EPA 910/9-91-020
PTI
ENVIRONMENTAL SERVICES
1990 Puget Sound Pesticide
Reconnaissance Survey
Prepared for
U.S. Environmental Protection Agency
Region 1.0, Office of Puget Sound
Seattle, Washington
August 1991
-------
199Q PUGET SOUND PESTICIDE
SURVEY
Prepared for
U.S. Environmental Protection Agency
Region 10, Office of Puget Sound
Seattle, WA
EPA Contract 68D80085
PIT Contract C744-14
August 1991
-------
CONTENTS
Page
LIST OF FIGURES iv
LIST OF TABLES iv
LIST OF ACRONYMS v
EXECUTIVE SUMMARY vi
INTRODUCTION 1
SAMPLING PROTOCOLS 2
SAMPLING LOCATIONS 2
SELECTION OF SIGNIFICANT RAINFALL EVENT FOR WATER
SAMPLING 2
SAMPLE COLLECTION 2
Water Samples 2
Sediment Samples 5
CHEMICAL ANALYSES 5
RESULTS 8
TOXICOLOGICAL RELEVANCE: REVIEW OF
WATER AND SEDIMENT QUALITY DATA 20
Toxicity Test Species 20
Water Quality Evaluation 25
Sediment Quality Evaluation 27
Uncertainties of the Evaluation 30
Recommendations 30
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RECOMMENDATIONS FOR FUTURE MONITORING EFFORTS 33
ROUTINE MONITORING 33
REGIONAL RECONNAISSANCE 34
RESEARCH STUDIES 35
REFERENCES 37
APPENDIX A - Sampling Reports
APPENDIX B - Rainfall Runoff Model
APPENDDC C - Description of Water Sampling Apparatus
APPENDK D - Chain-of-Custody Forms
APPENDK E - Sediment Quality Criteria
APPENDK F - Quality Assurance Report for Chemical Analyses
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LIST OF FIGURES
Page
Figure 1. Drainages sampled
LIST OF TABLES
Page
Table 1. Sampling dates for water samples 4
Table 2. Pesticides analyzed for in Puget Sound waters and
sediments 6
Table 3. Summary of analytical methods 7
Table 4. Concentrations of pesticides in water samples 9
Table 5. Summary of pesticide data for waters 12
Table 6. Concentrations of pesticides in sediment samples 13
Table 7. Summary of pesticide data for sediments 15
Table 8. Estimated pesticide usage of primarily non-urban-specific
pesticides in the Puget Sound basin 17
Table 9. Estimated usage of primarily urban-specific pesticides in
the Puget Sound basin 18
Table 10. Water quality evaluation data 21
Table 11. Sediment quality evaluation data 22
IV
-------
LIST OF ACRONYMS
CCC criterion continuous concentration
CMC criterion maximum concentration
2,4-D 2,4-dichlorophenoxyacetic acid
EPA U.S. Environmental Protection Agency
IRIS Integrated Risk Information System
MSMA monosodium methanearsonate
-------
EXECUTIVE SUMMARY
The 1989-1990 Pesticide Reconnaissance Survey was conducted by the U.S.
Environmental Protection Agency Region 10, Office of Coastal Waters, and the
Puget Sound Estuary Program to assess the extent and lexicological significance
of water-soluble and sediment-bound pesticide residues present in Puget Sound
drainages. Fifteen water samples and six sediment samples were collected from
five drainage areas that empty into Puget Sound and analyzed for 33 different
pesticide residues. Five pesticides were detected in at least one water sample:
diazinon, 2,4-dichlorophenoxyacetic acid (2,4-D), dicamba, bromacil, and diuron.
The most commonly detected pesticide in water samples was 2,4-D, which was
detected in 13 samples at concentrations from 0.077 to 0.70 /xg/L. Four
pesticides, or their degradation products, were detected in at least one sediment
sample: dichlobenil, pentachlorophenol, DDT/DDE/DDD, and endosulfan I and
II. Pentachlorophenol was detected in all six sediment samples at concentrations
up to 33 /xg/kg.
Results from water and sediment sampling were compared to lexicological
values. Pesticide concentrations detected in water samples were below or did not
exceed published acute or chronic lexicological values. Two pesticides, diazinon
and endosulfan I, were detected in al leasl one sedimenl sample al concentrations
that are potentially hazardous to aquatic life thai may conlacl contaminated
sediments. Recommendations for future pesticide monitoring efforts include
routine monitoring, regional reconnaissance surveys, and detailed research
studies.
VI
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INTRODUCTION
The 1989-1990 Pesticide Reconnaissance Survey was conducted by the U.S.
Environmental Protection Agency (EPA) Region 10, Office of Coastal Waters,
and the Puget Sound Estuary Program. The objectives of the survey were to:
• Assess water-soluble pesticide residues during two time intervals
immediately following a significant rain event
• Assess sediment-bound pesticide residues at locations consistent
with the water-soluble pesticide sampling strategy
• Assess sediment-bound and water-soluble pesticides at areas
representing the lower portions of three distinct watersheds: urban,
suburban, and semirural land-use patterns
• Compare results of the current survey with results from a previous
reconnaissance of pesticide residues in sediments of Puget Sound
drainages
• Summarize the results of the present study in the context of the
published information on the toxicology of the pesticides detected
• Make recommendations for future pesticide monitoring activities.
In the following section, the design of the reconnaissance survey is
described, with emphasis on the rationale for how an appropriate storm event and
sampling period were selected for each drainage basin. In subsequent sections,
results for the water and sediment analyses conducted in 1989 and 1990 are
summarized and a review of toxicity data from the literature is presented. The
review provides a biological context for interpreting the concentrations of
pesticides detected in the reconnaissance survey and for assessing the adequacy
of detection limits attained for undetected compounds. In the final section, a
summary is provided in which continued monitoring of selected pesticides is
recommended and additional research needs are identified.
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SAMPLING PROTOCOLS
SAMPLING LOCATIONS
Twelve water samples and six sediment samples were collected from four
Puget Sound drainages (Figure 1) in 1990. Specific sampling locations are
provided in Appendix A. The Big Ditch Slough drainage, located near the mouth
of the Skagit River, and Padilla Bay sloughs are representative of agricultural
runoff. Mercer Creek is representative of urban runoff, and the Swamp Creek/
Sammamish River drainage is representative of suburban runoff. Three additional
water samples were collected by EPA staff from Muck Creek in southern Puget
Sound. Muck Creek discharges to the Nisqually River and is representative of
drainage from the Ft. Lewis military base.
SELECTION OF SIGNIFICANT RAINFALL EVENT FOR WATER SAMPLING
Sampling was conducted during high-rainfall precipitation events to enhance
the probability that pesticides would be present in water runoff. A hydrographic
model that incorporated area-specific physiographic, hydraulic, and precipitation
data was used to predict the amount of precipitation and the length of time after
the start of the event needed at each sampling area to produce runoff. A 6-hour
duration, 2-year return precipitation event was used as a basis for sampling
program design. Model results indicated that 0.5-2.1 inches of rain, depending
on the area and the season, must occur in the 5 days preceding the 6-hour, 2-year
precipitation event for runoff to occur. Details of model development and criteria
used for sampling are found in Appendix B.
SAMPLE COLLECTION
Water Samples
Twelve water samples were collected during four sampling events in 1990
(Table 1). Samples were collected using 2.5-liter glass bottles held in a ring at the
end of a 4.5-meter stainless steel pole. A complete description of the sampling
apparatus used for water sampling is included in Appendix C. Samples were
taken from below the water surface at a minimum of 3 meters from the bank.
Each sample listed in Table 1 was collected as a composite that was divided into
a set of twelve 2.5-liter bottles for chemical analysis. Two to eight pairs of
40-mL volatile organic analyte vials were also collected with each sample by
transferring water from the sample bottle used to create the composites. Three
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BIG DITCH
SLOUGH
Olympic
Peninsul
Figure 1. Drainages sampled.
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TABLE 1. SAMPLING DATES
FOR WATER SAMPLES
Sample
Date Sampled
Muck Creek*
MKCR-1
MKCR-2
MKCR-3
Big Ditch Slough
BGDHJ1
BGDHJ2
BGCHJ3
BGDH01
BGDH02
BGDH03
Mercer Creek
MRCR-1
MRCR-2
MRCR-2
Swamp Creek
SWMP-1
SWMP-2
SWMP-3
21 June 1989
21 June 1989
21 June 1989
7 June 1990
7 June 1990
7 June 1990
16 October 1990
16 October 1990
16 October 1990
30 August 1990
30 August 1990
30 August 1990
4 October 1990
4-5 October 1990
5 October 1990
• Muck Creek, near Ft. Lewis, was not resampled in 1990,
and no hydrograph was prepared for this location.
-------
sets of twelve bottles each were collected at each location during a storm event,
representing three time periods on the flow curve. All samples were stored on
ice until delivery to the laboratory. Chain-of-custody records were completed
each day for each sample and are included in Appendix D.
Water samples collected in 1989 near Ft. Lewis were obtained using a
battery-powered submersible pump. Water drawn through Tygon® tubing was
collected in 2.5-liter bottles for chemical analysis. This system was replaced with
the apparatus shown in Appendix C to eliminate any concern about the possibility
of pesticides being absorbed into the walls of the tubing.
Sediment Samples
Six composite sediment samples were collected on 25 and 26 October 1990
using a hand-held Ekman grab sampler (0.023 m2). Each composite sample
consisted of three to four grab samples at each location. Grab samples were
taken in water depths of 6 inches to 3 feet and, unless insufficient fine-grained
material was found, were generally collected within 10 feet of each other.
Exceptions were grab samples collected within 300 feet of each other along the
slough near Conway (Figure 1) and grab samples collected within 1,300 feet of
each other along Swamp Creek. Samples were stored on ice until delivery to the
laboratory. Chain-of-custody records were completed each day for each sample,
and are included in Appendix D.
CHEMICAL ANALYSES
Water and sediment samples were analyzed for the pesticides listed in
Table 2 by EPA-approved methods (Table 3). Target pesticides were selected
from the list found in Pesticides of Concern in the Puget Sound Basin: A Review
of Contemporary Pesticide Usage (Tetra Tech 1988). Some pesticides suggested
in the 1988 report were not determined because of 1) analytical difficulties (e.g.,
benomyl in sediment); 2) nonspecific analysis [e.g., vernolate or butylate by
carbon disulfide generation, monosodium methanearsonate (MSMA) by arsenic
detection]; or 3) environmental interferences (e.g., substitution of bromine in
methyl bromide by chlorine in natural waters).
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TABLE 2. PESTICIDES ANALYZED FOR IN
PUGET SOUND WATERS AND SEDIMENTS
Organophosphate
Pesticides
Diazinon
Malathion
Dichlorvos
Fenamiphos
Chlorpyrifos
Parathion (ethyl)
Disulfoton
Methyl parathion
Azinphos-methyl
Phorate
Chlorinated
Pesticides'
Trifluralin
Chlordane
Endosulfan
Lindane
Dichlobenit
DDT
DDE
DDD
Chlorinated
Herbicides
2,4-D
Dicamba
Dinoseb
Triclopyr
Triazine
Herbicides
Alachlor
Atrazine
Amitrole
Hexazinone
Prometon
Simazine
Polar Phosphorous Carbamates and
Pesticides'* Urea Pesticides Miscellaneous
Acephate Bromacil 1,3-Dichloropropeneb and
Methamidophos Carbaryl Chloropicrin6
Propham Glyphosate
Methomyl Benfluralin
Diphenamid Pentachlorophenol*
Tebuthiuron Fenvalerateb
Diuron
Pronamide
Bendiocarb
Terbacil
" Sediment samples only.
b Water samples only.
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TABLE 3. SUMMARY OF ANALYTICAL METHODS
Analytical Group
Organophosphate pesticides
Chlorinated pesticides (sediment only)
Chlorinated herbicides and trichlopyr
Triazine herbicides and alachlor
Carbamate pesticides and terbacil
Polar phosphorous pesticides (water only)
Miscellaneous (water only)
Chloropicrin and 1 ,3-dichloropropene
Glyphosate
Instrument
Technique
GC/FPD"
GC/ECD"
GC/ECD
GC/NPD0
HPLCd
GC/FPD
GC/ECD
HPLC
Method
EPA Method 1618
EPA Method 608
EPA Method 61 5
EPA Method 61 9
EPA Method 632
Method AB 1 803
EPA Method 504
Modified EPA Method 547*
Miscellaneous (sediment only)
Benfluralin
Pentachlorophenol
Pydrin and Fenvalerate
GC/ECD or HPLC
GC/ECD
GC/ECD
Modified EPA Method 608 or
modified Method 619
EPA Method 8040
Modified EPA Method 608
* Gas chromatography/flame photometric detection.
b Gas chromatography/electron capture detection.
c Gas chromatography/nitrogen-phosphorous detection.
d High performance liquid chromatography.
" Ruorescence detection.
-------
RESULTS
Five pesticides were detected in water samples: diazinon, 2,4-dichloro-
phenoxyacetic acid (2,4-D), dicamba, bromacil, and diuron (Table 4a). Diuron
and 2,4-D were the only pesticides detected in water samples from Muck Creek
in the June 1989 sampling event (Table 4b). Diazinon and 2,4-D were detected
in water samples from Big Ditch Slough from the June 1990 (BGDHJ) sampling
event, but were not detected during the October 1990 sampling event (BGDHO).
Diazinon was also detected in samples from Mercer Creek (MRCR) and Swamp
Creek (SWMP). Dicamba was detected in samples from Swamp Creek.
Dicamba and 2,4-D were the only pesticides detected in water samples from a
study of Padilla Bay and surrounding sloughs conducted in 1987 and 1988
(Table 5) (Mayer 1989). The concentrations of 2,4-D found in the present survey
are similar to those found in the previous Padilla Bay study, but the concen-
trations of dicamba found in the previous Padilla Bay study were 1-2 orders of
magnitude higher than those found in the present Swamp Creek samples. Water
samples from the June 1990 sampling of Big Ditch Slough also had detectable
concentrations of bromacil and diuron, while no detectable concentrations of these
pesticides were observed in Big Ditch Slough samples collected in October 1990.
Four pesticides were detected in sediment samples: dichlobenil, DDT and
its breakdown products (DDE and DDD), endosulfan, and pentachlorophenol
(Table 6). Pentachlorophenol was detected in all six sediment samples at con-
centrations from 0.0021 to 0.033 mg/kg. Pentachlorophenol was also detected
in all 17 sediment samples collected for the 1988 pesticide survey, at similar
concentrations to those found in the present study (Table 7) (Crecelius et al.
1989). Dichlobenil was detected in three sediment samples in the present study
[MRCR-S, SWMP-S, and LACO-S (Padilla Bay sloughs/north Skagit delta)].
During the 1988 survey, dichlobenil was detected in four samples collected
from around J^ake Washington, at similar concentrations. The sediment sample
from Mercer Creek (MRCR-S) had a detectable concentration of endosulfan.
DDT and/or its breakdown products were detected in samples MRCR-S,
SWMP-S, LACO-S, and CNWY-S at levels from 0.0078 to 0.0209 mg/kg (total
DDT+DDE+DDD). Endosulfan, DDT, DDE, and DDD were not analyzed for
during the 1988 survey.
During the 1988 survey, several pesticides were reported as detected:
clorpyrifos was detected at three stations, lindane (7-hexachlorocyclohexane) at
nine stations, dicamba at two stations, and 2,4-D at four stations. Dicamba was
also detected in sediment samples from Padilla Bay drainages during 1987 (Mayer
1989).
8
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TABLE 4a. CONCENTRATIONS OF PESTICIDES IN WATER SAMPLES
Sampla
Compound BGDHJ1 BGDHJ2 BGDHJ3 BGDHJCb
Azinophos
methyl
Chlorpyrifos
Oiazinon
Dichlorvos
Disulfoton —
Fenamiphos —
Malathion
Methyl
parathion
Parathion -
Phorate —
Chloropicrin
1 ,3-Dichloropro- -
-------
TABLE 4a. (Continued)
Sample
Compound
Amimole
Methomyl
Tebuthiuron
Bromacil
Terbacil
Bendiocarb
Carbaryl
Diuron
Prop ham
Oiphenamid
Pronamido
Acephate
Methamidophos
Gyphosate
BGDHJ1
NRb
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
BGDHJ2
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.3
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
BGDHJ3 BGDHJC"
NR
5.0
2.0
3.3
2.0
5.0
2.0
3.3
2.0
2.0
1.0
1.0
1.0
5.0
NR
U
U
-
U
U
U
--
U
U
U
U
U
U
MRCR-1
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
MRCR-
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
2
U
U
U
U
U
U
U
U
U
U
U
U
U
MRCR-3
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
SWMP-1
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
SWMP-2
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
SWMP-3
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
BGOH01
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
BGDH02
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
BGDH03
NR
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
1.0
1.0
1.0
5.0
U
U
U
U
U
U
U
U
U
U
U
U
U
' BGDHJC - composite of BGDHJ1, BGDHJ2, and BGDHJ3. Results are reported for the composited sample (BGOHJC), except for polar phorphorous pesticides, carbamate and urea pesticides, and
glyphosata, which were analyzed in individual samples rather than as a composited sample.
b U - Undetected at the detection limit shown.
Bold - Detected values.
NR - Analysis not required.
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TABLE 4b. CONCENTRATIONS OF PESTICIDES
IN WATER SAMPLES (//g/L)'
Sample
Compound
Azinophos methyl
Chlorpyrifos
Diazinon
Dichlorvos
Disulfoton
Fenamiphos
Malathion
Methyl parathion
Parathion
Phorate
Chloropicrin
1 ,3-Dichloropropene
2.4-D
Dicamba
Dinoseb
Trichlopyr
Alachlor
Atrazine
Hexazinone
Prometon
Simazine
Amimole
Methomyl
Tebuthiuron
Bromacil
Terbacil
Bendiocarb
Carbaryt
Oiuron
Propham
Diphenamid
Pronamide
Acephate
Methamidophos
Gyphosate
MKCR-1"
1
1
1
1
1
1
.0
.0
.0
.0
.0
.0
1.0
1.0
1
.0
u
u
u
u
u
u
u
u
u
NR
0
0
.22
.22
u
u
0.7
0
0
0
1
1
1
1
1
.40
.40
.40
.0
.0
.0
.0
.0
5.0
5
.0
2.0
2
2
5
2
2
2
2
2
10
10
5
.0
.0
.0
.0
.9
.0
.0
.0
.0
.0
.0
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
MKCR-2C
1.
1.
1.
1.
1.
1.
0
0
0
0
0
0
1.0
1.0
1.0
NR
0.22
0.22
u
u
u
u
u
u
u
u
u
u
u
0.69
0.4
0.4
0.4
1.0
1.0
1.0
1.0
1.0
5.0
5.0
2.0
2.0
2.0
5.0
2.0
2.1
2.0
2
2
10
10
5
.0
.0
.0
.0
.0
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
MKCR
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NR
-3d
U
U
u
u
u
u
u
u
u
MKCR-
1.
1.
1.
1.
1.
1.
1.
1.
1.
0
0
0
0
0
0
0
0
0
4'
U
U
U
U
U
U
u
u
u
NR
0.22 U
0.22 U
0.58
0.4
0.4
0.4
1.0
1.0
1.0
1.0
1.0
5.0
5.0
2.0
2.0
2.0
5.0
2.0
2.2
2.0
2.0
2.0
10.0
10.0
5.0
U
U
U
U
U
U
U
U
U
U
u
u
u
u
u
u
u
u
u
u
u
0.
0.
0.
0.
1.
1.
1.
22
22
4
4
4
4
0
0
0
1.0
1.0
5.0
5.0
2.0
2.0
2.0
5.0
2.0
1
2
2
2
10
10
5
.0
.0
.0
.0
.0
.0
.0
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
* Samples from A/luck Creek were collected in 1989.
Bold—detected values.
11
-------
TABLE 5. SUMMARY OF PESTICIDE DATA
FOR FUGET SOUND WATERS
Compound
Diazinon
2,4-D
Dicamba
Bromacil
Diuron
Concentration Range
(//g/U
Mayer* 1 990 Survey
0.054-0.14
(5 of 1 4 samples)5
0.14-1.3(4) 0.077-0.70
(10 of 14 samples)
10- 170 (10) 0.11 -0.27
(3 of 1 4 samples)
3.3
(1 of 16 samples)
1.3-3.3
(5 of 1 6 samples)
•Mayer (1989).
b ( ) - number of samples with detectable pesticide.
12
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TABLE 6. CONCENTRATIONS OF PESTICIDES
IN SEDIMENT SAMPLES (mg/kg)
Sample
Compound
Azinophos methyl
Chlorpyrifos
Diazinon
Dichlorvos
Disulfoton
Fenamiphos
Malathion
Methyl parathion
Parathion
Phorate
2,4-D
Dicamba
Dinoseb
Trichlopyr
Alachlor
Atrazine
Hexazinone
Prometon
Simazine
Methomyl
Tebuthiuron
Bromacil
Terbacil
BGDH-S
0.0086
0.0045
0.0045
0.0045
0.0045
0.0086
0.0045
0.0045
0.0045
0.0045
0.0018
0.0018
0.0018
0.0022
0.053
0.053
0.053
0.053
0.053
2.6
0.3
0.3
0.1
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
LSAM-S
0.0073
0.0038
0.0038
0.0038
0.0038
0.0073
0.0038
0.0038
0.0038
0.0038
0.0015
0.0015
0.0015
0.0019
0.044
0.044
0.044
0.044
0.044
2.2
0.2
0.2
0.1
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
MRCR-S
0.013
0.0065
0.0065
0.0065
0.0065
0.013
0.0065
0.0065
0.0065
0.0065
0.0026
0.0026
0.0026
0.0032
0.092
0.092
0.092
0.092
0.092
3.8
0.4
0.4
0.2
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
SWMP-S
0.01
0.0052
0.0052
0.0052
0.0052
0.01
0.0052
0.0052
0.0052
0.0052
0.002
0.002
0.002
0.0025
0.061
0.061
0.061
0.061
0.061
3
0.3
0.3
0.1
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
LACO-S
0.015
0.0077
0.0077
0.0077
0.0077
0.015
0.0077
0.0077
0.0077
0.0077
0.003
0.003
0.003
0.0038
0.091
0.091
0.091
0.091
0.091
4.5
0.5
0.5
0.2
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
CNWY-S
0.019
0.01
0.0088
0.01
0.01
0.019
0.01
0.01
0.01
0.01
0.0039
0.0039
0.0039
0.0049
0.13
0.13
0.13
0.13
0.13
5.8
0.6
0.6
0.2
U
U
T
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
-------
TABLE 6. (Continued)
Sample
Compound
Bendiocarb
Carbaryl
Diuron
Propham
Oiphenamid
Pronamide
Dichlobenil
Trifluralin
Benfluralin
Lindane
4,4'-DDE
4,4'-DDD
4,4'-DDT
Endosulfan 1
Endosulfan II
Fenvalerate
Chlordane
Pentachlorophenol
BGDH-S
0.3
0.3
0.1
1
1
0.3
0.0022
0.0022
0.0022
0.0022
0.0022
0.0032
0.0032
0.0022
0.0032
0.0055
0.011
0.0039
U
u
U
u
u
u
u
u
u
u
u
u
u
u
u
u
u
E
LSAM-S
0.2
0.2
0.1
0.9
0.9
0.2
0.0018
0.0018
0.0018
0.0018
0.0018
0.0027
0.0027
0.0018
0.0027
0.0047
0.0093
0.0021
U
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
E
MRCR-S
0.4
0.4
0.2
1.5
1.5
0.4
0.022
0.0032
0.0032
0.0032
0.0038
0.0074
0.0097
0.0113
0.0080
0.0080
0.016
0.0130
U
u
u
u
u
u
u
u
u
E
U
u
E
SWMP-S
0.3
0.3
0.1
1.2
1.2
0.3
0.0026
0.0025
0.0025
0.0025
0.0015
0.0020
0.0023
0.0025
0.0036
0.0064
0.013
0.0330
U
U
u
u
u
u
u
u
u
T
T
T
U
u
u
u
LACO-S
0.5
0.5
0.2
1.8
1.8
0.5
0.0021
0.0038
0.0038
0.0038
0.0052
0.0066
0.0029
0.0038
0.0054
0.0095
0.019
0.0038
U
U
u
u
u
u
T
U
u
u
E
E
TE
U
U
U
u
E
CNWY-S
0.6
0.6
0.2
2.3
2.3
0.6
0.0049
0.0049
0.0049
0.0049
0.0045
0.0041
0.0070
0.0049
0.0070
0.0120
0.025
0.0020
U
u
u
u
u
u
u
u
u
u
E
E
UR
U
U
U
U
E
U - Undetected at the detection limit shown.
T - Detected below quantification limit.
E - Estimate.
/? - Rejected.
Bold - Detected values.
-------
TABLE 7. SUMMARY OF PESTICIDE DATA FOR SEDIMENTS
Concentration Range
U/g/kg)
Compound
Chlorpyrifos
Dichlobenil
Mayer" 1 988 Survey"
2.7 - 7.6 (3)c
2.0 - 4.9 (4)
1 990 Survey
2.1 22
Lindane
Dicamba
2,4-D
Pentachlorophenol
DDT/DOE/DDD (total)
Endosulfan I and II
(3 of 6 samples)
2,100- 17,100(10)
2.2 - 20 (9)
1.2-12 (2)
12 - 43 (4)
6.7-56 (17)
2.0 - 33
(6 of 6 samples)
5.8 - 20.9
(4 of 6 samples)
19.3
(1 of 6 samples)
'Mayer (1989).
b Crecelius et al. (1989).
c () - number of samples with detectable pesticide.
15
-------
Of the 11 pesticides detected in Puget Sound sediments and waters during the
three studies mentioned above, 6 are currently used primarily for non-urban
applications: pentachlorophenol, 2,4-D, diazinon, dicamba, bromacil, and diuron
(Tetra Tech 1988). Historically, pentachlorophenol, detected in all samples in
both the 1988 and 1990 reconnaissance studies, has been the most heavily used
pesticide in the Puget Sound area (Table 8). Pentachlorophenol is used exten-
sively as a wood preservative; thus, treated railroad ties may also serve as a long-
term source for this material. The other 5 pesticides detected are among the
12 most heavily used pesticides in the area, supporting the correlation between
pesticide usage and detection of these pesticides in runoff. Dicamba, 2,4-D, and
mixtures of the two are used for control of broadleaf weeds in grain crops, lawns
and golf courses, right of ways, and forestry applications. Diuron, at low
application rates, is used to selectively control broadleaf and grass weeds in
alfalfa and tree crops. Diuron, at high rates, and bromacil are nonselective
herbicides that are used alone or in combination on non-cropland. Diazinon, an
insecticide, is used for a wide variety of agricultural, industrial, and home uses.
Pesticides used primarily in urban areas (Tetra Tech 1988) detected in the
Puget Sound area include chlorpyrifos, lindane, and dichlobenil. Chlorpyrifos,
the fifth-most heavily applied pesticide in Puget Sound (Table 9), is used for
insect control on lawns, vegetables, ornamental plants, and stored products. It
is also used for control of mosquitoes and termites. Lindane is used as a seed
treatment for soil insect control; as a foliar spray in vegetables, fruit trees, and
ornamental plants and trees; and as a wood preservative. Dichlobenil is used to
control herbaceous weeds in woody ornamental or food crops such as rhododen-
drons, grapes, and fruit trees. It is also used as a general, nonselective weed
killer in nurseries, industrial areas, and parking lots.
There are several possible reasons why other heavily used pesticides listed
in Tables 8 and 9 have not been detected. Sampling locations may not have been
located in areas where these compounds are specifically used. However,
malathion, which is used primarily in the Puget Sound on Puyallup and Nisqually/
Deschutes military bases (Tetra Tech 1988), was not detected (U 1 pg/L) in water
samples from Muck Creek flowing through the Ft. Lewis military base.
Pesticides may also degrade into compounds that were not on the target list, or
volatilize into the atmosphere. Malathion hydrolyses in water, and trichlopyr is
subject to rapid photodegradation. Methyl bromide is a gas (above 4°C) that is
used as a space, stored commodity, and soil fumigant.
Endosulfan was not listed in the Tetra Tech (1988) report as currently being
used in Puget Sound area; however, endosulfan is still registered for use against
foliar feeding insects on a wide variety of plants, and its use in the Puget Sound
area is not unlikely. The use of DDT in the United States has been prohibited
since 1973 and has not been domestically available since its registration was
canceled. Therefore, it is doubtful that any significant illegal use of DDT has
occurred. The fact that DDT and its degradation products have been detected in
Puget Sound sediments 17 years after its use has been banned is further indication
16
-------
TABLE 8. ESTIMATED PESTICIDE USAGE OF PRIMARILY NON-
URBAN-SPECIFIC PESTICIDES IN THE PUGET SOUND BASIN*
Pounds Active
Active Ingredient Ingredient Per Year
Pentachlorophenol 720,000
2.4.-D Species 311,406
Malathion 203,326
Prometon 108,744
Simazine 97,283
Diazinon 83,127
Dicamba 55.446
Triclopyr 54,633
Atrazine 44,391
Bromacil 40,817
Carbaryl 37,297
Diuron 37,120
Glyphosate 35,088
Tebuthiuron 33,043
Vernolate 16,199
Cuprous Oxide 15,745
Dichloropropene 15,330
Parathion 13,746
Sodium Metaborate 13,689
Dinoseb 12,392
Butylate 12,000
Alachlor 9,402
Phorate 8,156
Methyl Parathion 7,856
Lime Sulfur 7,417
Oisulfoton 7,340
Methamidophos 5,976
Pronamide 5,850
Trifluralin 5,547
Oryzalin 5,397
Metolachlor 5,301
Boric Acid 4,995
Sulfometuron-methyl 4,992
Acrolein 4,765
Fenvalerate 4,753
Benfluralin 4,435
Diquat 4,152
Propham 4,128
Methomyl 4,013
Tributyltin 3,686
Fosamine Ammonium 3,680
Hexazinone 2,592
Diphenamid 2,400
All others (total) 79,000
• From Tetra Tech (1988); pesticides shown in bold were detected in the 1990
reconnaissance survey.
17
-------
TABLE 9. ESTIMATED USAGE OF PRIMARILY URBAN-SPECIFIC
PESTICIDES IN THE PUGET SOUND BASIN*
Pounds Active
Active Ingredient Ingredient Per Year
Methyl Bromide ???.???b
Sulfuryl Fluoride 120,900
Metaldehyde 54,200
Chlordane 49,800
Chlorpyrifos 39,400
Sulfur 34,800
Xylene 21,600
Acephate 19,400
Ziram 17,600
Endosulfan 14,020
MCPP 11,290
Glyphosate 11,423
Heptachlor 10,990
Amitrole 10,170
Azinphos-methyl 8,070
Propoxur 7,540
Dichlobenil 7,070
Benomyl 6,660
Chlorothalonil 6,150
Chloropicrin 3,810
Lindane 2,640
Dichlorvos 2,490
Propetamphos 2,280
1 From Tetra Tech (1988); the pesticides shown in bold print were detected in the
1990 reconnaissance survey.
b Estimated usage is unknown.
18
-------
of the extreme persistence of this material, or that it may be a byproduct or
process residue associated with other chlorinated pesticides.
19
-------
TOXICOLOGICAL RELEVANCE: REVIEW OF
WATER AND SEDIMENT QUALITY DATA
The following review of water and sediment quality data for tributaries of
Puget Sound is limited to a comparison of the observed site-specific chemical
concentrations with available indices of toxicity. No quantitative estimates of risk
were developed as part of this project. Pesticide concentrations measured in
water and sediment samples were evaluated for their potential to cause adverse
effects on aquatic communities based on EPA chronic water quality criteria (U.S.
EPA 1987) and the lowest observed chronic effects values provided by EPA's
Integrated Risk Information System (IRIS) (U.S. EPA 1990). Aquatic acute
toxicity values summarized by Tetra Tech (1988) were used when chronic toxicity
values were not identified by EPA. Literature searches for indices of toxicity to
aquatic organisms in addition to those described above were beyond the scope of
this effort.
EPA requires chronic and/or acute toxicity data from a minimum of eight
families of organisms (U.S. EPA 1987) to derive water quality guidelines. This
array of species should adequately represents the communities of Puget Sound and
its tributaries. However, the species represented in acute toxicity test data (Tetra
Tech 1988) are not necessarily found in Puget Sound (Table 10). The evaluation
of the degree to which toxicity to these species may reflect similar effects on
Puget Sound resources presented below is based on available information and
professional judgment.
Using the results of water and sediment sampling (Tables 4, 5, and 6),
potential adverse impacts on the marine environment were evaluated. The
evaluation was based on the conservative assumption that contaminant concentra-
tions found in the tributaries are maintained in the marine environment.
Conditions in the water and sediments of Lake Washington were also assumed to
be the same as conditions in its tributaries.
Finally, an approach to conducting screening level evaluations of water and
sediment contaminant data for fresh and marine waters of the Puget Sound region
is recommended.
Toxicity Test Species
The specific names of the organisms used to establish chronic water quality
criteria provided by Tetra Tech (1988) and summarized in Table 11 are not
available. The data were compiled from a variety of sources, and retrieval of
20
-------
TABLE 10. WATER QUALITY EVALUATION DATA
Acute Water Quality Criteria Value
Chronic Water Quality
Criteria Value
1 ,000.000
22
4<
22
1.0001
3OO
~
--
87-122
-
2,000-5,700
10O-710
5"
116.000
370,000-420,000
40.OOO
> 100.0OO"
71.OOO"
7.400-9,1 OO
112.OOO
-
1.45O1
2.0OO-6.76O
Trout*
100.000-1,100,000
3.2-20
3
380*
187
1.850
110
-
87-310
-
2.75O-5.3OO
2.OOO*
11-16
4.50O-8.80O
32O.OOO-42O.OOO
12.0OO
5,OOO-6O,OOO"
75,000"
2,400-23,000
1 44.00O
-
1.550
1.070-1.500
Marine L(
Shrimp*
3,800-10,000
0.03
2.8*
20.0001
4
50.000-58,000"
-
-
330- 1.OOO"
-
1'
430*
-
10.000-33,000"
< 1OO.OOO
-
> lOO.OOO"
-
38-285
-
-
-
10-40*
%
-so
Killifish"
85,000
-
0.6
1.470
2,400
740
~
-
14
-
790
20
0.4
-
-
-
~
—
15
-
--
-
1.750
-------
TABLE 10 (Continued)
Class
Anilines
Anilides
Substituted Amides
Halogenated
Hydrocarbons
PhenoxyaJiphatic
Acids
Benzole Acids
Phenols
Pyridine Carboxylic
Acids
Miscellaneous
Pesticides
Pesticide
Methomyl
Propham
Alachlor
Diphenamid
1 ,3-Dichloropro-
pene
2,4-D
Dicamba
Oinoseb
Trichlopyr
CNoropicrin
Pronamide
Acute Water Quality Criteria Value
Chronic Water Quality
Criteria Value Freshwater LC^, Marine LCM
0/g/L)1 Concentration Range/ Mean (//g/L(d Q/g/Ud
Freshwater Marine (//g/U 0/g/U Bluegill* Trout' Shrimp" Killifishh
•/5.0
* - '/2.0 -- 32,000" 4,000-14,000
*/1.0 -- 3,200 1,400
•/2.0 - - - 58,000k
244 -- '10.22 - 700-1,100 110-320
0.077-1.3/0.05 0.267 1, 500-2,500* 1,5OO-2,200k 2,000
0.11-170/0.05 0.19 135,000 50,000 > 100,000 > 180,000
"/0.05 -- 105,000 179,000k 5,100 2,300
•/0.17 - 148,000 117,000 895,000
•10.22 - 105 17
•/1 .0
* Source: EPA Quality Criteria for Water guidelines (U.S. EPA 1987; last update 5/90).
b From current survey and Mayer (1988).
c Value reported is a arithmetic mean of concentrations detected. w
d Source: Tetra Tech (1988): Table 10, Toxicity Data, pp. 49-52. Value reported if for a a 96-hour averaging period unless otherwise noted. Reported by Tetra Tech (1988) in parts per million.
* Species studied: Lepomis macrochirus.
1 Species studied: unknown.
0 Species studied: unknown.
h Species studied: unknown.
1 - indicates that data is not available.
' 24-hour exposure period.
k 48-hour exposure period.
" Pesticide was not detected in any of the samples.
-------
TABLE 11. SEDIMENT QUALITY EVALUATION DATA
Compound
Azinophos methyl
Chlorpyrifos
Diazinon
Dichlorvos
Disulfoton
Fenamiphos
Malathion
Methyl parathion
Parathion
Phorate
Atrazine
Hexazinone
Prometon
Simazine
Bromacil
Diuron
Tebuthiuron
Terbacil
Bendiocarb
Carbaryl
Methomyl
Propham
Alachlor
2,4-D (acid)
Dicamba
Dinoseb
Lowest Available
Toxicity Value
0.03b
0.1 2d
22h
4.00b
300h
110'
14'
1b
0.013d
0.4b
4,500'
100,000b
1 2,000'
5,000'
7 1 ,000h
15'
112,000*
-
1,450h
10b
428h
4,000'
1 ,400'
1,500'
50,000'
2.300'
Calculated
KOC
(L/kg)
3.695°
14,350"
264"
138"
267"
796"
458"
1,172"
2,816"
267"
684"
0.096"
6"
370"
292"
692"
433m
4"
2,733m
28"
0.276"
203"
924"
227"
2,363"
2423"
Sediment Quality Value*
forfoc = 0.01
(mg/kg)
0.001
0.017
0.058
0.006
0.802
0.876
0.064
0.012
->
0.001
30.770
0.096
0.758
18.507
207.137
0.104
484.610
--
39.625
0.003
0.001
8.115
12.930
3.406
1,181.544
55.730
Sediment Quality Value*
forfoc = 0.05
(mg/kg)
0.006
0.086
0.290
0.028
4.009
4.379
0.321
0.059
0.002
0.005
153.852
0.481
3.789
92.534
1,035.687
0.519
2,423.048
--
198.125
0.014
0.006
40.576
64.651
17.032
5,907.721
278.649
Concentration Range (of
Samples with Detectable Detection Limit
Pesticide) Range
(mg/kg) (mg/kg)
0.0073-0.019
0.01 9* 8 0.038-0.01
0.00889 0.0038-0.0077
0.0038-0.01
0.0038-0.01
0.0073-0.019
0.0038-0.01
0.0038-0.01
0.141'-8 0.0038-0.01
0.0901-8 0.0038-0.01
0.044-0.13
0.044-0.13
0.044-0.13
0.044-0.13
0.2-0.6
0.0038-0.01
0.2-0.6
0.1-0.2
0.2-0.6
0.2-0.6
2.2-5.8
0.9-2.3
0.044-0.13
0.043 0.0013-0.0039
17.1 0.0015-0.0039
0.001 R-0.0038
-------
TABLE 11. (Continued)
N>
Lowest Available Calculated Sediment Quality Value' Sediment Quality Value*
Toxicity Value K^ for 1,^ = 0.01
Compound U/g/L) (L/kg) (mg/kg)
4,4'-DDD -- 44,862"
4,4'-DDE -- 32,637"
4,4'-DDT 0.001° 42,777" 0.428
Chlordane -- 1,487' 0.0001
Dichlobenil 14,700 3,479° 511.424
Diphenamid 58° 1,035° 0.600
Endosulfan I 0.056"-° 2,033' 1.138
Endosulfan II -- 2,220'
Fenvalerate 36 18,903* 6.805
Lindane -- 795'
Pentachlorophenol 13° 12,660' 1.646
Trifluralin - 19,141'
for 1^ = 0.05
(mg/kg)
--
--
2.139
0.0005
2,557.121
3.001
5.692
--
34.026
--
8.229
--
* Sediment quality values determined from current survey, Crecelius et al. (1989), and Mayer (1989), unless
b Lowest shrimp LC60 reported by Tetra Tech (1988).
° Vershueren (1983).
d Freshwater criterion continuous concentration.
* Tetra Tech (1988).
' Tentatively identified compound; concentrations not confirmed.
9 Concentration detected >0.1 times the sediment quality value for f^ = 0.01.
h Lowest bluegill LC60 reported by Tetra Tech (1988).
' Lowest trout LC60 reported by Tetra Tech (1988).
' Lowest killifish LC50 reported by Tetra Tech (1988).
k - indicates data were not available.
' Windholz (1976).
m Kenaga and Goring (1980).
n Lowest aquatic toxicity value for fresh water available in the literature. Identified
0 Chronic freshwater quality criteria for endosulfan, provided in EPA's Integrated
endosulfan II were not differentiated. Value based on a risk assessment that has
f Pentachlorophenol was detected in all sediment samples.
through EPA's Integrated
Risk Information System
not been reviewed.
Concentration Range (of
Samples with Detectable
Pesticide)
(mg/kg)
0.002-0.0074
0.0015-0.0052
0.0023-0.0097"
0.0021-0.022
0.0113"
0.008
0.01
0.02
0.02-0.056
otherwise noted.
Risk Information System (U.S
(U.S. EPA 1990). Isomers
Detection Limit
Range
(mg/kg)
0.0018-0.0022
0.0027-0.0032
0.0027-0.0032
0.0093-0.025
0.0018-0.0022
0.9-2.3
0.0018-0.0022
0.0018-0.0022
0.0047-0.012
0.0018-0.0049
U°
0.0018-0.0049
. EPA 1990).
endosulfan 1 and
-------
species names was beyond the scope of this report. However, the sensitivity of
each type of test organism is discussed below.
Mayer and Ellerseik (1986) provide a concise summary and analysis of
common aquatic bioassays and their relative sensitivity. These authors collected
data from over 4,000 bioassays conducted on 66 species at the Columbia National
Fisheries Research Laboratory. They report that insects are generally the most
sensitive test group, followed by crustaceans, fishes, and amphibians. More
specifically, Mayer and Ellerseik (1986) analyzed the standardized data from all
tests to derive a sensitivity ranking. They report that species may be ranked, in
descending order of sensitivity, as follows: stoneflies (Claassenia sabulosa,
Pteronarcys californica, Pteronarcella badia), glass shrimp (Palaemonetes
kadiakensis), daphnids (Daphnia magna, D. pulex), amphipods (Gammarus
fasciatus), daphnids (Simocephalus semdatus), rainbow trout (Oncorhynchus
myidss), bluegills (Lepomis macrochirus), largemouth bass (Micropterus salmo-
ides), seed shrimp (Cypridopsis vidua), coho salmon (O. Jdsutch), cutthroat trout
(Salmo clarid), yellow perch (Percaflavescens), brown trout (5. trutta), channel
catfish (Ictalurus punctatus), common carp (Cyprinus carpid), green sunfish (L.
cyanellus), fathead minnow (Pimephales promelas), goldfish (Carassius auratus),
black bullheads (/. melas), western chorus frog (Pseudacris triseriata), and
Fowler's toad (Bufo woodhouseifowleri). Thus, although the precise species for
which toxicity values are presented by Tetra Tech (1988) are not known, it is of
interest that trout, bluegill, and shrimp all appear to be among the most sensitive
common aquatic test species. The relative sensitivity of killifish was not
discussed by Mayer and Ellerseik (1986). However, Mayer and Ellerseik (1986)
also noted that testing daphnids, gammaridae, and rainbow trout provided the
lowest toxicity value 88 percent of the time. This observation, coupled with the
list of species in descending order of sensitivity, indicates that toxicity data for
daphnids and amphipods would have added an important measure of sensitivity
to this analysis, especially with respect to evaluating ecological effects of
pesticide residues.
Bluegill and several trout and char species [brook, brown, cutthroat, Dolly
Vardon, and rainbow (including steelhead)] are common game fish in Washington
(Wydosky and Whitney 1979). According to Bailey et al. (1960), the California
killifish (Fundulus parvipinnis) is the only species of marine killifish that inhabits
Pacific waters. The majority of Fundulus species are freshwater fish or live in
the Atlantic. Several shrimp species of the genus Heptacarpus inhabit Puget
Sound (Kozloff 1983). However, the specific shrimp species used in toxicity tests
summarized by Tetra Tech (1988) are unknown. Thus, some species used for
toxicity tests summarized by Tetra Tech (1988) are common to Puget Sound, but
it cannot be said that they represent a full cross-section of Puget Sound resources.
Mayer and Ellerseik (1986) observed changes in pesticide toxicity with
changing conditions in ambient water. Alteration in water temperature resulted
in changes in toxicity for 40 percent of the 66 chemicals; increased temperature
enhanced the toxicity of most chemicals (DDT and methoxychlor were excep-
25
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tions). Water hardness does not generally affect toxicity of organic contaminants
in water. Mixtures of chemicals used in pesticide formulations increased the
toxicity of technical grade material in 32 percent of the cases and decreased it in
11 percent of the cases. Finally, sensitivities of test fish and invertebrates were
reduced as these organisms progressed developmentally or increased in size.
These observations suggest that the relative toxicity of pesticides may change with
different ambient conditions.
Because EPA requires toxicity data from eight families to develop a
criterion, it was assumed for the purposes of this report that organisms used by
EPA for criteria development adequately represent species found in Western
Washington waters. A critique of EPA's method and the basis for criteria is not
provided here. The method used to derive ambient water quality guidelines can
be found in EPA's Gold Book (U.S. EPA 1987).
Water Quality Evaluation
Table 10 provides a summary of water quality data from the sites sampled.
The range of measured pesticide concentrations, the mean of the concentrations
of those pesticides that were detected, and the detection limits are provided (a full
data report of water sample analyses is given in Table 4). EPA's chronic water
quality guidelines and the acute lethal concentrations from Tetra Tech (1988) are
also provided in Table 10. EPA's chronic water quality criteria guidelines were
selected for comparison because they provide a somewhat conservative measure
of the presence of a hazard in the aquatic system. In contrast, acute lethality
values do not address chronic or sublethal effects and are, therefore, less protec-
tive. Thus, these sets of toxicity indices together provide a range of potential
adverse effects concentrations for contaminants in water.
Because all but three of the pesticides tested in the water analyses lack
appropriate regulatory standards and criteria, several of the measured pesticide
concentrations had to be compared to acute toxicity values. U.S. EPA (1985)
indicates that, in the case of complex mixtures of effluents, a factor of 0.1 applied
to acute toxicity values will provide a sufficient estimate of chronic toxic
concentrations in water. Based on this conclusion, the following conditions are
applied to measured concentrations of pesticides for this analysis:
• A concern for potential acute and chronic effects in Puget Sound
exists if the pesticide concentration is equal to or greater than 0.1
of the lowest LC50 values. These pesticides should be included as
contaminants of concern in monitoring programs for Puget Sound.
• A concern for at least potential chronic effects exists if the pesti-
cide concentration is between 0.01 of the LC50 and 0.1 of the
lowest LC50. These pesticides are recommended for discretionary
sampling in Puget Sound monitoring programs.
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• There is little concern that can be documented if the pesticide
concentration is below 0.01 of the lowest LC50, especially if few
pesticides are detected. These pesticides have a low priority for
inclusion in future monitoring programs as contaminants of con-
cern, but may warrant one additional round of sampling in Puget
Sound to document this conclusion.
The potential for random error increases near the detection limit. This
potential for error causes the level of uncertainty in determining whether the
measured concentration exceeds a chronic value or LC50 to increase as the
detection limit approaches these toxicity indices. Therefore, detection limits were
considered to be inadequate where they exceeded the chronic criterion or 0.1 of
the lowest LC50 value provided by Tetra Tech (1988).
Reported detection limits were inadequate for 3 of the 34 pesticides tested.
The detection limit of parathion exceeds its chronic water quality criteria value
by a factor of 4. Similarly, the marine shrimp LC50 for azinophos methyl is
0.03 parts per billion, approximately one-third of the concentration of the
0.1 ng/L detection limit. The detection limit for phorate is greater than 0.1 of
its LC50 value for Irillifish. These detection limits are inadequate to identify
contaminant levels that may have adverse effects on aquatic communities.
The data in Table 10 show that the majority of pesticides were undetected at
the four sites. However, some pesticides warrant closer examination. Diazinon
was detected in Swamp Creek, Mercer Creek, and Big Ditch Slough at concentra-
tions ranging from O.OS4 to 0.14 jtg/L. Water quality criteria are not available
for this pesticide. However, the highest levels detected, which were seen in three
Swamp Creek samples, are within 2 orders of magnitude of the LC50 value for
bluegill (Lepomis macrochirus). It is not possible to judge from the LC50 value
the chronic effects of the lower contaminant level. However, based on the
criteria for this analysis described above, there is a potential for adverse chronic
effects in waters with the concentrations of diazinon observed in Swamp Creek.
Thus, it is recommended that discretionary sampling for diazinon be included in
Puget Sound monitoring programs. In addition, diuron was detected in two
samples from Big Ditch Creek (1.2 and 1.3 ng/L) and in all three samples from
Muck Creek (average 2.4 /*g/L). These values are within 1 order of magnitude
of the lowest LC50 provided by Tetra Tech (1988), 15 ftg/L for killifish. Diuron
should be included as a contaminant of concern in Puget Sound monitoring
programs. Concentrations of the other three pesticides detected in water samples
were 4-5 orders of magnitude below their respective LC50 values.
27
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Sediment Quality Evaluation
A summary of results for sediment analyses is provided in Table 11. The
range of measured concentrations, the mean concentrations, and the analytical
detection limits are included.
No relevant sediment quality standards are available for comparison with
these pesticide results. Two approaches were employed to analyze as many of
the data as possible within the constraints of the project scope. The analytical
approaches employed are as follows:
• A comparison was made of pesticide concentrations with sediment
quality values estimated for pesticides using available chronic water
quality criteria. Sediment quality values were estimated from
EPA's chronic water quality standards using the equilibrium
partitioning approach discussed below. Chronic water quality
criteria are available for chlorpyrifos, parathion, p,p'-DDT,
endosulfan, and pentachlorophenol.
• Where no standards for water or sediment have been promulgated,
sediment quality data were compared with estimated acute sediment
toxicity values. Sediment toxicity indices were estimated using the
equilibrium partitioning approach and the lowest acute toxicity
value for aquatic species provided by Tetra Tech (1988). Those
toxicity values are summarized in Table 11.
Equilibrium partitioning theory was used to estimate acute and chronic indices of
toxicity for sediment-associated contaminants from aquatic toxicity values. This
method is based on the assumption that sediment-associated contaminants will
approach a state of equilibrium with the environment and that equilibrium
concentrations can be predicted from properties of the contaminants and the
sediments (additional assumptions and uncertainties are discussed below, under
UTicertainties of the Evaluation). Thus, a water quality value (e.g., a water
quality criterion or toxicity level) can be employed using these assumptions to
estimate a corresponding sediment quality value. Sediment quality values
provided in Table 11 were calculated using the following equation:
C^ (mg/kg) = [C^ 0*/L)/1,000 /xg/mg x K^. (L/kg) x f ]
where:
C-sed = concentration of contaminant in sediment (mg/kg) ("Sedi-
ment Quality Value" in Table 11)
Cwater = concentration of contaminant in water 0*g/kg) ("Lowest
Available Toxicity Value" in Table 11)
28
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= partition coefficient normalized for organic carbon (L/kg)
= fraction of organic carbon in the sediments.
For this analysis, C,^, was either a water quality criterion, the lowest freshwa-
ter chronic toxicity value found in IRIS (U.S. EPA 1990), or an acute toxicity
value taken from Tetra Tech's (1988) summary (Table 10). Because of small
sample sizes, it was not possible to determine the organic carbon content of the
sediment collected for pesticide analysis. Instead, the f^. in sediment samples
was estimated to range from 0.01 to 0.05 (1 to 5 percent), based on a frequency
analysis of 806 values for total organic carbon found in Puget Sound sediments.
Frequency analysis of f^ of Puget Sound sediments reported on EPA's Region 10
SEDQUAL database indicated that 66 percent of the sediments in Puget Sound
have a f^, ranging from 1 to 5 percent. Values for K^. were estimated from
available K^ values using Equation 4.8 from Lyman et al. (1982):
log K^. = [0.544 x log K^J + 1.377
K^ values were obtained from Tetra Tech (1988) for most compounds. If KQW
values were not available in either of these two sources, they were calculated
from solubility data using Equation 2.14 from Lyman et al. (1982):
log 1/S (mol/L) = 1.214 x log K^J - 0.85.
where:
S = solubility.
Analysis of pesticide concentrations found in sediments and summarized in
Table 11 (a full data report is provided in Table 4) is limited by the same con-
straints of the water quality analysis. The limited availability of sediment quality
criteria and the use of LC50 values to evaluate the potential adverse effects of the
measured pesticide levels resulted in several uncertainties, which are outlined in
the Uncertainties of the Evaluation section. Because of these limits, the criteria
used to identify potentially hazardous pesticide concentrations in water were
applied to evaluate sediment-associated pesticides. These criteria are:
• A concern for potential acute and chronic effects in Puget Sound
exists if the pesticide concentration is equal to or greater than 0.1
of the lowest LC50 values. These pesticides should be included as
contaminants of concern in monitoring programs for Puget Sound.
• A concern for at least potential chronic effects exists if the pesticide
concentration is between 0.01 of the LC50 and 0.1 of the lowest
29
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LC50. These pesticides are recommended for discretionary sam-
pling in Puget Sound monitoring programs.
• There is little concern that can be documented if the pesticide
concentration is below 0.01 of the lowest LC50, especially if few
pesticides are detected. These pesticides have a low priority for
inclusion in future monitoring programs as contaminants of concern,
but may warrant one additional round of sampling in Puget Sound
to document this conclusion.
Here, LC50 means the sediment quality value that was derived by adjusting an
aquatic LC50 value to account for partitioning into the organic carbon fraction of
the sediments.
Detection limits were considered to be inadequate where they exceed the
sediment quality value estimated from chronic criterion or where they are within
0.1 of the lowest LC50-derived sediment quality value. Based on these evaluation
criteria, the reported detection limits for 5 of the 39 pesticides tested in sediments
were not sensitive enough to identify pesticide concentrations in sediments
associated with potential adverse effects. The detection limit for parathion
(0.038-0.01 mg/kg) exceeded the sediment quality value estimated from para-
thion's chronic water quality criterion. For both malathion and methyl parathion,
the higher detection limits were within 1 order of magnitude of the more
conservative sediment quality value. The range of detection limits for hexazinone
was within 1 order of magnitude of the range of sediment quality values associat-
ed with 50 percent mortality of exposed organisms. Finally, the higher detection
limit for phorate exceeded the higher sediment quality value derived from the
aquatic LC50, and the lower detection limit exceeded the lower sediment quality
value derived from an aquatic LC50. Therefore, in future evaluations of sediment
contamination at these sites, testing for these pesticides should be repeated using
larger sample sizes and detection limits that are sensitive enough to determine
where potentially harmful concentrations may be present.
The detected concentration of diazinon in sediments from Big Ditch Slough
is within 1 order of magnitude of its LC50-derived sediment toxicity index.
Similarly, the detected concentration of endosulfan I observed in Mercer Creek
sediments was half the LC50-derived sediment toxicity index. Both diazinon and
endosulfan I appear to be present in concentrations that are potentially hazardous
to aquatic life making contact with sediments. Although LC^-derived sediment
quality guidelines do not provide a precise definition of the presence of a hazard,
these two pesticides should be monitored in future surveys. In addition, concen-
trations of three pesticides detected in the 1988 survey (chlorpyrifos, parathion,
and phorate), although not confirmed, were above calculated sediment quality
criteria. These compounds should be monitored in future sampling events.
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Uncertainties of the Evaluation
Because the specific names of organisms for which toxicity data are
summarized by Tetra Tech (1988) are not known, the extent to which these data
predict toxicity to Puget Sound species cannot be provided with certainty. In
addition, it is critical to note that an LC50 or an LD^ value is not a protective
standard for environmental media. The LC50 bioassay measures lethality; it does
not address adverse sublethal effects. Thus, the modification of LC50 values in
this report to predict chronic toxicity levels using a factor of 0.1 is an important
source of uncertainty. Also, evaluation of LC50s for single chemicals does not
account for possible synergistic or multiple chemical interactions. An additional
uncertainty in assessing the toxicity Of commercial pesticides is the effect of inert
ingredients, such as surfactants or carriers.
In addition, predictions using the sediment-water equilibrium partitioning
approach incorporate the uncertainties of that method as well as the uncertainty
in the estimate of organic carbon content for this survey. A primary source of
uncertainty in the theoretical approach is the implicit assumption that the time
scale for attaining thermodynamic equilibrium is short relative to the time scale
of kinetic factors (e.g., disruptions of bedded sediments, short-term changes in
physicochemical conditions). Other sources of uncertainty in the approach relate
to predictions in measured and estimated KQQ values and the assumption that
organisms follow sediment-biota equilibrium partitioning and are unaffected by
the route of contaminant exposure (e.g., dermal absorption vs. ingestion of
sediments). In systems where flow is sufficient to suspend large amounts of
sediment, ingestion of particulates may be of importance.
Recommendations
The approach to screening-level evaluations of pesticide concentrations found
in site-specific samples can be conducted in phases. State and federal standards,
results of toxicity tests, and extrapolation methods are useful in preliminary
analyses of the potential for adverse biological effects of site-specific concentra-
tions. The following approach is recommended for screening level analyses of
site-specific data for water and sediment quality.
Water Quality—Site-specific water quality should first be evaluated for
potential harm to aquatic communities using EPA's water quality criteria (U.S.
EPA 1987). EPA provides freshwater and marine water quality guidelines for
protection of aquatic life following acute and chronic exposure scenarios. Acute
water quality criteria are expressed as a criterion maximum concentration (CMC)
for a 1-hour averaging period. The criterion continuous concentration (CCC)
assumes a 4-day maximum exposure period. These levels are not to be exceeded
more than once every 3 years. Comparison of water quality measurements with
the CCC provides a screening level estimate of potential adverse effects to aquatic
31
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communities. When a more conservative approach is warranted, based on the
presence of endangered or threatened species, it is recommended that a safety
factor of 0.1 be applied to the CCC before comparison with water quality data.
In this type of situation, contaminant levels should not exceed 0.1 of the CCC.
It is noteworthy that the CMC and CCC values are derived for individual
pesticides and do not account for potential synergistic, additive, or antagonistic
effects of the pesticides, or for associated inert ingredients, surfactants, and other
additives.
When water quality guidelines are not available, site-specific water bioassays
are recommended. Unlike sediment quality, however, water quality conditions
are frequently transient and unpredictable. This behavior reduces the reliability
of water toxicity bioassays that are based on single or poorly timed sample
collections. A screening-level approach is to sample water for toxicity testing or
chemical analysis during peak flow and low flow events. Sample collection
during a high flow event following a dry spell (i.e., a first flush event) provides
a worse-case scenario: contaminants that have built up in a watershed during the
dry period will be washed into the stream water during this type of event.
Alternatively, continuous monitoring or very frequent sampling over extended
periods (1-2 years) would provide a relatively complete profile of water contami-
nation.
There is no standard set of water quality bioassays that can be recommended
for all site evaluations. Aquatic systems vary with their geographic locations, as
do the valued species that are the targets of protection. Therefore it is recom-
mended that the design of water quality studies be determined on a site-specific
basis with consideration for the species that are to be protected, food chain
interactions (e.g., where loss of keystone species may lead to large impacts), the
presence of endangered or threatened species, other conditions specific to the
individual system, and the specific project objectives.
Sediment Quality—Sediment management standards have not yet been
proposed for regulation of pesticides in marine sediments in Puget Sound
(Ecology 1990). There are also no national or Washington state standards or
guidelines available for freshwater sediments. However, sediment quality
guidelines have been derived by several other government agencies. The
Wisconsin Department of Natural Resources has derived sediment quality
guidelines for some metals, pesticides, and polychlorinated biphenyls (Appen-
dix E, Table E-l). In addition, the Ontario Ministry of the Environment has
estimated sediment management guidelines (Geisy and Hoke 1990) using no effect
levels, lowest effect levels, and limits of tolerance. These guidelines are based
on overt effects on benthic invertebrates and do not account for indirect effects
of contaminants such as food chain alteration or bioaccumulation potential (Geisy
and Hoke 1990). Finally, the National Oceanic and Atmospheric Administration
(Long and Morgan 1990) has recently summarized levels of concern for numerous
contaminants found in both freshwater and marine sediments (Appendix E,
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Table E-2). When state or federal guidelines are not available, the sources just
cited should be employed where possible.
In the absence of available marine or freshwater sediment quality criteria, the
preferred approach for evaluating potential sediment toxicity is to conduct a suite
of site-specific sediment bioassays. As in the case of water quality evaluations,
no standard set of bioassays can be recommended for sediment toxicity evalua-
tions. Each study design should be based on site-specific resources, site uses, and
program objectives.
Finally, levels of sediment contamination that are unlikely to result in
adverse biological impacts can be estimated by extrapolating available water
quality criteria values to sediment quality values using the equilibrium partitioning
approach. As discussed previously, this method assumes that contaminants
associated with the solid phase of sediments will reach a state of equilibrium with
the environment and that equilibrium concentrations can be predicted from
properties of the contaminant and the sediments. The approach has been
developed primarily for nonionic organic compounds and is applicable to
sediment-associated pesticides in both marine and fresh waters. Geisy and Hoke
(1990) observe that this approach has utility in establishing general criteria, but
that it should not be used to determine site-specific criteria.
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RECOMMENDATIONS FOR FUTURE
MONITORING EFFORTS
Continued monitoring of selected pesticides in waters and sediments of the
Puget Sound basin is recommended. Monitoring of ambient pesticide concen-
trations has been limited in the past, especially when compared to monitoring
efforts for other pollutants such as metals and industrial organic compounds. In
addition, little is known about the potential effects of pesticides on Puget Sound
biota, on transport mechanisms in estuarine and marine environments, and on
specific sources of contamination. This information is necessary to determine
whether pesticides are contributing to environmental degradation of the basin,
and, if so, what control strategies are needed to eliminate this contamination.
Three levels of monitoring are proposed in the following sections: routine
local monitoring, regional reconnaissance surveys, and in-depth research studies.
ROUTINE MONITORING
Frequent routine monitoring is needed to provide information on the spatial
and temporal distribution of pesticides in the Puget Sound basin. Because detailed
knowledge of the specific sampling area is important, routine sampling by county
extension agents with local knowledge offers a cost-effective means of data collec-
tion. Standardized protocols for sampling, uncomplicated sampling equipment,
and basic training are required to ensure that sampling results will be consistent
among all areas. Sampling should occur frequently, possibly on a monthly basis,
and should be performed during high runoff events and during periods immediate-
ly following pesticide applications to specific areas. Because of constantly
changing conditions encountered in the field, there is likely to be high spatial and
temporal variability associated with these samples. Data from Mayer (1989)
indicate that sampling from the same area over time may result in several
sampling episodes where high levels of a pesticide are found, while other
sampling episodes produce no detectable pesticide concentrations.
Because of the frequency of sampling and potential for high analytical costs,
compounds targeted for routine monitoring should be limited to those that have
been recently applied to the specific areas being sampled, plus the following
compounds that have been detected in this and previous reconnaissance surveys:
34
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• Diuron, diazinon, 2,4-D, dicamba, and bromocil in water
• Pentachlorophenol, chlorpyrifos, dichlobenil, lindane, dicamba,
2,4-D, DDT and its metabolites, diazinon, parathion, phorate, and
endosulfan I in sediments.
In addition, chemicals that are extensively used, such as glyphosate,
malathion, and metaldehyde, should be included in the target list even though they
have not been previously detected in sediment or water samples, since previous
sampling may have not been conducted when maximum residue concentrations
were present. The results of this and previous surveys indicate that the current
EPA priority pollutant list is out of date and needs revision. Although a few of
the pesticides detected in Puget Sound drainages (e.g., DDT, endosulfan) are on
the current list, most of the compounds found in this and the 1988 study, as well
as other heavily used pesticides, are not.
Compounds that are not detected in this routine monitoring after 1 year of
repeated sampling should be deleted from future sampling events, unless changes
in pesticide application suggest a need for resampling or unless the cost of
analysis will not be affected by their inclusion. For three reasons, frequent
collection of water samples during this routine monitoring is recommended as a
higher priority than frequent collection of sediment samples. First, relatively
nonpersistent pesticides discharged in storm events may nevertheless produce
toxic effects in the aquatic environment and may only be detected in frequently
collected water samples. Second, analyses of unfiltered water samples, including
suspended particulates, over time provide the most direct evidence of the potential
for and seasonal pattern of pesticide transport from freshwater basins to Puget
Sound. Third, water samples are easier to routinely collect and analyze than are
sediment samples, and there were no pesticides of concern detected exclusively
in sediment that have not already been included in standard analyses for chlorinat-
ed pesticides (i.e., endosulfan I). Details of an easy-to-use, low-cost water
sampling apparatus are given in Appendix C. Occasional collection of sediment
samples (e.g., once every 1-2 years) is still recommended in depositional areas
to determine if there are accumulations over time of particle-bound pesticides that
may be present at undetectable levels in the more frequently collected water
samples.
REGIONAL RECONNAISSANCE
The routine monitoring efforts discussed in the previous section are narrowly
focused with regard to targeted pesticides and are limited to specific areas of local
concern. On a broader scale, reconnaissance surveys for pesticides should
continue on a regional basis as funding permits. Such surveys should include
several different classes of pesticides, such as those included in the present
survey. Reconnaissance surveys should also include collection of water,
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sediment, and possibly biota samples (i.e., when the potential for bioaccumulation
is high) so that all media of potential concern are addressed. In addition,
degradation products and pesticides registered since the previous reconnaissance
survey should be included in the list of compounds for analysis, provided that
analytical methods exist for their determination in the media of interest.
Diazinon and diuron, found in this drainage basin survey at levels potentially
associated with chronic or acute toxic effects, should be added as chemicals of
concern for Puget Sound ambient monitoring programs. A link to major land
sources has been documented for these pesticides, but it is unknown whether they
persist at similar levels in Puget Sound proper. Therefore, analyses for these
pesticides should be conducted in Puget Sound reference areas and near major
drainages. Endosulfan I was also detected in sediment samples collected in the
Mercer Creek drainage to Lake Washington. Previous analyses for this com-
pound in selected Puget Sound sediments have been reported, but it has not been
identified as a chemical of concern in the marine environment. Continued
monitoring for endosulfan I in Puget Sound is recommended, based on the results
of this reconnaissance survey.
RESEARCH STUDIES
While this reconnaissance survey has provided important information
concerning the levels of pesticides found in Puget Sound drainages, it has also
highlighted gaps in knowledge about the impacts of pesticides in estuarine
environments. The interpretation of the data gathered in this and future surveys
would be enhanced by formulating research studies that address the following
general questions:
• What is the ecological significance of the different mixtures of
pesticides documented in Puget Sound drainages? Are the available
toxicity data representative of effects on Puget Sound estuarine
species? Even if present below individual LC^ values, are these
mixtures likely to produce effects on migrating fish or their prey
organisms indigenous to Puget Sound?
• For compounds detected in Puget Sound drainages, what is their
potential for further degradation, both abiotic and biotic, under
marine and estuarine conditions? Are these pesticides transported
primarily in the particulate or dissolved phases, and are they
ultimately dispersed in the water column or accumulated in localized
areas of sediment contamination?
• Is there any evidence of bioaccumulation or biomagnification of the
major pesticides found in Puget Sound drainages in harvestable
invertebrates (e.g., clams, mussels), fish, birds, or marine mam-
mals of the sound?
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• To what extent are safety factors applied to acute criteria protective
of chronic effects for the pesticides detected in Puget Sound drain-
ages, or for undetected pesticides that nevertheless have major
sources on land? Are routine detection limits attained in this survey
adequate for assessing the potential for chronic effects or are
specialized analyses required?
• What are the major sources of persistent pesticides that were widely
detected in Puget Sound drainages (e.g., pentachlorophenol in
sediment)?
• How can routine analytical techniques be improved for pesticides
that were apparently subject to substantial interferences in some
media (e.g., triazines in sediment)? Are the general holding times
of 1-2 weeks between collection and analysis sufficient for all
classes of pesticides; can any of these holding times be extended to
facilitate episodic sampling in different areas?
• What is the threat to water quality in Puget Sound drainages from
inert ingredients found in pesticide formulations? What are the
persistence, bioaccumulation, and toxicity characteristics of the
materials?
• What is the impact of other agricultural chemicals (fertilizers, soil
amendments, plant growth regulators) on Puget Sound water
quality?
Finally, regional reference materials should be formulated for these pesti-
cides to provide a means for assessing the comparability of monitoring and
reconnaissance results over time.
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and scientific names of fishes from the United States and Canada. Second
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Crecelius, E.A., D.L. Woodruff, and M.S. Myers. 1989. 1988 reconnaissance
survey of environmental conditions in 13 Puget Sound locations. Final Report.
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Sound, Seattle, WA. Battelle Ocean Sciences, Duxbury, MA.
Geisy, J.P., and R.A. Hoke. 1990. Freshwater sediment quality criteria:
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Kozloff, E.N. 1983. Seashore life of the northern Pacific coast. Second edition.
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Lyman, W.J., W.F. Reeml, and D.M. Rosenblatt. 1982. Handbook of chemical
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communities) in Padilla Bay, Washington. Final report submitted to Washington
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Mayer, F.L., and M.R. Ellerseik. 1986. Manual of acute toxicity: interpreta-
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Tetra Tech. 1988. Pesticides of concern in the Puget Sound basin: A review
of contemporary pesticide usage. Final Report. Prepared for U.S. Environmen-
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Tech, Inc., Bellevue, WA.
U.S. EPA. 1985. Technical support document for water quality-based toxics
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U.S. EPA. 1987. Quality criteria for water 1986: update #2. U.S. Environ-
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U.S. EPA. 1990. Integrated risk information system: pentachlorophenol;
CASRN 87-86-5 (1/1/90). U.S. Environmental Protection Agency, Washington,
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Verschueren, K. 1983. Handbook of environmental data on organic chemicals.
Second edition. Van Nostrand Reinhold, New York.
Windholz, M. (ed.) 1976. The Merck Index, 9th edition. Merck & Co., Inc.
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Wydosky, R.S., and R.R. Whitney. 1979. Inland fishes of Washington.
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APPENDIX A
©atnpllng Bepotts
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1990 Pesticide Reconnaissance Survey
Big Ditch Slough Sampling Report
Water samples were collected from three locations on Big Ditch Slough on June 7,1990,
by Dena Hughes and Bob Stuart of E.V.S. Consultants. Weather conditions were partly
cloudy with light winds fr&n the southwest The temperature was estimated to be in the
high 50s to the low 60s. Water turbidity, flow and depth in Big Ditch Slough appeared to
be greater than on the previous day. Water was observed flowing into the slough from
several drainage ditches along its length. The ditches appeared to be draining standing
water from fields adjacent to the slough. According to Mr. Richard Norgaard, a fanner
with cultivated fields adjacent to the slough, it had rained heavily the night before. Because
of recent heavy rains, Mr. Norgaard stated that most fanners in the area had not begun
applying pesticides to their crops. Mr. John Garret of the Washington Department of
Wildlife, the game ranger for the Skagit Wildlife-Recreation area, also stated that farmers in
the area had not yet begun pesticide application.
Station 1
The station is within the Skagit Wildlife Area and access is controlled by the Washington
Department of Wildlife. It was necessary to contact John Garret to unlock the gate across
the road to the site, which is located approximately one-half mile from the gate. The one-
lane gravel road leads to a gravel parking lot adjacent to the site.
Station one is located approximately 75 feet north of the tide gates on the east bank of Big
Ditch Slough. The west bank is ten to fifteen feet high and forms pan of the dike for the
south fork of the Skagit River. The slough is approximately 45 feet wide and three feet
deep at this point A drainage ditch on the east bank was observed emptying into the
slough about 200 feet north of the sampling station.
Stream flow measurements were taken by measuring the traversal time of an orange over a
measured distance along the slough. Three measurements were taken over a 45 foot
course. The three readings were 18.74,16.13 and 19.51 seconds for a mean time of 18.13
seconds. The mean velocity was calculated to be 2.48 feet per second. Discharge was
calculated based on the cross-sectional area of die slough and the mean velocity:
Discharge * (2.48 ft/sec.) x (3 ft x 45 ft) * 335 cubic feet/sec.
Sampling commenced at 0942. Bob Stuart collected the samples and Dena Hughes
transferred the contents of the collection bottle to sample bottles. Twelve 2.5 liter sample
bottles and two 40 ml vials were collected according to protocol and were numbered 1-1
through 1-12 and VOA 1-1 and VOA 1-2, respectively, Six additional 15 liter bottles and
two 40 ml vials were also collected as duplicates and were numbered 1-1D through 1-6D
and VOA 1-3 and VOA 1-4, respectively. All samples were stored on ice, The last sample
was collected at 1055 and the site was vacated at 1140.
Shrtinn 2
Station two is located 1.4 miles north of station one on the farm of Mr. Richard Norgaard.
Because of heavy rains it was necessary to cany the sampling equipment about one quarter
mile to the slough. Because of steep banks and thick overgrowth, it was necessary to
collect samples from a wooden foot bridge spanning the slough.
A-l
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The width of the slough at this point was measured at 46 feet with a mean depth of 4.3 feet.
Three depth measurements were taken across the channel: 4,5 and 4 feet Mean velocity
was calculated to be 0.4 feet/second based on two velocity measurements taken over a 20
foot course with times of 52 and 48 seconds. Discharge was calculated to be 79.1 cfs.
Sampling commenced at 1240 and ended at 1315. Twelve 2.5 liter sample bottles and two
40 ml vials were collected The bottles were numbered 2-1 through 2-12 and the vials were
numbered VOA 2-1 and VOA 2-2. The samples were stored on ice and the site vacated at
1430.
Staring ^
Station three is located 2.3 miles north of station one on the west side of Highway 530 and
approximately ten feet to the west of the railroad tracks on the south bank. The slough
passes under the highway and the railroad tracks. A more suitable sampling location was
sought, but because of inaccessible roads and steep, overgrown banks, this was the only
location mat was accessible.
The width of the slough appeared to be approximately 45 feet Because of the location* it
was not possible to get depth measurements or velocity measurements, but the velocity
appeared to be similar to that at station two.
Hi 1542 tuul ended ai 1(520. Twelve 2.D1 liter sample bottles and two
40 ml vials were collected. The bottles were numbered 3-1 through 3-12 and the vials were
numbered VOA 3-1 and VOA 3-2. The samples were stored on ice and the site was
vacated at 1445.
Contact*,
Mr. John Garret, Washington Department of Wildlife, Skagit Wildlife-Recreation Area.
Telephone: 445-4441
Mr. Richard Norgaard Telephone: 629-2014
A-2
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PESTICIDE RECONNAISSANCE SURVEY
Mercer Creek Sampling Report
August 30, 1990
Water samples were collected from Mercer Creek on 30 August 1990 during and
immediately following a major storm event Sampling took place between 1745 and
2400 hrs. The sampling site was located on the north bank of Mercer Creek approximately
50 m below the culvert passing east-west under Interstate 405 and 118th Avenue
Southeast. Access to the site was through the Bellefield Business Park. Weather
conditions during the sampling period ranged from 100 percent cloud cover with heavy rain
to broken clouds with no rainfall. A moderate to light wind from the southwest persisted
during the entire sampling period. The temperature was estimated to be between 10-12° C.
The field crew consisted of Nancy Musgrove and Dave Jansen of E.V.S. Consultants.
Samples were collected using 2.51 bottles held in a ring at the end of a 4.5 m stainless steel
pole. Samples were taken from below the water surface at a minimum of 3 m from the
bank. Three series of samples were collected during the storm event Each series
consisted of 12 composite samples. Composites were made by splitting each sample
among 12-2.51 bottles. The first series was collected in the first hour of the sampling
effort (1745 to 1845 hrs). Sample bottles were labelled 1-1 through 1-12. The second
series of samples was collected between 1915 and 2045 hrs. and bottles were labelled 2-1
through 2-12. The final series was collected between 2115 and 2400 hrs. and bottles were
labelled 3-1 through 3-12. During the sampling period, 8 pairs (duplicates) of VOA
samples were collected in 40 ml vials from a sample bottle used to create the composites, at
the following times:
1745 • 2215
1845 • 2245
1945 • 2315
2045 • 2345
Mercer Creek is a broad (-30 m), shallow (<3 m) slough in the vicinity of the sampling
site. Changes in elevation in the area are slight. Banks on both sides of the creek are low
and the creek meanders through the grounds of Bellefield Park. In most areas, the banks
are over grown with dense, low-growing shrubs and blackberry brambles. During the
sampling effort, stream velocity at mid-channel and changes in the level of the water were
measured. Velocity measurements were taken at the sampling site, while changes in
elevation were measured from the bridge entering the office park near the sampling site.
The following velocity measurements were crude and represent surface velocity only:
Time Velocity
1910 0.08 m*sec-1
2115 0.14m*sec'1
2315 0.09 m* sec"1
During the sampling event, water in the creek was extremely turbid with a lot of floating
duckweed on the surface. Water color was greenish brown. A slight change in water level
was noted during the sampling period. The following measurements represent changes in
water depths (in meters) during the sampling event
A-3
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Time North Bank Mid-Channel South Bank
1910 1.83 1.93 1.47
2010 1.80 1.88 1.37
2115 1.80 1.85 1.40
2230 1.80 1.85 1.40
Based on an approximate channel width of 30 m and the mid-channel depth, estimates of
discharge rate were made as follows:
Discharge = velocity * channel area
Time Discharge
1910 4.63 cubic m*sec'1
2115 7.77 cubic n
2315 5.00 cubic n
A-4
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1990 PESTICIDE RECONNAISSANCE SURVEY
Swamp Creek Sampling Report
October 4,5, 1990
Water samples were collected from Swamp Creek on October 4 and 5,1990 during and
immediately following a major storm event Sampling took place between 2000 (Oct. 4)
and 0545 (Oct. 5). The sampling site was located on the west bank of Swamp Creek
immediately upstream of a bridge on NE 175th St. Access to the site was via this bridge.
Weather conditions during the sampling period ranged from 100 percent cloud cover with
heavy rains to broken clouds with no rainfall Moderate to heavy rains occurred between
2000 to about 0130, after which clearing occurred with very little rain. Very little wind
was observed. The temperature was estimated between 45 and 50 SF. Flow in the stream
was moderate to high; water was turbid and brown. The field team consisted of Mark
Munn and Jim Starkes of E.V.S. Consultants.
Samples were collected using 2.5 liter bottles held in a ring at the end of a 4.5 meter
stainless steel pole. Samples were collected from below the water surface at a minimum of
2 meters from the bank. Three series of samples were collected during the storm event.
Each series consisted of 12 composite samples. Composites were made by splitting each
sample among 12 - 2.5 liter bottles. The first series was collected between 2000 and 2300
hours. Sample bottles were labelled 1-1 through 1-12. The second series of samples were
collected between 2300 and 0200 hours. Six field duplicate samples were also collected
during this time period. Bottles were labelled 2-1 through 2-18. The final series was
collected between 0200 and 0545 hours and bottles were labelled 3-1 through 3-12.
During the sampling periods, 8 pairs of VOA samples were collected in 40 ml vials from a
sample bottle used to create the composites at the following times:
• 2050 • 0030
• 2200 • 0100
• 2300 • 0315
• 2350 • 0545
The last sample was collected at 0545 and the site was vacated at 0630. All samples were
stored on ice.
Swamp Creek is a small (7 meters wide), shallow (-1 meter maximum depth) stream in the
vicinity of the sampling site. Stream banks were steep and heavily vegetated with
deciduous trees and shrubs. On two occasions a beaver was observed in the stream. The
animal was observed entering a dense overhanging canopy of vegetation on the east bank
of the stream opposite the sampling site.
During the sampling effort, stream velocity at mid channel was measured and changes in
the level of water was observed. Surface velocity was measured by the traversal time of an
orange placed in the middle of the stream over a measured distance (8.2 meters). Velocity
was calculated twice during the sampling effort.
Time Velocity
2240 1.37 m/sec
0615 1.03 m/sec
A-5
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A slight decrease in water level was observed during the second velocity measurement
Actual measurements of changes in depth could not be made. Based on an approximate
stream width of 7 meters and average depth of 0.6 meters, the following estimates of
discharge were made:
Time Discharge
2240 19.2 cubic m/sec
0615 14.4 cubic m/sec
A-6
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1990 Pesticide Reconnaissance Survey
Big Ditch Slough Sampling Report
October 16, 1990
Water samples were collected from three locations on Big Ditch Slough on October 16,
1990, by Dena Hughes and Bob Stuart of E.V.S. Consultants. Weather conditions were
partly cloudy with light winds from the southwest. The temperature was estimated to be in
the low to mid 50s. How in the slough was very low and no water was observed flowing
into the slough from several drainage ditches along its length as in the first sampling
episode on June 7,1990. Most of the fields near the slough appeared recently plowed with
nothing growing in them, although a few fields did have com growing. The soil in the
fields and along the sides of the road appeared slightly damp but there was no standing
water.
Station 1
The station is within the Skagit Wildlife Area and access is controlled by the Washington
Department of Wildlife. Station one is located approximately 75 feet north of the tide gates
on the east bank of Big Ditch Slough. The west bank is ten to fifteen feet high and forms
part of the dike for the south fork of the Skagit River. The slough is approximately 45 feet
wide and three feet deep at this point
Stream flow measurements were taken by measuring the traversal time of an orange placed
in the middle of the slough over a measured distance (37 feet) along the slough. The
velocity was calculated to be 0.82 feet per second. Discharge was calculated based on the
cross-sectional area of the slough and the velocity:
Discharge = (0.82 ftysec.) x (3 ft. x 45 ft.) = 111 cubic feet/sec.
Sampling commenced at 0955. Bob Stuart collected the samples and Dena Hughes
transferred the contents of the collection bottle to sample bottles. Twelve 2.5 liter sample
bottles and eight 40 ml vials were collected according to protocol and were numbered 1-1
through 1-12 and V1-1 and VI-8, respectively. Six additional 2.5 liter bottles and two 40
ml vials were also collected as duplicates and were numbered 1-1D through 1-6D and VI-
1D and V1-2D, respectively. All samples were stored on ice. The last sample was
collected at 1100 and the site was vacated at 1130.
Station 2
Station two is located 1.4 miles north of station one on the farm of Mr. Richard Norgaard.
Because of heavy rains it was necessary to carry the sampling equipment about one quarter
mile to the slough. Because of steep banks and thick overgrowth, it was necessary to
collect samples from a wooden foot bridge spanning the slough.
The width of the slough at this p . s measured at 46 feet with a mean depth of 4.3 feet.
Three depth measurements w ,cn across the channel: 44.5,62.5 and 49 inches.
Velocity was calculated' leet/second based on one velocity measurement taken
over a 30 foot course wiu.. crsal time of 162 seconds. Discharge was calculated to be
36.6 cfs.
A-7
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Sampling commenced at 1205 and ended at 1315. Twelve 2.5 liter sample bottles and eight
40 ml vials were collected. The bottles were numbered 2-1 through 2-12 and the vials were
numbered V2-1 and V2-8. Two duplicate VOA samples were also collected and labeled
V2- ID and V2-2D. The samples were stored on ice and the site vacated at 1430.
Station 3
Station three is located 2.3 miles north of station one on the west side of Highway 530 and
approximately ten feet to the west of the railroad tracks on the south bank. The slough
passes under the highway and the railroad tracks.
The width of the slough was measured to be 34 feet with an approximate depth of three
feet One velocity measurement was taken over a 40 foot length. Traversal time was 41 1
seconds for a velocity of 0.097 feet/sec. Discharge was calculted to be 9.9 cfs.
Sampling commenced at 1350 and ended at 1440. Twelve 2.5 liter sample bottles and eight
40 nil vials were collected. Two duplicate VOA samples were also collected. The bottles
were numbered 3-1 through 3-12 and the vials were numbered V3-1 and V3-8 and V3-1D
and V3-2D. The samples were stored on ice and the site was vacated at 1500.
Mr. John Garret, Washington Department of Wildlife, Skagit Wildlife-Recreation Area.
Telephone: 445-4441
Mr. Richard Norgaard Telephone: 629-2014
A-8
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01 -- i- „„.;,;, r.-U. *C5 442 0165 WATER DIVISION -»->•* PTI 3)002'008
PESTICIDE RECONNAISSANCE SURVEY
Sediment Sailing Report
October 25th 6 26th, 1990
Indian Slough, Higgins Slough, and Sullivan Slough Composite
Sample (INHI/SUSL) :
The Indian Slough portion of this sample was obtained on October
25th at approximately 1200 hours. The sample was collected from
the landward side of the southern tidegate immediately east of La
Conner and Samish Road. The tidegate was closed due to an
extremely high tide. Four sediment grabs were made using a hand-
held Eckman dredge. Each grab was de-watered and released from
the dredge onto grass on the top of the dike. Using a lab-cleaned
stainless steel spatula, the top centimeter from the center of
each sample*was collected into lab prepared 200 mg glass jars.
Sample depth varied between 6 inches and 3 feet.
Two grabs were taken from the bottom of a small pool in an un-
named creek entering Higgins Slough at about 1300 hours. Creek
velocity was estimated at 1 meter/ second, depth 1 foot, and width.
2 feet. The grabs were collected from the east side of the
northernmost culvert under La Conner and Samish Road in section
(T 34 N, R 3 E) . The same collection procedures were followed.
The Sullivan Slough portion of this sample was also taken on
October 25th at approximately 1340 hours. Two grabs were taken
from the west side of the culvert at the southern crossing of La
Conner and Samish Road and the un-named creek in section 30 (T 34
N, R 3 E) . Flow was estimated at 1 meter second, depth 1 foot,
and width 2 feet. The same collection procedures were followed.
All samples were immediately placed in coolers packed with both
crushed and block ice. Samples were marked as INHI and SUSL,
respectively.
Conway Composite Sample (CNWY,CNWY2,CNWY3) :
These samples were also taken on October 25th between 1400 and
1440 hours. Three grabs were taken from each of the two drainage
ditches that enter the northernmost section of Big Ditch, just
north and east of Convay. Grabs were collected from off of the
railroad trestle along the west ditch, and from a one-hundred
meter section of the east ditch, before it enters Big Ditch. Flow
in both ditches was estimated at .1 meter per second, depth 3
feet, and width 4 feet. Sample depths were approximately 3 feet.
The same collection procedures were followed. These samples were
marked as CNWY, CNWY2, CNWYS.
Big Ditch Sample (BGDH) :
*, that was not in contact with the grass, A-9
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01 u »i ua:31 FAI 206 442 0185 WATER DIVISION -.-»-» PTI 3]003.'008
This was the last sample to be collected on October 25th. Pour
grabs were taken from the landward side of the tidegate which is
approached from the Skagit Wildlife Refuge access road. The
tidegate was closed and thus no flow was observed. Samples were
collected at approximately 1520 hours. Sample depth was
approximately 2-3 feet. The same collection procedures were
followed. This sample was marked as BGDH.
Lower Sammamish River (LSAM):
Three grabs were taken October 26th between 0630 and 0800 hours
along a one hundred meter section of river immediately west of
the 68th Avenue N.E. bridge at Kenmore. The flow velocity was
estimated at .8 meter per second, average depth 4 feet, and width
30 feet. The depths of the grabs varied between 6 inches and 2
feet. Same collection procedures were followed.
Two additional grabs for this sample were collected from
underneath a private bridge which crosses the Sammamish River at
about 84th Avenue N.E. Sample depth was about eighteen inches.
Sample time was about 1030. Same collection procedures were
followed. This sample was marked LSAM.
Swamp Creek (SWMP):
Samples were collected on October 26th between 0830 and 1000
hours. Six grabs were taken during a stream-walk along the
lowermost portion of Swamp Creek, beginning at N.E. 175th Street
and ending just before Swamp Creek enters the Sammamish River.
Flow velocity was estimated at 1.2 meter per second, average
creek depth 3 feet, and average width 20 feet. Sample depths
varied between 2 and 4 feet. Same collection procedures were
used. This sample was marked as SWMP.
Mercer Creek (MRCR):
Four grabs were taken from the Beliefield Business Park bridge as
it crosses Mercer Creek on October 26th at 1130 hours, samples
were taken from between 3 and 6 feet. Estimated flow velocity was
. 1 meter per second, depth 6 feet, and width 60 feet. Again, the
samples were drained and released from the dredge onto a grassy
area. Only the top centimeter from the center of the sample was
collected. Samples were immediately placed in ice. This sample
was marked as MRCR.
A-10
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Rainfall Runoff Model
-------
RAINFALL RUNOFF MODEL
SELECTION OF SIGNIFICANT RAINFALL EVENT FOR WATER SAMPLING
Sampling was concentrated during precipitation events to enhance the
probability of sampling pesticides possibly being flushed into Puget Sound. The
following approach to sampling was developed in 1990 based on an evaluation of
the specific sites and on consultation with county agents, regional hydrogeolo-
gists, and weather forecasters. Hydrographic data for each of the sites sampled
in 1990 were also reviewed (see discussion in the Rainfall Runoff Analysis
section). Application times for the pesticides of concern vary over a period of
several months but are maximized during the late spring and summer growing
season. A peak in pesticide concentrations is expected during or soon after rains
of sufficient magnitude and duration have soaked pesticide application areas and,
subsequently, produced a flush of surface runoff. Based on available information
on runoff characteristics in each area and best professional judgment, estimates
were made for 1) appropriate antecedent conditions to prime each area for runoff,
2) minimum rain accumulations to produce runoff in each area, and 3) the poten-
tial elapsed time between the start of precipitation and the discharge of runoff at
each sampling point. These criteria, which describe the conditions that may
constitute a significant precipitation event, are summarized in Table B-l.
Rainfall Runoff Analysis
Rainfall runoff modeling was completed for the four watersheds sampled in
1990 in order to develop guidelines for sampling. The Soil Conservation Service
(SCS) TR-20 model was used to produce storm hydrographs and simulate the
rainfall runoff response for each of the watersheds. The model input required for
these simulations included watershed physical characteristics, hydraulic param-
eters developed using watershed physical characteristics and empirical relation-
ships, and synthetic precipitation data. Watershed physical characteristics were
determined using topographic maps and information contained in the soil surveys
for King County (SCS 1973), Snohomish County (SCS 1978), and Skagit County
(SCS 1960). A synthetic storm hyetograph, which shows the time distribution of
rainfall, was developed using historical precipitation data; a dimensionless storm
distribution developed by the SCS (1986); and published statistical data for depth,
duration, and frequency of precipitation events for the specific watershed
locations (NOAA 1973).
B-1
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TABLE B-1. CRITERIA FOR SAMPLING RUNOFF FROM A 6-HOUR DURATION,
2-YEAR RETURN PERIOD PRECIPITATION EVENT*
Sampling Location
Swamp Creek
Mercer Creek
Big Ditch Slough
(Skagit River)
Antecedent
Precipitation6
(inches)
0.8
0.8
1.4
Antecedent
Period
(days)
5
5
5
Total Precipitation
Depth Required to
Meet Abstractions0
and Produce Runoff
(inches)
0.35-0.7
ssO.7
0.35-0.7
Time Between Start
of Precipitation and
Start of Runoff
(hours)
2
3
2.5
Time of Sampling
After Start of
Precipitation*
(hours)
2-5
5-7
7-12
3-4.5
4.5-6.5
6.5-9
2.5-4.5
4.5-6.5
6.5-9
* These criteria were developed specifically for the 6-hour duration, 2-year return period precipitation event for the
watersheds of the listed drainages. Precipitation events with different durations and frequencies will result in different storm
hydrographs.
6 Cumulative amount of precipitation necessary in the antecedent period for runoff to occur.
e Abstractions are differences between rainfall and runoff.
d Sampling times based on simulated storm hydrographs.
B-2
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Model Input Development—Land use conditions in the four study
watersheds range from agricultural to urban. Section a of Table B-2 lists physio-
graphic data for the watersheds and streams that were sampled. Predominant soil
types and land uses that exist in each watershed are also listed.
Hydraulic parameters developed from the data in Table B-2 (Section a)
include curve number and time of concentration. The curve number is a
empirically based parameter that relates rainfall, runoff, and the difference
between rainfall and runoff (abstractions). Abstractions may occur as a result of
interception by vegetation, infiltration into soil, and retention of water on
impermeable ground surfaces (i.e., depression storage). Land use and soil
hydraulic characteristics are used to determine the curve numbers that best
represent hydrologic conditions in specific areas of a watershed. In general,
larger curve numbers indicate that a larger volume of runoff will be produced for
a given precipitation event. A single curve number was chosen for each
watershed based on predominant soil types and land use characteristics in each
watershed. The time of concentration for a watershed is the time required for a
particle of water to travel from the most distant point in the watershed to the
watershed outlet. The time of concentration for each of the watersheds was
estimated using an empirical relationship that relates the curve number, hydraulic
length (length of the longest watercourse), and the average watershed slope. The
curve numbers and times of concentration for each of the watersheds are listed
in Table B-2 (Section b).
Precipitation event data required for rainfall runoff modeling include
precipitation intensity, duration of precipitation, and total depth of precipitation.
The return period for a precipitation event is defined as the average length of time
between events equaling or exceeding a certain depth. The return period is also
defined as the inverse of the probability of exceeding a certain depth and
duration. Therefore, if the return period of a 6-hour storm that produces 2 inches
of rain is 100 years, then there is a 1 in 100 chance of a storm of equal or greater
magnitude occurring in any one year.
Location-specific data for precipitation depths, durations, and return periods
were determined using maps contained in the National Oceanic and Atmospheric
Administration's (NOAA) Precipitation-Frequency Atlas for Washington State
(NOAA 1973). Because the maps in the atlas were developed from historical data
for the entire year, seasonal data may be somewhat different. For example,
historical data from 108 storms that were analyzed for the Bellevue Urban Runoff
Program indicate that the average amount of rain per storm during the months of
March through September was 82 percent of the average annual amount of rain
per storm (Pitt and Bissonette 1984). The average duration of storms that
occurred during the months of May, June, and July was 8 hours.
The storm duration chosen for modeling was 6 hours. Precipitation depth
and frequency data for this storm duration in the Seattle area and at the mouth of
the Skagit River were determined using the precipitation-frequency atlas. Rainfall
B-3
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TABLE B-2. DATA FOR STUDY STREAMS AND WATERSHEDS
Data
Big Ditch Slough
Swamp Creek
Mercer Creek
a. Physiographic Data
Watershed area (mile2)
Average slope (%)
Hydraulic length* (miles)
Predominant land use
Predominant soil type
b. Hydraulic Parameters
Curve number
Time of concentration
(hours)
10
1
2
Agriculture
Puget silty clay loam
85
3.0
22
5
10
Urban/suburban
Alderwood
Gravelly sandy loam
85
4.8
12
10
6
Urban
Alderwood
Gravelly sandy loam
80
2.6
c. Precipitation Depth. Duration, and Frequency
Rati irn PorinH
nviui ii r 01 iwu
(years)
2
5
10
25
50
100
Mouth of Skagit
0.8
1.1
1.2
1.4
1.6
1.8
Depth
(inches)
River
Seattle
1.0
1.2
1.4
1.6
1.8
2.0
* Hydraulic length is defined as the length of the longest watercourse within the watershed.
B-4
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depths for return periods ranging from 2 to 100 years for the 6-hour duration
storm are listed for both locations in Section c of Table B-2. The 2-year and
25-year return periods were chosen as bounding conditions to be used in
modeling. Because depths at the two locations were within 0.2 inches of one
another, a mean depth was calculated. These values were adjusted for seasonal
differences in precipitation depth from March through September by multiplying
by 0.82. The resulting storm depths for the 6-hour duration, 2-year and 25-year
storms that were used in modeling were 0.7 inches and 1.2 inches, respectively.
Two synthetic storm hyetographs were developed for the rainfall runoff
analysis by applying the calculated storm depths to a dimensionless hyetograph.
The dimensionless hyetograph was developed by the SCS for use in the United
States for storms with 6-hour durations (SCS 1986). A graph of the resulting
cumulative precipitation for the 2-year and 25-year return period storms is
included in this appendix.
The amount of water contained in the soil prior to a precipitation event is
termed the antecedent moisture condition. Antecedent moisture conditions were
simulated using specific scenarios established for use with the model. Antecedent
Condition I simulates dry soils where less than 0.5 inches of rain have fallen in
the previous 5 days during the dormant season and less than 1.4 inches of rain
have fallen in the previous 5 days during the dry season. Antecedent Condition n
simulates average conditions where between 0.5 and 1.1 inches of rain have fallen
in the previous 5 days during the dormant season and between 1.4 and 2.1 inches
of rain have fallen in the previous 5 days during the growing season. Average
conditions are simulated using the curve number, as determined by the methods
discussed above. The model simulates the dry antecedent condition by decreasing
the curve number input for average conditions. This decrease in curve number
results in a prediction of less runoff occurring for a given precipitation event,
which would be expected under drier antecedent conditions.
Model Results—Four simulations were completed for each watershed: dry
and average antecedent conditions for both the 2-year and 25-year storms. An
example model output is included in this appendix. Storm hydrographs were
developed for each of the simulations. These hydrographs are also included in
this appendix.
Antecedent conditions were found to strongly affect total volumes and rates
of runoff. No runoff occurred in any of the watersheds for the 2-year return
period storm that occurred after Antecedent Condition I. Peak flows occurring
from 25-year return period storms after Antecedent Condition I constitute
approximately 20 percent of the peak flows that occurred after Antecedent
Condition n.
Sensitivity analyses were completed for the 2-year return period storm and
average antecedent condition scenario to determine the amount of precipitation
B-5
-------
required to satisfy abstractions and produce runoff. Each hourly rainfall
increment was decreased by one-half to retain the shape of the hyetograph and to
decrease total rainfall from 0.7 to 0.35 inches. No runoff occurred in any of the
watersheds when the total precipitation was decreased from 0.7 to 0.35 inches,
indicating that abstractions are between 0.35 and 0.7 inches. Initial abstractions
vary depending on antecedent conditions, total storm depth, and the distribution
of precipitation within specific storm events.
Guidelines for Sampling Events
The 6-hour duration, 2-year return period precipitation event has a high
probability of occurring and was used as the basis for the sampling program
design. Model results indicated that 0.5-2.1 inches of rain must occur in the
5 days preceding this precipitation event in order for runoff to occur, with the
specific amount of antecedent precipitation dependent on the season. The higher
range of this required antecedent precipitation will be interpreted as applying to
agricultural lands where significant evapotranspirative losses occur during the
growing season. Therefore, sampling at the Big Ditch Slough occurred after
approximately 1.4 inches of rain had fallen during the 5-day antecedent period.
It was determined that the 5-day antecedent precipitation needed at the Mill Creek
and Swamp Creek watersheds was only approximately 0.8 inches due to a lower
evapotranspirative demand from land highly developed with commercial or
residential structures.
Sensitivity analyses indicated that between 0.35 and 0.7 inches of precipita-
tion must occur during the 6-hour storm under average antecedent conditions for
runoff to result in any of the watersheds. Because peak runoff from the Mercer
Creek watershed is only 30 cubic feet per second, at least 0.7 inches of rain
would have to fall for runoff to occur.
Sampling was planned according to the hydrographs shown in this appendix.
Actual sampling times and conditions are recorded in Appendix A.
Model results are based on available data regarding watershed and precipita-
tion characteristics. More accurate modeling results would be possible if the
model was calibrated with actual precipitation and discharge data. It is recom-
mended that rain gauges be established concurrent with sampling and that rainfall
depth data be collected every 30 minutes. Stream discharge measurements will
be made at the same time that rainfall measurements are made to calibrate the
model if future simulations are anticipated. Real-time modeling using short-term
precipitation forecasts and the calibrated model would result in more refined
sampling guidelines for future sampling programs at these sites. For this survey,
sampling personnel used best judgment in adjusting the time periods indicated
based on actual conditions during each precipitation event.
B-6
-------
REFERENCES
Pitt and Bissonnette. 1984. Bellevue urban runoff program summary report.
Robert Pitt, Consulting Environmental Engineer, Mounds, WI, and Pam
Bissonnette, Storm and Surface Water Utility, Bellevue, WA.
PTI. 1990. Pesticide reconnaissance survey quality assurance plan. Prepared
for U.S. Environmental Protection Agency Region 10, Office of Puget Sound,
Seattle, WA. PTI Environmental Services, Bellevue, WA.
SCS. 1960. Soil survey for Skagit County Washington. U.S. Department of
Agriculture Soil Conservation Service, in cooperation with Washington Agricul-
tural Experiment Station.
SCS. 1973. Soil survey for King County area Washington. U.S. Department
of Agriculture Soil Conservation Service, in cooperation with Washington
Agricultural Experiment Station.
SCS. 1978. Soil survey for Snohomish County area Washington. U.S. Depart-
ment of Agriculture Soil Conservation Service, in cooperation with Washington
Department of Natural Resources and Washington State University Agriculture
Research Center.
SCS. 1986. Urban hydrology for small watersheds. Technical Release No. 55.
U.S. Department of Agriculture, Soil Conservation Service, Washington DC.
B-7
-------
1.5 -i
Cumulative Precipitation for 6 hr Duration
2 and 25 Year Return Period Storms
25 Year Storm
(ft
-------
200 n
Swamp Creek Storm Hydrograph
6 hour duration 2 year return period
5 10
Time Since Start of Precipitation (hrs)
15
B-9
-------
1600-
Swamp Creek Storm Hydrograph
6 hour duration 25 year return period
0
-i—i—i—i—i—i—i—i—i—i—i—i—i—r
5 10
Time Since Start of Precipitation (hrs)
• •_• •_• Dry Antecedent Conditions
Ave. Antecedent Conditions
B-10
-------
40-1
Mercer Creek Storm Hydrograph
6 hour duration 2 year return period
30-
in
o
&20-
\_
o
.c
u
en
10-
T
4
1 i
8
12
16
Time Since Start of Precipitation (hrs)
B-11
-------
120CH
1000:
0
Mercer Creek Storm Hydrograph
6 hour duration 25 year return period
8 12
Time Since Start of Precipitation (hrs)
• •_• •_• Dry Antecedent Conditions
» . . . . Ave. Antecedent Conditions
16
B-12
-------
100-1
Big Ditch Slough Storm Hydrograph
6 hour duration 2 year return period
T 8 12
Time Since Start of Precipitation (hrs)
B-13
-------
1200-,
1000:
800-
™ 600:
Big Ditch Slough Storm Hydrograph
6 hour duration 25 year return period
o
.c
u
400-
200:
4812
Time Since Start of Precipitation (hrs)
• •_• •_• Dry Antecedent Conditions
Ave. Antecedent Conditions
B-14
-------
MS25D.OUT
TR-20 S/N: 32001325
DATE: 05/08/1990
TINE: 11:00:40.49
DATA FILE: MS25D.DAT
00
01
page 1
f
w
f
ya
1
PI
f
-------
33
3)
JOB TR-20
TITLE
TITLE
4 DIHHYD
8
8
8
8
8
8
8
9 ENDTBL
5 RAINFL 3
8
8
9 ENDTBL
6 RUNOFF 1
ENDATA
7 INCREN 6
7 COMPUT 7
ENDCNP 1
ENDJOB 2
FULLPRINT
.000
.470
1.0
.680
.280
.055
.011
.05
.93
1
1
SIMULATION
.02
.030
.660
.990
.560
.207
.040
.005
.5
.1
1.1
1 12.
0.5
1 0.0
# 2: 6 HOUR
MERCER
.100
.820
.930
.460
.147
.029
.000
.16
1.6
80.
1.0
SUMMARY
. 25 YEAR
CREEK
.190
.930
.860
.390
.107
.021
.32
1.11
2.6
1.0
STORM
.310
.990
.780
.330
.007
.015
.72
1.15
1 1
3 1
10
20
3
40
50
60
70
80
90
100
110
115
120
.84 130
1.2 140
145
111 150
155
160
1 170
180
190
•********«***«*******««*******«EUD op 80-80
-------
TR20 XEQ 05/08/1990 SIMULATION * 2: 6 HOUR, 25 YEAR STORM 20 JOB 1 PASS 1
REV 09/01/83 MERCER CREEK 3 PAGE 1
COMPUTER PROGRAM FOR PROJECT FORMULATION - HYDROLOGY USER NOTES
THE USERS MANUAL FOR THIS PROGRAM IS THE MAY 1982 DRAFT OF TR-20. CHANGES FROM THE 2/14/74 VERSION INCLUDE:
REACH ROUTING - THE MODIFIED ATT-KIN ROUTING PROCEDURE REPLACES THE CONVEX METHOD. INPUT DATA PREPARED FOR
PREVIOUS PROGRAM VERSIONS USING CONVEX ROUTING COEFFICIENTS UILL NOT RUN ON THIS VERSION.
THE PREFERRED TYPE OF DATA ENTRY IS CROSS SECTION DATA REPRESENTATIVE OF A REACH. IT IS RECOMMENDED THAT
THE OPTIONAL CROSS SECTION DISCHARGE-AREA PLOTS BE OBTAINED WHENEVER NEW CROSS SECTION DATA IS ENTERED.
THE PLOTS SHOULD BE CHECKED FOR REASONABLENESS AND ADEQUACY OF INPUT DATA FOR THE COMPUTATION OF »M"
VALUES USED IN THE ROUTING PROCEDURE.
GUIDELINES FOR DETERMINING OR ANALYZING REACH LENGTHS AND COEFFICIENTS (X,H) ARE AVAILABLE IN THE USERS
MANUAL. SUMMARY TABLE 2 DISPLAYS REACH ROUTING RESULTS AND ROUTING PARAMETERS FOR COMPARISON AND CHECKING.
HYDROGRAPH GENERATION - THE PROCEDURE TO CALCULATE THE INTERNAL TIME INCREMENT AND PEAK TIME OF THE UNIT
03 HYDROGRAPH HAVE BEEN IMPROVED. PEAK DISCHARGES AND TIMES MAY DIFFER FROM THE PREVIOUS VERSION. OUTPUT
-^ HYDROGRAPHS ARE STILL INTERPOLATED, PRINTED, AND ROUTED AT THE USER SELECTED MAIN TIME INCREMENT.
INTERMEDIATE PEAKS - METHOD ADDED TO PROVIDE DISCHARGES AT INTERMEDIATE POINTS WITHIN REACHES WITHOUT ROUTING.
OTHER - THIS VERSION CONTAINS SOME ADDITIONS TO THE INPUT AND NUMEROUS MODIFICATIONS TO THE OUTPUT. USER
OPTIONS HAVE BEEN MODIFIED AND AUGMENTED ON THE JOB RECORD, RAINTABLES ADDED, ERROR AND WARNING MESSAGES
EXPANDED, AND THE SUMMARY TABLES COMPLETELY REVISED. THE HOLDOUT OPTION IS NOT OPERATIONAL AT THIS TIME.
PROGRAM QUESTIONS OR PROBLEMS SHOULD BE DIRECTED TO HYDRAULIC ENGINEERS AT THE SCS NATIONAL TECHNICAL CENTERS:
CHESTER, PA (NORTHEAST) -- 215-499-3933, FORT WORTH, TX (SOUTH) -- 334-5242 (FTS)
LINCOLN, NB (MIDWEST) -- 541-5318 (FTS), PORTLAND, OR (WEST) -- 423-4099 (FTS)
OR HYDROLOGY UNIT, ENGINEERING DIVISION, LANHAM, MO -- 436-7383 (FTS).
PROGRAM CHANGES SINCE HAY 1982:
12/17/82 - CORRECT PEAK RATE FACTOR FOR USER ENTERED DIMHYD
-------
CORRECT REACH ROUTING PEAK TRAVEL TIME PRINTED WITH FULLPRINT OPTION
5/02/83 - CORRECT COMPUTATIONS FOR ---
1. DIVISION OF BASEFLOU IN DIVERT OPERATION
2. HYDROGRAPH VOLUME SPLIT BETWEEN BASEFLOU AND ABOVE BASEFLOU
3. CROSS SECTION DATA PLOTTING POSITION
4. INTERMEDIATE PEAK UHEN "FROM" AREA IS LARGER THAN "THRU" AREA
5. STORAGE ROUTED REACH TRAVEL TIME FOR MULTIPEAK HVDROGRAPH
6. ORDERING "FLOU-FREQ" FILE FROM SUMMARY TABLE #3 DATA
7. BASEFLOU ENTERED UITH READHYD
8. LOU FLOW SPLIT DURING DIVERT PROCEDURE #2 UHEN SECTION RATINGS START AT DIFFERENT ELEVATIONS
ENHANCEMENTS ---
1. REPLACE USER MANUAL ERROR CODES (PAGE 4-9 TO 4-11) UITH MESSAGES
2. LABEL OUTPUT HYDROGRAPH FILES UITH CROSS SECTION/STRUCTURE, ALTERNATE AND STORM NO'S
09/01/83 - CORRECT INPUT AND OUTPUT ERRORS FOR INTERMEDIATE PEAKS
CORRECT COMBINATION OF RATING TABLES FOR DIVERT
CHECK REACH ROUTING PARAMETERS FOR ACCEPTABLE LIMITS
ELIMINATE MINIMUM REACH TRAVEL TIME UHEN ATT-K1N COEFFICIENT EQUALS ONE
00
-------
TR20 XEQ OS/08/1990
REV 09/01/83
SIMULATION * 2: 6 HOUR. 25 YEAR STORM
MERCER CREEK
20
3
JOB 1 PASS
PAGE
EXECUTIVE CONTROL OPERATION INCREM
ME INCREMENT * 0.50 HOURS
RECORD ID
160
EXECUTIVE CONTROL OPERATION COMPUT RECORD ID
RUCTURE 1 TO STRUCTURE 1
STARTING TIME > 0.00 RAIN DEPTH « 1.00 RAIN DURATION- 1.00 RAIN TABLE NO.- 3 ANT. MOIST. COND- 1
ALTERNATE NO.- 0 STORM NO.-10 MAIN TIME INCREMENT • 0.50 HOURS
170
OPERATION RUNOFF STRUCTURE 1
OUTPUT HYDROGRAPH- 1
AREA* 12.00 SQ Ml INPUT RUNOFF CURVE- 80. TIME OF CONCENTRATION- 2.60 HOURS
COMPUTED CURVE NO. * 63. INTERNAL HYDROGRAPH TIME INCREMENT- 0.3467 HOURS
PEAK TIME(HRS)
4.85
PEAK DISCHARGE(CFS)
86.44
PEAK ELEVATION(FEET)
(RUNOFF)
TIME(HRS) FIRST HYDROGRAPH POINT • 0.00 HOURS TIME INCREMENT • 0.50 HOURS
0.00 DISCHG 0.00 0.00 0.00 0.00 0.00 0.00 0.08
5.00 DISCHG 85.59 70.42 44.65 27.00 10.47 2.47 1.77
DRAINAGE AREA - 12.00 SQ.MI.
10.90 44.42 81.79
0.46 0.00
RUNOFF VOLUME ABOVE BASEFLOW • 0.02 WATERSHED INCHES. 191.02 CFS-HRS, 15.79 ACRE-FEET; BASEFLOW - 0.00 CFS
--- HYDROGRAPH FOR STRUCTURE 1, ALTERNATE 0. STORM 10. ADDED TO OUTPUT HYDROGRAPH FILE ---
EXECUTIVE CONTROL OPERATION ENDCMP
TIONS COMPLETED FOR PASS 1
RECORD ID
180
EXECUTIVE CONTROL OPERATION ENDJOB
RECORD ID
190
-------
APPENDIX C
Description of Water Sampling Apparatus
-------
WATER SAMPLING APPARATUS
The apparatus used to collect water samples during this investigation can be
easily made and used for routine water monitoring efforts. It consists of an
all-Teflon* closure (which screws directly onto a 2.5-liter sampling bottle) that
has water inlet and air outlet ports separated by a fixed vertical distance
(Figure C-l). The closure is the top from a Teflon* wash bottle (Cole-Parmer
Instrument Company, 7425 North Oak Park Avenue, Chicago, Illinois, 60648).
The narrowed tip of the port is clipped off, leaving a constant-bore tube. A
second hole is drilled in the lid, and a section of glass or Teflon* tubing is
inserted into the hole. To avoid breaking the glass sample bottles, a bottle
holder, which partially encases the bottle, is used. Attached to the bottle holder
is a rigid handle and extension rods. These are used to control the depth of the
sampler in the water column.
This sampling system had the advantage that the sample only contacts glass
and Teflon® and that the number of sample transfer steps is reduced. To
minimize aeration of the sample as it flows into the sample bottle, the Teflon*
inlet tube can be extended to the lowest point of the sample bottle, thereby
reducing splashing. Decontamination between samples is simplified because of
the size and simplicity of the Teflon* closure. The primary functional difference
between this ported closure and the United States Geological Survey (USGS)
depth integrating samplers is that the filling rates of the USGS samplers can be
controlled with the inlet nozzles of various diameters, whereas the ported Teflon®
closures have a fixed diameter. Both systems allow depth integrated sampling.
C-1
-------
o
rb
WATER
IN
TEFLON
CLOSURE
2.5 LITER
GLASS BOTTLE
Figure C-1. Water sampling apparatus.
-------
APPEND IX D
C*\BbT-BdM3u3toflY Forms
-------
i'
Analyfjcal1echnologies,lnc.
560 Naches Avenue SW. Suite 101 Renton.WA 98055
9
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1,
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1200 Slnh Anno.
S«*nK WA 9BIOI
Project Code:
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-------
APPENDIX E
Sediment Quaftf Criteria
-------
TABLE E-1. SEDIMENT QUALITY CRITERIA (//g/g DRY WEIGHT
FOR METALS AND NUTRIENTS) PROPOSED BY THE
ONTARIO MINISTRY OF ENVIRONMENT
Metals
Arsenic
Cadmium
Chronium
Copper
Iron (%)
Lead
Manganese
Mercury
Nickel
Zinc
Organic Compounds"
£-Chlordane
Heptachlor
Endrin
Aldrin
Mirex
Chlordane
p.p-DDT
p,p-DDD
p,p-DDE
o,p-DDT
PCB 1254
PCB 1248
PCB 1016
PCB (Total)
Dieldrin
No Effect
Level
4.0
0.6
22.0
15.0
2.0
23.0
400.0
0.1
15.0
65.0
0.001
0.001
0.002
0.001
0.001
0.001
0.005
0.002
0.003
0.001
--
--
--
0.020
0.006
Lowest Effect
Level
5.5
1.0
31.0
25.0
3.0
31.0
457.0
0.12
31.0
110.0
0.005
0.002
0.003
0.007
0.002
0.008
0.009
0.008
0.005
0.006
0.058
0.034
0.007
0.041
0.019
Limit of
Tolerance Level
33.0
10.0
111.0
114.0
4.0
250.0
1,100.0
2.0
90.0
800.0
fjg Contaminants/g Carbon
(TOO
6.6
0.5
33.1
128.4
9.1
6.2
13.6
9.0
21.3
11.3
34.4
150.5
53.3
69.8
59.0
E-1
-------
TABLE E-1. (Continued)
No Effect Lowest Effect JJQ Contaminants/g Carbon
Level Level (TOO
BHC
-------
TABLE E-2. SUMMARY OF ER-L. ER-M. AND OVERALL APPARENT EFFECTS THRESHOLD CONCENTRATIONS
FOR SELECTED CHEMICALS IN SEDIMENT (DRY WEIGHT)
Chemical Analyte
Trace Elements (mg/kg)
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
m Tin
<•> Zinc
ER-L
Concentration
2
33
5
80
70
35
0.15
30
1
NAb
120
ER-M
Concentration
25
85
9
145
390
110
1.3
50
2.2
NA
270
ER-LER-M
Ratio
12.5
2.6
1.8
1.8
5.6
3.1
8.7
1.7
2.2
NA
2.2
Overall Apparent
Effects Threshold
25
50
5
No
300
300
1
NSD"
1.7
NA
260
Subjective Degree
of Confidence in
ER-L/ER-M Values
Moderate/moderate
Low/moderate
High/high
Moderate/moderate
High/high
Moderate/high
Moderate/high
Moderate/moderate
Moderate/moderate
NA
High/high
PotychJorinated Biphenyts 0/g/kg)
Total PCBs
50
400
7.6
370
Moderate/moderate
DDT and Metabolites (pg/kg)
DDT
DDD
DDE
Total DDT
Other Pesticides (pg/kg)
Lindane
Chlordane
Heptachlor
Dieldrin
Aldrin
1
2
2
3
NA
0.5
NA
0.02
NA
7
20
15
350
NA
6
NA
8
NA
7
10
7.5
117
NA
12
NA
400
NA
8
NSD
NSD
No
NSD
2
NSD
No
NSD
Low/low
Moderate/low
Low/low
Moderate/moderate
NA
Low/low
NA
Low/low
NA
-------
TABLE E-2. (Continued)
m
Chemical Analyte
Endrin
Mirex
Potycydic Aromatic Hydrocarbons (po/kg)
Acenaphthene
Anthracene
Benz(a)anthracene
Benzo(a)pyrene
Benzo(e)pyrene
Biphenyl
Chrysene
Dibenz(a.h)anthracene
2.6-Dimethylnaphthylene
Fluoranthene
Fluorene
1 -Methylnaphthalene
2-Methylnaphthalene
1 -Methylphenanthrene
Naphthalene
Perylene
Phenanthrene
Pyrene
2,3,5-Trimethylnaphthalene
Total PAH
ER-L
Concentration
0.02
NA
150
85
230
400
NA
NA
400
60
NA
600
35
NA
65
NA
340
NA
225
350
NA
4,000
ER-M
Concentration
45
NA
650
960
1.600
2,500
NA
NA
2,800
260
NA
3,600
640
NA
670
NA
2,100
NA
1,380
2,200
NA
35,000
ER-LER-M
Ratio
2,250
NA
4.3
11.3
7
6.2
NA
NA
7
4.3
NA
6
18.3
NA
10.3
NA
6.2
NA
6.1
6.3
NA
8.8
Overall Apparent
Effects Threshold
NSD
NSD
150
300
550
700
NSD
NSD
900
100
NSD
1.000
350
NSD
300
NSD
500
NSD
260
1,000
NSD
22,000
Subjective Degree
of Confidence in
ER-L/ER-M Values
Low/low
NA
Low/low
Low/moderate
Low/moderate
Moderate/moderate
NA
NA
Moderate/moderate
Moderate/moderate
NA
High/high
Low/low
NA
Low/moderate
NA
Moderate/high
NA
Moderate/moderate
Moderate/moderate
NA
Low/low
Source: Long and Morgan (1990)
• NSD - not sufficient data.
b NA - not available.
-------
_ ^Assurance Report
£^fe-«8^i£i>-^'• -'^^ i**^^ • jf'^1-- ' '
for Chemical Analyses
-------
CONTENTS
Page
LIST OF TABLES F-iii
LIST OF ACRONYMS F-iv
INTRODUCTION F-l
OVERALL CASE ASSESSMENT F-l
COMPLETENESS F-3
HOLDING TIMES F-3
ANALYTICAL METHODS F-6
Sample Preparation and Analysis F-6
Calibration F-6
Detection Limits F-7
ACCURACY F-10
Surrogate Recoveries F-10
Blank Spike and Matrix Spike Recoveries F-10
Standard Reference Material F-14
PRECISION F-14
BLANKS F-14
COMPOUND CONFIRMATION F-14
REFERENCES F-l 8
F-ii
-------
LIST OF TABLES
Page
Table F-l. Data qualifier codes F-2
Table F-2. Sample extraction groups for pesticide analyses F-4
Table F-3. Pesticides analyzed for in Puget Sound waters and
sediments F-5
Table F-4. Detection limits for pesticides F-8
Table F-5. Percent recovery for surrogate compounds for organo-
phosphorus and organochlorine pesticides F-ll
Table F-6. Matrix spike recovery data for pesticides F-12
Table F-7. Analytical results for pesticides in standard reference
materials F-15
Table F-8. Matrix spike duplicate analysis for pesticides F-l6
F-iii
-------
LIST OF ACRONYMS
MS matrix spike
MSD matrix spike duplicate
QAPP quality assurance project plan
PSEP Puget Sound Estuary Program
RPD relative percent difference
RRF relative response factor
RSD relative standard deviation
TEA tributyl ammonium agent
F-iv
-------
INTRODUCTION
This report documents the results of a quality assurance review of analytical
data for pesticides in water and sediment samples from Puget Sound drainages
and deltas. This quality assurance report is provided in support of the quality
assurance project plan (QAPP) for 1990 Pesticide Reconnaissance Survey (PTI
1990).
Pesticide analyses were performed by Analytical Technologies Incorporated
in Renton, Washington; San Diego, California; and Fort Collins, Colorado.
The quality assurance review included examination and validation of the
following laboratory data:
• Sample preparation and extraction logs and laboratory worksheets
• All instrument printouts
Instrument calibration and calibration verification procedures and
results
• Sample holding times and custody records
• Manual data transcriptions and computer algorithms.
Data qualifiers were assigned as necessary during the quality assurance review.
Following the validation procedures, data quality was assessed with respect to
accuracy, precision, and completeness. All qualifier codes used in this report are
defined in Table F-l.
OVERALL CASE ASSESSMENT
All data for pesticides, with one exception, are acceptable as qualified in this
review. Data qualified E (estimated) are acceptable, but a greater degree of
uncertainty is associated with these values than with unqualified data.
The DDT result for Sample CNWY-S was rejected because DDT degradation
in the associated continuing calibration standard was greater than 20 percent and
DDT was not found in the sample. Results for DDE and DDD for Sample
F-1
-------
TABLE F-1. DATA QUALIFIER CODES
Qualifier Code Description
E Estimate
R Rejected
T Detected below quantification limit
U Undetected at the detection limit shown
F-2
-------
CNWY-S and for DDT, DDE, and ODD for Sample LACO-S were qualified as
estimated.
The detection limits for chloropicrin and 1,3-dichloropropene for Sample
BGDHJC were qualified as estimated because the holding time between sample
collection and extraction was exceeded.
Results for pentachlorophenol for samples BGDH-S, LSAM-S, MRCR-S,
LACO-S and CNWY-S were qualified as estimated because the percent difference
in the associated continuing calibration standard exceeded control limits.
A T qualifier was assigned to several results for dichlobenil, DDT, DDE,
and DDD to indicate that the compound was detected, but at a concentration less
than the calibrated quantification limit.
COMPLETENESS
Complete data packages were submitted by Analytical Technologies Incor-
porated for 12 water and 6 sediment samples. The samples were divided into five
extraction groups, as indicated in Table F-2, and analyzed for the pesticides listed
in Table F-3. Method blanks, matrix spikes (MSs), matrix spike duplicates
(MSDs), and standard reference material samples (chlorinated herbicides,
triazines, and chloropicrin/ 1,3-dichloropropene only) were analyzed with the
samples. For sample group BGDH-J, the laboratory analyzed for carbamates,
glyphosate, acephate, and methamidophos on a composite of samples BGDHJ1,
BGDHJ2, and BGDHJ3.
During the quality assurance review, 12 results (2 percent) were qualified E
as discussed above. One result was rejected. Data completeness was 99.8
percent of the total requested analysis.
HOLDING TIMES
Holding times specified in the project QAPP (7 days from sampling to
extraction for water samples, 1 month for frozen sediment samples) were met for
all analyses, with two exceptions. For sample group BGDH-J, the holding time
between sampling and extraction for the chloropicrin and 1,3-dichloropropene
analyses was 8 days. Chloropicrin and 1,3-dichloropropene were not detected in
the samples. The detection limits for chloropicrin and 1,3-dichloropropene in
Sample BGDHJC were qualified as estimated (E). Samples for triazine analyses
in sample group BGDH-J were extracted 7 days after sampling. Concern over
spike recoveries led to another extraction 11 days after sampling. Because the
results of the two extractions were the same, no data were qualified. All samples
were analyzed within 40 days of extraction.
F-3
-------
TABLE F-2. SAMPLE EXTRACTION GROUPS
FOR PESTICIDE ANALYSES
BGDH-J
BGDHJ1
BGDHJ2
BGDHJ3
BGDHJC"
MERCER
MRCR-1
MRCR-2
MRCR-3
SWAMP
SWMP- 1
SWMP- 2
SWMP-3
BGDH-0
BGDH01
BGDH02
BGDH03
SEDMNT
BGDH-S
LSAM-S
MRCR-S
SWMP-S
LACO-S
CNWY-S
' BGDHJC - composite of BGDHJ1, BGDHJ2, and BGDHJ3.
F-4
-------
TABLE F-3. PESTICIDES ANALYZED FOR IN
PUGET SOUND WATERS AND SEDIMENTS
Organophosphate
Pesticides
Diazinon
Malathion
Dichlorvos
Fenamiphos
Chlorpyrifos
Parathion (ethyl)
Disulfoton
Methyl parathion
Azinphos-methyl
Phorate
Chlorinated
Pesticides*
Trifluralin
Chlordane
Endosulfan
Lindane
Dichlobenil
DDT
DDE
DDD
Chlorinated
Herbicides
2,4-D
Dicamba
Dinoseb
Triclopyr
Triazine
Herbicides
Alachlor
Atrazine
Amitrole
Hexazinone
Prometon
Simazine
Polar Phosphorous Carbamates and
Pesticides6 Urea Pesticides Miscellaneous
Acephate Bromacil 1,3-Dichloropropeneb and
Methamidophos Carbaryl Chloropicrinb
Propham Glyphosate
Methomyl Benfluralin
Diphenamid Pentachlorophenol"
Tebuthiuron Fenvalerateb
Diuron
Pronamide
Bendiocarb
Terbacil
* Sediment samples only.
b Water samples only.
F-5
-------
ANALYTICAL METHODS
All sample extraction and analysis procedures, instrument calibration
procedures, and quality control checks conformed to PSEP (1989) and QAPP
requirements, except as noted below.
Sample Preparation and Analysis
Water and sediment samples were extracted according to requirements
specified in the project QAPP. The extraction of the triazine blank spike and MS
for sample extraction group BGDH-J was done twice. The laboratory originally
extracted the sample, blank, and spikes on 13 June 1990. Because of concern
over inconsistent spike recoveries, a second extraction of the MS and blank spike
was done on 5 July 1990. In sample extraction group SEDMNT, sample CNWY-
S, the MS and MSD were analyzed before and after a tributyi ammonium agent
(TEA) cleanup. TBA is used to remove sulfur in the sample extracts. The
laboratory reported that a large interference was observed in the original extract
of Sample CNWY-S and the MS and MSD. The interference was present in the
area where phorate, diazinon, and disulfoton elute. The laboratory performed a
TBA cleanup on the three extracts. Results for the post-cleanup analyses were
only used for phorate, diazinon, and disulfoton.
Sample extracts were analyzed by gas chromatography/flame photometric
detection (organophosphorus pesticides), gaschromatography/nitrogen-phosphorus
detection (triazine herbicides and alachlor), gas chromatography/electron capture
detection (organochlorine pesticides, chlorinated herbicides, trichlopyr, chloro-
picrin, 1,3-dichloropropene, benfluralin, pentachlorophenol, and fenvalerate), and
high performance liquid chromatography (carbamates, urea, terbacil, and
glyphosate). Two columns were used for all gas chromatography analyses, one
for compound quantification and a second for compound confirmation.
Calibration
Initial calibration for all analyses was performed in accordance with Puget
Sound Estuary Program (PSEP) guidelines (PSEP 1989) for each sample
extraction group. Calibration of chlorpyrifos was calculated from the total
response factor for chlorpyrifos plus methyl parathion, since chlorpyrifos coeluted
with methyl parathion on one column and parathion on the second column. A
5-point calibration was performed for each analyses as recommended by PSEP
(1989). Initial calibration criteria [relative response factor (RRF) relative
standard deviation (RSD) of less 30 percent] were met for all analyses with the
following exceptions:
F-6
-------
• 25 May 1990—The RSDs for methyl-parathion and fenamiphos
were 42 and 39 percent, respectively. These compounds were not
detected in the samples and no data were qualified.
• 28 November 1990—The laboratory performed a 5-point calibration
for the organochlorine pesticides, but only used 4 points, dropping
the low end standard out. The low end standard was dropped to
meet the criteria of less than 30 percent RSD for DDE and endo-
sulfan n. The low end standard could have been used for the other
organochlorine pesticides, thus providing lower detection limits.
For lindane, the laboratory dropped two standards on the low end
of the calibration to obtain an RSD of less than 30 percent. This
still meets the PSEP (1989) requirement of a minimum of three
initial calibration standards.
Continuing calibrations were performed during all analyses to verify
instrument calibration. In the course of each analytical sequence, RRFs of
several compounds for one or more continuing calibrations felled to meet the
contract-required criteria of ± 15 percent difference from the initial calibration
RRF. Results for endosulfan n in sediment Sample MRCR-S, DDT in sediment
Sample LACOS, and pentachlorophenol in sediment samples BGDH-S, LSAM-S,
MRCR-S, LACOS, and CNWY-S were qualified as estimated because the
associated continuing calibration standard exceeded the control limit. For all
other continuing calibration standards where control limits were exceeded, no
compounds were detected in the associated samples.
DDT degradation was determined during continuing calibration of organo-
chlorine pesticides. DDT degradation was less than 20 percent in all cases except
for the continuing calibration standard associated with samples LACO-S and
CNWY-S. DDT degradation in this standard was 33 percent. DDT was detected
in Sample LACO-S, and the result was qualified a estimated (E). DDT was not
detected in Sample CNWY-S; this result was rejected (R). DDE and DDD were
found in both samples. Results were qualified as estimated (E).
Detection Limits
Detection limits for all water analyses met the levels specified in the project
QAPP (Table F-4). Detection limits for sediment samples were within project
guidelines with the exception of the carbamates. The laboratory reported high
levels of interferences in the samples during carbamate analysis, necessitating
extra cleanup and dilution of the samples. This resulted in higher than expected
detection limits for the sediment carbamate results.
F-7
-------
TABLE F-4. DETECTION LIMITS FOR PESTICIDES
Compound
Azinophos methyl
Chlorpyrifos
Diazinon
Dichlorvos
Disulfoton
Fenamiphos
Malathion
Methyl parathion
Parathion
Phorate
Chloropicrin
1 ,3-Dichloropropene
2,4-D
Dicamba
Dinoseb
Trichlopyr
Alachlor
Atrazine
Hexazinone
Prometon
Simazine
Methomyl
Tebuthiuron
Bromacil
Terbacil
Bendiocarb
Carbaryl
Ciuron
Propham
Diphenamid
Water
U/g/U
0.1
0.05
0.05
0.05
0.05
0.1
0.05
0.05
0.05
0.05
0.22
0.22
0.05
0.05
0.05
0.17
1.0
1.0
1.0
1.0
1.0
5.0
2.0
2.0
2.0
5.0
2.0
1.0
2.0
2.0
Sediment (Range)3
(mg/kg)
0.0073 -0.019
0.0038 -0.010
0.0038 -0.010
0.0038 -0.010
0.0038 -0.010
0.0073 -0.019
0.0038-0.010
0.0038 -0.010
0.0038-0.010
0.0038-0.010
NRb
NR
0.0015 -0.0039
0.0015 -0.0039
0.0015-0.0039
0.0019 -0.0049
0.044 -0.13
0.044 0.13
0.044 -0.13
0.044 -0.13
0.044-0.13
2.2-5.8
0.2-0.6
0.2-0.6
0.1 -0.2
0.2-0.6
0.2-0.6
0.1 -0.2
0.9-2.3
0.9 - 2.3
F-8
-------
TABLE F-4. (Continued)
Compound
Pronamide
Acephate
Methamidophos
Gyphosate
Dichlobenil
Trifluralin
Benfluralin
Lindane
4,4'-DDE
4,4'-DDD
4,4'-DDT
Endosulfan 1
Endosulfan II
Fenvalerate
Chlordane
Pentachlorophenol
Water
Oug/D
1.0
1.0
1.0
5.0
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Sediment (Range)3
(mg/kg)
0.2-0.6
0.0018-
0.0018-
0.0018-
0.0018-
0.0018-
0.0027 -
0.0027 -
0.0018 -
0.0027 -
0.0047
0.0093
0.0008 -
NRb
NR
NR
0.0049
0.0049
0.0049
0.0049
0.0047
0.0070
0.0070
0.0049
0.0070
-0.012
- 0.025
0.0019
3 Detection limit reported on dry weight basis. Detection limits
for sediment samples were adjusted on a sample-by-sample basis
to account for percent moisture.
b Analysis not required.
F-9
-------
ACCURACY
Accuracy was assessed by evaluating recoveries of surrogate compounds.
blank spikes, MSs, and MSDs and by the analysis of a standard reference
material.
Surrogate Recoveries
To asses the accuracy of organophosphorus pesticide and organochlorine
pesticide analyses, surrogate compounds were added to all samples and blanks
prior to extraction. Ethyl azinophos was used as a surrogate for the organo-
phosphorus pesticide analysis, and decachlorobiphenyl and dibutylchlorendate
were added as surrogates to samples analyzed for organochlorine pesticides.
Surrogate recoveries for all samples were within the QAPP guidelines of
50-125 percent, with the exception of the recovery for ethyl azinophos in the
4 September 1990 blank (189 percent) (Table F-5). The laboratory reported that
this blank was double-spiked, so the true recovery of ethyl azinophos is 89 per-
cent.
Blank Spike and Matrix Spike Recoveries
Blank spike, MS, and MSD samples were analyzed for all analyses, with the
following exceptions. The laboratory did not add phorate to the MS for sample
group BGDH-J. An MSD was not analyzed for sample group BGDH-J for
organophosphorus pesticides, chlorinated herbicides, triazines, chloropicrin, or
1,3-dichloropropene. No blank spikes were analyzed for glyphosate for any
sample group. The recovery of cnlorpyrifos was calculated from the total
recoveries for chlorpyrifos plus methyl parathion, since cnlorpyrifos coeluted with
methyl parathion on one column and parathion on the second column.
Percent recoveries for MSs or blank spike for several compounds in each
sample group were outside of the QAPP-specified control limits of 50-125
percent (Table F-6). Pentachlorophenol was spiked at a level below the concen-
tration found in the unspiked sample; therefore, the QAPP-specified control limits
are not applicable for the MS recovery. No data were qualified because 1) pesti-
cides were not detected in samples for which the associated MS or blank spike
had a recovery outside of the control limit, 2) surrogate recoveries were all within
PSEP (1989) control limits (organophosphorus pesticides), and 3) results for
standard reference material analysis were acceptable (chloropicrin, 1,3-dichloro-
propene, chlorinated herbicides, and triazines).
F-10
-------
TABLE F-5. PERCENT RECOVERY FOR SURROGATE
COMPOUNDS FOR ORGANOPHOSPHORUS AND
ORGANOCHLORINE PESTICIDES
Sample
Blank 6/1 3
BGDHOC
Blank 9/04
MRCR-1
MRCR-2
MRCR-3
Blank 10/10
SWMP-1
SWMP-2
SWMP-3
Blank 1 0/22
BGDH01
BGDH02
BGDH03
Blank 11/08
BGDH-S
LSAM-S
MRCR-S
SWMP-S
LACO-S
CNWY-S
EAP
90
76
189
100
115
107
70
72
66
70
96
83
87
86
100
79
63
55
71
73
80
Surrogate"
DCB
__b
--
--
--
• -
--
-
--
--
--
--
--
--
--
89
65
63
86
63
76
83
DBC
—
--
-
--
--
--
-
--
--
--
--
--
--
--
94
64
59
68
61
62
70
• EAP - Ethyl azinophos
DCB - Decachlorobiphenyl
DBC - Dibutylchlordendate.
b Not required.
F-11
-------
TABLE F-6. MATRIX SPIKE RECOVERY DATA FOR PESTICIDES"
Sample Extraction Group
BGOH-J
Compound
Azinophos methyl
Chlorpyrifos
Diazinon
Oichlorvos
Oisulfoton
Fenamiphos
Malathion
Methyl parathion
Parathion
Phorate
Chloropicrin
1 ,3-Dichloropropene
2.4-D
Dicamba
Dinoseb
Trichlopyr
Alachlor
Atrazine
Hexazinone
Prometon
Simazine
Methomyl
Tebuthiuron
Bromacil
Terbacil
Bendiocarb
Carbaryl
MSb
90
NO
119
41"
66
89
82
83
93
ND
79
58
82
89
48"
85
87
68
79
82
20"
76
75
77
8O
70
80
MSD°
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
84
85
97
90
84
9O
BSd
93
ND
93
62
72
91
90
70
72
ND
70
54
104
96
67
106
1408
180"
120
120
53
88
85
90
85
84
90
BGDH-J
Re -extract
MS
NR'
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
90
69
88
98
88
NR
NR
NR
NR
NR
NR
BS
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
90
60
97
100
70
NR
NR
NR
NR
NR
NR
MERCER
MS
46«
83
87
36"
60
55
75
78
81
66
45"
61
85
103
56
93
92
92
93
98
84
102
115
113
108
37°
74
MSD
52
92
89
43»
66
53
84
92
91
66
66
84
83
108
69
99
95
94
101
99
84
120
111
129"
127°
48"
93
BS
85
83
83
74
66
65
90
83
89
65
66
79
85
89
94
113
100
102
1448
120
100
117
121
135"
131g
10°
35"
SWAMP
MS
80
94
117
76
85
70
90
88
89°
81
46"
3O"
88
101
96
40"
65
67
53
83
73
76
96
113
103
70
87
MSD
67
89
101
63
78
64
81
88
88
66
49"
37"
106
120
82
44"
70
67
53
84
86
69
69
87
80
48"
59
BS
94
87
90
75
78
51
88
70
88
72
49a
46"
118
82
135"
35"
70
65
62
110
81
76
93
93
85
5"
21°
BGDH-0
MS
92
105
108
48°
71
89
90
94
93
64
53
33«
95
96
163"
84
75
80
93
99
124
92
70
81
98
19"
38"
MSD
80
97
97
41"
71
86
87
90
93
68
42"
26°
86
89
149"
80
71
85
90
94
127a
82
71
80
86
4»
18°
BS
96
83
95
72
0"
68
100
80
8O
51
25"
23"
92
86
151°
64
71
77
93
83
108
94
73
77
97
35°
5O
MS
68
71
88
38"
100
75
57
53
66
67
NR
NR
548"
81
38"
49°
43"
51
35°
64
121
104
91
75
62
64
62
SEDMNT
MSD
68
60
101
31
41"
69
68
55
59
63
NR
NR
1,667s
81
Oa
0"
75
67
45«
80
133°
77
69
55
46"
57
43°
SEDMNT
with Cleanup
BS
92
92
84
50
42"
89
92
84
92
61
NR
NR
86
90
Oa
50
107
77
100
88
85
115
82
1O4
91
13"
32°
MS
5«
49"
85
13"
61
60
39°
28"
51
58
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
MSD
4"
40°
77
0»
62
48"
33"
21"
54
50
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
-------
TABLE F-6. (Continued)
CO
Sample Extraction Group
Compound
Diuron
Propham
Diphenamid
Pronamide
Acaphate
Methamidophos
Gyphosate
Pentachlorphenol
Dichlobanil
Trifluralin
Benfluralin
Lindane
4,4'-DDE
4,4'-DDD
4,4'-DDT
Endosulfan 1
Endosulfan II
Fenvalerate
Chlordane
All values are oercenl
MSb
74
70
80
75
120
40C
113
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
t recovery.
BGDH-J
MSD°
94
80
85
90
ND
NO
ND
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Percent i
BGDH-J
Re -extract
BSd
80
80
85
70
90
40°
ND
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
MS
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
BS
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
(measured value
ecoverv *
MERCER
MS
112
81
92
118
36"
81
102
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
MSD
111
89
112
123
48
27
107
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
BS
1369
93
121
115
117
121
ND
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
- sample concentration)
SWAMP
MS
96
60
72
88
104
95
94
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
x 100.
MSD
82
75
69
76
106
96
86
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
BS
93
79
79
68
107
94
ND
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
BGDH-0
MS
121
74
108
71
125
97
101
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
MSD
122
81
110
86
107
75
101
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
BS
98
94
94
60
124
78
ND
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
SEDMNT
MS
63
66
51
59
NR
NR
NR
156"
56
95
105
50
86
80
107
77
68
91
1.046h
MSD
42
29
44
0
NR
NR
NR
570°
54
91
99
45"
SO
79
102
74
62
96
975h
BS
97
74
109
89
NR
NR
NR
135"
47"
61
76
73
81
76
109
77
88
122
1.128h
SEDMNT
with Cleanup
MS MSD
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
spike added
b MS - matrix spike.
0 MSD - matrix spike duplicate.
d BS - blank spike.
8 ND - analysis not performed.
1 NR - analysis not required.
0 Results exceeded Puget Sound Estuary Program control limits.
h Sample spiked at 10 times reported spike added.
-------
Standard Reference Material
Standard reference samples were extracted and analyzed for chloropicrin and
1,3-dichloropropene (water samples only), chlorinated herbicides, and triazine
herbicides (water and sediment samples). Results of all analyses were within 25
percent of the true value (Table F-7).
PRECISION
Precision for pesticides was assessed using the duplicate MS results
(Table F-8). The PSEP (1989) control limit of ±50 percent relative percent
difference (RPD) between spiked results was not exceeded for pesticides, with the
following exceptions. The RPDs for 2,4-D (51 percent), dinoseb (100 percent),
trichlopyr (100 percent), pronamide (100 percent), and pentachlorophenol
(57 percent) in sample group SEDMNT; for acephate (80 percent) in sample
group MERCER; and for bendiocarb (65 percent) in sample group BGDH-0
exceeded PSEP (1989) control limits. Pentachlorophenol was spiked at a level
below the concentration found in the unspiked sample; therefore, the QAPP-
specified control limits for precision are not applicable. No other pesticides
whose RPD exceeded PSEP (1989) control limits were detected in the associated
samples, and no data were qualified.
BLANKS
A method blank was prepared and analyzed for each extraction group as
required by PSEP (1989). No contaminant was found in any blank.
COMPOUND CONFIRMATION
Chromatograms for all analyses were examined during the quality assurance
review to confirm the presence or absence of target compounds. Pesticides
detected at concentrations below the detection limit were assigned T qualifiers to
indicate that the concentrations are less than the calibrated quantification limit.
F-14
-------
TABLE F-7. ANALYTICAL RESULTS FOR PESTICIDES
IN STANDARD REFERENCE MATERIALS"
Sample Group
Compound
Chloropicrin
1 ,3-Dichloropropene
2,4-D
Dicamba
Dinoseb
Trichlopyr
Prometon
Atrazine
Simazine
Alachlor
Hexazinone
Pentachlorophenol
BGDH-J
10.7
1.8
1.5
-1
0.8
3.5
7
-13
-12
8
4
NR
MERCER
-10
-1.7
8
12
-10.3
-14.5
-1
-1
4.1
15
1.3
NR
BGDH-0/
SWAMP
__b
--
0
5.6
0
8.7
-9.2
-5.6
-10.5
11.4
-3.3
NR
SEDMNT
NRC
NR
0.8
14
8
8.9
10
3.5
4
20
4.5
8.9
a Percent difference from true value.
b -- Analysis not performed.
c NR - not required.
F-15
-------
TABLE F-8. MATRIX SPIKE DUPLICATE ANALYSIS FOR PESTICIDES*
Sample Extraction Group
Compound
Azinophos methyl
Chlorpyrifos
Diazinon
Dichlorvos
Disulfoton
Fenamiphos
Malathion
Methyl parathion
Parathion
Phorate
Chloropicrin
1 ,3-Dichloropropene
2,4-D
Dicamba
Dinoseb
Trichlopyr
Alachlor
Atrazine
Hexazinone
Prometon
Simazine
Methomyl
Tebuthiuron
Bromacil
Terbacil
Bendiocarb
Carbaryl
Diuron
Propham
Diphenamid
Pronamide
Acephate
Methamidophos
Gyphosate
Pentachlorphenol
Dichlobenil
Trifluralin
BGDH-J
NDb
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
5
6
11
6
9
6
12
7
3
9
NR
NR
NR
NR
NR
NR
MERCER
6
5
1
9
5
2
6
8
6
0
19
16
1
2
10
3
2
1
4
1
0
8
2
7
8
13
11
0
5
10
2
80d
50
2
NR
NR
NR
SWAMP
9
3
7
9
4
4
5
0
1
10
3
10
9
9
8
5
4
0
0
1
8
5
16
13
13
19
19
8
11
2
7
1
1
4
NR
NR
NR
BGDH-0
7
4
5
8
0
2
2
2
0
3
12
12
5
4
4
2
3
3
2
3
1
6
1
1
7
65"
36
0
5
1
10
8
13
0
NR
NR
NR
SEDMNT
0
8
7
10
42
4
9
2
6
3
NRC
NR
51d
0
100d
100d
27
14
13
11
5
15
14
15
15
6
18
20
39
7
100d
NR
NR
NR
57d
2
2
SEDMNT
with Cleanup
11
10
5
100
1
11
8
14
3
7
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
F-16
-------
TABLE F-8. (Continued)
Sample Extraction
Compound
Benfluralin
Lindane
4,4'-DDE
4,4'-DDD
4,4'-DDT
Endosulfan 1
Endosulfan II
Fenvalerate
Chlordane
* All values are
Relative perct
BGDH-J
NR
NR
NR
NR
NR
NR
NR
NR
NR
MERCER
NR
NR
NR
NR
NR
NR
NR
NR
NR
SWAMP
NR
NR
NR
NR
NR
NR
NR
NR
NR
BGDH-0
NR
NR
NR
NR
NR
NR
NR
NR
NR
Group
SEDMNT
3
5
4
1
2
2
5
3
4
SEDMNT
with Cleanup
NR
NR
NR
NR
NR
NR
NR
NR
NR
relative percent difference.
>nt difference = lmatrix
spike - matrix spike
duplicate |
xlOO.
(matrix spike duplicate)/2
b NO - analysis not performed.
c NR - analysis not required.
d Results exceeded Puget Sound Estuary Program control limits.
F-17
-------
REFERENCES
NOAA. 1973. Precipitation-frequency atlas of the western United States,
Volume DC-Washington. U.S. Department of Commerce, National Oceanic and
Atmospheric Administration, National Weather Service, Silver Springs, MD.
PSEP. 1989. Recommended protocols for measuring selected environmental
variables in Puget Sound. Prepared for Puget Sound Estuary Program by PTI
Environmental Services, Bellevue, WA.
F-18
------- |