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Persistence curves obtained for parathion in six California soils are partially de-
pendent on soil type. The possibility that l o n g - t e r m , l o w - l e v e l parathion soil resi-
dues can exist is confirmed. Each soil was fortified at 20 ppm, kept in an enameled
tray, and maintained at 30°C with a soil moisture level of approximately 40 percent
of saturation. The parathion residue in Laveen loamy sand drops rapidly to about
0.2 ppm in 30 days. In Mocho silt loam, Linne clay, and Madera sandy loam, it
drops to between one and two ppm in 30 days and gradually decreases to about
0.2 ppm in 130 days. The rapid parathion residue decline is attributed to microbial
degradation° In Windy loam, the residue after eight months remains above three ppm.
In two experiments differing slightly in soil moisture, the residue in Santa Lucia silt
loam is about 1.5 ppm after eight months in one experiment and about 0.5 ppm
after six months in the other. The latter two soft types give linear semi-logarithmic
persistence curves, suggestive of degradation by hydrolysis.
Aminoparathion, above the detectable level of one ppm, is not found in Madera
sandy loam after fortification with parathion at 200 ppm. However, a sharp decline
of the parathion residue after ten days suggests microbial degradation. Three ppm
aminoparathion were recovered after seven days when Madera sandy loam was for-
tified at 20 ppm with parathion and submerged under water. In contrast, the de-
gradation of parathion remaining in Windy loam (3.2 ppm) and Santa Lucia silt
loam (2.2 ppm) 7.7 months after fortification is not greatly accelerated when
flooded with water.
Lichtenstein and Schulz (1964) report that 97 percent o f the parathion applied to silt
loam field plots disappears within 90 days. In their laboratory experiments, parathion is most
84
persistent in dry soil and least persistent in those kept under permanently wet conditions;
metabolites and degradation products are short-lived relative to the parent compound.
Voerman and Besemer (1970) find 0.06 ppm parathion in the top ten cm of a manure-
treated, light sandy soil that had been surface-treated regularly over a 15-year period.
Chisholm et al. (1955) report that parathion disappears rapidly from field plots of sandy
loam soft. The concentration in the top six inches after five annual spring applications
(1949-1953) of 15.7 ppmwas 0.5 ppm in the fall of 1953;in 1964, the level was only 0.2
ppm. In the 1949±1969 period, there was little downward movement of parathion in
these plots even though the average precipitation was 42 inches per year. In the spring of
1969, 16 years after the last application of parathion, 0.06 ppm of parathion is still present
in the top four inches of soil (Stewart et al. 1971).
Since the soft ultimately receives most of the applied pesticides either by direct appli-
cation or by indirect routes, long-term persistence of pesticide residues in soft can possibly
lead to contamination of other components of our ecosystem. Since the fate of parathion
and related compounds, as influenced by soil properties, is incompletely understood,
there was a need for a study of its degradation characteristics in several distinct soft types.
Experimental
Fortification. An appropriate quantity of parathion dissolved in hexane (1.0 mg/ml)
was added to 300 g of air-dried soft. The soft was thoroughly mixed until the solvent
evaporated. This fortified subsample was added to a quantity of unfortified soft suf-
ficient to yield a total weight equivalent to 1.5, 2.0, or 3.0 kg of oven-dry soft. Three
grams of t w o - m m sieved, nonagrarian soft was added to insure the presence of micro-
organisms (See Discussion). The entire sample was mixed for one hour in a Twin Shell
Dry Blender, placed in a 10-1/8 in. x 16-1/8 in. x 2-3/8 in. enameled tray, and distilled
water was added to adjust the moisture content to 40 percent of saturation.
Storage. Each tray was covered with a glass plate to minimize water evaporation which
averaged about 28 g/week. The trays were kept on shelves in a plant growth-chamber
maintained at 30+1°C and about 70percent relative humidity, and continuously illumina-
ted with overhead fluorescent tubes. Evaporation losses were replaced with distilled water
at least weekly to maintain the softs at a constant moisture level; each sample was hand-
mixed at this time, and tray positions in the chamber were interchanged.
rinsed with 80 ml of hexane. The cloudy extract was immediately clarified by swirling
with 10 g of anhydrous Na2SO 4.
The extract was reduced in volume to approximately 10 ml using a Kudema-Danish
concentrator and analyzed by GLC following appropriate dilution or concentration.
Recovery. Six samples of Madera sandy loam, with a moisture content of 40 percent
of saturation and equivalent to 20 g of oven-dry soft, were each placed in a 4 - o z bottle.
After addition of 40 ml of the benzene-acetone mixture (3:1 by volume) to each bottle,
20 #g of parathion in 2 ml of hexane were added, and the mixture was extracted by the
extraction procedure given above. (The recovery of parathion obtained was 98+3 percent
of that added.)
Fortified Madera sandy loam soft. The soil was fortified with 200 ppm parathion, ex-
tracted, and analyzed by the procedures described above. In addition to the three samples
extracted with a benzene-acetone solvent mixture (3:1 by volume) and used for GLC
analysis for parathion, three additional samples were extracted with a chloroform-acetone
mixture (9:1 by volume)(Lichtenstein and Schulz 1964) and analyzed for aminoparathion
using the Averell-Norris colorimetric method (Sutherland and Miskus 1964) for para-
thion but omitting the reduction step.
Flooded softs. Madera sandy loam was fortified with 20 ppm parathion, extracted,
and analyzed by the procedures described above. Aliquots of the fortified soil, equivalent
to 20 g of oven-dry soft, were placed into separate 4 - o z bottles, and were immediately
flooded with 10 ml of distilled water. The bottles were capped and kept in the plant
growth-chamber described above. Extraction was conducted as described above except
that 20 g of anhydrous Na2 SO,, was added with the initial 40 ml of the benzene-acetone
Persistence of Parathion in Soils 87
mixture. The extracts were first analyzed for parathion by GLC and for aminoparathion
by the colorimetric method described above.
Experiments with Santa Lucia silt loam and Windy loam soils differed in that 1) the
soils were flooded, 7.7 months after fortification with parathion (20 ppm), with 20 ml of
distilled water, and that 2) two 10-g portions of anhydrous Na2SO4 were added prior
to the second and third extractions.
In the present study, the test soil was prepared by tumbling a subsample, which had
been fortified with a hexane solution of parathion, with the bulk of the soil sample. This
simulated the incorporation of the pesticide into the soil by surface contamination or ap-
plication followed by discing. A small quantity of freshly collected soil from a single source
was added to each test soil prior to mixing to insure the presence of soil microorganisms
which may not have survived the three- to four-year storage of the air-dried soils prior
to this use. Since each soil was treated in the same manner, meaningful information con-
cerning the relative behavior of parathion in different soil types was obtained.
The parathion persistence curves were obtained using layers of test soil, two to five
cm in depth, contained in an enameled tray and covered with a loosely fitted glass plate
to retard water evaporation. The illuminated, moist, warm layers of soil favored the
growth of microorganisms. Thus, the pesticide chemical present was subject to microbial
degradation, chemical degradation (such as hydrolysis and oxidation), and adsorption to
soil colloids, but not to losses through leaching and soil transport. The glass cover plate
retarded losses from volatilization and photodecomposition.
The properties of the six soils studied, as determined by Hermanson and Rible (1967),
are given in Table I. The parathion persistence curves obtained with the soils are shown
in Fig. 1 tt~rough Fig. 5. (Two independent experiments were conducted to obtain the per-
sistence curves shown for each soil.) In Fig. 1, each curve was generated using the mean
values of the data from two independent replicates because the two replicates for a single
soil gave virtually identical persistence curves; in the remaining figures, the data from each
replicate are plotted separately. Each point represents the mean value obtained from three
replicate samples (six for Figure 1). Each point represents the amount of parathion found
in the final soil extract; it is not corrected for unextracted pesticide chemical or for pro-
cedural losses. (The procedural loss of approximately two percent found for 20 #g of
parathion (one ppm) appears to be representative for the extraction procedure used.)
2o_L
10
g
,q
D_
* "El.o..
0.2
0 30 60 90 120 days
Fig. 1. Recovery (mean) of parathion from 20 ppm fortified soils: © Mocho silt loam with
soil moisture at 40% of saturation; D Linne clay at 43% of saturation; • Madera sandy loam
at 41% of saturation
90 Y. Iwata et al.
It is possible that the samples contain some "unextractable" residues. This possibility
exists because Guenzi and Beard (1970) were unable to recover all the radio-labeled
lindane and DDT from their soils even using Soxhlet extraction with an acetone-hexane
mixture. In Fig. 1 through Fig. 4, the average deviations found for the mean values falling
between 20.0 and 10.0 ppm, 9.9 and 2.0 ppm, 1.99 and 0.20 ppm, and 0.1999 and 0.020
ppm, were -+0.5, -+0.2, -+0.3 and -+0.005 ppm, respectively. In Fig. 5, the average deviation
found for the mean values falling between 200 and 20 ppm and 19.9 and 7.0 ppm were
±3 and -+0.5 ppm, respectively. (The soil moisture levels associated with each experiraent
are given in the legend associated with each figure.)
The behavior pattern of parathion residues in the 20 ppm fortified soils falls basically
into two types. The residue patterns in Mocho silt loam, Linne clay, and Madera sandy
20
10
2
E
E
8
C
.o
...E
e,
0.2 O
w
0.1 - I
xa.
0.02
I I '1 I I I I I I I I I I I
0 30 60 90 120 days
Fig. 2o Recovery of parathion from 20 ppm fortified Laveen loamy sand with soil moisture
at o 39% and • 43% of saturation
Persistence of Parathion in Soils 91
loam soils (Fig. 1) are virtually identical. In general, the residue level ten days after forti-
fication remains relatively high at about ten ppm; after 30 days it is lower, falling between
one and two ppm. Samples taken periodically up to 130 days after fortification show that
the parathion residues steadily decline to approximately 0.2 ppm. The degradation of
parathion in the Laveen loamy sand (Fig. 2) differs in that the drop from the t e n - p p m
to the 0 . 2 - p p m level is quite rapid. The direct cause for the dissimilar residue ievel found
in Fig. 2 thirty days after fortification is not known; there is not any reason to believe
that it is caused by the soil moisture difference. The persistence curves in Fig. 1 and Fig. 2
appear to be leveling off and, thus, suggest that detectable levels of parathion will remain
in the soil for some time. This is in accord with Steward et al. (1970) who reported that
about 0.1 percent of the total parathion applied to sandy loam field plots can be detected
16 years after the last application, and who suggested that some of the parathion might
2o'
10
r~
,=
o \ 0
..c \
I -
-
- o\
_ ~.
0" "-.0--
0°5'-
I I I I I I I I I,,,
0 2 4 6 8 months
Fig. 3. Recovery of parathion from 20 ppm fortified Santa Lucia silt loam with soil
moisture at D 33%, • 53%, • 43%, and o 63% of saturation
92 Y. Iwata et al.
have dissolved in lipids, of the soil organic matter, and thus protected from bacterial de-
gradation and hydrolysis.
In sharp contrast to the behavior in other soils, the quantity of parathion recovered
from Santa Lucia silt loam and Windy loam softs (Fig. 3 and Fig. 4) remains relatively
high over first four months. Even after a substantial moisture increase 134 days after for-
tification, the paiathion recovered from Santa Lucia silt loam continues to give a nearly
linear semi-logarithmic persistence curve for a period of eight months. The cause for the
lack of response to the increase in soil moisture is not known because the dependence of
persistence on soil moisture seems to be demonstrated by comparison of the two plots.
In the eight-month experiment with Windy loam soil, the linear plot was found to level
off at a relatively high residue level of approximately three ppm. The linear portions of
the plots in Fig. 3 and Fig. 4 are analogous to that obtained for the pseudo first-order
hydrolysis of parathion in water with a half-life of 25 days (Cowart et al. 1971).
After 7.7 months had elapsed, 2 0 - g aliquots of Santa Lucia silt loam and Windy loam
soils were placed in bottles and flooded with 20 ml of water for four weeks. In the f o u r -
week period, the residue level of Windy loam soil kept moist in a tray remained at 3.2
2oL
10
E
e~
n
- o .
.g_
¢-
- •
c.
2 -
I I I I I I I I I
0 2 4 6 8 months
Fig. 4. Recovery of parathion from 20 ppm fortified Windy loam with soil moisture at
c347%, • 73%, • 37%, and o 57% of saturation
Persistence of Parathion in Soils 93
ppm parathion while the residue level in the flooded soil decreased by only 0.6 ppm.
In the same period, the residue level in the Santa Lucia silt loam kept moist in a tray
dropped from 2.2 to 1.6 ppm, while the residue level in the flooded soil decreased from
1.3 to 1.0 ppm. Since the initial flooded soil sample was extracted immediately, the dis-
crepancy between 2.2 and 1.3 ppm probably resulted from the difficulty in extracting
the wet soil high in organic matter. After allowing for the low recovery from this flooded
soil, the residue level under flooded conditions was estimated to have decreased by approxi-
mately 0.5 ppm. After the second week, the flooded soils were inoculated with several
drops of water in which reduction of parathion had occurred, and the growth of algae was
noted. However, the data show that the bulk of the parathion was not released by the soil
and subjected to degradation.
2ooL
E
t~
o. 20
8
10
0 10 20 30 days
Fig. 5. Recovery of parathion from 200 ppm fortified Madera sandy loam with soil
moisture at o 39% and • 42% of saturation
94 Y. Iwata et al.
Madera sandy loam was fortified at 200 ppm with parathion and sampled every three
to four days for the purpose of detecting the presence of aminoparathion. Since the
presence of a relatively large quantity of parathion would interfere with the GLC deter-
mination of a minute quantity of aminoparathion, the aminoparathion was determined
colorimetrically. Also, the background encountered in unfortified soil extracts dis-
couraged the use of TLC(Lichtenstein and Schulz 1964) to determine the presence of
aminoparathion. As a result of high background interference in the colorimetric analysis,
the presence of less than one ppm aminoparathion could not be ruled out. If aminopara-
thion was produced in the soil, its concentration did not build up above one ppm.
Lichtenstein and Schulz (1964) fortified a loam soil with 20 ppm of aminoparathion,
and they found that most of it disappeared after one day and that none could be detected
by TLC after four days. However, they detected aminoparathion in their soils and they
attributed its formation primarily to the action of soil yeasts.
The amount of parathion recovered from the 200 ppm fortified Madera sandy loam soil
is shown in Fig. 5. The initially high residue level followed by a sharp decline after ten
days suggests an incubation period followed by vigorous microbial activity. Studies on soil
microorganism populations by Naumann (1970) demonstrated that parathion, methyl
parathion, and 4-nitrophenol can be used as substrates by several groups of soil micro-
organisms; thus, these organisms can temporarily multiply until the substrate is depleted.
Parathion incubated with cultures of Rhizobium japonicum and R. melitoti is metabolized
primarily by nitro reduction (Mick and Dahm 1970). Raymond and Alexander (1971) re-
port that 4-nitrophenol metabolizes in soil. In addition, Fig. 5 suggests that the high
initial fortification of 200 ppm results in a high long-term residue.
In Madera sandy loam fortified at 20 ppm and flooded with water, the disappearance of
parathion is rapid. The parathion residues after one week, two weeks, and one month are
about 1, 0.2, and 0.07 ppm, respectively. In contrast to the moist soils, the presence of
aminoparathion in the submerged soil is readily detected by GLC and confirmed colorime-
trically. The aminoparathion residues after one week, two weeks, and one month are about
3, 1, and 0.5 ppm, respectively. GLC can be used because the quantities of parathion and
aminoparathion in a sample does not differ by more than a factor of ten. Also, smaller
quantities of aminoparathion can be confirmed colorimetricalty because flooded soil ex-
tracts give tess background than the moist soil extracts. It is possible that the reduction
occurred in the aqueous phase in which the growth of algae was noted after several weeks.
Solubility of parathion is 24 ppm in water at 25°C (Sutherland and Miskus 1964). Zucker-
Persistence of Parathion in Soils 95
man et al. (1970) isolated aminoparathion as the major metabolite of parathion from
Chlorella pyrenoidosa protease cultures after seven days. The flooded Madera soil experi-
ment show that parathion-reducing microorganisms were present in the flooded soft;
therefore, it is reasonable to assume that they were also active in the moist soils.
Conclusions
In general, the literature reports suggest that most of the parathion applied to the soil
disappears rapidly but that low levels are retained by the soil for extremely long periods.
The results of this study support this conclusion. In addition, they confirm that the per-
sistence of parathion is partially dependent on soil type and they show that two types of
persistence curves are involved. In Mocho silt loam, Linne clay, Madera sandy loam, and
Laveen loamy sand, degradation is rapid and is attributed to a combination of hydrolysis
and strong microbial activity that overshadows diffe;ences in soil type. In contrast, loss
from Santa Lucia silt loam and Windy loam soils is slow and is attributed to hydrolysis.
The organic matter contents of the six soils correlate well with the parathion persistence.
Parathion disappears faster in the softs with lower organic matter. This finding is contrary
to expectations because soils with a higher organic matter content should support a higher
level of metabolic activity. A reasonable expectation is that, in such soils, parathion ap-
parently is not available for degradation. Since soil organic matter correlates with other
soil properties influencing pesticide behavior, caution should be exercised in interpreting
correlations as causative relations.
Acknowledgments
The assistance of Daniel E. Ott in preparing this manuscript is gratefully acknowledged.
This work was supported by W-45 Regional Research.
References
Chisholm, D., A. W. MacPhee, and C. R. MacEachern: Effects of repeated applications of
pesticides to soil. Canad. J. Agr. Sci. 35,433 (1955).
Cowart, R. P., F. L. Bonner, and E. A. Epps, Jr.: Rate of hydrolysis of seven organo-
phosphate pesticides. Bull. Environ. Contam. Toxicol. 6, 231 (1971).
Guenzi, W. D., and W. E. Beard: Volatilization of lindane and DDT from soils. Soil Sci.
Am. Proceed. 34, 443 (1970).
Harris, C. R., and E. P. Lichtenstein: Factors affecting the volatilization of insecticidal
residues from softs. J. Econ. Entomol. 54, 1038 (1961).
Hermanson, H. P., and J. M. Rible: Unpublished data (1967).
Lichtenstein, E. P., and K. R. Schulz: The effects of moisture and microorganisms on
the persistence and metabolism of some organophosphorous insecticides in soils,
with special emphasis on parathion. J. Econ. Entomol. 57,618 (1964).
96 Y. Iwata et al.