ENVIRONMENTAL PROTECTION AGENCY

            OFFICE OF ENFORCEMENT
                 EPA-330/2-75-007
    South Dakota Toxaphene Use Study

           June -  September  1975
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER

                     AND
                                         x.
                  REGION VIM              JX

              DENVER, COLORADO        r  	'-
                OCTOBER 1975

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      ENVIRONMENTAL PROTECTION AGENCY
           Office of Enforcement
     South Dakota Toxaphene Use Study
            June-September 1975
               October 1975
National  Enforcement Investigations Center
                    and
                Region VIII
             Denver, Colorado

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                     CONTENTS


  I   INTRODUCTION	   1

 II   SUMMARY AND CONCLUSIONS   	   2

III   STUDY AREA	   3

       South Dakota Sunflower  Belt   ...   3
       Brown-Spink County Study Area  .  .   4
       Sampling Stations, Schedules
         and Methods	4

 IV   STUDY FINDINGS 	  .....   7

       June 1975 Study	7
       July 1975 Study	10
       September 1975 Study	10

     REFERENCES . . . .	12

     APPENDICES
       A  Region VIII Request  to NEIC  .  .  13
       B  Field Sampling Methods  ....  16
       C  Analytical Methods   	  18


                      TABLES

  1   Analytical Results  of Toxaphene
       Use Study, June 1975   	9

  2   Toxaphene Analysis  from Fish
       Collected in the  Area of a
       Fish Kill, July 1975   	11

  3   Analytical Results  of Toxaphene
       Use Study	11


                      FIGURES

  1   Sampling Station Locations 	   5

  2   Acreage Cultivated  in Sunflowers
       and Treated with  Toxaphene ....   8

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                           I.   INTRODUCTION
     During the spring of 1975,  the State of South Dakota reported an
infestation of cutworms which threatened the sunflower production in
twenty-three counties.  To suppress the cutworm population and prevent
the projected damage to 20,000 ha (50,000 acres) of crop, the State
requested a special  exemption from the Environmental  Protection Agency
(EPA) to use toxaphene.*  Pursuant to Section 18 of the Federal In-
secticide, Fungicide and Rodenticide Act, the EPA granted an exemption,
allowing South Dakota to use toxaphene from 4 June to 15 July to control
the cutworms.

     On 11 June 1975, the National Enforcement Investigations Center
(NEIC) was requested by the Enforcement Division, EPA Region VIII,
Denver, Colorado, to investigate the environmental impact of toxaphene
spraying in South Dakota.  The request [Appendix A] lists the exemption
restrictions set forth by the EPA Pesticide Registration Division,
Washington, D. C.

     Following the request from EPA Region VIII, NEIC conducted a field
investigation in Brown and Spink Counties, South Dakota.  The principal
objectives of the study were to:

          1.   Assess the short-term effects of toxaphene on the ecosystem
               adjacent to fields being sprayed to control cutworms.

          2.   Determine the efficacy of using toxaphene to control
               cutworms in young sunflower plants.
* The name Toxaphene is registered for common usage.—Merck Index, 8th Ed.

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                     II.   SUMMARY AND CONCLUSIONS
     On 4 June 1975, EPA issued a 42-day permit to South Dakota, allowing
the State to use toxaphene on the commercial  sunflower crop to control a
cutworm infestation.  The NEIC was asked by EPA Region VIII to help its
Pesticides Branch monitor the application of toxaphene, assess the
environmental impact of it, and determine how effectively toxaphene
controlled cutworms.

     A field investigation began in June 1975 at two areas adjoining the
James River in Brown County, South Dakota.   A reference area, where use
of toxaphene was prohibited, was selected near the Sand Lake National
Wildlife Refuge.  Another area 30. km (18 mi)  south, which included
toxaphene-treated fields and adjacent wetlands, was used to monitor the
environmental effects of toxaphene.

     The June study showed that toxaphene provided adequate control of
cutworms on young sunflower plants.  Also,  measurable amounts of toxaphene
(0.1 to 0.51 yg/g) were found in minnows collected from nearby streams.
Surveillance of the area by EPA and U. S. Fish and Wildlife Service
revealed no other environmental impact.

     The second phase of the toxaphene use  study was conducted in July
1975, following a fish kill near the Sand Lake Refuge reference area.
NEIC reported the .probable cause of the kill  to be a lack of oxygen in a
reach of the James River.  Chemical analyses of vital organs removed
from the fish confirmed the fact that toxaphene did not kill the fish.

     The final phase of the study was completed in September 1975.
Neither harm nor detectable residues from toxaphene were apparent in
fish or crayfish from the treated area.

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                           III.   STUDY AREA
SOUTH DAKOTA SUNFLOWER BELT

     The sunflower belt begins near the northeastern border of South
Dakota and extends south and west through the James River Valley.   Its
gently undulating terrain is elevated 274 to 427 m (900 to 1,400 ft)
above sea level.1  Much of the area is dotted with ponds or lakes,  lying
adjacent to extensive marshlands -- 280,000 ha (700,000 acres) of wetlands.
A portion of the sunflower production area is drained by the James
River.

     Commercial sunflower production in South Dakota began about 1966.
The crop is grown principally for vegetable oil  but has other uses,
including confectioneries and bird seed.   Young  sunflower plants are
annually subjected to a barrage of insect pests.  One of the most trouble-
some is the larvae of a moth known as cutworm (Chorizagrotis sp).   This
insect larvae feeds on the sunflower stems and leaves, often cutting the
plant off near the soil.  Many of these larvae have infested fields  and
have been responsible for complete crop failure.

     In 1975, about 26,000 ha (65,000 acres) in  South Dakota were culti-
vated with sunflowers.  In May a cutworm outbreak threatened the com-
mercial sunflower crop.  The State requested and received permission
from the EPA to apply toxaphene (an organochlorine insecticide) to
control the cutworm infestation in 23 counties of northeastern South
Dakota.  The EPA restricted the applicators to minimize environmental
damage to wetlands adjacent to the sunflower fields.  NEIC conducted the
toxaphene monitoring program described in this report to specifically
measure the environmental impact.

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BROWN AND SPINK COUNTY STUDY AREA

     Brown and Spink Counties lie in the James  River Valley.   The river
flows southward, dividing each county into approximately equal halves.
More than 10,000 ha (25,000 acres) of sunflowers are grown in the two
counties; the majority of crop is produced adjacent to the James River.

     A reference area at the northern boundary  of Sand Lake National
Wildlife Refuge in Brown County was selected for the field evaluation.
The Refuge is comprised of wetlands used by migratory waterfowl as a
major breeding area.  Contributing to the selection of the reference
area was the fact that it was not subjected to  aerial spraying of toxaphene.
Also, since the area lay north of the sunflower belt, runoff water from
toxaphene-treated fields did not flow into the  reference area wetlands.

     The study area selected to monitor environmental effects of toxa-
phene application included treated fields and a portion of the James
River and its principal tributaries south of Sand Lake Refuge in Brown
and Spink Counties.  This portion of the study  area was directly sub-
jected to aerial spraying of toxaphene.  Furthermore, water runoff from
the fields drained into the streams being monitored for pesticide
contamination.
SAMPLING STATIONS, SCHEDULES AND METHODS

     Ten sampling stations were established to monitor toxaphene.   One
station was in the reference area at the northern boundary of Sand Lake
Refuge (Station 01).   The remaining 9 stations were in the toxaphene-
treated fields in Brown and Spink Counties and in the James River and
its tributaries.   From these sampling stations, fish, invertebrates,
water, sediment,  aquatic vegetation and soil  were collected [Fig.  1].

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                                                                                               5
                                                                  BROWN
                                                                  COUNTY ROAD 5
             ABERDEEN |—I
 = FISH
 = WATER
 = SED/MENT
 = INVERTEBRATES
 = 5011
f=VEGETAT/ON
KILOMETERS
L	if	
10     STATE ROAO 20
     figure I. Sampling Station  localioni, Brown and Spink  Counties, South Ookolo

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     From 25-27 June 1975, toxaphene applications were monitored,  and
the efficacy of toxaphene for control  of cutworms on young sunflower
plants was evaluated.  When a fish kill  occurred near the reference area
on 5 July, fish were collected on 9 July for examination at NEIC.   On 2-
3 September, the possibility of short-term translocation of toxaphene
from treated sunflower fields into the surrounding environment was
investigated.

     Grab sampling techniques (one sample per station per sampling
period) were used to collect water, soil, sediments and biota for
pesticide analyses.  Times and types of samples were varied to correlate
with toxaphene-spray applications and  rain-runoff periods.   Detailed
methods for field sampling and analyses are presented in Appendices B
and C.

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                          IV.   STUDY FINDINGS
     An infestation of cutworms (chorizagrotis sp)  was discovered in the
commercial sunflower crop of Brown County,  South Dakota on 1  June 1975.2
Three days later (4 June 1975)  the EPA granted a special  permit to the
State to use a toxaphene formulation to suppress the cutworm population
and to reduce the threat of severe sunflower crop destruction.   Immediately,
an intensive pesticide spraying program began on cutworm-infested sun-
flower fields throughout Brown  County as well as the northeast corner of
South Dakota.  As shown in Figure 2, farmers and commercial  applicators
applied toxaphene in 12 counties with air and ground equipment at the
EPA specified rate of 2.3 kg/ha (2 Ib/acre).
JUNE 1975 STUDY

     NEIC began a field monitoring program in Brown County, South Dakota
on 25 June 1975.  Approximately 99% of the planned toxaphene applications
on sunflower fields in the county were completed by that time.3'4

     Following aerial pesticide application, samples of water, sediment,
soil and biota were collected from and adjacent to treated fields and
from the reference area in Sand Lake Refuge.  Analysis of these samples
[Table 1] showed measurable amounts of toxaphene in field soils (Station
5: 0.32 yg/g) and minnows from nearby streams (Stations 2, 8 and 9:
0.12, 0.51 and 0.10 yg/g).  Environmental Protection Agency and U. S.
Fish and Wildlife Service personnel* inspected these areas.  They
   Robert R. Johnson, Manager, Waubay National Wildlife Refuge,  South
   Dakota; William Bair, Manager, Sand Lake National Wildlife Refuge,
   South Dakota

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           Figure 2. Acreage Culrivafed in Sunflowers in South Dakota  and Treated with Toxaphene (  ) at Authorized by the f P A,(June 4 — July 15, 1975)
                                                                                                                                                                          00

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                                     Table  1
                    ANALYTICAL RESULTS OF TOXAPHENE USE STUDY
                    IN BROW! AND SPINK COUNTIES, SOUTH DAKOTA
                                    June  1975
Station
No.

01

02
03
04
05
06
07
08
08
08
09
10
Location
Reference Area
James R. , Brown Co. Hwy 5
. Toxaphene Sprayed Area
Elm R. Brown Co. Hwy 14
Pond, W. side S. 28
Putney Twp
Drain, SW of SE Sec 30
Putney Twp
Sunflower field SW of
SW Sec 28 Henry Twp
Sunflower field NE 1/4
Sec. 10, E. Gem Twp.
Ditch west of field NE 1/4
Sec 10, E. Gem Twp
Sunflower field 1/4 mile west
of Mud Cr. Brown Co. Hwy 21
Ditch from field west of Mud
Cr. Brown Co. Hwy 21
Mud Ck. , W. Hanson Twp.
Brown Co. Hwy 21
Mud Ck, Spink Co. Hwy 11
James R. , S. Dakota Hwy 20
Type off
Sample

Sediment
Water
Fathead minnow
N. pike (kidney)
Aquatic vegetation

Sediment
Water
Fathead Minnow
W. Crappie (liver)
Sediment
Water
Sediment
Water
Soil
Soil
Soil
Soil
Soil
Sediment
Water
Fathead Minnows
Crayfish
Aquatic Vegetation
Sediment
Water
Fathead Minnows
Crayfish
Sediment
Water
Bullhead (kidney)
Carp tf
Crayfish
Toxaphene
Concentration

<0.2
<0.8 vg/1

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                                                                       10
found that toxaphene provided control  of cutworms  on  sunflowers.   And
they found no fish and wildlife mortalities  or substantial  decline in
species or wildlife numbers.


JULY 1975 STUDY                                 .

     On 5 July 1975, a fish kill occurred in the James  River near the
Sand Lake National Wildlife Refuge.   The kill, in  the reference area
used by NEIC for the toxaphene study,  was investigated  by an NEIC senior
fishery biologist.  The NEIC  biologist joined a team  of scientists from
the State of South Dakota and the U.  S.  Fish and Wildlife Service.  The
team surveyed the affected reach of the James River and estimated 600
fish were killed, principally northern pike.  Because water samples
collected and analyzed at various points along the James River revealed
a low dissolved oxygen level  (2.0.mg/l), oxygen deficiency was suspected
to be the cause of the kill.

     Live fish (perch and northern pike) were collected on 9 July,
preserved by freezing and returned to NEIC for further  examination.
External and internal examination of fish showed no gross abnormalities.
Whole-body, young-of-the-year yellow perch were analyzed for toxaphene
residue, and kidneys were removed from the larger  fish, northern pike,
and also analyzed for toxaphene; however, no toxaphene  was detected
[Table 2].


SEPTEMBER 1975 STUDY

     On 2-3 September, fish samples were collected at four sites [Table 3],
In June, fathead minnows collected at Station 08 in Mud Creek contained
0.51 yg/g toxaphene.  However, in September Mud Creek was dry at Station
08 and no fish were collected there.   Downstream at Mud Creek Station 09
and at all other locations no toxaphene was  detected  in any of the fish.

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                                                                        11
                                Table 2
                TOXAPHENE ANALYSIS FROM FISH COLLECTED
                      IN THE AREA OF A FISH KILL
                  North and South Dakota - July 1975
   Location                       Type of                 Toxaphene
                                   Sample               Concentration
                                                           (yg/g)

James R., Dickey Co.  Hwy 5
  N. Dak.                       Northern pike (kidney)     <0.50

James R., Brown Co.  Hwy 5
  S. Dak.                       Northern pike (kidney)     <1.7
                                Yellow perch1"              <0.2

                                Yellow perch1"              <0.2


t  Young-of-the-year
                                Table 3

               ANALYTICAL RESULTS OF TOXAPHENE USE STUDY
               IN BROWN AND SPINK-COUNTIES,  SOUTH DAKOTA
                            September 1975
Station
No. -
Location
Type
of Sample
Toxaphene
Concentration
(vg/g)
                 Reference Area

    01       James R., Brown Co.
               Hwy 5                 Carp (viscera)            <0.5

                 Toxaphene Sprayed Area

    02       Elm R., Brown Co.
               Hwy 14                W. Crappie (viscera)      <0.4

    09       Mud Ck., Spink Co.
               Hwy 11                Carp (viscera)            <0.3
                                     Fathead Minnows           <0.3
                                     Crayfish                  <0.3

    10       James R., S. Dakota
               Hwy 20                Carp (viscera)            <0.2
                                     Bullhead                  <0.2

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                                                                      12
                              REFERENCES
1.   Westin, F.  C.,  L.  F.  Ruhr and G.  J.  Buntley,  1967.   Soils  of South
     Dakota.  Soil  Survey Series No.  1;  Agronomy Dept.  S.  Dakota State
     Univ., Brookings,  S.Dak., 32 p.

2.   Berndt, Wayne,  S.  Dakota State Univ.,  Brookings,  S.Dak.   Personal
     Communication  (verbal)  to John Hale, Environmental  Protection
     Agency, Denver, Colo.  [June 17,  1975].

3.   Caven, James,  Aberdeen  Flying Service,  Aberdeen,  S.Dak.   Personal
     Communication  (verbal)  to John Hale, Environmental  Protection
     Agency, Denver, Colo.  [June 25,  1975].

4.   De Hoog, Marvin, Brown  County Agricultural  Extension Agent.
     Personal Communication  (verbal)  to  John Hale,  Environmental Protection
     Agency, Denver, Colo.  [June 26,  1975].

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          Appendix A
EPA Region VIII  Request to NEIC
         11  June 1975

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                  UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
SUBJECT: Section 18 Exemption
                                                               DATE:   June  11 •  1975
FROM:    David A. Wagoner, Director
         8AH

TO:      Thomas P. Gallagher, Director
              Pursuant to Section 18 of the FIFRA,  EPA has granted  an  exemption
         to the State of South Dakota on June 4,  1975 to use a toxaphene form-
         ulation to suppress populations of cutworms destroying young  plants
         on 50,000 acres of the commercial  sunflower crop in South  Dakota.   The
         exemption is subject to the following restrictions:

              1.  The dosage rate shall not exceed  2.0 pounds per acre actual
         toxaphene.

              2.  Treated acreage shall not exceed  50,000 acres.

              3.  The counties to be treated are  limited as follows:   Beadle,
         Brookings, Brown, Campbell, Clark, Codington, Day, Deuel ,  Edmunds,
         Faulk, Grant, Hamlin, Hand, Hughes, Hyde,  Kingsbury, Marshall, McPherson,
         Potter, Roberts, Spink, Sully, and Wai worth.

              4.  Leaves and stalks are not to be used for livestock feed.

              5. • The South Dakota Cooperative Extension Service must  supervise
         any aerial application to avoid or minimize drift to non-target areas.

              6.  No toxaphene applications are permitted on or near reservoirs,
         rivers, streams or wetlands.  This will  reduce probability of con-
         tamination of domestic water supplies as well as minimize  impact of
         toxaphene on waterfowl .

              7.  This exemption will expire July 15, 1975.

              8.  The South Dakota Cooperative Extension Service will  collect
         data on efficacy, residues, and environmental impact of toxaphene spray
         program.  Pesticide personnel of EPA Region VIII shall be  informed  of
         the times and places of toxaphene applications so that monitoring
         activities of EPA can be coordinated with those of the Cooperative
         Extension Service.

              9.  A residue level not to exceed 7.0 ppm in or on sunflower seeds
         has been determined to be adequate to protect public health.   The Food
         and Drug Administration, DHEW, has been  advised of this action.  Sunflower
         seeds  not to exceed this level may be offered in interstate commerce.
EPA Form 1320-6 (Rev. 6-72)

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However, it should be emphasized that sunflower seeds harvested from
acreages treated with toxaphene must be used for oil  and are excluded
from use for confectioneries, bird seed or any non-oil  use.

     Due to the magnitude of the exemption, the potential  for misuse
and environmental  effects and the need for data in order to  evaluate
expected future use of toxaphene in this manner, I feel  that it is
important to thoroughly investigate a few large toxaphene applications
to sunflowers.  Hhatever support that you can provide to assist in this
effort would be appreciated.

     If you are able to participate in this investigation, program
coordination should be  through:

     Ivan W. Dodson, Chief
     Pesticides Branch

     Robert W. Harding, Chief
     Field Operations Section
     Pesticides Branch

     I hope that such a short notice does not present undue  problems
for your program.

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      Appendix B
Field Sampling Methods

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                                                                      17
                        FIELD SAMPLING METHODS

SEDIMENT
     Samples were collected with  an  Eckman  dredge.   Each  sample was
     placed in a glass wide-mouth quart bottle  and  sealed with a  teflon
     lined lid.  The glass bottles were properly  labelled and refrig-
     erated on crushed ice for shipment to  the  analytical  laboratory at
     NEIC in Denver, Colorado.

WATER
     Samples were collected in glass wide-mouth quart jars,  sealed with
     a teflon-lined lid, labelled and preserved on  crushed ice for
     shipment.

VEGETATION
     Aquatic vegetation was collected by hand and wrapped in acetone-
     washed aluminum foil, labelled  and preserved on crushed ice  for
     shipment.

SOIL
     Samples were collected with  a metallic coring  device capable of
     collecting a core sample 5 cm (2 in) in diameter by  7.5 cm  (3 in)
     deep.  Each sample was wrapped  in acetone-washed aluminum foil,
     labelled and refrigerated on crushed ice for shipment.

FISH AND CRAYFISH
     Specimens were collected with a 10.5 m (35 ft) seine with 6.3 mm
     (1/4 in) bar mesh.  At each  collection site, species were wrapped
     separately in acetone-washed aluminum foil,  and properly labelled.
     Samples of fish and crayfish were preserved  on crushed  ice  until
     the end of the day and then  placed in  a freezer.  The frozen samples
     were returned to the NEIC laboratories in  Denver for pesticide
    .residue analyses.

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    Appendix C
Analytical Methods

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                                                                      19
                          ANALYTICAL METHODS

WATER
     Approximately 1 liter of water was extracted in series with 150,
     100, and 100 ml of hexane.   The container of solvent was  then
     placed on a hot plate under a gentle stream of air and evaporated
     to 10 ml.  A 1  yl  aliquot of the extract was analyzed on  a gas
     chromatograph (GC) with an  electron capture detector (EC) for
     toxaphene.

SOIL AND SEDIMENT
     These were analyzed using a method developed by D.  F. Goerlitz for
     the ASTM.*  A 50 g portion  of the sample is dried overnight in an
     oven to determine moisture  content.  All results are reported on
     the basis of dry weight.  Another 50 g portion is extracted with  a
     40 ml acetone/80 ml hexane  mixture, then re-extracted twice with  a
     20 ml acetone/80 ml hexane  mixture.  The sample is back-extracted
     three times with water and  dried using sodium sulfate (NapSO*).
     The extract is then evaporated to 10 ml in a Kuderna-Danish evaporative
     concentrator.  After an alumina column cleanup, a 1 yl aliquot of
     the sample was analyzed on  an EC/GC for toxaphene.

VEGETATION
     Twenty grams of aquatic vegetation was put into a blender and
     extracted in series using 17o ml and 175 ml of hexane. The hexane
     extracts were combined and  filtered through Whatman No. 1 filter
     paper.  The sample was then evaporated to 10 ml on a hot  plate
     under a gentle stream of air.  A 1 yl aliquot of the extract was
     analyzed for toxaphene using an EC/GC.
   American Society fop Testing and Materials

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                                                                      20
FISH AND CRAYFISH
     A 20 g sample of whole organism or a smaller amount of organs,  was
     extracted in a blender using 175 ml  and 175 ml  of hexane.   The
     hexane extracts were combined and filtered through a Whatman No.  3
     filter paper.  The hexane extract was evaporated to 15 ml  on a  hot
     plate under a gentle stream of air and then partitioned with four
     25 ml portions of hexane-saturated acetonitrile.   The acetonitrile
     was evaporated to dryness on the hot plate and  10 ml of hexane
     added.  After an alumina column cleanup, a 1 ul  aliquot of the
     extract was injected in an EC/GC and analyzed for toxaphene.

ALUMINA COLUMN CLEAN-UP
     The 10 ml extracts were added to 2 x 15 cm columns of activated
     alumina deactivated with 3% water and pre-wetted with hexane.   The
     columns were eluted with 10% ethyl ether in hexane and four 50  ml
     fractions were collected.  Toxaphene elutes in  fractions 1  through
     3, with the majority eluting in fraction 2..

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