NEIC
PESTICIDE USE OBSERVATION
AINSWORTfl, NEBRASKA
August 1981
November 1981
oEPA
national enforcement investigations center
denver federal center bldg 53, box 25227 denver, co 80225
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
PESTICIDE USE OBSERVATION
AINSWORTH, NEBRASKA
August 1981
November 1981
Bruce A. Binkley
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER, COLORADO
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CONTENTS
EXECUTIVE SUMMARY
INTRODUCTION 1
SUMMARY OF INVESTIGATION 3
CONCLUSIONS 3
TECHNICAL REPORT
STUDY DESCRIPTION 5
IN-SITU FISH EXPOSURES 5
FLOW MEASUREMENTS 9
DISCUSSION OF FINDINGS 10
IN-SITU FISH EXPOSURES 11
FLOW MEASUREMENTS 15
MAGNACIDE H,n INJECTIONS 18
TABLES
1 Station Descriptions 7
2 In-Situ Exposure Survival Data 12
3 Chemical Analysis , 16
FIGURES
1 Ainsworth Irrigation District .
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EXECUTIVE SUMMARY
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INTRODUCTION
At the request of EPA Region VII, the National Enforcement Investi-
gations Center (NEIC) conducted a pesticide use observation in Nebraska
during August 1981. Specifically, Region VII had requested that NEIC
investigate the use of the restricted herbicide Magnacide H™.* Citizens
complaints have been made, alleging that this practice has caused fish
kills in the canal systems and receiving waters.
The agricultural industry is basic to Nebraska's economy. Because
of the erratic rainfall patterns much of the tillable land is irrigated
to increase crop production. Water is provided to landowners for a fee
from a group of privately maintained irrigation districts, Excessive
growth of aquatic weeds in irrigation canals is a chronic problem. If
not controlled, such growth severely restricts water flow and the
increased volume of the weed mass can cause breaching of the canal banks
resulting in serious erosion. Weed control in Nebraska is achieved
primarily through the use of the aquatic herbicide acrolein, marketed
TM
under the trade name Magnacide H (EPA Registration Number 10707-9).
Attributes that promote the widespread use of Magnacide H™ are its high
efficacy as an aquatic herbicide and comparative low cost of treatment.
Magnacide H™ (acrolein 92% by weight) is a clear colorless liquid
with a slightly aldehydic odor and is a powerful lacrimator. Because of
its toxicity by inhalation it is classified by EPA as a Restricted Use
Pesticide for use only by certified applicators or persons under their
direct supervision. The product is supplied by distributors in pressurized
steel cylinders. To achieve weed control the herbicide is forced from
the cylinder by oxygen-free nitrogen through a metering device into the
irrigation water. Normal injections of Magnacide into irrigation
canals provide final concentrations of the product ranging from 5 to 15
TM-Registered Trademark
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ppm. This range is well above the level known to be toxic to fish. For
instance, rainbow trout have been shown to suffer 70% mortality when
exposed to 0.41 ppm acrolein for 48 hours.*
To allow for the protection of non-target aquatic organisms the
TM
registered label for Magnacide H bears the warning "Do not release
treated water for 6 days after application into any fish bearing waters
or where it will drain into them." The 6 day holding period is designed
to allow for complete detoxification of the treated water, however, the
Nebraska Game and Parks Commission has received complaints of fish kills
TM
allegedly occurring in receiving waters as a direct result of Magnacide H
injections into irrigation canals.
From June 1 through June 5, 1981, NEIC and Region VII personnel did
a reconnaissance inspection of three irrigation districts in Nebraska;
the Farmers Irrigation District at Scottsbluff, the Ainsworth Irrigation
District at Ainsworth, and the North Loup Irrigation District at Ord,
Nebraska. Based on the reconnaissance a decision was made to conduct
use observation studies on the Ainsworth and North Loup Irrigation
Districts. Specific objectives for the study were to:
TM
* Determine if Magnacide H use is consistent with label instructions
and federal (FIFRA) regulations.
TM
" Determine if Magnacide H injected into the irrigation canals is
translocated to fish-bearing receiving waters.
TM
' Determine the effects, if any, of Magnacide H on fish populations
in the receiving waters.
Acrolein Residues in Irrigation Water and Effects on Rainbow Trout.
T.R. Bartley, et al, Bureau of Reclamation, Denver, Colorado, May
1975.
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3
SUMMARY OF THE INVESTIGATION
The field work for the study was conducted from 3 August through
17 August 1981. On the 4th and 5th of August, exceptionally heavy rain
and hail (4-6 inches) was encountered at Ainsworth and Ord, Nebraska.
As a result of the heavy rainfall and its effect on the irrigation
system, much of the work intended to meet the study objectives was not
completed. The rainfall caused a severe cutback in herbicide appli-
cations at Ainsworth, and resulted in complete cancellation of appli-
TM
cations at Ord. At no time during the study was Magnacide H used on
any portion of the North Loup Irrigation District canal system. At
Ainsworth, NEIC conducted a limited pesticide use investigation which
included caged fish exposures, flow measurements, and observation and
TM
limited sampling of Magnacide H injections.
CONCLUSIONS
As a result of the limited use observation study done in Ainsworth,
Nebraska during August 1981, the following conclusions were drawn.
TM
Injection of Magnacide H for aquatic weed control is lethal
to fish within the confines of the canal system.
Because of the hydrology of the irrigation system, it is
unlikely that treated water can be held for six days for
injections made in the Airport and Sand Draw lateral canals.
Significant mortality occurred among fish exposed in Sand Draw
Creek at its confluence with the Airport Lateral irrigation
return. However, it could not be confirmed that the mortality
was directly related to acrolein toxicity.
It was not determined that use of acrolein in the irrigation
system has had an adverse affect on Long Pine Creek.
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TM
In general, Magnacide H ' injections were found to conform
with existing regulations defining the proper use of this
restricted pesticide. An inconsistency with label instructions
TM
was noted concerning storage of Magnacide H tanks. The
tanks at the Ainsworth facility were stored uncovered in the
open, whereas, the label requires that storage be under cover
in a well ventilated area.
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TECHNICAL REPORT
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5
STUDY DESCRIPTION
Evaluation of the operation of the Ainsworth Irrigation System was
done through observations of field inspectors, and review of information
provided by the District Supervisor and irrigation district maps. Water
is supplied to the district from Merritt Reservoir, an impoundment on
the Snake River approximately 53 miles west of Ainsworth. Water is
delivered to the Ainsworth area through a single concrete-lined main
canal. This canal has an initial capacity of 580 cfs flow and services
approximately 34,000 acres of farmland. At Ainsworth water is diverted
to cropland through 5 main lateral canals and numerous minor laterals
for a total length of 169.7 miles (Figure 1). In order to insure
sufficient water delivery to all parts of the district, an excess must
be drawn from Merritt Reservoir. When all water demands have been
satisfied this excess water is "wasted." Two methods of "wasting" are
used; collection in waste impoundments which are small, shallow con-
tainment ponds and direct discharge into local creeks. A major concern
in the Ainsworth area is Long Pine Creek, an established trout stream
and recreational area. A gradual degradation of the quality of the
creek and declining trout populations has been alleged by local citizens
to be due to the Irrigation District wasting acrolein laden water into
the creek system. The following studies were done to determine if
TM
Magnacide H , when properly used by the Irrigation District, is having
an adverse effect on the aquatic environment of receiving waters.
In-Situ Fish Exposures
Live blueqilis (Lepomis machrochirus) were exposed in floating
cages at 12 locations in the canal system and receiving waters to
evaluate the effects of acrolein injections. Stations 2, 3, and 4 were
in Long Pine Creek (Table 1, Figure 2). Station 4, located upstream of
any possible irrigation discharge served as a control. Stations 6 and 7
were in Bone Creek and Stations 5 and 8 located in Sand Draw Creek. The
remaining five stations (1, II, 15, 25. 29) were located in the canal
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Figure 1
AINSWORTH IRRIGATION DISTRICT
AINSUORTH, NEBRASKA
August 1981
CT»
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1
2
3
4
5
6
7
8
11
15
24
25
29
30
31
32
7
Table 1
STATION DESCRIPTIONS
AINSWORTH, NEBRASKA
AUGUST 1981
LOCATION
100 feet above Ainsworth main syphon at Bone Creek
Overflow.
Long Pine Creek approximately 1 1/4 miles downstream
from confluence of Bone Creek.
Long Pine Creek approximately 1/8 mile downstream from
confluence of Bone Creek.
Long Pine Creek 4 miles south of city of Long Pine
Control Station.
End of line Airport Lateral (A 12.1) confluence with
Sand Draw.
Bone Creek 3/4 mile downstream from Bone lateral overflow
17.1.
Bone Creek at confluence of Ainsworth syphon overflow.
End of line of Sand Draw lateral at confluence with
Sand Draw.
Sand Draw lateral mile post 1.8.
Sand Draw lateral mile post 6.8.
Bone lateral B-15.0 - 2.8.
Bone lateral B-20.75
Bone lateral end of line B-25.2.
Bone lateral B-12.3 Headgate.
Bone lateral B-12.3 - 5.0.
Bone lateral B-12.3 - 7.0.
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;Pine Creek
Scale 2 miles
o Containment Pond
Bone /•
Creek
Figure 2
SAMPLING LOCATIONS
AINSUORTII IRRIGATION DISTRICT
August 1981
Uillow: r .
Creek
Long Pine
03
©\
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9
system. Twelve fish were exposed in each cage for a 96-hour period.
Measurements were taken daily at each station of water temperature, pH,
and dissolved oxygen concentration.
Flow Measurements
Flow measurements using fluorscent Rhodamine WT dye were done at
three locations in the canal system: lateral 52.6 mile marker 0.9
(Figure 1), Sand Draw lateral at mile markers 0.0 and 1.2 (Figure 2).
Magnacide Injection
Inspections were made of the Ainsworth Irrigation Districts facilities
TM
and observations made of five Magnacide H injections by NEIC and/or
Region VII inspectors to verify that users:
TM
Were properly certified and trained to inject Magnacide H
herbicide.
Adhere to all registered label instructions and precautions.
Properly clean and maintain all injection and protective
equipment.
Store and dispose of herbicide containers in the prescribed
manner.
TM
Maintain complete and accurate records of all Magnacide H
injections.
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10
DISCUSSION OF FINDINGS
There are two possible modes through which the Operations of the
Ainsworth Irrigation System might effect an adverse impact on Long Pine
Creek: acrolein toxicity and habitat destruction by excessive siltation.
If irrigation return flow contains acrolein, the possibility exists that
it could be toxic to fish in Long Pine Creek during times of low flow.
It was observed that the stretch of Long Pine Creek below the confluence
of Bone Creek (Station 3, Figure 2) bears a heavy silt load. Very
little habitat is available for either benthic organisms or trout which
in turn feed primarily on the benthos. During the study period, the
silt contribution coming from Bone Creek was very evident. However it
must be realized that due to the extremely heavy rainfall, wasted
irrigation water, and natural runoff were abnormally high. It was also
observed that some growers appeared to irrigate excessively. Water was
allowed to breach the field borders and run down the hillside into Bone
Creek, also increasing the silt load.
Prior to the installation of the Ainsworth irrigation system, Sand
Draw Creek, a tributary to Bone Creek, was an intermittent stream of low
flow. However due to irrigation return and field runoff the Creek now
flows continually during the irrigation season and adds to the silt
burden.
It appears that under normal flow conditions, there is no need to
have excessive wasted irrigation water. Of the six containment ponds
inspected, only one located at the end of Bone lateral 15.0 (Figure 2)
had any possibility of returning irrigation water to any local creeks.
In general the containment ponds were small and shallow allowing wasted
water tc dissipate through evaporation and percolation. The pond at
Bone lateral 15.0 did contain an overflow pipe. If the water level
rises tc the pipe, irrigation water would flow through Rattlesnake Gulch
directly into Long Pine Creek. It seems unlikely however, that such an
overflow would normally be toxic. During the study fishermen were
observed catching mature bullhead from this pond indicating the pond
water was probably not toxic for at least several years.
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11
Four areas were observed where wasted water directly enters local
receiving waters:
1) The overflow at the main Ainsworth Syphon (Station 1,
Figure 2). This overflow was observed to discharge irrigation water
directly to Bone Creek following the heavy rainfall.
2) The overflow on Bone lateral at mile post B-17.1. This overflow
discharges directly into Bone Creek. No active discharge was observed
during this study.
3) Airport lateral A-12.1 discharges directly into Sand Draw
Creek through a syphon at Station 5 (Figure 2). This discharge was
active continually during the study period.
4) Sand Draw lateral discharges directly into Sand Draw Creek
through a syphon at' Station 8 (Figure 2). This discharge was active
continually during the study period.
In-Situ "ish Exposures
Results of the in-situ fish exposures are inconclusive. Eleven
exposures consisting of 12 fish per exposure cage were done from August 9
through August 13. Survival of the exposed fish for the 96-hour period
ranged from 0-100% (Table 2, Figure 2). Of particular note is the fact
that no nortality occurred at any of the stations located in Long Pine
Creek (Stations 2, 3, 4). Extensive mortality occurred at Stations 25
and 29 located in the Bone lateral canal. Survival at these stations
was only 17% and 0% respectively. Irrigation district records show
Magnacide H™ was injected into this canal on August 7 and 8 just prior
to the fish being placed into the exposure cages. Eight injections were
done on August 7, starting at mile post 12.7 and occurring at approxi-
mately mile intervals to mile post 20.5. On August 8, injections were
done at mile posts 21.53 22.9 and 24.0. Stations 25 and 29 are located
at mile posts 20.75 and 25.2 respectively.
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Table 2
Station No.
1
2
3
4
(Control)
IN SITU EXPOSURE
SURVIVAL DATA*
AINSWORTH, NEBRASKA
August 1981
Date Hours of Exposure No. Surviving % Survival Temperature pH Dissolved Oxygen
9 Aug. 81
0
12
12
22.5
11 Aug. 81
48
8
66
21.5
8.0
7.5
12 Aug. 81
-72
8
66
22.7
7.9
7.1
13 Aug. 81
96
8
66
22.0
7.9
9 Aug. 81
0
12
100
22.0
10 Aug. 81
24
12
100
21.0
7.9
8.1
11 Aug. 81
48
12
100
21.5
8.4
7.5
12 Aug. 81
72
12
100
18.8
7.7
9.0
13 Aug. 81
96
12
100
17.9
7.8
6.9
9 Aug. 81
0
12
100
21.0
10 Aug. 81
24
12
100
19.0
7.6
8.8
11 Aug. 81
48
12
100
21.5
8.4
7.5
12 Aug. 81
72
12
100
17.8
8.0
9.5
13 Aug. 81
96
12
100
17.3
8.0
7.6
9 Aug. 81
0
12
100
21.0
10 Aug. 81
24
12
100
19.0
7.6
8.8
11 Aug. 81
48
12
100
21.5
8.4
7.5
12 Aug. 81
72
12
100
17.8
8.0
9.5
13 Aug. 81
96
5**
100
17.3
8.0
7.6
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Table 2 (Continued)
IN SITU EXPOSURE
SURVIVAL DATA
Ainsworth, Nebraska
August 1931
Station No. Date Hours of Exposure No. Surviving % Survival Temperature phi Dissolved Oxygen
9 Aug. 81
0
12
100
25.0
0 Aug. 81
24
8
66
27.0
9.1
7.9
1 Aug. 81
48
2
17
31.9
9.1
6.0
2 Aug. 81
72
1
8
28.5
8.2
7.5
3 Aug. 81
96
1
8
23.9
8.6
7.5
9 Aug. 81
0
12
100
23.0
0 Aug. 81
24
12
100
1 Aug. 81
48
12
100
24.6
8.2
6.6
2 Aug. 81
72
12
100
18.2
7.9
8.2
3 Aug. 81
96
9
75
18.7
8.0
6.6
9 Aug. 81
0
12
100
18.5
0 Aug. 81
24
1 Aug. 81
48
8
66
21.4
8.2
7.6
2 Aug. 81
72
7
58
15.3
6.1
4.6
3 Aug. 81
.96
6
50
18.4
7.1
5.9
9 Aug. 81
0
12
100
22.5
0 Aug. 81
24
1 Aug. 81
48
6
50
20.6
7.9
6.9
2 Aug. 81
72
1
8
21.6
8.6
7.3
3 Aug. 81
96
1
8
21.6
8.2
5.8
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Table 2 (Continued)
IN SITU EXPOSURE
SURVIVAL DATA
Ainsworth, Nebraska
August 1981
Station No. Date
Hours of Exposure No. Surviving I Survival Temperature pH Dissolved Oxygen
¦irk
15
9
10
Aug. 81
Aug. 81
0
24
12
100
23.0
11
Aug. 81
48
11
92
21.9
8.0
6.4
12
Aug. 81
72
10
83
22.2
7.8
6.8
13
Aug. 81
96
10
83
21.5
7.8
4.0
25
9
Aug. 81
0
12
100
24.0
10
Aug. 81
24
10
83
24.0
7.8
5.9
11
Aug. 81
48
4
33
25.7
9.0
11 ."
12
Aug. 81
72
2
17
23.6
8.5
10.4
13
Aug. 81
96
2
17
22.3
8.4
7.7
29
9
Aug. 81
0
12
100
26.0
10
Aug. 81
24
7
58
26.5
8.2
8.7
11
Aug. 81
48
4
33
30.0
8.8
8.3
12
Aug. 81
72
0
0
28.5
8.9
10.2
13
Aug. 81
96
0
0
23.0
8.3
7.6
Vandeli s
m not mortality.
Security seal
was broken indicating cage had been opened.
No data
all fisi
is recorded for
released.
station 8. This
site was vandelized
within
the first 24 hours
of exposure
and
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15
At Station 5 only 8% (one fish) survived the exposure period
(Table 2). This station was located directly in the overflow from the
Airport lateral end on line discharge at the confluence with Sand Draw
Creek. Irrigation District records show injections occurred on the
Airport lateral on August 10 at mile posts 1.8, 3.0, 4.5, 6.7, 8.5, 9.7,
12.6, 14.2, and 15.6.
Significant mortality also occurred at Stations 7 and 11 where 50%
TM
and 8% was recorded, respectively. Ho specific injection of .Magnacide H
correlated with mortality at these stations.
TM
These data indicate that Magnacide H injections into the canal
system are lethal to fish living within the confines of the canal
itself. This is substantiated by visual observations made during the
study when dead fish could be observed on almost any occasion in the
various laterals. The high mortality of caged fish in receiving water
at Sand Draw Creek,(Station 5) indicates that the discharge at this
point can be lethal. However, this does not prove that acrolein injections
have been lethal to indigenous fish. Given the opportunity, fish will
avoid acrolein and it is quite probable this occurs in the receiving
waters. Chemical analysis of waters from the canal and receiving waters
during the period mortalities occurred did not show acrolein to be
presen- and were inconclusive (Table 3). However since injections move
through the canal system in waves, acrolein may have been present at
earlier times and missed in the NEIC sampling.
Flow Measurements
The results of three sets of flow measurements indicate the grade
is quite consistent through the canal system. In all three tests, the
calculated flow was approximately 1 ft/sec or approximately Q.7 mile per
hour. This indicates that injections in the Sand Draw and Airport
laterals flowing toward the syphons emptying into Sand Draw Creek would
probably reach the receiving water within 24 hours. The Magnacide H™
label (Figure 3) states "Do not release treated water for 6 days after
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16
Table 3
CHEMICAL ANALYSIS
AINSWORTH IRRIGATION DISTRICT
August 1981
Station No.
Location
Date
Acrolein (ug/1)
1
3
4
5
5
11
29
24
30
31
32
Ainsworth Syphon 8/11/81
Long Pine Creek 8/12/81
Long Pine Creek 8/12/81
Airport Lateral Discharge 8/10/81
Airport Lateral Discharge 8/12/81
Sand Draw Lateral 8/12/81
Mile Post 1.8
Bone Lateral Mile Post 25.2 8/10/81
Bone Lateral B-15.0 8/15/81
Mile Post 2.3
Bone Lateral B-12.3 Headgate 8/15/81
Bone Lateral B-12.3 8/15/81
Mile Post 5.0
Bone Lateral B-12.3 8/15/81
ND*
ND*
ND*
ND*
ND*
ND*
ND*
6400**
15000
%
6600**
5100**
* ND = None detected. The detection limit was 25 yg/1 acrolein.
** The methodology may have yielded low results by a factor of 2 to 3
at this level of acrolein. There was insufficient sample to reanalyze
these samples at lower dilutions.
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Figure 3
NEBRASKA USE OBSERVATION
August 1981
E¥iAOI\I^OBOe ™H HERBICIDE (Acrolein,Inhibited)
CONTENTS UNDER PRESSURE
NET WEIGHTS
Cylinder-370 lbs.
Skid Tank-2450 lbs.
DANGER
EXTREMELY FLAMMABLE
TION. SKIN CONTACT OR
EPA Reg. No. 10707-9
EPA Est. 10707 CA-5
ACTIVE INGREDIENT BY WEIGHT
Acrolein 92%
INERT INGREDIENTS 8%
TOTAL 100%
(MAGNACIDE'" H Herbicide contains 6.5 pounds ol
active Ingredient per gallon.)
DANGER
POISON
KEEP OUT OF REACH OF CHILDREN
AND IRRITATING VAPOR AND LIQUID. POISONOUS BY INHALA
SWALLOWING. DO NOT BREATHE VAPOR DO NOT GET IN EYES.
OR SKIN OR ON CLOTHING. KEEP AWAY FROM FIRE. SPARKS AND HEATED SURFACES.
If spilled on clothing, gloves or shoes, remove them Immediately and wash thoroughly before re-use.
CAUTION: Acrolein, Ihe aclive ingredient In MAGNACIDE H Hcrblcido is highly reactive chemically and readily
lorms polymers. II alkalies (such as ammonia and caustic) or strong acids aro brought in contact wilh the
MAGNACIDE H Herbicide in a closed system, the Herbicide can polymerize with sufficient violence to rupture Iho
container. Oo not apply with equipment used for acids and alkalies. Contamination of MAGNACIDE H Herbicide
with any foreign matter must be avoided.
RESTRICTED USE
PESTICIDE
For retail salo to and use only by Certified App-
licators or persons under their direct supervision
and only for those uses covered by the Certified
Applicator's certification.
This product will Mil fish and wildlife Keep oul of lakes. sfieams or ponds. Fish, shrimp and crab will he killed at
application rates recommended. Do not apply whero they arc important resources Do not apply to water drainage
areas where runoff or Hooding will contaminate ponds, lakes, streams, tidal marshos and estuaries. Do not con-
taminate water by cleaning of equipment or disposal ol wastes. Consul! your State Fish and Game Agency before
applying this product. Use only as specified.
Do not reuse empty container. Roturn empty containers to Magna Corporation.
ANTIDOTE AND FIRST AID TREATMENT
CALL A PHYSICIAN IMMEDIATELY IN ALL CASES OF SUSPECTED POISONING
INTERNAL: If the material has been swallowed, give two glasses of water and induce vomiting immediately hy
introducing a finger into the throat. NEVER GIVE ANYTHING BY MOU1H TO AN UNCONSCIOUS PERSON. Keep
patient prone and quiet
A supply ot sodium carbonate (soda ash) or a 10% sodium sulfite solution should bo readily available for de-actlvatlng
spilled MAGNACIDE H Ail spills should be confined and do-activoted before disposal. See the MAGNACIOE H
Horbicido Application and Safety Manual for additional information.
STORAGE OF MAGNACIDE H TANKS
Full trnks of acrolein should be stored In a cool, shady, woll-ventilated area which is protected from the weather
and away from other chemicals. (No alkalies or oxidizing materials should be near.)
The storage area preferably should bo remotely located,and should be ol fireproof construction. An open shod
type structure Is suitable. AH olcctricat equipment should bo explosion-proof and all equipment properly groun-
ded.
GENERAL DIRECTIONS
MAGNACIDE H Horbicido Is a water sofublo matorial for tho control of submersed and floating weeds and algae In
iirkjalinn cnn.its This material should only be applied in accordance with directions In Iho MAGNACIOE H Hnrhicldo
Application and Safoty Manual by a certified applicator or undnr a corlified applicators supervision. Do not permit dairy
animals to drink treated water. Do not uso whoro waters will eilher flow into or transfer via underground streams to
potnnti.il xourcos of drinking water Do not rotoaso trcntod wnlor lor 6dnys after application into any fish boarlng waters
or where it will dram inlo them.
PRECAUTIONS IN USING
Wear lace shields or goggtos during handling. Uso wllh adequate ventilation. Keep available at atl limes, a gas
mask of a typo approved by the U S. Bureau of Mines for organic vapor protection. Clean application equipment
with targe amounts of water after using.
tf inhaled, get victim inlo frosh air Immediately and give artificial respiration if breathing has
slopped.
EXTERNAL If spilled on the skin, remove all contaminated clothing and wash skin with soap and running water. If
tho material gets Inlo the eyes, wash Immediately with running water for at feast 15 minutes. For eyes get medical
attention.
NOTETO PHYSICIANS
WARNING SIGNS AND SYMPTOMS* Liquid MAGNACIDE H Heiblcido Is absorbed by Ihe skin and is particularly
irritating to any lesion and to Ihe eyes. The vapors act principally on the mucous membranes sure.
NOTICE OF WARRANTY
MAGNA CORPORATION MAKES NO WARRANTY OF MERCHANTABILITY FITNESS TOR ANY PURPOSE . OR
OTHERWISE. EXPRESS OR IMPLIED concerning this product or it* uses which citend beyond the use of Iho
product under noimal conditions in accord with Ihe statements made on this labol
RnvKod" .1-77-80
DISTRIBUTED BY: MAGNA CORPORATION, 11808 South Bloomlletd Ave. Sanla Fe Springs, California 90670
Sojicrrwlrs I-7A
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18
application into any fish bearing waters or where it will drain into
them." It appears that any discharge from this canal system following
an injection would occur in less than 6 days. Studies need to be done
to determine if sufficient dilution and degrading of acrolein occurs so
as to be undetectable in less than the stated six day period.
Magnac'de H Injections
TM
Personnel performing Magnacide H injections were found to be
properly certified or under direct supervision of a certified applicator
TM
as required for use of a restricted pesticide. The Magnacide H is
purchased from a distributor in 2300 pound portable skid mounted tanks.
The tanks are mounted at the Irrigation District on a trailer along with
the various other equipment required for herbicide injections. It was
noted that skid tanks and trailer mounted tanks were stored on the
premises in the open. This is inconsistent with label instructions
which state "Full tanks of acrolein should be stored in a cool, shady,
well-ventilated area which is protected from the weather " The
TM
Magnacide H Herbicide Application and Safety Manual further states "At
a minimum, Magnacide H containers should be stored in open construction
buildings of fire resistant material, which are capable of maintaining
container temperatures below 100°F."
TM
Five injections of Magnacide H were observed on August 15, 1981.
The equipment was inspected at this time and appeared to be well-maintained
and meet Magnacide Inc. requirements. The applicator was familiar with
the equipment and made all injections in an efficient manner. Injection
TM
was accomplished by pressurizing the Magnacide H tank with nitrogen
forcing the liquid through a polypropelene hose into the canal. The
injections were made at points (headgates) where water turbulence
effected rapid mixing. The end of the delivery hose was left submerged
so that no objectionable vapor loss was noted in proximity of the
application. The injection rate was determined by the flow rate of the
canal and regulating the nitrogen pressure and orifice plate. The
operator had available and used adequate safety equipment. The
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addition of a portable eye wash would however be very desirable. It was
noted that when the injection was made at Station 31, the applicator
delayed treatment until a second "Ditch-rider" confirmed by radio that a
poppet valve in this area was closed. This valve if left open could
allow irrigation return to Long Pine Creek. Water samples were taken at
four injection sites (stations 24, 30, 31, 32) by NEIC to determine if
dose rates were accurate. The results of 3 of the 4 samples were lost
due to laboratory error. The analysis of the fourth sample showed
acrolein present at 15 ppm (Table 3). The intended dose rate was 10.5
ppm. This is not an inconsistency, since injections up to 15 ppm are
recommended; however, it may indicate a need for greater accuracy when
injecting this product.
TM
Copies of Magnacide H injection records for 1981 were provided to
EPA by the Ainsworth Irrigation District. In general these records were
found to be in order, up-to-date and complete.
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APPENDIX
SAMPLING AND ANALYTICAL METHODS
In-Situ Fish Exposures
In-situ fish exposures were done using indigenous bluegills live
trapped by the Nebraska Game and Parks Commission. The exposure cages
were of epoxy-coated plywood construction. Wire covered openings on
four sides allowed free circulation of water through the cage. The
cages were anchored and allowed to float freely at the surface level at
each station. Cages were inspected daily for mortalities and measure-
ments taken for pH, water temperature and dissolved oxygen concentration.
Environmental Measurements
Measurements for pH, water temperature and dissolved oxygen con-
centration were taken with a Hariba Model U-7 Water Quality Checker.
The pH mode was calibrated using pH 4, 7, and 11 standard buffer solutions.
Dissolved oxygen was calibrated by using the saturated water method.
The temperature mode was checked against a NBS calibrated thermometer.
Water Samples
Water samples for acrolein analyses were collected in glass bottles
with Teflon-lined caps. Sample bottles were completely filled to preclude
air bubbles, acidified with dilute sulfuric acid to pH 4-5 and stored in
ice. Holding tests showed this collection method retains 70-80% of the
acrolein for a 5-day period.
Analytical Methods
The acrolein is reacted with 2,4-dinitrophenylhydrazine (2,4-DNPH)
to form a highly colored hydrazone which is extracted with toluene. The
toluene is back washed with NaOH to eliminate the excess 2,4-DNPH.
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21
1. Prepare a 2,4-DNPH solution by addition of 0.792 g of 2,4-DNPH and
167 ml of concentrated HC1 to 500 ml of water in a 1000 ml volumetric
flask. Stir with a magnetic stirrer until the 2,4-DNPH is completely
dissolved. Dilute the solution to the 1000 ml mark. The solution
should be stored in darkness and remade weekly.
2. Empty the sample bottle into a 1 liter graduated cylinder and
record the sample volume.
3. Transfer the sample to a 2 liter separatory funnel and add 40 ml of
2,4-DNPH solution to the sample. Shake gently and let stand for
two hours with occasional, gentle shaking.
4. After two hours, extract with 25 ml of toluene follfyed by a second
extraction with an additional 15 ml of toluene. Combine the two
extracts in a 125 ml separatory funnel.
5. Backwash the toluene extract twice with 100 ml portions of saturated
NaCl. Discard the NaCl washes. Backwash the extract with 100 ml
of 3N NaOH by shaking for approximately 15 seconds. Discard the
NaOH wash.
6. Pass the toluene through a small amount of the Na2S0. packed in a
funnel. Wash the Na^SO^ with 10 ml of toluene. Combine the wash
with the extract for a total volume of 50 ml.
The hydrazone derivative is not stable. Analysis must be completed
on the same day as extraction.
Quality Control
A field blank was analyzed and no acrolein was detected. Sample
#752-030 was analyzed in duplicate and a concentration of 15 mg/L was
found both times. Sample #752-030 was spiked with 5.1 mg/L of acrolein
and the recovery was 80%.
Chain of Custody Procedures
Sample chain of custody and document control methods used during
this study are those detailed in the NEIC Policies and Procedures Manual
(EPA 330/9/78/001-R).
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
REGION VI!
324 EAST ELEVENTH STREET
KANSAS CITY, MISSOURI - 64106
April 2, 1982
Mr. William Blacknan, Jr.
Deputy Director, EPA-NEIC
Building 53, Box 25227
Denver Federal Center
Denver, Colorado 80225
Dear Mr. Blackman:
As previously discussed by telephone, this office is holding a ireeting to
determine the possibility of resolving a problem with respect to the tse
of the herbicide acrolein in Nebraska irrigation canals. The problem is
relative to the release of treated waters into fish bearing waters prior
to the six day waiting period as specified on the label.
The meeting will begin at 8:30 a.m. on Tuesday, May 4, 1982, ir rootr 148,
Federal Office Building, 100 Centennial Mall North, Lincoln, Nebraska,
and will probably last until late afternoon.
Enclosed is a list of those persons who have been notified and have stated
that they or their representatives will attend.
I look forward to you or your designated representative attendfrg this very
important meeting and if you have any questions, please do not hesitate to
write or call me at (816) 374-6538.
Sincerely yours,
C. E. Poindexter
Consumer Safety Officer
Air and Waste Compliance ranch
Air and Waste Management Division
Enclosure
cc: Bob Schneider
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EPA MEETING
ACROLEIN USE IN NEBRASKA IRRIGATION SYSTEMS
FEDERAL OFFICE BUILDING
LINCOLN, NEBRASKA
MAY 4, 1982
8:30 A.M. Introductions, Regional Office Position, and
Statement of Purpose - EPA
9:00 A.M. The Registration Process - EPA
Poindexter
Adamczyk
9:15 A.M. Weed Problems and Control In Irrigation
Canals - Irrigation District Managers
Long
Pritts
Welch
Davi s
Laverack
Sell
10:15 A.M. The Bureau's Viewpoint -
Bureau of Reclamation, USDI
10:30 A.M. BREAK
10:45 A.M. Commission Concerns - Nebraska Game
and Parks Commission
11:00 A.M. Environmental Concerns - Nebraska Department of
Environmental Control
11:15 A.m. Other Voluntary Statements
State Department of Agriculture
Nebraska Department of Water Resources
Nebraska Water Resources Association
University of Nebraska - Environmental Programs
11:30 A.M. The Registrant's Position - Magna Corporation
Kutz
Thomas
Lund
McDonald
Stennett
12:00 A.M. LUNCH
1:00 P.M. Open Discussion by Participants Poindexter
2:00 P.M. BREAK
2:15 P.M. Formulation of Ideas and Preliminary Decision for Poindexter
Problem Approach
EPA, GPC, DEC, Magna
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Figure 3
NEBRASKA USE OBSERVATION
August 1931
'T.M
EPA Reg. No. 10707-9
EPA Est. 13707 CA-5
H HERBICIDE (Acrolein^ Inhibited)
CONTENTS
ACTIVE INGREDIENT BY WEIGHT
Acrolein 92%
INEFT INGREDIENTS 8%
TOTAL 100%
(MAG NACIDE,M H Herbicide contains 6.5 pounds ol
active ingredient per gallon.)
DANGER
PRESSURE
POISON
NET WEIGHTS
Cylinder-370 lbs.
Skid Tank-2450 lbs.
DANGER
EXTREMELY FLAMMABLE
TION, SKIN CONTACT OR
OR SKIN OR ON CLOTHING. KEEP AWAY FROM FIRE. SPARKS AND HEATED SURFACES
II spilled on ciolhing. gloves or shoes, icmove them immediately and wash thoroughly before re use
KEEP OUT OF REACH OF CHILDREN
AND IRRITATING VAPOR AND LIQUID. POISONOUS BY INHALA
SWA.LOWING. DO NOT BREATHE VAPOR Dg-NgT^7jr^YES.
KEEP AWAY FROM FIRE.
CAUTION: Acrolein, the active Ingredient In MAGNACIDE H Herbicide is highly reactive chemically and readily
forms polymers. If alkalies (such as ammonia and caustic} or strong acids are brought in contact with the
MAGNACIDE H Herbicide in a closed s/stem, the Herbicide can polymerize with sufficient violence to rupture the
container. Da not apply with equipmert used for acids and alkalies. Contamination of MAGNACIDE H Herbicide
win any foreign matter must be avoided.
A supply of solium carbonate (soda ash - or a 10% sodium sulfite solution should be readily available for de-activating
spilled MAGNACIDE H All spills should be confined and de-activated before disposal. See the MAGNACIDE H
Herbicide Application and Safety Marual for additional information.
STORAGE OF MAGNACIDE H TANKS
Full
arfr
t£nk^£fBacrolein^tTiOulidbestorecJna is protected from the weather
awaylTon *rh*ch em'ic a"s.( fVo'aTF aff??o?oxi31zTngmalerJal^nouT3^ near.)
The storage area preferably should be remotely located and should be of fireproof construction. An open shed
type structure Is suitable. All electrical equipment should be explosion-proof and all equipment properly groun-
ded.
GENERAL DIRECTIONS
MAGNACIDE H Horbicide is a water soluble material for the cont'd of submersed and floating weeds and algao in
ii rigation cnmls This material should only bo applied in accordance with directions in the MAGNACIDE H Horbicldo
Application a id Safety Manual by a cert fied applicator or under a certified applicators supervision. Do not permit dairy
animals to dr nk treated water. Do not .iso where waters will either flow into or transfer via underground streams to
po'ential sources of drinking water. Do r oUcjoasc trcntcd water for 6 days after application into any fisMKradnc^vaten^
or where it w l! drain irtc them.
PRECAUTIONS IN USING
Wear face shields or goggles during nandting Uso with adequate ventilation. Keep available at all limes, a gas
mask of a ty>o approved by the U.S. T.urcau of Mines for organic vapor protection. Clean application equipment
with largo amounts of water after using.
RESTRICTED USE
PESTICIDE
For retail salo to and use only by Cenified App-
licators or persons under theirdirect supervision
and only for those uses covered by the Certified
Applicator's certification.
This product will kill fish and wildlife. Kee^ou^Majj^s^lreams^r^onc^ Fish, shrimp and crab will be kilted at
application rates recommended. Do no^^PITwRer^ne^r^mporlanTresources. Do not apply to water drainage
areas where runoff or flooding will contaminate ponds, lakes, streams, tidal marshes anc estua'les. Do not con-
taminate water by cleaning of equipment or disposal of wastes. Consult your S ate Fish ar d Game Agency before
a^gl^in^N^roduc^Use only as specified. l"nllBMW^Ma*p,a>a
Do not reuse empty container. Return empty containers to Magna Corporation.
ANTIDOTE AND FIRST AID TREATMENT
CALL A PHYSICIAN IMMEDIATELY IN ALL CASES OF SUSPECTED POISONING
INTERNAL: If the material has been swallowed, give two glasses of water ard induce vomiting immediately by
introducing a finger into the throat. NEVER GIVE ANYTHING BY MOUTH TO AN UNCONSCIOUS PERSON. Keep
patient prone and quiet
If inhaled,
stopped.
get victim Into fresh air Immediately and give artificial respiration if breathing has
EXTERNAL: If spilled on the skin, remove all contaminated clothing and wash skin with soap and runninc water. If
the material gets Into the eyes, wash immediately with running water for at least 15 minutes. For eyes ge medical
attention.
NOTETO PHYSICIANS
WARNING SIGNS AND SYMPTOMS: Liquid MAGNACIDE H Herbicide is absorbed by thf skin and is particularly
irritating to any lesion and to the eyes. The vapors act principally on the mi.cous membranes of the eyes and
respiratory tract. Because of the extreme lachrymatory warning effect, the concentration tolerable by man is far
below the minimum lethal concentration.
TREATMENT: Treat exposed area as a chemical burn. Thoroughly flush thc_eyos witr- water and treat Symp-
tomatically. Persons exposed to MAGNACIDE H HerbiaW'WtffTrsTTavo^wleTayerrWSCTW? and experience
irritation of the respiratory tract. In severe cases, this may progress to pulmonary edema Therefore, it is ad-
visable to keep persons exposed to MAGNACIDE H Herbicide undei observation for 24 hours following exposure.
NOTICE OF WARRANTY
MAGNA CORPORATION MAKES NO WARRANTY OF MERCHANTABILIT Y FITNESS TOR ANY PURPOSE , OR
OTHERWISE. EXPRESS OR IMPLIED concerning this product or it* uses which extend beyond the lsc ol the
product under normal conditions in accord with the statements made on this label
Revived: 3 77 -BO
DISTR1B JTED BY: MAGNA CORPORATION, 11808 South Bloomlield Ave, Santa Fe Springs, California 90670
Siif>ercedos: 1-78
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PERSONS/ORGANIZATIONS EXPECTED TO ATTEND - SPECIAL MEETING ON ACROLEIN
LINCOLN, NEBRASKA - May 4, 1982
Douglas Campt, Director j
EPA Registration Division (TS-767)
401 M Street, S.W.
Washington, D.C. 20460
William Blackman, Jr.
Deputy Director, EPA-NEIC
Building 53, Box 25227
Denver Federal Center
Denver, Colorado 80225
Allan Abramson, Director
Water Division - EPA
324 East 11th Street
Kansas City, Missouri 64106
Robert Kutz, Project Manager
NE/KS Projects Office
Bureau of Reclamation
U. S. Department of the Interior
P. 0. Box 1607
Grand Island, Nebraska 68802
George C. "Charley" McDonald
Regulatory Affairs Manager
Magna Corporation
7505 Fannin, P. 0. Box 33387
Houston, Texas 77033
Richard Reiman, Acting Chief
Bureau of Plant Industries
Nebraska Department of Agriculture
P. 0. Box 94756, State House Station
Lincoln, Nebraska 68509
Bill Bailey, Assistant Director
Nebraska Fish and Game Commission
P. 0. Box 30370
Lincoln, Nebraska 68503
Bob Wall, Chief
Water and Waste Management Division
Nebraska Department of Environmental
Control
Box 94877
Lincoln, Nebraska 68509
Michael Jess, Director
Nebraska Department of Water Resources
301 Centennial Mall South
Lincoln, Nebraska 68509
. Jack Odgaard
Executive Vice President
Nebraska Water Resources Association
512 South 13th Street
Lincoln, Nebraska 68508
Roger Gold, Ph.D.
Coordinator, Environmental Programs
Institute of Agriculture and
Natural Resources
University of Nebraska, East Campus
101 Former Vet Science Building
Lincoln, Nebraska 68583
Paul Fishbach
Extension Irrigationist
Cooperative Extension Service
Agriculture Engineering Annex
L. W. Chase Hall, 2nd Floor
University of Nebraska
Lincoln, Nebraska 68583
Don Long, Secretary/Treasurer
Nebraska State Irrigation Association
c/o Central Nebraska Public Power and
Irrigation District
P. 0. Box 356
Hoi dredge, Nebraska 68949
^Harlan Welch, Manager
Ainsworth Irrigation District
Route 2, Box 33
Ainsworth, Nebraska 69210
Paul E. Pritts, Manager
Bostwick Irrigation District
P. 0. Box 446
Red Cloud, Nebraska 68970
Keith Davis, Manager
Farwell Irrigation District
Box 137
Farwell, Nebraska 68838
Vernon E. Laverack, Superintendent
Frenchman-Cambridge Irrigation District
P. 0. Box 116
Cambridge, Nebraska 69022
Wes Sell
Farmers Irrigation District
P. 0. Box 307
Scottsbluff, Nebraska 69361
Prepared by: C. E. Poindexter
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