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Soil Science and Agricultural Chemistry Group, Department of Plant Biology and Soil Science, Science Faculty,
University of Vigo, E-32004 Ourense, Spain
b
Nutrition and Bromatology Group, Department of Analytical and Food Chemistry, Science Faculty,
University of Vigo, E-32004 Ourense, Spain
c
Physical Chemistry Department, Science Faculty, University of Vigo, E-32004 Ourense, Spain
d
Physical Chemistry Department, Chemistry Faculty, University of Santiago de Compostela, E-15782 Santiago de Compostela, Spain
Received 20 February 2007; received in revised form 20 July 2007; accepted 23 July 2007
Available online 14 September 2007
Abstract
Pesticides, the most cost-effective means of pest and weed control, allow the maintenance of current yields and so contribute to economic
viability. Concern about the environmental impact of repeated pesticide use has prompted research into the environmental fate of these agents,
which can emigrate from treated fields to air, other land and waterbodies. How long the pesticide remains in the soil depends on how strongly it
is bound by soil components and how readily it is degraded. It also depends on the environmental conditions at the time of application, e.g.,
soil water content. Pesticide use must ensure public safety and environmental protection with regards to both the chemical itself and their
potentially harmful metabolites. This paper reviews what is known of the influence of the physical and chemical characteristics of the soil
system, such as moisture content, organic matter and clay contents, and pH, on the sorption/desorption and degradation of pesticides and their
access to groundwater and surface waters. An understanding of the fate of pesticides is essential for rational decision-taking regarding their
authorization. To reach an adequate understanding will require the concourse of soil science, clay mineralogy, physical chemistry, surface
chemistry, environmental microbiology, plant physiology and, no doubt, other disciplines. Only through a multidisciplinary approach to
environmental research will it be possible to plan, manage, pursue and integrate the results of the studies that will be necessary for the
development of tools and techniques allowing effective environmental decision-making. There seems to be a great potential to develop
microbially derived pesticides, which are effective, reliable and have a low environmental risk. In addition, new application techniques, for
example precision band spraying, can reduce the dose, which can be a very effective way to minimize transport and emission but also to avoid
a build-up of resistance in target organisms. Improved formulations will also be needed to reduce off-target deposition, improve retention on
target, and enhance uptake and translocation.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Pesticides in soil; Sorption; Persistence; Degradation; Transport; Fate; Water pollution
Contents
1.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1. Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2. Environmental residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Corresponding author.
E-mail address: jsimal@uvigo.es (J. Simal-Gandara).
0167-8809/$ see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.agee.2007.07.011
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1. Introduction
1.1. Pesticides
Any substance or mixture of substances intended for
preventing, destroying, repelling, or mitigating any pest or
weed is a pesticide. Pesticides can be classified according to
their target, their mode or period of action, or their chemistry
(Table 1). More than 500 different pesticide formulations are
being used in our environment, mostly in agriculture
(Azevedo, 1998), although the control of biological public
health hazards also continues to be an important field of
application. In the last 50 years, the use of pesticides has
greatly increased the quantity and improved the quality of food
for the growing world population. However, with increasing
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Table 1
Classifications of pesticides
By target
Type
Target
Type
Action
Bactericide (sanitizers
or disinfectants)
Defolianta
Desiccanta
Fungicide
Herbicide
Bacteria
Contact
Crop foliage
Crop foliage
Fungi
Weeds
Eradicant
Fumigants
Nonselective
Post-emergence
Insecticide
Insects
Pre-emergence
Miticide (acaricide)
Molluscicide
Preplant
Protectants
Nematicide
Plant growth regulatora
Rodenticide
Wood preservative
Nematodes
Crop growth processes
Rodents
Wood-destroying
organisms
Selective
Soil sterilant
Stomach poison
Systemic
By chemical structure
In U.S. law the term pesticide is defined to cover not only pesticides proper, but also these other classes of agrochemical.
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Table 2
Factors influencing the persistence of pesticides in soil
Pesticide
Soil/site
Climate
Experimental variables
Chemical nature
Volatility
Solubility
Site
- Elevation, slope, aspect, geographical location
- Plant cover (species, density, distribution,
history at site)
- Fauna (species, density, distribution, history at site)
- Microbial populations (species, density,
distribution, history at site)
- Use of fertilizers, lime, mulches and green manures
- Use of other pesticides and chemicals
- Tillage, cultivation, drainage, irrigation (type,
depth, amount, timing, frequency)
- Fire, e.g., burning of crop residues
- Adjacent environments (hedges, field borders,
woodlots, waterbodies)
- Presence of pollutants
Soil type
- Texture, especially clay content
- Structure, compaction
- Organic matter and humus contents
- Soil moisture, leaching
- pH
- Mineral ion content
Formulation
Concentration
Application
- Method
- Time (of year and day)
- Frequency
- Amount
biological processes, including sorptiondesorption, volatilization, chemical and biological degradation, uptake by
plants, run-off, and leaching (Table 2). These processes
directly control the transport of pesticides within the soil and
their transfer from the soil to water, air or food. The relative
importance of these processes varies with the chemical
nature of the pesticides and the properties of the soil, but two
processes stand out: degradation and sorption (Linn et al.,
1993).
Degradation is fundamental for attenuating pesticide
residue levels in soil (Guo et al., 2000). It is governed by
both abiotic and biotic factors (the latter including
enzymatic catalysis by microorganisms), and can follow
complex pathways involving a variety of interactions among
microorganisms, soil constituents, and the pesticide (Topp
et al., 1997). Thus, degradation rates depend on many
microbiological, physical and chemical properties of the
soil, as well as the properties of the pesticide (Rao et al.,
1983).
Sorption plays a fundamental role in the advective
dispersive transport dynamics, persistence, transformation
and bioaccumulation of pesticides (De Jonge et al., 1996).
The sorption of neutral compounds has been extensively
investigated (Gao et al., 1998), and appears to depend on soil
organic matter content (Spark and Swift, 2002; Coquet,
2003). The molecular nature of soil organic matter has been
proved to be key in determining sorption of nonionic
pesticides (Ahmad et al., 2006). The pesticides which are
most likely to bind covalently to soil humic matter have
functionalities similar to the components of humus.
Oxidative coupling reactions contribute to link humus
together during humification and are mediated not only by
251
Fig. 2. Schematic diagram of the sorption reactions (small k) and instantaneous sorption equilibria (capital K) which may occur with a pesticide in
soil water, as neutral basic or acidic molecule. Slow sorption reactions may
also occur with cationic or anionic species. Ps and Pw are the potentially
available adsorbed-phase and dissolved phase pesticide levels.
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Table 3
Comparison of risk assessment methods categories for water pollution
Methods category
Expertise required
Data requirements
Output
Limitations
Variable. Sensitivity
methods require as few as
two and as many as seven
or more factors. Scale for
assessment decisions dictates
the quantity of data required
Hydrogeological setting
classification methods
output consists of
sensitivity classes
(i.e., low, medium,
high). The output from
scoring methods is a
numerical score.
Outputs of both may
be mapped or listed
- Simulation models
- Pesticide leaching
subcategory
Pesticide use/loading
information is often
based on pesticide
sales, which may be
a misleading indicator
of pesticide loading
If extensive data
collection is
necessary, it may be
expensive and timeconsuming to collect.
Expensive verification
may be necessary.
Substantial ground
water modelling skills
may be required
Generally not suitable
over large land areas.
Pesticide travel times
and resulting
concentrations in
different media are not
addressed. Not usually
used for field-by-field
assessments
Application
Aquifer sensitivity
- Hydrogeologic setting
classification
- Scoring
4. Future prospects
4.1. Improved formulations and application techniques
Use of pesticides in agriculture will lead to their
occurrence in non-agricultural environments. Therefore,
the present environmental concerns over agrochemical
residues in the atmosphere, water, soil and foodstuffs will
not vanish. To guarantee minimal negative side-effects in
ecosystems other than the soilplant system, pesticides,
whether natural or synthetic, should have no or low toxicity,
except for the target organisms. There seems to be a great
potential to develop microbially derived pesticides, which
are effective, reliable and have a low environmental risk. In
addition, new application techniques, for example precision
band spraying, can reduce the dose, which can be a very
effective way to minimize transport and emission but also to
avoid a build-up of resistance of target organisms.
Improved formulations will be needed to reduce offtarget deposition, improve retention on target, and enhance
uptake and translocation. It is also necessary to use the
lowest rates of pesticides for each treatment on an annual
basis. The difficulties in forecasting formulation behaviour
and the cost of empirical field screening can only be reduced
by developing a better understanding of the mode and action
of adjuvants in spray formulations. This approach, in turn,
leads itself to the development of either empirical or
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256
5. Recommendations
5.1. Multidisciplinary approach to environmental
research
Fig. 4. Flow scheme of the use of distribution models with GIS in the
assessment of the environmental fate of pesticides. SAC-C (Satelite de
aplicaciones cientficas-C) and SRTM2000 (Shuttle Radar Topography
Mission launched on February 11, 2000 to collect 3D measurements of
the Earths surface).
Acknowledgements
This work was supported by the Xunta de Galicia under
contracts PGIDIT03PXIB38302PR, PGIDIT03RAG38301PR, PGIDT03PXIC20905PN and PGIDIT04TMT209003PR,
and by the Spanish Ministry of Science and Technology under
contracts AGL2003-02244, CTQ2005-04779, AGL200604231 and AGL2007-62075. We are also grateful by the
Ramon y Cajal contracts awarded to Manuel Arias-Estevez
and Eugenio Lopez-Periago, and also by the Parga Pondal
contract to Elena Martnez-Carballo.
References
Ahmad, R., Nelson, P.N., Kookana, R.S., 2006. The molecular composition
of soil organic matter as determined by 13C NMR and elemental
analyses and correlation with pesticide sorption. Eur. J. Soil Sci. 57,
883893.
Albarran, A., Celis, R., Hermosn, M.C., Lopez-Pineiro, A., Cornejo, J.,
2002. Effect of solid olive-mill waste amendment on pesticide sorption
and leaching in soil. Waste Management and the Environment.In:
International Conference on Waste Management and the Environment,
Cadiz, Spain, September 46, pp. 351359.
Alexander, M., 2000. Aging, bioavailability, and overestimation of risk from
environmental pollutants. Environ. Sci. Technol. 34, 42594265.
Aller, L., Bennett, T., Lehr, J.H., Petty, R.J., Hackett, G., 1987. DRASTIC:
A standardised system for evaluating groundwater pollution potential
using hydrogeologic settings. US Environment Protection Agency, Ada,
Oklahoma, EPA/60012-87/035.
Ares, J.O., Del Valle, H.F., Olinuck, J.A., 2006. Exploring improved
pesticide management in sub-tropical environments with GIS-supported
fate modeling. Agric. Syst. 91 (3), 189210.
Arias-Estevez, M., Soto-Gonzalez, B., Lopez-Periago, E., Cancho-Grande,
B., Simal-Gandara, J., 2005a. Atrazine sorption dynamics in organic
matter rich-soils. Bull. Environ. Contam. Toxicol. 75, 264271.
Arias-Estevez, M., Torrente, A.C., Lopez-Periago, E., Soto-Gonzalez, B.,
Simal-Gandara, J., 2005b. Adsorptiondesorption dynamics of cyprodinil and fludioxonil in vineyard soils. J. Agric. Food Chem. 53 (14),
56755681.
Azevedo, A.S.O.N., 1998. Assessment and simulation of atrazine as influenced by drainage and irrigation. An interface between RZWQM and
ArcView GIS. Doctor Thesis. Iowa State University, Ames, Iowa.
Barriuso, E., Houot, S., SerraWittling, C., 1997. Influence of compost
addition to soil on the behaviour of herbicides. Pesticide Sci. 49, 6575.
Barriuso, E., Koskinen, W.C., Sadowsky, M.J., 2004. Solvent extraction
characterization of bioavailability of atrazine residues in soils. J. Agric.
Food Chem. 52, 65526556.
Baskaran, S., Bolan, N.S., Rahman, A., Tillman, R.W., 1996. Effect of
exogenous carbon on the sorption and movement of atrazine and 2,4-D
by soils. Aust. J. Soil Res. 34, 609622.
257
258
Gao, J.P., Maguhn, J., Spitzauer, P., Kettrup, A., 1998. Sorption of pesticides
in the sediment of the Teufelsweiher pond (Southern Germany). I:
equilibrium assessments, effect of organic carbon content and pH. Water
Res. 32 (5), 16621672.
Gevao, B., Semple, K.T., Jones, K.C., 2000. Bound pesticide residues in
soils: a review. Environ. Pollut. 108, 314.
Gramatica, P., Di Guardo, A., 2002. Screening of pesticides for environmental partitioning tendency. Chemosphere 47 (9), 947956.
Guo, L., Wagenet, R.J., Jury, W.A., 1999. Adsorption effects on kinetics of
aldicarb degradation: equilibrium model and application to incubation
and transport experiments. Soil Sci. Soc. Am. J. 63, 16371644.
Guo, L., Jury, W.A., Wagenet, R.J., Flury, M., 2000. Dependence of
pesticide degradation on sorption: nonequilibrium model and application to soil reactors. J. Contam. Hydrol. 43 (1), 4562.
Gustafson, D.I., 1989. Groundwater ubiquity score: a simple method for
assessing pesticide leachability. Environ. Toxicol. Chem. 8, 339357.
Hallberg, G.R., 1989. Pesticide pollution of groundwater in the humid
Unites States. Agric. Ecosyst. Environ. 26, 299367.
Helweg, A., 1975. Degradation of 14C-maleic hydrazide in soil
as influenced by adsorption on activated carbon. Weed Res. 15,
129133.
Hesketh, N., Brookes, P.C., Addiscott, T.M., 2001. Effect of suspended
soil material and pig slurry on the facilitated transport of pesticides,
phosphate and bromide in sandy soil. Eur. J. Soil Sci. 52,
287296.
Hillel, D., Baker, R.S., 1988. A descriptive theory of fingering during
infiltration into layered soils. Soil Sci. 146, 5156.
Hutson, J.L., Wagenet, R.J., 1992. Leaching Estimation and Chemistry
Model, Version 3. Department of Soil, Crop and Atmospheric Sciences,
Research Series No. 92-3. Cornell University, New York.
Jarvis, N.J., 1991. MACROa model of water movement and solute
transport in macroporous soils. Reports and Dissertations No. 9. Department of Soil Sciences, Swedish University of Agricultural Sciences,
Uppsala.
Jayachandran, K., Steinheimer, T.R., Somasundaram, L., Moorman, T.B.,
Kanwar, R.S., Coats, J.R., 1994. Occurrence of atrazine and degradates
as contaminants of subsurface drainage and shallow groundwater. J.
Environ. Qual. 23 (2), 311319.
Johnson, D.C., Selim, H.M., Ma, L., Southwick, L.M., Willis, G.H., 1995.
Movement of Atrazine and Nitrate in Sharkey Clay Soil. Evidence of
Preferential Flow. Report No. 846. Louisiana State University Agricultural Center, Louisiana Agricultural Experimental Station, Baton
Rouge, LA.
Jones, R.L., Mangels, G., 2002. Review of the validation of models used in
Federal Insecticide, Fungicide, and Rodenticide Act environmental
exposure assessments. Environ. Toxicol. Chem. 21 (8), 15351544.
Kim, Y.J., Hamm, S.Y., 1999. Assessment of the potential for groundwater
contamination using the DRASTIC/EGIS technique, Cheongju area,
South Korea. Hydrogeol. J. 7, 227235.
Knisel, W.G. (Ed.), 1980. CREAMS: A Field Scale Model for Chemical,
Runoff, and Erosion from Agricultural Management Systems. Conservation Research Report, No. 26. U.S. Dept. Agric. Washington, DC.
Koskinen, W.C., Cox, L., Yen, P.Y., 2001. Changes in sorption/bioavailability of imidacloprid metabolites in soil with incubation time. Biol.
Fert. Soils 33, 546550.
Koskinen, W.C., Anhalt, J.A., Sakaliene, O., Rice, P.J., Moorman, T.B.,
Arthur, E.L., 2003. Sorptiondesorption of two aged sulfonylaminocarbonyltriazolinone herbicide metabolites in soil. J. Agric. Food
Chem. 51, 36043608.
Kristensen, G.B., Johannesen, H., Aamand, J., 2001. Mineralization of
aged atrazine and mecoprop in soil and aquifer chalk. Chemosphere
45, 927934.
Laabs, V., Amelung, W., Pinto, A., Zech, W., 2002. Fate of pesticides in
tropical soils of Brazil under field conditions. J. Environ. Qual. 31,
256268.
Larson, S.J., Capel, P.D., Majewski, M.S., 1997. Pesticides in surface
watersdistribution, trends, and governing factors. In: Gilliom, R.J.
259
260