ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
A Pesticide Residue Stud\
Wa reh it m. M nss a ch it setts
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER, COLORADO
C®.
%
MARCH 1978
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ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
A PESTICIDE RESIDUE STUDY
Wareham, Massachusetts
March 1978
National Enforcement Investigations Center
Denver, Colorado
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CONTENTS
I INTRODUCTION 1
II SUMMARY AND CONCLUSIONS 5
III DESCRIPTION OF THE STUDY 6
IV DISCUSSION AND RESULTS 12
Pre-Harvest Assessment 12
During-Harvest Assessment 15
Fish Physiological Assessment 16
Estuarine Assessment 17
REFERENCES 22
APPENDICES
A ANALYTICAL METHODS 23
B REVIEW OF CHAIN-OF-CUSTODY PROCEDURES 27
TABLES
1 Chemical Applications Applied to Tremont Bog, 1977 . . 10
2 Samples Collected from the Wareham, Massachusetts Study
Area, October, 1977 13
3 Water, Soil, Sediment, Fish, Shellfish - Analytical
Results 18
FIGURES
1 Cranberry Bog Site in Wareham, Massachusetts 4
2 Pre-Harvest Sampling and Fish Exposure Sites 7
3 Harvest Sampling Sites 9
4 Estuarine Station Locations 21
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I. INTRODUCTION
Cranberries, as a commercial crop, are raised in a relatively few
adaptable areas in North America. The crop is grown almost exclusively
in man-made or natural bogs. The few states with extensive acreage of
bogs suitable for commercial cranberry crops include Massachusetts, New
Jersey, Oregon, Washington, and Wisconsin; less extensive acreages are
cultivated in Connecticut and Rhode Island.1 Of these areas, the bogs
of Massachusetts serve as the major cranberry growing area in the United
States. They are estimated to produce half the world supply of cran-
berries with a wholesale value approaching $60 million.2
Cranberries, like many other fruit crops, are plagued by infesta-
tions of insect pests throughout the growing season. However, the
intensive use of insecticides over the past few decades is considered
one of the main factors that have raised cranberry yields per acre to
their present levels.
During the course of a growing season, a cranberry bog may be
plagued by almost a dozen different species of insects which attack the
plant from its root system to the growing berry. Some of the insecti-
cides used in the past, and still used in integrated control methods,
are carbyl, parathion, Guthion and diazinon. Parathion has been used on
many Massachusetts bogs for more than 15 years. Presently, Parathion is
applied 2 to 3 times on a bog during a growing season at the volume rate
of 0.47 1/0.4 ha (1 pt/acre).
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2
Flooding of a cranberry bog is a practice used to prevent damage
from various elements. In the winter it is used to prevent desiccation —
a condition called winter-kill, in summer to relieve drought conditions
and under certain conditions is used to control infestation of insect
pests without resorting to insecticides. Nevertheless, copious amounts
of water are used on each occasion. Estimates place the volume at
300,000 gallons of water per acre.3
These large volumes of water may be contaminated with pesticides
previously applied on the cranberry crop. Since the waters eventually
discharge into streams or estuarine systems, the potential for trans-
locating pesticides is likely to occur. As a result, there is a like-
lihood of harm to the environment and a possible health hazard to the
public that consume potentially contaminated fish or shellfish.
Evidence of pesticide contamination was found in Buzzards Bay,
Massachusetts in May, 1974. Shellfish (Mya arenaria) collected in this
estuarine system contained ethyl parathion concentrations ranging from
0.01 to 0.03 mg/g (ppm).4 Reportedly, this contamination was caused by
drainage from nearby pesticide treated cranberry bogs.
With this background, EPA Region I requested the National Enforce-
ment Investigations Center (NEIC) to conduct a study in the most productive
cranberry growing area in southeastern Massachusetts with the following
objectives: determine if pesticide residues were present in cranberry
bogs following a season of treatment with insecticides, and determine
the extent and effect, if any, of pesticide translocation from cranberry
bogs to adjacent wetlands and receiving waters.
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The study site selected by EPA Region I and the University of
Massachusetts Cranberry Experiment Station was located near Wareham,
Massachusetts, and is crossed by Pierceville Stream. Waters from this
stream join the east branch of the Sippican River and eventually discharge
into Buzzards Bay [Figure 1].
A five-day study began on October 11, 1977. Samples of soil,
sediment, water, and fish were collected from the bogs as well as shell-
fish and sediments from a nearby estuary. The chemical analyses on
these samples for selected pesticides residue were performed at the NEIC
laboratories in Denver, Colorado.
A second investigation will be conducted prior to and during the
first pesticide application in the spring of 1978. This study will be
designed to determine if the field application of pesticides on cran-
berry bogs are performed consistent with registered labeling, FIFRA
regulations and appropriate State codes.
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Figure 1 Cranberry Bog Study Site in Warehara, Massachusetts
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5
II. SUMMARY AND CONCLUSIONS
During the 1977 cranberry growing season in Wareham, Massachusetts,
parathion was applied on the Tremont Bog on three occasions to control
insect infestations. The pesticide applications were made through a
sprinkler system at the rate of 0.47 liters/hectare (1 pt/acre).
Approximately three months after the last parathion application,
the NEIC conducted a field study at Tremont Bog. The 5-day study (October
11-15, 1977) was conducted before and during the cranberry harvest to
determine if a parathion residue existed in the bog or if the pesticide
had been translocated from the treated bog to adjacent wetlands and
receiving waters.
Soil from the bog contained ethyl parathion in concentrations
ranging from 0.6 to 5.6 mg/g (ppm). Water that flooded the bog during
the cranberry harvest and drained into Pierceville Stream contained no
measurable amounts of pesticides. Examination of sediments and fish or
shellfish from the drainage ditch (Pierceville Stream) and downstream
estuaries (Weweantic River and Buzzards Bay) showed no pesticide accumu-
lations .
Based upon the sampling and analyses described in this report, it
was concluded that harvest flooding did not translocate measurable
amounts of parathion from the soil of Tremont Bog into receiving waters
or nearby wetlands. Furthermore, if pesticide-contaminated water drained
from treated cranberry bogs into Pierceville Stream or into downstream
estuaries prior to the EPA study, the chemicals apparently have been
diluted or dissipated sufficiently and environmental harm has not
occurred.
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6
III. DESCRIPTION OF THE STUDY
The cranberry bog selected for study is identified by the grower as
the north piece of the Tremont Bog located in Wareham, Massachusetts
[Figures 1 and 2]. This particular piece consisted of 9.75 hectares
(19.7 acres) which was flooded during a portion of the EPA study. The
Pierceville Stream flows through the middle of the bog and joins the
east branch of the Sippican River, which eventually discharges into
Buzzards Bay south of the Cape Cod Canal [Figures 1 and 4]. Water for
flooding, sprinkler irrigation, and pesticide applications through the
sprinkler system is obtained from Pierceville Stream.
The pre-harvest investigation was designed to obtain background
information prior to harvesting operations which involved flooding of
the upper Tremont Bog. To determine possible insecticide contamination
from upstream bogs, preliminary sampling of water and sediments were
obtained from the reservoir upstream of the bog (Stations 07, 06). To
assess the presence of insecticide residues in the study site, water
samples were taken from the Pierceville Stream and soil samples from the
adjacent exposed bog (Stations 04, 05, 08). Downstream at the lower
extremity of the Tremont Bog, samples of water and sediment were taken
from the Pierceville Stream to determine the likelihood of pesticide
translocation from the entire bog [Figure 2].
At the time of cranberry harvesting, a resampling of the study site
was conducted. At the reservoir, designated as the control area, sediment
and water samples were taken (Station 07, 04) to determine if pesticide
residual influx from upstream harvesting operations had taken
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LEGEND
A Water Samples
ta Sediment Samples
© Soil Samples
Fish Exposure Sites
' . SCALE
0.4 cm = 90 meters
Figure 2
Pre-harvest Sampling and Fish
Exposure Sites
October 11, 1977
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8
place. During the same period soil samples from the flooded bog were
taken in close proximity to those obtained during the pre-harvest investi
gation. Samples of sediment and water (Stations 02, 03) were also taken
in Pierceville Stream at the southern end of the Tremont Bog to assess
possible runoff of insecticide contaminated water from the flooded upper
bog [Figure 3].
Rainbow trout, Sal mo gairdneri, were held in submerged cages in the
storage reservoir (Station 07) upstream of the test cranberry bog in
Pierceville Stream upstream of the first sluice gate (Station 04), and
at the third sluice gate in the lower bog (Station 02) to monitor acute
physiological effects of pesticide exposure [Figure 2].
To determine the chronic effects of possible pesticide trans-
location from cranberry bogs to adjacent wetlands and receiving waters,
samples of shellfish and sediments were obtained from the estuarine area
of the Weweantic River and inner Buzzards Bay [Figure 4]. A summary of
the sampling effort is contained in Table 1.
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LEGEND
A Water Samples
@ Sediment Samples
© Soil Samples
Flooded
Bog
Figure 3
Harvest Sampling Sites
October 15, 1977 .
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10
Table 1
SAMPLES COLLECTED FROM THE
WAREHAM, MASS A CHUSETTS
STUDY AREA
October 1977
Tremont Bog - Before Harvest - 10/11/77
Station No. Water Soil Sediment
00 X+
02 X
04 X
07 X
05 X
08 X
03 X
06 X
Tremont Bog - During Harvest - 10/15/77
Station No. Water Soil Sediment Fish
02 X
04 X^
07 X
05 X
08 X
03 X
06 X
02 x
04 x
07 x
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11
Table 1 (Cont.)
SAMPLES COLLECTED FROM THE
WAREHAM, MASSACHUSETTS
STUDY AREA
October 1977
Weweantic River and Buzzards Bay
Station No.
Sediment
Shellfish
09
X
10
X
11
X
12
X
13
X
14
X
15
X
16
X
17
X
18
X
From the Massachusetts Department of Fish & Wildlife Fish Hatchery
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IV. DISCUSSION AND RESULTS
12
During the course of the 1977 cranberry growing season, several
applications of chemicals were introduced into the Tremont Bog [Table
2]. In late June, when weeds were apparently hindering the flow of
water in the drainage ditches, kerosene was used as a herbicide to
retard further growth. Throughout the remainder of the season three
applications of parathion were made at the rate of 0.47 1/ha (1 pt/acre).
Carmol, which is a blend of carbyl and molasses, was applied with parathion
via the sprinkler system in July and acted as a holding agent for the
pesticides. When insect infestation was apparent during June and July,
a total of 13.74 liters of parathion was sprayed on the 9.75 ha of the
Tremont Bog.
PRE-HARVEST ASSESSMENT
Prior to harvesting operations a series of water, sediment and soil
samples were collected from Tremont Bog to assess the background levels
of pesticides before the bog ecosystem was disturbed by the mechanical
processes used during wet harvesting. Pre-harvest sampling was completed
on October 11, 1977.
All sampling stations were located at strategic points on and in
the vicinity of the bog to assess the background levels of malathion*,
methyl parathion, and ethyl parathion.
Analyses for malathion were done because of possible application to
bogs upstream of the Tremont Bog.
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13
Table 2
CHEMICAL APPLICATIONS
APPLIED TO TEEMONT BOG> 1977
Date
Chemical
Rate
Area (ha)
Method
Total
5/25/77
Kerosene
304 1/0.4 ha
.016
Hand Spray
4.86 1
6/3/77
Parathion-
0.47 1/0.4 ha
9.75
Sprinklers
4.58 1
Carmol*
1.90 1/0.4 ha
9.75
Sprinklers
18.5 1
7/14/77
Parathion
0.47 1/0.4 ha
9.75
Sprinklers
4.58 1
mim
Parathion
0.47 1/0.4 ha
9.75
Sprinklers
4.58 1
Total Parathion 13.74 1
*Blend of Carbyl and molasses
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14
Analysis of the water sample taken from the reservoir (Station 07)
contained non-detectable levels of pesticides which indicated no apparent
influx of pesticides from bogs upstream of the reservoir. A sample of
water taken from Pierceville Stream (Station 04) as it flowed through
Tremont Bog also proved to contain non-measurable amounts of pesticide,
indicating that no leaching of water containing pesticides was taking
place on the upper bog. Water obtained at Station 02, located at the
southernmost point of the bog, also proved negative. It showed that
runoff from the lower section of Tremont Bog contained no measureable
amounts of pesticides.
Sediment samples were obtained from two locations on the study site
during this period. Sediment from Station 06 in the reservoir contained
non-detectable levels of pesticides indicating no translocation of
pesticides was taking place from bog locations upstream. Sediment from
Pierceville Stream at the lower end of Tremont Bog (Station 03) also
contained non-detectable amounts of pesticides. This fact indicated
that there was no apparent pesticide influence from Tremont Bog.
Two soil samples (Stations 05, 08) taken from the unflooded growing
area of the upper half of the Tremont Bog contained an ethyl parathion
concentration of 5.6 and 1.8 mg/g (ppm) respectively. According to
Deubert and Gray the persistence of parathion (ethyl-parathion) in soil
is not surprising in view of the findings that this chemical forms
strong complexes with organic matter and clay.4 The presence of this
concentration of ethyl parathion bound to the soil of the cranberry bog
had no influence on the water or sediments of Pierceville Stream.
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DURING-HARVEST ASSESSMENT
15
On October 13, flooding of the cranberry bog was accomplished and
harvesting begun. On October 15, when three-quarters completed, harvest-
ing had to be suspended because of weather forecasts predicting storms
accompanied by torrential rain. Wet harvesting can ordinarily be
continued in a light rain, but concern of over-flooding by heavy rain
and the subsequent loss of floating cranberries cause a suspension of
harvest activities.* Another practice in the wet harvesting of cran-
berries is the conservation of water. Thus, when one bog, or section of
bog, has been harvested the water is passed down to a lower bog to
repeat the process. When all bogs capable of re-using the same water
have been harvested, only then is the majority of water allowed to
discharge into a stream or river.
Because of the impending storm and the lengthy operation involved
in completing the entire harvest on the Tremont bog, a decision was made
to terminate the pesticide residue investigation. It appeared that
enough flood water was escaping through the sluice gate to sufficiently
bathe the caged fish and lower sampling area. On October 15, the pre-
harvest sampling routine was repeated and the fish retrieved for AChE
and pesticide analyses.
Analysis of the water sample taken from the reservoir (Station 07)
revealed no detectable traces of pesticides from the increased flow of
water from the upstream bogs. The Station 04 water sample obtained at
the sluice gate of the upper bog also showed no presence of a detectable
concentration of pesticide which indicated little or no dissociation of
pesticides from the cranberry bog soil. At the lower extremity of the
This is method involving a machine called a "water-reel" or "egg-
beater" which knocks the berries off of the vines and -permits them
to float to the surface of the flooded bog. The berries are then
loaded into trucks by conveyor.
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16
bog, water from Pierceville Stream at Station 02 proved also to contain
nor\-de tec table amounts of pesticide, suggesting that no leaching was
taking place from the lower bog soil.
Two sediment samples were obtained at the study site during harvest-
ing. Sediment from Station 06 in the reservoir contained non-detectable
levels of pesticides, suggesting no translocation had taken place from
upstream bogs. The Pierceville stream sediment taken at the lower end
of Tremont Bog {Station 03) also proved to contain nor\-
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17
Field analytical results, on one set of fish from the three test
locations, showed that the range in the acetylcholinesterase activity of
the fish brain of exposed fish was similar to the activity in the brain
of fish from a local hatchery (control fish). No inhibition, or
indication of pesticide poisoning in the vicinity of the Tremont Bog
could be shown.
This was further substantiated when tests on the livers of the
duplicate set of fish were analyzed. No detectable concentrations of
pesticides were found in any of the three groups of fish exposed in
the vicinity or on the Tremont cranberry bog (Table 3).
ESTUARINE ASSESSMENT
A field study was conducted on October 13 to determine the chronic
effects of possible pesticide translocation from cranberry bogs to
adjacent wetlands and receiving waters.
Waters used to irrigate the Tremont Bog drain to Weweantic estuary
and eventually to Buzzards Bay. If pesticide contamination of drainage
waters occurs, the possibility exists that accumulation of pesticides
is occurring in the waters, sediment and biota of these estuarine
systems. Although most organophosphate pesticides are readily
hydrolized, some have been shown to be very persistent; for example,
methyl parathion can remain active in water for nearly two years, and
5 6
in soils for twenty years ' .
During the field study three species of commercial shellfish, Mya
arenaria, Mercenaria mercenaria, and Crassostrea virqinica, were dug
from two separate mud flats (Station 09, 10) on the Weweantic River
(Figure 4). On the same day, several sediment samples (Stations 11-18)
were collected in this river and in Buzzards Bay. Analyses of these
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Station
Nunber
Location
Type
Sample
Before Harvest
10/11/77
00
Hatchery
Water
02
Lower bog
Water
04
Upper bog
Water
07"
Reservoir
Water
05
Upper bog
Soil
03
Upper bog
Soil
03
Lower bog
Sediment
06
Reservoir
Sediment
During Harvest
10/15/77
02
Lower bog
Water
04
Upper bog
Water
07
Reservoir
Water
05
Upper bog
Soil
08
Upper bog
Soil
03
Lower bog
Sediment
06
Reservoir
Sediment
02
Loucr bog
Fish*
04
Upper bog
Fish
07
Reservoir
Fish
TABLE 3
Analytical Results
Malathion, Methyl and Ethyl Farathion
Residue
Malathion Methyl ParatMon Ethyl Parathlon
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
5.6
1.8
N.D.
N.D.
N.D.
N.D.
N.D.
0.6
1.4
N.D.
N.D.
N.D.
N.D.
N.D.
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TABLE 3-(Cont'd.)
Weweantic River and Buzzards Bay
Station Type Residue
Number Location Sample Malathlon Methyl Parathion Ethyl Parathion
Weweancic River and Buzzards Bay
09 Weweantlc River Shellfish**
10
11
12
13
14
15
16
17
18
Weweantic River Shellfish
U'eweantic River Sediment
Ucweantlc River Sediment
Buzzards Bay
Buzzards Bay
Buzzards Bay
Buzzards Bay
Buzzards Bay
Buzzards Bay
Sediment
Sediment
Sediment
Sediment
Sediment
Sediment
fit NtD*
b. N.D.
c. N.D.
a. N.D.
b. N.D.
c.- N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.I).
N.D.
N.D.
N.D.
* Fish - Rainbow Trout - Snlmo r.alrdrveri
** Shellfish - a. Soft clam - Mya arcnarla
b. Hard clam - Mercc-narla mercenarin
c. Eastern Oyster - Crassostrea vlrp.lnlca
+ Values in water expressed as mg/1; in soil, fish, shellfish and sediment as mg/g
f |
None detected.
Water samples: The detection limit for both ethyl and methyl parathion was 0.1 ug/1 (ppb).
The detection limit for oialathion was 0.5 ug/1 (ppb).
Tissue results reported on basis of wet weight; sediment samples reported on basis of dry weight.
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20
samples were done at NEIC laboratories in Denver, Colorado using EPA
standard methods [Appendix A]. The samples did not contain detectable
concentrations of the type of pesticides used on cranberry bogs [Table
3]. Based upon the sampling and analyses described in this report, it
was concluded that harvest flooding did not translocate measurable
amounts of parathion. Furthermore, if pesticide-contaminated water
drained from treated cranberry bogs in Pierceville Stream or the down
stream estuaries prior to the EPA study, the chemicals apparently have
been diluted or dissipated sufficiently and environmental harm did not
occur.
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BUZZARDS
BAY
Sippican R.
hi
\
Weweantic R.
MARION
^ Shellfish Samples
© Sediment Samples
© 13
Locations
SCALE
WAREHAM
Weweantic R.
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22
REFERENCES
1. Demoranville, I.E. Cranberry Varieties. Mass. Agr. Exp. Stat.
Publ. 112, pp. 83-84, 1975.
2. Mass. Agr. Exp. Sta. Publ. 112, p. 1, 1975.
3. Cross, C.E. Flood and Water Management on Massachusetts
Cranberry Bogs. Mass. Agr. Exp. Sta. Publ. 112, p. 1, 1975.
4. Deubert, K.H. and Gray, R.S., Parathion Residues in Environ-
mental Samples from Untreated Areas. Bulletin of Envir.
Contamination and Toxicology, Vol. 15, No. 5, pp. 613-616,
1976.
5. Ground Water Newsletter. Publ. by Water Information Center,
Inc. Vol. 6, No. 20, Oct. 31, 1977.
6. Pest Control: Vol. Ill Cotton Pest Control, 1975, National
Academy of Sciences. Wash. D.C., 139 p.
7. National Pollutant Discharge Elimination System, Appendix A,
Federal Register, 38, No. 75, PA II.
8. Goerlitz, D.F. and Law, L.M., Journal of the AOAC, 57,
No. 1, 1974, 178 p.
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APPENDIX A
ANALYTICAL METHODS
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23
ANALYTICAL METHODS
METHODS
A. Acetylcholinesterase Inhibition Tests. Evaluation of AChE
inhibition in rainbow trout (Salmo gairdneri) was accomplished by
exposing ten fish for four day intervals at each of three stations
in the reservoir, stream and pool in the vicinity of the study bog.
Fish used in the study were obtained from the Massachusetts Department
of Fish and Wildlife Hatchery at Sandwich and ranged in size from
10-16 cm total length.
After the exposure period, the fish were removed from the cages
and transported live to the field laboratory facility where the
brains were removed for AChE analysis.
The principal equipment used for AChE analyses is a recording
pH-stat. Briefly, the procedure was: brains of 4-5 fish from the
same exposure site were pooled, wet-weighed, and homogenized in
distilled water. The brei was diluted with distilled water to a
final tissue concentration of 5 mg/ml. Two ml of diluted homogenate
was then mixed with 2 ml of acetylcholine iodide (a specific substrate
for the enzyme AChE). The pH-stat was used to titrate the acetic
acid end-product of the enzyme substrate reaction with 0.01M NaOH.
The test was performed at pH 7.0 and 22°C with a nitrogen purge over
the surface of the reaction vessel to prevent absorption of
atmospheric carbon dioxide.
Micromiles of acetylcholine hydrolized was calculated from the
micromiles of NaOH required to neutralize the free acetic acid. The
AChE activity was expressed as micromiles of acetylcholine hydrolized
per hour mg of brain tissue.
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24
B. Fish and Shellfish Analysis. Fish samples were prepared for
pesticide analysis in the following manner. The liver from each of
the rainbow trout was removed and frozen. The frozen liver was then
chopped into small pieces and extracted. The shellfish were prepared
by removing the viscera from each animal, weighing the viscera into
10 gram samples, and freezing the viscera. The frozen viscera was
then chopped into small pieces and extracted.
The extraction of all fish samples was done in an explosion-proof
blender using 200 ml of 15% methylene chloride in cyclohexane. The
samples were blended for 1-1/2 - 2 minutes. The extract was then
filtered through Whatman #1 filter paper, dried with Na2S04 and concen-
trated to 10 ml in an evaporative concentrator.
Three of the samples were cleaned to eliminate interference peeks
using the standard EPA acetonitrile clean-up''. The remaining samples
were processed using a Gel Permeation Unit packed with SX-3 resin and
eluted with 15% methylene chloride in cyclohexane. The samples were
analyzed on a gas chromatograph equipped with an alkali flame
ionization detector.
In addition, one of the samples was processed further using a
2 x 15 cm neutral alumina column, deactivated with 3% h^O and eluted
with three 50 ml portions of benzene.
C. Sediment Analysis. Sediment samples were seived through a 2 mm
mesh sieve. The percent moisture in each sample was determined
by drying 10 gm of sample overnight in a 120°C oven and determining
weight loss.
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25
O
The samples were extracted using the USGS method for soil analysis
Briefly, this method involves two serial extractions with a combination
of acetone and hexane using a wrist action shaker. The extract is fil-
tered through Whatman#l filter paper, back extracted with water, and
concentrated to 10 ml in an evaporative concentrator. The extracts were
then analyzed on a gas chromatograph equipped with an alkali flame
ionization detector.
The presence of ethyl parathion was confirmed in two of the
samples using a GC/MS. However, the other two samples suspected of
containing ethyl parathion possessed too many interference peeks to
analyze by GC/MS. These samples were processed using the neutral
alumina column cleaning method described previously. Ethyl parathion
in these two samples was identified based on gas chromatographic
retention time and alumina column elution pattern.
Quality Control
A. Water Analysis. A series of tests were performed to determine the
recovery and holding time for ethyl and methyl parathions in water.
One liter samples of tap water were spiked with 2 ug of ethyl
parathion and 2 ug of methyl parathion. The pH of the water had been
adjusted to 4 before spiking. Two of the spikes were analyzed
immediately using the method previously described. The others were
held in a refrigerator until analyzed.
Results: % Recovery
Date Analyzed
Methyl Parathion
Ethyl Parathion
Spike 1
10/21/77**
101
99
Spike 2
10/21/77**
95
93
Spike 3
10/26/77*
93
86
Spike 4
10/31/77**
97
97
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26
B. Sediment. A 50 gm sample from Station 06 was spiked with 20 ug each
of ethyl parathion, methyl parathion and malathion. The sample was
analyzed according to the procedure previously described for sediment.
A solvent blank was also analyzed.
Results:
% Recovery
Methyl Ethyl
Malathion Parathion Parathion
Spike 114 129 88
Blank — —
C. Fish. Two different types of shellfish viscera were spiked
with 0.5 ug of each of the following pesticides: malathion, ethyl
parathion, methyl parathion. The samples were then analyzed for
the method previously described.
Results: Hard clams, Station 09
% Recovery
Malathion Methyl Parathion Ethyl Parathion
76 84 66
Results: Soft clams, Station 10
% Recovery
Malathion Methyl Parathion Ethyl Parathion
38 47 40
* pH not adjusted to 7 before extraction
** pH adjusted to 7 before extraction
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APPENDIX B
REVIEW OF CHAIN-OF-CUSTODY PROCEDURES
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27
REVIEW OF CHAIN-OF-CUSTODY PROCEDURES
Cranberry Bog Study
Wareham, Massachusetts
Records regarding the Cranberry Bog Study were evaluated against
the established NEIC chain-of-custody procedures. There was no recon-
naissance of the study site made by NEIC personnel. Field data records,
log books, sample tags, and chain-of-custody records were reviewed to
determine if there were any deviations from the procedures. Where de-
viations were discovered, an assessment was made as to what effect,
if any, this had on survey results. The result of this evaluation is
described in the following paragraphs.
The AChE analyst on the survey did not maintain a laboratory note-
book. Instead, the data for each fish brain analysis was recorded on
the recording pH stat graph paper and not re-recorded into a bound
notebook. Between each analysis standard calibrations of the AChE
equipment was conducted, but not recorded.
Although daily calibrations for accuracy were made on the Mettler
H45 analytical balance, these were not recorded in a laboratory note-
book.
These above described deviations are considered minor and had no
impact on the results and conclusions contained in this report.
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