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REMOVAL OF DICOFOL (KELTHANE ®) RESIDUES

FROM APPLE POMACE


T. E. ARCHER
Department o f Environmental Toxicology
University o f California
Davis. Calif. 95616

Chemical and physical decontamination procedures for dicofol [1,1'-bis(p-chlor-


ophenyl)-2,2,2-trichloroethanol; Kelthane®], as applied to apples under controlled
laboratory conditions, were studied on Red Delicious apple pomace (stems, cores,
seeds, and peelings). Oven heating the contaminated pomace at 100°C for 24 hours,
with and without excess moisture, removes 59.0% to 81.7% of the total dicofol
residues. If the pomace is mixed with dry powdered alkali and heated, the residues
are reduced 85.5% to 94.1%. If the pomace is mixed with dry powdered alkali and
excess moisture, and heated, the total residues are reduced 98.7% to 99.1%. Vapor
washing the pomace with water reduces the dicofol residues from 31.0% to 51.6%.
Vapor washing the pomace with isopropanol reduces the dicofol by 65.6%. Cool-air
drying, sunlight drying, ultraviolet light drying, and hot-air drying further reduces
the total dicofol levels by 43.3%, 30.7%, 24.2%, and 40.6%, respectively, for the
water-vapor-washed pomace, and 68.0%, 71.0%, 83.2%, and 94.0%, respectively, on
the isopropanol-vapor-washed pomace. Dicofol residues can be effectively reduced
on apple pomace by the above physical and chemical decontamination procedures.
The decontaminated pomace can be utilized as a valuable feed by-product from
apples.

Dicofol [ 1 ,l'-bis-(p-chlorophenyl)-2,2,2-trichloroethanol; Kethane ® ] is recommended


in California for insect control on apples. The possibility exists that dicofol residues could
be present on dicofol-treated apples at the time of harvest and therefore, would be found
in the pomace by-product (stems, cores, seeds, and peelings) of processed apples.

The nutritive value of apple waste for livestock has been reported (Atkeson and
Anderson 1927, Burris and Priode 1957, Knott e t al. 1932), and the problem of pesticide
accumulation in adipose tissue of beef cattle fed contaminated apple processing wastes
has been discussed (Bovard e t al. 1961, Rumsey et al. 1969, Wilson et al. 1970).

Specific decontamination procedures for removing dicofol contaminants from whole


apples and pomace have been published (Archer and Toscano 1971, Archer and Toscano
1972). The study reported here was undertaken to investigate 1) the fate of dicofol
residues intentionally applied to apples under controlled laboratory conditions, and 2) the
reduction of these residues in the pomace by chemical and physical procedures. Higher
281

Archives of Environmental Contamination and Toxicology,


Vol. 1, No. 3, 1973, © 1973 by
Springer- Verlag New York Inc.
282 T.E. Archer

than normal levels of dicofol were applied to the apples so that alteration compounds,
which could possibly be formed from the dicofot by the treatments, could be detected by
the analytical procedures used rather than being overlooked if the dicofol residues were 5
ppm or lower.

Materials and m e t h o d s
Apple sample and pesticide application. Red Delicious apples, which had not been
treated with dicofol, were obtained from Placerville, California, in October1971. One
hundred twenty apples were sprayed with 1 liter of acetone containing 1.6 g of pure
dicofol by using a Hudson hand sprayer (Archer 1969b). After air drying for
approximately 5 minutes, the sprayed apples were stored at 4°C in 1 gallon glass pickle
jars containing 6 apples per jar. These apples served as starting materials for the research
investigators. The average percent of the total apple weight for the peels was 9.5%, for the
flesh, 81.0%, and for the cores, 9.5%. The average weight of an apple was 202 g and the
average moisture content was 79%.

Apple pulping. The contaminated apples were cut into quarters and placed in a
laboratory scale pulper-finisher equipped with a 1.52-mm screen (Food Processing
Equipment Co., Kalamazoo, Michigan, Model #LP100). The pomace (seeds and skins)
was separated from the pulp containing the juice. The whole fruit contained 8.4% pomace
(40% moisture), and 91.6% pulp and juice, on a weight basis. The pulp and juice was
composed of 41% pulp and 59% juice. As has been previously reported (Archer and
Toscano 1971), the dicofol residues are mainly found in the pomace; so, only this
product is the material used for investigating the decontamination procedures.

Chemical treatment of the pulp. To each 25-g sample of apple pulp, in a large
evaporation dish, was added 4% by weight each of powdered calcium hydroxide, sodium
carbonate, and sodium hydroxide; and the material in the dish was mixed well. To a
similar series of samples was added 50 mt of deionized water in addition to the alkali. The
samples were heated in a warm-air convection-type oven for 24 hours at 100°C, removed,
and analyzed.

Pomace vapor washing. Seventy-five grams of pomace were vapor washed with either
water or isopropanol vapors of such volumes as to result in 2 liters of condensate of each
solvent. [The specific details of procedure and equipment for vapor washing the samples
have been previously published (Archer and Crosby t968).] The vapor-washed pomace
and the vapor condensates were either analyzed immediately or the washed pomace was
subjected to drying by air, sunlight, and ultraviolet light irradiation as described by
Archer and Toscano (1972) and analyzed for dicofol residues. The ultraviolet light and
sunlight-dried, vapor-washed pomace was dried to 12% moisture and the air-dried,
vapor-washed pomace was dried to 14% moisture.
Removal of Dicofol Residues from Apple Pomace 283

Plant extraction and cleanup. All plant samples were extracted by three 30-min
refluxes with benzene; the solvent was pooled, concentrated, and analyzed (Archer
1969a). The solvent extracts were cleaned up on a chromatographic column packed with
Flofisil (activated at: 270°C for 3 hours). Dicofol and 4,4'-dichlorobenzophenone were
eluted from the Florisil with 390 ml of a diethyl ether-pentane mixture (3:7 by volume),
and recoveries were in excess of 90% as checked by standards and fortified samples
subjected to the same analytical procedures.

Gas-liquid chromatography (glc) and thin-layer chromatography (tic). These proce-


dures were employed routinely, either separately or in combination (Archer 1969a).

Chemicals. All chemicals used were reagent grade. The pesticide chemicals were
analytical standards. The reagent solvents were redistilled shortly before use.

Results and discussion


As shown in Table 1, oven heating of the pomace for 24 hours at 100°C, without or
with excess moisture, removes 81.7% and 59.6% of the total dicofol residues present,
respectively. If powdered calcium hydroxide, sodium carbonate, or sodium hydroxide are
mixed with the pomace and heated, the total dicofol residues are reduced 89.5%, 90.8%,
and 94.1%, respectively. However, if moisture is added to excess in the presence of the
alkali and heat treatments, the total dicofol residues are reduced 98.7%, 99.1%, and
98.7%, respectively. An increased loss of dicofol residue occurs in the pomace samples
with alkali and excess water, over that for the alkali addition only, probably because the
pomace contained only 40% moisture which is insufficient to allow the powdered alkali
optimum conditions for the pesticide degradation. In all the samples, 4,4'-dichlorobenzo-
phenone (DBP) was detected; the DBP residues were converted to the dicofol equivalent
in computing the total dicofol levels.

The effect of vapor washing the pomace with either water or isopropanol for the
removal of the dicofol residues is shown in Table II. Vapor washing with water and
isopropanol removes 31.0% and 65.6% of the total dicofol, respectively. However, in the
experiment with the water-vapor washing and greater temperature exposure, larger
amounts of DBP are formed from the dicofol than in the isopropanol-vapor washing
experiments. Since DBP is much less toxic than dicofol, it is reasonable to consider that
only the remaining dicofol residues are significant. On this basis, vapor washing the
pomace with water removes 51.6% or the original dicofol contaminants.

Table III shows the levels of dicofol and DBP found in the water and isopropanol
vapor condensates as analyzed in each of the four fractions of the total 2-liter washes for
each solvent. Less DBP is washed from the pomace by the water vapors than by the
isopropanol vapors. The total dicofol residues detected in the vapor condensates and the
washed pomace are 86.8% and 92.2%, respectively, of the total original residue for the
tO
Oo
4~

T a b l e I. The Effect of Heat, Moisture, and Alkali on Dieofol- and 4,4 "Diehlorobenzophenone
Residue on Red Delicious Apple Pomaee

Residue present, p p m a

DBP b c a l c u l a t e d
Treatment description Dicofol DBP b as d i c o f o l Total dicofol

U n t r e a t e d c - n o heat 702.1 7.8 10.9 713.0


Oven h e a t e d d .- n o alkali 116.0 11.0 15.4 130.4
Oven h e a t e d w i t h added p o w d e r e d e Ca(OH) 2 62.0 9.8 14.0 76.0
Oven h e a t e d w i t h a d d e d p o w d e r e d e N a 2 C O 3 57.0 5.6 7.8 65.8
Oven h e a t e d w i t h a d d e d p o w d e r e d e N a O H 30.8 7.4 10.4 41.2 >
Oven h e a t e d plus excess m o i s t u r e 280.0 8.9 12.5 292.5
Oven h e a t e d w i t h a d d e d excess m o i s t u r e
plus p o w d e r e d e Ca(OH)2 7.8 0.5 0.8 8.6
Oven h e a t e d w i t h a d d e d excess m o i s t u r e
plus p o w d e r e d e Na z CO 3 6.0 0.4 0.5 6.5
O v e n h e a t e d w i t h a d d e d excess m o i s t u r e
plus p o w d e r e d e NaOH 7.8 0.7 1.0 8.8

aAll residues expressed on a dry-weight basis.


bDBP: 4,4'-dichlorobenzophenone.
cOriginal moisture content of pomace was 40%.
dOyen heated at 100°C for 24 hours.
eAlkali added to a level of 4% by weight of plant material.
Table II. The Effect of Vapor Washing Followed by Drying on Dicofol- and 4,4 "Dichloro-Benzophenone
Residues on Red Delicious Apple Pomaee

Residue present, ppma

DBP b calculated
Description of treatment Dicofol as dicofol Total dicofol

Water vapor
©
Washed p o m a c e 345.0 147.0 492.0
Washed pomace: air dried e 183.6 95.4 279.0
Washed p o m a c e : sunlight driedd 165.0 176.0 341.0
©
Washed p o m a c e : ultraviolet light dried e 138.6 234.3 372.9
Washed p o m a c e : oven d r i e d 180.0 112.0 292.0

Isopropanol vapor
Washed p o m a c e 232.5 14.5 247.0
©
Washed p o m a c e : air dried c 76.7 2.4 79.1
Washed p o m a c e : sunlight dried d 69.0 2.2 71.2 >
Washed p o m a c e : ultraviolet light dried e 34.1 7.4 41.5
Washed pomace: oven dried f 13.5 1.3 14.8 ©

No treatment

702.1 10.9 713.0

aAll residues expressed on a dry weight basis.


bDBP; 4,4'-dichlorobenzophenone.
CAir dried to 14% moisture at 24°C.
dSunlight dried to 12% moisture at 28°C.
eUltraviolet light dried to 12% moisture at 38°C. i'-.)
fOven dried to 0% moisture at 100°C.
b-)

T a b l e III. The
Amounts of Dicofol and 4,4"Dichlorobenzophenone Found
in the Water- and Isopropanol-Vapor Washesfrom the Apple Pomaee

Residue p r e s e n t , p p m a

Water v a p o r Isopropanol vapor

DBP b calculated DBP b calculated Total


Wash Dicofol a as dicofol T o t a l dicofol Dicofol a as dicofol dicofol
analyzed ppm ppm ppm ppm ppm ppm

Wash #1 85.6 19,3 104.9 284.5 33.2 317.7


Wash #2 t3.5 3.5 17.0 51.0 10.9 61,9
Wash #3 0.9 1.7 2.6 24.0 2,1 26,1 >
Wash #4 0.6 1.4 2.0 3.4 2,0 5.4
T o t a l dicofol in ;hes 126.5 411.1
T o t a l dicofol o n shed p o m a c e 492.0 247,0
T o t a l dicofol o n shed p o m a c e a n d in washes 618.5 658.1
P e r c e n t of u n t r e a t e d d i c o f o l residues ( T a b l e I)
f o u n d o n w a s h e d p o m a c e a n d in v a p o r washes 86.8% 92.2°/~

aAU residues expressed on a dry weight basis.


bDBP: 4,4'-dichlorobenzophenone.
Removal of Dicofol Residues from Apple Pomace 287

water and isopropanol treatments. The possibility exists that other products could be
present on the washed pomace; however, they are in amounts below detectability.

Drying the vapor-washed pomace by ambient air, sunlight, ultraviolet light, and hot air
further reduces the dicofol levels (Table II). The total dicofol residues on the
isopropanol-vapor-washed pomace are reduced by an additional 68.0% by cool-air drying,
71.0% by sunlight drying, 83.2% by ultraviolet light drying, and 94% by hot-air drying.
The total dicofol residues on the water-vapor washed pomace are reduced by an
additional 43.3% by cool-air drying, 30.7% by sunlight drying, 24.2% by ultraviolet light
drying, and 40.6% by hot-air drying. If the DBP formed on the water vapor washed
pomace is not considered, the dicofol residues on the vapor-washed pomace are reduced
by 46.8% by cool-air drying, 52.1% by sunlight drying, 59.9% by ultraviolet light drying,
and 47.8% by hot-air drying.

Acknowledgment
The author acknowledges the technical assistance of R. A. Toscano.

References

Archer, T. E.: Kelthane decontamination studies on almond hulls. J. Agr. Food Chem.
17, 1070 (1969a).

__ DDT and related chlorinated hydrocarbon residues on alfalfa hay exposed to drying
by sunlight, ultraviolet light, and air. J. Dairy Sci. 52, 1806 (1969b).

, and R. A. Toscano: Kelthane residues on Gravenstein apples and pomace -


application and removal. J. Anim. Sci. 33, t 327 (1971).

. _ Fate of kelthane residues on apple pomace exposed to drying in the dark, sunlight
and ultraviolet light irradiation. Bull. Environ. Contam. and Toxicol. 7,353 (1972).

__, and D. G. Crosby: Removal of DDT and related chlorinated hydrocarbon residues
from alfalfa hay. J. Agr. Food Chem. 16,623 (1968).

Atkeson, F. W., and G. C. Anderson: Apple pomace silage for milk production. Bull.
Idaho Agr. Exp. Sta. No. 150 (1927).
288 T.E. Archer

Bovard, K. P., B. M. Priode, G. E. Whitmore, and A. J. Ackerman: DDT residues in the


internal fat of beef cattle fed contaminated apple pomace. J. Amin. Sci. 20, 824
(1961).

Burris, M. J., and B. M. Priode: The value of apple pomace as a roughage for wintering
beef cattle. Va. Agr. Exp. Sta. Res. Report no. 12 (1957).

Knott, J. C., R. E. Hodgson, and E. V. Ellington: The feeding value of dried apple
pomace for dairy cows. Bull, Wash. Agr. Exp. Sta. no. 270 (1932).

Rumsey, T. S., K. P. Bovard, S. M. Shepherd, and B. M. Priode: DDT residues in beef


cows fed apple pomace. J. Anim. Sci. 28,418 (1969).

Wilson, L. L., D. A. Kurtz, J. H. Ziegler, M. C. Rugh, J. L. Watkins, T. A. Long, M. L.


Berger, and J. D. Sink: Accumulations of certaifi pesticides in adipose tissues and
performance of angus, hereford, and holstein steers fed apple processing wastes. J.
Anita. Sci. 31,112 (1970).

Manuscript received January 3, 1973; accepted March 10, 1973

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