Soil Pesticide Interactions &

their impact on the volatilization

process
Group Members
Ali Amjad (EE),
Ahmed Afraz Liaqat (EE)
Hammad Qadeer (EE)
Ali Shah Jatala (EE)
 Jawwad Ahmed (EE)
Nasurallah Khan (EE)
Usama (EE)
Outline
Introduction
◦ Field-Measured Volatilization Losses
◦ The Volatilization Process
Factors Controlling Pesticide Volatilization
◦ Properties of the Chemical
◦ Soil Environment
◦ Weather or Climatic Factors
◦ Management and Usage Factors
Conclusions
Introduction
 Volatilization – “loss of chemicals from surfaces in the vapor phase”
e.g. vaporization followed by movement into the atmosphere

 One of the dominant processes that controls the movement of applied pesticides into the
general environment and their lifetime & effectiveness within a specific area

 Potential volatility of a chemical is related to its inherent vapor pressure but actual
vaporization rates depends on the environmental conditions and other factors that control
the behavior of the chemical at the solid-air-water interface.

 Some important factors:

◦ Nature and rate of the interactions between the applied pesticide and the soil constituents
◦ Vapor pressure of pesticides are greatly decreased by their interactions with soil, mainly
resulting from adsorption
Field-Measured Volatilization Losses
 Aerodynamic method for measurement of volatilization losses – calculated from pesticide
concentration, wind speed and temperature gradients obtained in the atmosphere over a
treated field.
 Field measurements have shown that volatilization rates from moist soil surfaces can be
very large even for chemicals with vapor pressures less than 0.133 Pa
◦ Losses approaching 90% within 3 days
◦ Volatilization rates dependent on nature of pesticide and their usage
◦ Shallow soil incorporation and dry soil surfaces greatly restricted volatilization losses
 EPCT (a water soluble herbicide)
EPCT volatilized from water & wet soil after applied to soil as surface irrigation water:
◦ 6 hours – 28.4% volatilized
◦ 46 hours – 45.2% volatilized
◦ Max – 73.6%
Field-Measured Volatilization Losses
(Trifluralin – vapor pressure = 1.1 x 10-4 mmHg at
25°C)
Mode of application Percentage Lost Time elapsed
Soil Incorporation to 2.5 cm 22 120 days
Soil Incorporation to 7.5 cm 3.4 90 days
Surface, dry soil 2 – 25 50 hours
Surface, moist soil 50 3 – 7.5 hours
Surface, moist soil 90 2.5 – 7 days
Field-Measured Volatilization Losses
(Heptachlor – vapor pressure = 3.0 x 10-4 mmHg at 25°C)

Mode of application Percentage Lost Time elapsed

Soil Incorporation to 7.5 cm 7 167 days

Orchard grass 90 7 days

Surface, dry soil 14 – 40 50 hours

Surface, moist soil 50 6 hours

Surface, moist soil 90 6 days

Field-Measured Volatilization Losses
(Lindane – vapor pressure = 6.3 x 10-5 mmHg at 25°C)

Mode of application Percentage Lost Time elapsed

Surface, dry soil 12 50 hours

Surface, moist soil 50 6 hours

Surface, moist soil 90 6 days

Field-Measured Volatilization Losses
(Chlordane – vapor pressure = 1.0 x 10-5 mmHg at 25°C)

Mode of application Percentage Lost Time elapsed

Surface, dry soil 2 50 hours

Surface, moist soil 50 2.5 days

 Field-Measured Volatilization Losses
(DCPA – vapor pressure = 2.5 x 10-5 mmHg at 25°C)

Mode of application Percentage Lost Time elapsed

Surface, moist soil 2 34 hours

Volatilization Process
 Volatilization rates of pesticides from non-adsorbing surfaces are dependent only on vapor
pressure and rate of movement of the chemical away from the evaporating surface.
 Actual rate of loss, or the proportionality constant relating vapor pressure to the
volatilization rate, are almost entirely dependent upon external conditions that affect
movement away from the evaporating surface, like:
◦ Surface roughness
◦ Wind Speed
◦ Air Turbulence, etc
 The rate that a pesticide moves away from the surface is diffusion controlled. Close to a
solid surface, there is relatively no vertical movement of air, and vaporized substances are
transported from the surface through the stagnant air boundary layer only by diffusion.
 Actual rate of mass transfer away from the surface by diffusion is proportional to the
diffusion coefficient and the vapor density at the evaporating surface
Volatilization Process
 When a pesticide is mixed into the soil, it vaporizes at a rate which depends on 3 processes:
◦ Its rate of movement away from the surface
◦ Its effective vapor pressure at the surface or within the soil
◦ Its rate of movement to the vaporizing surface
 Soil incorporated pesticides volatilize at a greatly reduced rate dependent not only on the
equilibrium distribution between the air, water and soil matrix as related to vapor pressure,
solubility, and adsorption, but also on their rate of movement to the soil surface.
 Initial volatilization rate of soil-incorporated pesticides is a function of the vapor pressure of
the chemical at the soil surface as modified by adsorption.
 The small fraction of the pesticide that remains on the soil surface after mixing is readily
lost, and volatilization then becomes dependent on the rate of movement of the chemical to
the soil surface by diffusion and convection in the evaporating water compared with the rate
of movement through stagnant air boundary layer.
Volatilization Process
Wick Effect
 When water evaporates from the soil surface, the suction gradient produced results in
appreciable upward movement of water
 Any pesticides in the soil solution will move toward the surface by mass flow (convection)
with the evaporating water.
 This phenomenon i.e. the “wick effect” was experimentally demonstrated by Spencer and
Cliath to accelerate the volatilization of organic chemicals.
 Volatilization rates due to mass flow (convection) can be estimated from the water flux and
the concentration of the chemical is soil water. The dissolved concentration of chemical in
the soil water can be calculated from an adsorption coefficient for the specific soil or
estimated KOC values.
 When water is not evaporating, the volatilization rate depends on the rate of movement of
the chemical to the soil surface by diffusion, and diffusion equations can be used to predict
changes in concentration of the chemical within the soil and rate of volatilization.
Factors Controlling Pesticide Volatilization

Factors controlling pesticide volatilization include:

Properties of the chemical
Soil environment
Weather / Climatic factors
Management and usage factors under a farmer’s control
Factors Controlling Pesticide Volatilization
Properties of the chemical(s)
Properties of the chemical
◦ Vapor pressure
◦ Solubility
◦ Air water-partition coefficient or Henry’s law coefficient KH
◦ Soil water-partition coefficient KOC
◦ Diffusion coefficient in air
◦ Diffusion coefficient in water
◦ Degradation rate t1/2
Factors Controlling Pesticide Volatilization
Soil Environment
 Wet vs dry soil – greater adsorption of at least some pesticides (parathion,
lindane) on dry than on moist soil. Increasing soil-water content greatly
decreased the vapor adsorption of compounds such as benzenes and
chloronbenzenes. Attributed to lesser adsorption of organic compounds onto
moist soil to the adsorptive displacement by water of organics adsorbed on
the mineral matter within the soil.
 Mineral fraction of the soil functions as a conventional solid adsorbent and
the organic matter functions as partition medium. In aqueous systems,
adsorption on mineral matter is suppressed by water and the uptake by soil
consists primarily of solute partitioning into the organic matter. In dry soils,
it is the mineral fraction that strongly absorbs the nonionic compounds.
 Factors Controlling Pesticide Volatilization
Soil Environment

 Effect of soil water content, water flux and microclimate effects on

diurnal trifluralin volatilization rates
◦ Warm sunny day with high soil water loss rates resulting in the
water content in the surface 0.5 cm decreasing during midday to
about one molecular layer of water
◦ Pesticide flux began to increase in the morning but fell rapidly
when the soil water content in the surface 0.5 cm dropped to low
levels.
◦ Water flux from soil continued to increase > Conditions conducive
to high evaporative losses, but trifluralin flux remained low.
◦ Volatilization flux exhibits strong dependence on soil water content
than on water temperature, water flux or wind speed.
◦ On other days (with low evaporation) trifluralin flux showed
marked temperature dependence, and increased during the day as
temperature increased.
Factors Controlling Pesticide Volatilization
Soil Environment
 Diurnal changes in volatilization of some pesticides from a moist silt-load
soil – maximum flux intensities reached near noon when insolation was
highest. This pattern is observed in soils that contain sufficient water to
maintain a moist soil surface throughout the day when net radiation is
highest.
 For sandy soils, where sufficient drying occurred at the surface to restrict
vapor density, volatilization was greatly reduced near noon. During both
evenings, before and after midday, the sand soil surface was remoistened
from dew and the upward movement of water, which reactivated adsorbed
pesticides and resulted in an increased volatilization in the morning and
evenings.
Factors Controlling Pesticide Volatilization
Weather / Climatic Factors
Temperature
◦ Effects volatilization through effect on vapor pressure.
Vapor pressure of most pesticides increase three to four
time for each 10°C increase in temperature.
Relative Humidity
Wind Speed
Rainfall
Insolation
Summary & Conclusions

Intrinsic properties of individual pesticides are important,

but data from laboratory and field experiments suggest
that the volatilization rate of a specific pesticide in soil is
controlled mainly by soil conditions.
Meteorological variables like temperature, radiation, and
wind speed, are important as they control soil conditions