RESULTS OF THE LOW FLOW CARBON FILTER
WHEN USED AS A PESTICIDE SAMPLER
ABSTRACT
The Klamath Basin Study, a special project of the Federal Water
Pollution Control Administration, is studying pesticides in irrigation
water. One of the tools utilized for sampling the water is the low-flow
carbon filter. Pesticide determination in discrete water samples and
week long carbon filter composites are compared. In the two types of
sampling, endrin showed good comparison; DDT series pesticides did not.
KBS Technical Paper No. 1
Hopkins and Mausshardt
FWPCA
Southwest Region
October 28, 1966
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TABLE OF COHTEHTS
Paqe
INTRODUCTION 1
SAMPLING STATIONS & COLLECTION PROCEDURE 1
LABORATORY PROCEDURES 3
ANALYTICAL LIMITS OF LABORATORY PROCEDURES
UATER 3
CARBON COLUMNS 4
DISCUSSION OF RESULTS 5
SUMMARY & CONCLUSIONS 8
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LIST OF FIGURES & TABLES
FIGURES Paqe
I Schematic, Model LF-1 Organics Sampler 10
II Lost River System 11
III Graphical Comoarison of Water vs. Carbon 12
TABLES
I Graphical Comparison of Uater vs. Carbon Indian Springs 13
II Carbon Filters vs. Water Samples Pump "D" 16
III Results of Carbon Column with Glass Mool 18
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RESULTS OF THE LO.J FLO'..' CARBON FILTER
WHEN USED AS A PESTICIDE SV'PLER
Introduction
Durinn 1960-61 extensive water fowl kills occurred in the
Tule Lake-Lower Klamath national Mildlife Refunes. In 1963, the
U.S. Fish and 'Jildlife Service established that the deaths were
caused by pesticides. At that time, the States of Oregon and
California and the U.S. Fish and Wildlife Service requested U.S.
Public Health Service's technical assistance in deternininn the
source and movement of pesticides in and around the refuoes. The
Klamath Basin Study was initiated in December 1963 to study this
water pollution problem.
The enqineerinn staff of the Klamath Basin Study initiated a
water saroplinq pronram of collectinq discrete water "nrab" samoles
at regular intervals throughout the Lost River systen. As an adjunct
to this program, the low flow carbon filter was used to continuously
sample the stream. The "grab" samples were to qive instantaneous
nesticide concentration values and the carbon filter was to provide
a measure of average concentrations over a period of time. In order
to sample the same water as ths carbon filter, "irab" samples were
taken at the exit of the bypass valve (Point C on Fiqure 1).
This paper reports the results of the use of the low flow
carbon filter as a sampler of pesticides in water.
Sampling Stations and Collection Procedure
In conventional operation of the low flow carbon filter, approxi-
mately 1200 liters of water are pumped throuih ?n all-fines carbon
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2
column three inches in diameter and eighteen inches lonn (Figure 1).
Organics, includinn pesticides, in the water are adsorbed from the
water onto the carbon. In the laboratory, oesticides are desorbed
from the carbon using chloroform as a solvent.
The "grab" sample program soon indicated that the oesticides
used were appearing in relatively larqer amounts in the Tulelake
end of the Lost River Basin. Therefore, the two carbon filter
panels were installed at approximately the entrance and exit for
the irrigation water of Tulelake Irrigation District (TID). Fiqure
2, a schematic of the Lost River Basin, shows the location of the
two panels. Indian Springs (location of first panel) is located
on the Lost River about six miles upstream of the Lov;er Lost River
Diversion Dam. This dam diverts water to the "J" Canal which supplies
essentially all of the irrination water to TID. Return flow within
TID is collected in a series of drain canals all of which empty into
Tule Lake Sump. Pump "D" (the location of the second nanel) regulates
the level of the Tule Lake Sump by exporting the water via a tunnel
through the hill to Lower Klamath Lake.
At pump "D", water is sampled at the exit side of a 60 cfs
irrination drainage pumu. At Indian Sorings (the entrance panel),
water is supplied to the nanel by an Oberdorfer bronze rotary gear
pump driven by a 1/3 hp electric motor. The tubing inlet is placed
in the movina part of the two feet deep stream aporoximately fifteen
feat from shore. The end of the tubing is protected by a strainer
with 1/8 x 1 inch slots. The end of the tubing is bent upward slightly
so that the intake is several inches above the stream bed.
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The two qallon "qrab" sample is collected in two 1-nallon class
iuqs with an aluminum foil liner insulatinq the cap. Prior to use
bottles are washed with detergent and thorounhly rinsed to remove
all traces of deterqent. In the field the juqs are aqain rinsed
in the stream prior to the collection of the sample.
Laboratory Procedures
In the laboratory, pesticides are extracted from a 3-liter
aliquot of the "nrab" sample in a three sten process usinn a mixture
of 10% ethyl ether in petroleum ether. The extract is eluted
through a Florisil column for cleanup.
The carbon columns are first air dried at room temperature and
then extracted with chloroform in a large soxhlet fnr forty hours.
Partitioning and cleanup are accomplished usinq acetonitrile, ethyl
and petroleum ether mixtures and Florisil.
These procedures are described in detail by the Project Chemist,
R. E. White, in his naper, "Insecticide Analysis Procedures Used by
1
the Klamath Basin Study".
Analytical Limits of Laboratory Procedures
'•later
The procedures established by the Study's laboratory are able to
detect the chlorinated hydrocarbon compounds, DDE, ODD, heptachlor,
heptachlor epoxide, aldrin dieldrin, endrin, thiodan, and BHC at
an approximate sensitivity of 0.005 parts per billion (ppb) in a
1
Presented at the Pacific Northwest Pollution Control Association,
Vancouver, British Columbia, Movember 3-5, 1965
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4
3-kilorjram water sample. The sensitivity for DDT and chlordane
is 0.010 ppb and for toxaphene 0.050 pob. In addition to these
specific compounds, the water samples are also analyzed to deter-
mine total chlorinated hydrocarbon, based on a 50% haloqen content.
This measurement is possible due to unique soecificity of the
Dohrmann microcoulometric system to chlorinated hydrocarbons.
In the analysis of water, one often finds chlorinated hydro-
carbons which cannot be specifically catenorized. Since all of
the chlorinated hydrocarbon qroup are man-made pesticides, it is
logical to assume that the unidentifiable materials are metabolites
of pesticides used in the project area. While these "unknowns"
cannot be related to soscific toxicities to biota of the system,
they are an indication of the amounts of pesticide beinn washed
into the water community. These "unknowns" are included in the
total chlorinated hydrocarbon content of the samples here reported.
CARBON COLUMNS
Due to the 400 times larger sample size, the analytical
procedures are sinnificantly more sensitive to pesticides recovered
by the carbon columns. The sensitivity for DDE, DDD, DDT, heotachlor,
heptachlor epoxide, chlordane, dieldrin, and endrin is approximately
0.00015 ppb. Due to the unknown and variable background of the
carbon, it is not possible to calculate a maximum total chlorinated
hydrocarbon content of the carbon column extracts.
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Discussion of Results
Tables I and II show the results of carbon and water analyses
for the two locations - Indian Sprinos and Pump "D". The table
shows only those identifiable compounds which were actually found
in addition to total chlorinated hydrocarbons.
Comparing the water and carbon analyses shown in Table I, the
carbon filter method appears to be much more responsive to some
pesticides than others. For instance, there appears to be no
correlation between the sampling methods under DDE, ODD and DDT,
heptachlor, and heptachlor enoxide. There is not enough information
about dieldrin to make a positive evaluation, since the levels found
in the carbon are just below the approximate 0.005 ppb limit of
detection in the water samples. To increase the sensitivity in
the water sample to that of the carbon sample, the size of the
water sample would have to be increased at least five times; this is
neither practicable nor was the concentration of dieldrin in the water
significant enouqh to warrant this.
Endrin results show a oood comparison at the Indian Sprinas
station. Figure 3 is a graph of endrin concentration for the
water samples and carbon filter extracts. No explanation can be
offered as to why the second carbon filter run was not closer to
the "nrab" sample analysis. However, the next four runs do approxi-
mate the water results. After October the endrin level in the water
fell below the sensitivity of the procedures utilized by the Klamath
Basin Study. The siqnificant point is that the carbon filter results
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6
did represent a nood averaqe value of the endrin concentrations for
the water "qrab" samples shown.
At Pump "D", as shown in Table II, endrin and dieldrin were
consistently found, but only on the carbon extracts and there at a
level below the detection limit for water samples; therefore no
comparisons can be made. The DDE, ODD, and DDT results at Pump "D"
are similar to those at Indian Sorinns. In oeneral, the Pump "D"
carbon extract results were much lower than the discrete water samples.
However, due to a malfunction, the last two carbon filter samples
collected at Pump "D" represent about five times smaller than "normal"
volumes of water. It appears from these two samples that the
pesticide determinations for the DDT series in the lower-volume
carbon filter sample compare more favorably with those in the "grab"
samples than do the lamer-volume carbon filters.
Blank spaces in Table II can be taken to indicate (1) that the
compound was not present in detectable concentration or (2) if present,
v^as either not adsorbed on or was not desorbed fron the carbon.
To check on the desorption process, solvents other than
chloroform followed its use, including benzine, acetone and mixtures
of the two, with no siqnificant change in the results obtained.
The adsorption process was also explored for the possibility
that some of the pesticide in the discrete water is on particles
in the water which are partly retained on the carbon and partly
washed throuqh the carbon filter without losing this pesticide
residue load to the carbon. Approximately one-half inch of tiihtly
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7
packed nlass wool was placed on the inlet end of each of two carbon
filters. One carbon filter so packed was used at each station.
Realizing that the size ranne of particles stopped by the nlass
wool cannot be accurately defined, it was believed that larger
particles, such as alqae, chlodocera, and detritus would be stopped.
This was confirmed visually by the fact that previously the algae
would nive a greenish tint to the carbon as much as one third of
the way up the carbon. This condition was not observed with the
nlass wool in place.
The results, shown in Table III, are as follows: The filter
at Indian Sprinqs sampled 1257 liters of water. On the qlass wool,
DDE, ODD and/or DOT, and a chlordane-like substance were each found
at a level of 2 ppb, based on the damp weinht of sediment and nlass
wool. Convertino this to a more meaninnful value, if all of these
pesticides caunht on the glass wool had instead been extracted
with the carbon, then the apparent concentration in the 1257 liters
of voter would have increased by .000085 ppb (.085 pptr) for each of
these pesticides. As a percentaqe of the total amount of pesticide
in the wool and carbon extracts, this amount on the wool amounts
to 19% for DDE, 8% for ODD and DDT, and 50% for the chlordane-like
substance.
At the Indian Sprinns station dieldrin and endrin results
indicate that less than 1 and 9% respectively of the total amount
was in the qlass wool extract. At Pump "D", dieldrin and endrin
were found in the carbon extract but not in the nlass wool.
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8
However, for reasons not none into here, the analytical sensitivity
for this qlass wool sample was not as nood as it was for any orevious
sample at that station. If the Pump "0" qlass wool sample is assumed
to have an amount of pesticide equal to the sensitivity, then this
could be considered to be the upper limit of the amount in the sample.
Doing tiViS would indicate a maximum of 66% dieldrin and 50% endrin
on the Pump "D" qlass wool. These percentaqes are rather hi oh; if
the same amounts were present at Pump "0" as at the Indian Sprinns
stations, the percentages would be approximately 1 and 535 respectively,
Summary and Conclusions
1. The low flow carbon filter does extract and concentrate
pesticide from water.
2. Based on limited data, the method gives a reliable
averaqe concentration of endrin in the water sampled when compared
with results from "qrab" sample analyses.
3. Data for the DDT series of pesticides derived from
1200-liter carbon filter water samples do not compare favorably with
data derived from "qrab" samples. Limited data indicate, however,
that DDT comparison under the two methods of sampling improved when
a 200-liter water sample is used in the carbon filter process.
4. Sediment in the water, as reoresented by the amount
cauqht on a glass wool filter, has a minimal effect on pesticide
sampling efficiency.
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9
5. These are to be considered as preliminary conclusions
only, and the engineering staff of the Klamath Basin Study will
continue its carbon filter investigations durinq the 1966 irriga-
tion season.
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10
LEGEND
A— 3/8-in. glob* votve
B — l-gpm flow control volve
C -" Prewure relief voNe
D — Prewure gauge (0-15 p»i!
E ~*AII fine" carbon column
F — Prewure gouge (0 -iSp*0
G — Metering pump
H ~ Volumetric »tatur«m«nt tonk
I — Solenoid valve
J — Liquid level control relay
K ~ Disconnect twitch
L ~ Convenience outlet
M~ Oiaitol counter
SUPPLY-
POWER
1. Schematic, .-Jo
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Upper Klantofh
Lode
KlamaU Falls
irrigation dan
pumping plant
L-041 R i v a r
Diversion Channel
Klaroath
River
Lake
Ewauna
Gerbor
Reservoir
Bonanza
Springs
Lost River
Harpold
Dan
Miller Dam
Wilson Oam
@ Pumping Plant F
Indian Spr inq s"Entranee Panel
Lower Lost River Oam
Malonc
Oam
ower
Klama th
Lake
Pump 0"E>iit
Clear Lake
Fi g ure 2
L o si River System
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m
:iltt
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TABLE I
Summary
Carbon Filters vs Water Samples
Indian Sprinns - Parts °er Billion
Date
7/22
7/30-8/4
8/11
8/16-20
8/20
8/20-26
8/26
8/26-31
9/3
9/1-7
Type of
Sample
Water
CAM I/
Water
CAM
'.later
CAM
l/ater
CAM
'ifater
CAM
Size of
Sample
i/
1030 L
1248 L
1326 L
940 L
1221 L
Samole
Number Total
237
257
267
371
325
344
330
34£
369
372
3/ .133
DDE
.01
DOD
DDT
.01
not determined
3/ .23
3/ .14
3/ .033
.14
.015
.0002
.009
.0005
.007
.nnu
.007
.0005
.002
.003
.OQ35
.0025
I/ Carbon Filter
2/ ODD only
Heptachlor
Eooxide Dieldrin
.007
.002
.002
.0004 .0006
.002
.001 .001
.0016 .001
21 .0005 .001
Endrin
.037
.05
:oi3
.03
.029
.020
.073
.020
.024
Aldrin Other
.0002 .002
.001J/
.0005 .001 5/
3/ Lower Lost River Diversion Dam
All water samples are 3 liter
Heptachlor
F/ Chlordane
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TABLE I (Cont'd)
Type of
Date Sample
9/10 '.'later
9/22 Hater
9/22 Hater
9/15-22 CAM
10/1 Water
10/1 'Jater
10/8-13 CAM
10/11 Water
10/13-18 CAM
10/18 Hater
10/18-25 CAM
10/20 Water
10/29-11/5 CAM
]J Carbon Filter
21 ODD only
3/ Lower Lost River
4/ All water samples
5/ Heptachlor
F/ Chlordane
Size of Sample
Samole Number Total
381 3/ .17
399 .066
401 3/ .096
2271 L 423
451 .058
452 3/ .035
956 L 478
467 .042
990 L 491
492 .090
1377 L 527
512 3/ .047
1762 L 551
Diversion Dar*
are 3 liters
DDE
.007
.003
.003
.0002
.006
.0006
.007
.0005
.003
.0005
.019
.0002
DDD Heptachlor
DDT Epoxide Dieldrin
.017
.033 .005
.067 .003
.0002 .0002
.003
.0027
.010
.0012 .001
.006
.0007 .0005
.0002 .0003
Endrin Aldrin
.017
.006
.007
.0074
.0037
.003
.007
.0035
.0003
Other
.002. .5/
.004 6/
.010 6/
.004 6/
.0067 6/
.0015 6/
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TABLE I (Cont'd)
Date
11/5-12
11/9
11/12-19
11/19
11/19-26
12/3
12/3-10
12/10
1/18
Type of
Sample
CAM
Water
CAM
Uater
CAM
'.later
CAM
Mater
Water
Size of
Sample
2237
1267
1242
1312
L
L
L
L
Sample
Number Total
561
554 3J .104
566
567 .090
582
587 .053
602
597 ,061
634 3/
DDE
.0005
.007
.00036
.003
.007
.00015
,003
DDD Heptachlor
DDT Epoxide Dieldrin
.0005 .0005
.017
.00095
.017
.010
.00016
Endrin Aldrin Other
.0030 .009 6/
.007 .020 6/
.0001 6/
.007
.0015 6/
.010 6/
i
Ul
1
I/ Carbon Filter
F/ DDD only
?/ Lower Lost River Diversion Dam
4/ All water samples are 3 liters
IT/ Heptachlor
IT/ Chlordane
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TABLE II
Summary
Carbon Filter vs -Water Samples
Pump D - Parts Per Billion
Date
4/20
4 « i
4/16-20
7/21
7/22-28
10/1
10/1-6
10/6-11
10/11
10/11-16
10/20
10/29-11/4
Type of
Sample
iJater 3/
CAM I/
'tater
CAM I/
Uater
CAM
CAM
Water
CAM
Hater
CAM
Size of
Samole
710 L
1043 L
800 L
988 L
1782 L
816 L
Sample
Number Total
100 .100
101
228 .08
247
449 .041
462
466
471 .019
528
516 .062
529
DDE
.013
.010
.001
.003
.0006
.0005
.001
.007
.001
ODD Heptachlor
DDT Epoxide Dieldrin Endrin Aldrin
.027
.001
.001
.001 .0014 .07
.0030 .0025
.0006 .0001 .0020
.0022 .001 .0022
.002 .0003 .001
Other
.033 2/
.003 4/
.0080 2/
.0020 2/
.013 21
.0075 2/
cr»
i
I/ Carbon Filter
27 Chlordane like
37 All water samples are 3 liters
T/ Lindane like
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TABLE II (Cont'd)
Date
11/4-12
11/9
11/12-19
12/10
12/3-10
Type of
Sample
CAM
Hater
CAM
Mater
CAM
Size of
Sample
834 L
196 L
330 L
Sample
Number Total
560
556 .11
586
600 .025
603
DOE
.0011
.011
.0038
.003
.003
ODD Hsotachlor
DDT Eooxide Dieldrln Endrin
.0005 .0009
.013
.002 .0009 .0009
.004
Aldrin Other
.015 21
.02 2J
.027 2/
.066 21
I/ Carbon Filter
?/ Chlordane like
T/ All water samples are 3 liters
T/ Lindane like
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- 18 -
TABLE III
RESULTS OF CARBON COLUMN UITH GLASS IJOOL
Sample Sample
Number Location Size
566 Indian 53.6
Spri ngs grans
1257
liters
586 Pump "D" 50
qrams
196
liters
Pesticide
chlordane
DDE
ODD and/or
dieldrin
endri n
chlordane
DDE
ODD, DDT
dieldrin
endri n
chlordane
DDE
ODD, DDT
dieldrin
endri n
chlordane
DDE
ODD, DDT
dieldrin
endri n
like
DDT
like
like
none
none
like
I/
2
2
2
.23
1.1
0.0001
0.00036
0.00095
0.0016
0.0005
4
1
.7
sens 3.6
sens 7.2
.027
.0038
.002
.0009
.0009
21 3/
.000085
.00001
.000047
50%
19%
8%
1%
9%
.001
.00025
.00017
4%
6%
8%
66% 4/
50% 4/
\J Conventional basis (parts per billion)
2J Based on all pesticide being water sample (parts per billion)
3/ Pesticide on glass wool as a % of total
4/ Maximum value if level present has been only sliqhtly less than sensitivity
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