (80É87%) compared reasonably well with the 3.2.2.2 L indane. The leachates of the sandy loam and
model prediction (84É82). In the muck soil, however, the muck soil columns contained small amounts of
observed value was higher than the VARLEACH pre- [14C]lindane (1É05% and 0É012% respectively) indicat-
diction (27É92%), and may be attributed to a slower rate ing that leaching of lindane would be possible under

Fig. 1. [14C]2,4-D residues in the leachate and soil layers : a comparison between laboratory studies and a VARLEACH model
prediction.
60 Uan-Boh Cheah, Ralph C. Kirkwood, Keng-Y eang L um

Fig. 2. [14C]Lindane residues in the leachate and soil layers : a comparison between laboratory studies and a
VARLEACH model prediction.

Fig. 3. [14C]Paraquat residues in the leachate and soil layers : a comparison between laboratory studies and a VARLEACH model
prediction.
Mobility of pesticides in Malaysian agricultural soils 61

Fig. 4. [14C]Glyphosate residues in the leachate and soil layers : a comparison between laboratory studies and a VARLEACH
model prediction.
conditions of heavy rainfall, especially in a sandy loam amounts of 14C-radioactivity in the leachate (0É044%).
soil. The results were consistent with those of a Ðeld The observation was similar to that reported by Spran-
study reported by Adhya et al.,9 who observed the kle et al.14 and Roy et al.48 who found limited move-
migration of c-HCH to a lower depth of 30 cm in a soil ment of glyphosate in muck soils.
with sandy clay loam texture. Other studies, however, In the sandy loam soil column, a small quantity of
indicated very little movement of lindane to lower soil [14C]glyphosate was found in the leachate (0É073%),
layers,45,46 though the detection of lindane in suggesting slightly greater mobility of the herbicide in
groundwater47 strongly supports its mobility in the soil this soil. A greater mobility of glyphosate in a sandy soil
proÐle. proÐle has been observed by Damanakis17 and, more
Results showing the existence of [14C]lindane resi- recently, by Piccolo et al.21 who demonstrated possible
dues in the leachates (Fig. 2) indicate little di†erence leaching of the herbicide to lower soil layers with
between the observed (1É05 and 0É012% for sandy loam limited biological activity.
and muck soils, respectively) and predicted (0É24 and Small amounts of [14C]glyphosate residues were
0É00 for sandy loam and muck, respectively) values. obtained in the leachate of the sandy loam and muck
soil columns (0É073 and 0É044% respectively), while the
3.2.2.3 Paraquat. Paraquat leaching was not evident in
VARLEACH model predicted 0% in both cases (Fig. 4).
either sandy loam or muck soil columns, residues in the
There were di†erences in the distribution of 14C-
leachate being virtually absent according to the labor-
radioactivity in the soil columns. [14C]glyphosate resi-
atory study and model prediction (Fig. 3). It has been
dues were unevenly distributed in the laboratory study,
shown that, following application of paraquat at the
most of the radioactivity being found in the top 10 cm
agricultural dose rate, its leaching in peat soils is
(52É78 and 51É21% for sandy loam and muck soils
unlikely and no more important than in mineral soils.11
respectively). Corresponding Ðgures for the middle
The distribution of radioactivity in the soil layers,
(10 cm) and bottom (5 cm) segments were 4É31 and
however, was di†erent in the present work. An uneven
5É12% and 12É02 and 12É78% for sandy loam and muck
distribution of [14C]paraquat was observed in the
soils, respectively.
laboratory study, whereas the VARLEACH model pre-
dicted limited movement of [14C]paraquat (top 10 cm)
4 CONCLUSIONS
in the sandy loam and muck soil columns.
3.2.2.4 Glyphosate. There was little mobility of glypho- It was observed that adsorption of 2,4-D, lindane, para-
sate in the muck soil column, as indicated by the low quat and glyphosate to the sandy loam and muck soils
62 Uan-Boh Cheah, Ralph C. Kirkwood, Keng-Y eang L um

followed a Freundlich adsorption isotherm. High K diquat, paraquat and prometone by montmorillonite and
ads(f) kaolinite clay minerals. Proc. Soil Sci. Soc. Am., 32 (1968)
values were obtained for paraquat and glyphosate in
485È7.
the test soils, and much more lower values for 2,4-D 11. Damanakis, M. E., Drennan, D. S. H., Fryer, J. D. &
and lindane ; K and K values of the pesticides Holly, K., The adsorption and mobility of paraquat on
ads(f) des
were higher in the muck soil. Desorption of 2,4-D and di†erent soils and soil constituents. W eed Res., 10 (1970)
lindane was evident from the sandy loam and muck 264È77.
soils but it was not observed for paraquat ; desorption 12. Gamar, Y. & Mustafar, M. A., Adsorption and desorption
and diquat`2 and paraquat`2 on arid-zone soils. Soil Sci.,
of glyphosate occurred from the sandy loam only. 119 (1975) 290È5.
Under the conditions of these experiments, tem- 13. Kookana, R. S. & Alymore, L. A. G., Retention and
perature (20¡C/30¡C), pH (4É0/6É7) and application in release of diquat and paraquat herbicides in soils. Aust. J.
admixture with the other pesticides had no e†ect on the Soil Res., 31 (1993) 97È109.
adsorption of 2,4-D, paraquat, lindane and glyphosate 14. Sprankle, P., Meggitt, W. F. & Penner, P., Adsorption,
mobility and microbial degradation of glyphosate in the
to the sandy loam and muck soils. The e†ect of pesti- soil. W eed Sci., 23 (1975) 229È34.
cide mixtures was expected considering the di†ering 15. Hance, R. J., Adsorption of glyphosate by soils. Pestic.
adsorption mechanisms and sites for the pesticides. Sci., 7 (1976) 363È6.
Soil TLC and column studies showed that only 2,4-D 16. Nomura, N. S. & Hilton, H. W., The adsorption and deg-
was mobile in the sandy loam and muck soils. Leaching radation of glyphosate in Ðve Hawaii sugarcane soils.
W eed Res., 17 (1977) 113È21.
of paraquat and glyphosate was not apparent, while 17. Damanakis, M. E., Behaviour of glyphosate in the soil
leaching of lindane occurred in the sandy loam. In the (adsorption, leaching and degradation). Annals Inst. Phy-
case of 2,4-D, comparable results in leaching were ob- topath. Benaki (N.S.), 11 (1976) 153È67.
served between laboratory studies and a VARLEACH 18. McConnell, J. S. & Hossner, L. R., pH-dependent adsorp-
model prediction. tion isotherms of glyphosate. J. Agric. Food Chem., 33
(1985) 1075È8.
It was noted that the adsorption-desorption charac- 19. Torstensson, L., Behaviour of glyphosate in soil and its
teristics and leaching behaviour of 2,4-D, lindane, para- degradation. In T he Herbicide Glyphosate, ed. E. Gross-
quat and glyphosate in the Malaysian soils showed little bard & D. Atkinson. Butterworth & Co., UK, 1985, pp.
di†erence from the results reported in soils from other 137È56.
parts of world. 20. Glass, R. L., Adsorption of glyphosate by soils and clay
minerals. J. Agric. Food Chem., 35 (1987) 497È500.
21. Piccolo, A., Celano, G., Arienzo, M. & Mirabella, A.,
Adsorption and desorption of glyphosate in some Euro-
pean soils. J. Environ. Sci. Hlth, B29, 6 (1994) 1105È15.
REFERENCES 22. Allison, R. E., In Methods of Soil Analysis, ed. C. A. Black.
American Society of Agronomy, Madison, WI, 1965, Part
1. Cheah, U. B. & Ooi, G. G., Potential approaches towards II, pp. 1346È78.
the degradation of 2,4-D. Proceedings of the National 23. Nicholls, P. H., Walker, A. & Baker, R. J., Measurement
Seminar and W orkshop on Rice Field W eed Management, and simulation of the movement and degradation of atra-
Penang, Malaysia, 1988, 237È43. zine in a fallow soil. Pestic. Sci., 12 (1982) 484È94.
2. Lim, G. S. & Heong, K. L., Habitat modiÐcation for regu- 24. Walker, A., Evaluation of a simulation model for predic-
lating pest population in Malaysia. Malaysian Agriculture tion of herbicide movement and persistence in soil. W eed
Research and Development Institute (MARDI) Publication, Res., 27 (1987) 143È52.
Kuala Lumpur, Malaysia 1977, pp. 1È28. 25. Walker, A. & Welch, S. J., The relative movement and
3. Grover, R., The adsorptive behaviour of acid and ester persistence in soil of chlorsulfuron, metsulfuron-methyl
forms of 2,4-D on soils. W eed Res., 13 (1973) 51È8. and triasulfuron. W eed Res., 29 (1989) 375È83.
4. Ogram, A. V., Jessup, R. E., Ou, L. T. & Rao, P. S. C., 26. Walker, A. & Hollis, J. M., Prediction of pesticide mobil-
E†ects of 2,4-dichlorophenoxyacetic acid in soils. Appl. ity in soils and their potential to contaminate surface and
Environ. Microbiol., 49 (1985) 582È7. groundwater. Proc. Brit. Crop Prot. Counc. SymposiumÈ
5. Susarla, S., Bhaskar, G. V. & Bhamidimarri, S. M. R., Monograph No. 59, 1994, 211È24.
Adsorption-desorption characteristics of some phenoxya- 27. Frissel, M. J., The adsorption of some organic com-
cetic acids and chlorophenols in a volcanic soil. I. Equi- pounds, especially herbicides, on clay minerals. V ersl.
librium and kinetics. Environ. T echnol., 14 (1993) 159È66. landbouwk. Onderz. Ned., 67 (1961) 54.
6. Kay, B. D. & Elrick, D. E., Adsorption and movement of 28. Rhodes, R. C., Belasco, I. J. & Pease, H. L., Determination
lindane in soils. Soil Sci., 104 (1967) 314È22. of mobility and adsorption of agrichemicals on soils. J.
7. Wahid, P. A. & Sethunathan, N., Sorption-desorption of Agric. Food Chem., 18 (1970) 524È7.
a, b and c-isomers of hexachlorocyclohexane in soils. J. 29. Hamaker, J. W. & Thompson, J. M., Adsorption. In
Agric. Food Chem., 27 (1979) 1050È3. Organic Chemicals in the Soil Environment, ed. C. A. I.
8. Wahid, P. A. & Sethunathan, N., Sorption-desorption of Goring & J. H. Hamaker. Marcel Dekker, New York,
lindane by anaerobic and aerobic soils. J. Agric. Food 1972, pp. 49È143.
Chem., 28 (1980) 823È5. 30. McCall, P. J., Laskowski, D. A., Swann, R. L. & Dish-
9. Adhya, T. K., Rao, V. R., Dani, R. C., Panda, D. & Sethu- burger, H. J., Measurements of sorption coefficients of
nathan, N., Leaching of hexachlorocyclohexane isomers in organic chemicals and their use in environmental fate
a Ñooded Ðeld planted or unplanted to rice. W ater Air analysis. Proc. Assoc. Offic. Anal. Chem., 94 (1980) 89È109.
Soil Pollut., 81 (1994) 305È13. 31. Harris, C. I. & Warren, C. F., Adsorption and desorption
10. Weber, J. B. & Weed, S. B., Adsorption and desorption of of herbicides by soil. W eeds, 12 (1964) 120È6.
Mobility of pesticides in Malaysian agricultural soils 63

32. Nordmeyer, H., Pestemer, W. & Rahman, A., Sorption 42. Ogle, R. E. & Warren, G. R., Fate and activity of herbi-
and transport behaviour of some pesticides in ground- cides in soils. W eeds, 3 (1954) 257È73.
water sediments. Stygologia, 7 (1992) 3È11. 43. Bovey, R. W., Residues and fate of phenoxy herbicides in
33. Calvert, R., Adsorption-desorption phenomena. In Inter- the environment. In T he Science of 2,4,5-T and Associated
actions between Herbicides and the Soil, ed. R. Hance. Phenoxy Herbicides, ed. R. W. Bovey & A. L. Young.
European Weed Research Society, Academic Press, 1980, John Wiley & Sons Inc., USA, 1980, pp. 301È56.
pp. 1È30. 44. Waite, D. T., Grover, R., Westcott, N. D., Sommerstad, H.
34. Weber, J. B. & Scott, D. C., Availability of a cationic her- & Kerr, L., Pesticides in ground-water, surface-water and
bicide adsorbed on clay minerals to cucumber seedlings. spring runo† in a small Saskatchewan watershed. Environ.
Science (W ashington), 152 (1966) 1400È2. T oxicol. Chem., 11 (1992) 741È8.
35. Knight, B. A. G. & Tomlinson, T. E., The interaction of 45. Singh, G., Kathpal, T. S., Spencer, T. F. & Dhankar, J. S.,
paraquat (1 : 1@-dimethyl 4 : 4@-dipyridylium dichloride) Dissipation of some organochlorine insecticides in
with mineral soils. J. Soil Sci., 18 (1967) 233È43. cropped and uncropped soil. Environ. Pollut., 70 (1991)
36. Calderbank, A., The bipyridylium herbicides. Adv. Pest 219È39.
Control Res., 8 (1968) 127È235. 46. Martijn, A., Bakker, H. & Schreuder, R. H., Soil persist-
37. Akhavein, A. A. & Linscott, D. L., The dipyridylium her- ence of DDT, dieldrin and lindane over a long period.
bicides, paraquat and diquat. Res. Rev., 23 (1968) 97È145. Bull. Environ. Contam. T oxicol., 51 (1993) 178È84.
38. Nicholls, P. H. & Evans, A. A., Sorption of ionisable 47. Ritter, W. F., Pesticide contamination of groundwater in
organic compounds by Ðeld soils. Part 2 : Cations, bases the United StatesÈA review. J. Environ. Sci. Hlth, B25, 1
and zwitterions. Pestic. Sci., 33 (1991) 331È45. (1990) 1È29.
39. Freed, V. H., Vernetti, J. & Montgomery, M., The soil 48. Roy, D. N., Konar, S. K., Banerjee, S., Charles, D. A.,
behaviour of pesticides as inÑuenced by their physical Thompson, D. G. & Prasad, R., Persistence, movement
properties. Proc. W . W eed Control Conf., 19 (1962) 21È36. and degradation of glyphosate in selected Canadian
40. Helling, C. S. & Turner, B. C., Pesticide mobility : Deter- Boreal forest soils. J. Agric. Food Chem., 37 (1989) 437È40.
mination by soil thin-layer chromatography. Science
(W ashington), 162 (1968) 562È3.
41. Helling, C. S., Pesticide mobility in soils. I. Parameters of
soil thin-layer chromatography. Proc. Soil Sci. Soc. Am.,
56 (1971) 732È7.

You might also like