Methyl Iodide as a Replacement for Methyl Bromide:
Environmental Implications
Principal Investigator: S.R. Yates, U.S. Salinity Laboratory, Riverside,
CA.
Cooperators: J. Gan, F.F. Ernst, D. Wang, W.A. Jury, M.V.
Yates, F. Gao, A. Mutziger, U.S. Salinity Laboratory and University of California, Riverside.
Methyl iodide (MeI) has been recently proposed as an ideal
replacement for methyl bromide in soil fumigation. Current research
indicates that MeI is as effective as methyl bromide (MeBr) in controlling
pests and is readily degraded in the lower atmosphere; hence should not
significantly deplete stratospheric ozone. Since MeI is not a registered
pesticide, however, there is virtually no information regarding its
environmental behavior in agricultural soils. With the impending
cancellation of MeBr and previous cancellation of other soil fumigants, it
has become imperative to find and adopt methods for reducing emissions so
that the remaining soil fumigants do not suffer a similar fate. Also, any
decision to use alternative fumigants should be weighed in terms of the
probable environmental consequences and the associated economic
implications, and should be compared with methyl bromide.
There is a great need for more information on the soilchemical
parameters which characterize the fate and transport of MeI. Since MeI has
a similar chemical structure to MeBr, one would expect similar
environmental behavior. Some information which is important in determining
environmental fate and transport includes: atmospheric degradation,
fieldscale soil degradation, liquidgas phase and liquidsolid phase
partitioning, effective diffusion in soil and the various resistances to
mass transfer between the soil and the atmosphere
(e.g. volatilization). Other useful information on MeI which is generally
available from chemical handbooks includes: water solubility (14,190
mg/L), log Kow (octanolwater coefficient, 1.69), molecular
weight (141.9 g/mole), vapor pressure (400 mmHg @ 25C), vapor density
(4.89 mg/mL) and boiling point (42.5 C). We have recently
started to obtain basic information on MeI transport. For example,
although MeI and MeBr (1420 mmHg @ 20C) have very different vapor
pressures, their Henry's Law constants are similar (Kh,0.25
for MeBr and 0.22 for MeI at 25C). Henry's Law describes the equilibrium
partitioning between the gas and liquid concentration and is an important
measure of how readily a fumigant will diffuse through soils; since vapor
diffusion is much greater than liquid diffusion. The freeair diffusion
coefficients can be obtained using the FullerSchettlerGiddings
correlation (Broadkey and Hershey, 1988) and is 6.96 cm2/min
for MeBr and is 6.28 cm2/min for MeI. Coupling these values to
the gasphase tortuosity gives the gasdiffusion coefficient for the soil.
Soil degradation is the transport parameter which is least
known. Recent experiments indicate that the degradation halflife for
MeBr is approximately 10 days in a Greenfield sandy loam. Preliminary
studies suggest that the MeI halflife is approximately 50 days in this
soil. For a Linne clay loam soil with higher organic matter content, the
halflives were 5 and 10 days, respectively, for MeBr and MeI. A longer
halflife for MeI would promote an increased residence time in soils. This
may cause delays in planting, if the soil needs venting to reduce
phytotoxicity, and would produce a greater total emission into the
atmosphere compared to MeBr. Also, if irrigation follows fumigation, MeI's
high water solubility and long residence time coupled to the reduced
airfilled pore space after irrigation, will increase the probability of
ground water contamination.
To demonstrate these ideas, a simulation of gasphase diffusion in a
sandy loam soil was conducted. The selected soil conditions are typical
for fumigation and the model includes the affects of liquidgas and
liquidsolid partitioning, soil diffusion, degradation and volatilization
at the surface through either a polyethylene or highbarrier plastic
cover. The following soil properties were used for both MeBr and MeI:
porosity 0.4 cm3/cm3, water content 0.15
cm3/cm3, Kd 0.2 cm3/g, bulk
density 1.6 g/cm3 and mass applied 250 kg/ha at a depth of 25
cm. The Henry's law constants were 0.25 (MeBr) and 0.22 (MeI); soil
degradation halflives were 10 days (MeBr) and 50 days (MeI); and the
effective soil diffusion coefficients (e.g., De =
Dsoil/Rg) were 0.376 (MeBr) and 0.301 (MeI). The
resistance offered by the plastic material was obtained using Table 2 of
Yates et al. (1996) which reports the flux density of various fumigants
through polyethylene and Hytibar (highbarrier) plastics. For MeBr and
MeI, respectively, the resistance offered by the highbarrier plastic is
75 and 148 times greater than 1.4 mil polyethylene.
When 1.4
mil polyethylene plastic covers the soil, the model predicts that 43.5% of
the applied MeBr and 67% of the applied MeI will volatilize. The peak flux
densities were 0.10 mg/cm2/min for both MeBr and MeI. When a
highbarrier plastic is used, the model predicts that only 1.4% and 1.9%
of the applied MeBr and MeI escape from the soil. This suggests that the
use of highbarrier plastics offer a important control mechanism for
reducing emissions. Note that these estimates assume that the plastic
remains on the field until soil gasphase concentrations are zero, which
is considerably longer than the time period used in typical fumigations.
Clearly, field experiments and simulations using more comprehensive models
are necessary to refine these estimates. The model predicts
that MeI will move deeper into soils than MeBr and that using a
highbarrier plastic will enhance downward movement. When the surface is
covered with polyethylene, the model predicts that 2.0% and 0.2%,
respectively, of the applied MeBr will move below 3m and 5m deep in soil.
For MeI, 6.1% and 2.0% is predicted. When highbarrier plastic is used,
the fraction of MeBr moving below 3m and 5m is slightly higher at 3.5% and
0.4%. For MeI, using a highbarrier plastic causes significant increases
in deep movement: 17.9% of applied passes 3m and 5.5% at 5m. This is due,
principally, to slower degradation and improved containment.
Although this gives a first glimpse into the behavior of MeI in
soils, the effect of numerous model simplifications need to be
investigated before making any conclusions using the figures given above.
Also, there is a great need for more information on the relevant
environmental parameters for a wider range of soil and environmental
conditions.
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