UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/2-80-031
PINE RIVER CONTAMINATION SURVEY
St. Louis, Michigan
(June 2-6, 1980)
October 1980
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Denver, Colorado
v>EPA
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/2-80-031
PINE RIVER CONTAMINATION SURVEY
St. Louis, Michigan
[June 2-6, 1980]
October 1980
Russell W. Forba
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Denver, Colorado
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CONTENTS
EXECUTIVE SUMMARY
INTRODUCTION 1
SUMMARY 2
CONCLUSIONS 2
RECOMMENDATION 3
TECHNICAL ANALYSIS
BACKGROUND 4
STUDY METHODS 6
ANALYTICAL RESULTS 11
TOXICITY AND HEALTH EFFECTS 14
EVALUATION OF FINDINGS 17
APPENDICES
A ELUTRIATION STUDY, PINE RIVER SEDIMENT
B SUMMARY OF ANALYTICAL METHODOLOGY
C TOXIC DATA COMPLETION METHODS
TABLES
1 River Water Sampling Stations (RWS) Locations 8
2 River Sediment Sampling (RSS) Locations 9
3 Sediment Core Descriptions 10
4 River Sediment Samples (RSS) 13
5 Priority Pollutants 15
FIGURE
River Sampling Locations . .
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EXECUTIVE SUMMARY
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INTRODUCTION
*
A survey conducted in 1974 by the Michigan Department of Natural Re-
sources (DNR) indicated severe contamination of the Pine River sediments in
**
the St. Louis, Michigan Reservoir and below the Velsicol Chemical Corpo-
ration (VCC) plant site. Several organic compounds were identified in the
study including: DDT and associated analogs (total . DDT: 293 mg/kg) ,
phthalates (19.5 mg/kg), polybrominated biphenyls (PBB : 9.0 mg/kg), and
oils (19,000 mg/kg)v. Flesh analyses of Pine River fish showed high levels
of PBB (0.87 mg/kg), polychlorinated biphenyls (PCB 1254: 1.99 mg/kg), and
total DDT (1.65 mg/kg). A Michigan Department of Public Health warning
against consumption of Pine River fish from St. Louis 60 km downstream to
the confluence with the Chippewa River was issued in November 1974, because
of PBB contamination. This warning was renewed in 1976 and still remains
in effect.
*
In a publication dated June 15, 1979, concerning the contaminated
Pine River the Michigan DNR recommended the following: (1) The St. Louis
dam should be maintained in sound condition and precautions taken in any
extensive drawdown to reduce the possibility of flushing polluted sediment
downstream in the Pine River. (2) Dredging in the St. Louis impoundment
and the Pine River directly below the impoundment should not be permitted
without approved disposal of contaminated dredge spoils and. precautions to
prevent contaminant flushing downstream.
In a meeting on February 27, 1980, between USEPA and Michigan DNR per-
sonnel concerning the Velsicol Chemical Corporation, St. Louis plant site,
the National Enforcement Investigations Center (NEIC) was requested
* "Biological Survey of the Pine River 1974 and 1978 Water Quality Divi-
sion" - Michigan Department of Natural Resources, June 15, 1979. Pub-
lication No. 4833-5159.
** Reservoir is adjacent to VCC plant site.
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by EPA Region V, Enforcement Division to conduct a limited sampling survey
of the Pine River. Objectives of this survey were to:
Document the contamination contributed to the Pine River by the
Velsicol Chemical Corporation;
Determine additional information needed to assess remedial action
for the contaminated Pine River.
SUMMARY
Thirteen sediment samples and 14 water samples were collected June 2
to 6, 1980 from the Pine River between the Cheeseman Road bridge and the
St. Louis Municipal wastewater treatment plant outfall to document contami-
nation of the Pine River.
Polybrominated byphenyl (PBB), hexabromobenzene (HBB), DDT and ana-
logs, and tris(2,3-dibromopropy1)phosphate (Tris) analyses, as well as, a
limited organic scan were conducted on collected samples. An elutriate
test [Appendix A] was conducted on two sediment samples (RSS-12 and RSS-13)
for DDT and analogs, PBB, and HBB [Appendix B].
The literature was searched to determine toxicityYandhealth effects
A /
of the substances identified in the samples.
Based on the pollutants found in the Pine River and sediments, addi-
tional information necessary to assess feasible remedial action is identi-
fied.
CONCLUSIONS
Sediment in the Pine River Reservoir at St. Louis, Michigan is con-
taminated by DDT and analogs (44,000 (jg/g max), PBB (270 ug/g max), HBB
(540 ug/g max), chlorobenzene (2,000 ug/g max), and oils. The DDT, PBB,
and HBB can be attributed directly to former Velsicol Chemical Corporation
plant site operations.
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The Pine River water does not contain measureable concentrations of,
11
HBB, PBB, and DDT. Elutriate testing under laboratory conditions showed
that these materials do not readily desorb from the sediments to the water.
However, Michigan DNR data shows that Pine River fish have accumulated DDT
and PBB above tolerance levels for human consumption.
Information needed before any remedial action can be taken includes
the following:
The vertical and areal distribution and magnitude of contaminated
sediments in the St. Louis Reservoir.
The extent and magnitude of DDT, PBB, and HBB contamination in
the Pine River sediments below the St. Louis Reservoir.
The current levels of contaminants in the Pine River biota.
Alternative remedial methods to contain or remove the contami-
nants.
The environmented impact of the remedial methods (including no
action).
Approved disposal areas for contaminated dredge spoils, if dredg-
ing is a viable alternative.
RECOMMENDATION
The Velsicol Chemical Corporation should determine the extent and mag-
nitude of contamination in the Pine River and Pine River Reservoir, and
propose alternative methods to EPA/DNR for protecting the Pine River en-
vironment.
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TECHNICAL ANALYSIS
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BACKGROUND
The Pfne River is located in central Michigan and flows eastward
160 km to the Saginaw Valley to join the Chippewa River at Midland. The
Chippewa River eventually discharges to Saginaw Bay (Lake Huron) at Bay
City, Michigan. The average flow of the river at Alma, Michigan (9 km
upstream of the St. Louis municipal dam) is 213 ftVsec. A maximum flow
rate of 4,400 ft3/sec, a 30-day low flow of 34 ft3/sec, and a 30-day high
flow of 1,580 ft3/sec have been recorded.
The watershed is mainly agricultural except for the population centers
of Alma and St. Louis located about 100 km from the Pine River headwaters.
The river is impounded at Alma and St. Louis. Major rehabilitation of the
St. Louis concrete gravity power dam, constructed in 1901, was started in
December 1977 and completed in May 1979. The dam is now used not only to
generate electricity but for flood control. The operator has a practical
reservoir level control of 6 ft ranging from a MSL elevation of 714 ft to
720 ft with an average operating elevation of 718 ft. The reservoir level
(MSL elevation) during the NEIC survey was approximately 718 ft.
Present or former wastewater dischargers to the Pine River include the
Velsicol Chemical Corporation, Total Petroleum, the Lobdell-Emery Manu-
facturing Company, Alma Products Company, and the City of St. Louis and the
City of Alma wastewater treatment plants.
Of particular interest in this study is the Velsicol Chemical Corpora-
tion, formerly the Michigan Chemical Company, which began as a bromine and
salt extraction facility obtaining brine from local wells. Over the years
the company has produced DDT (1945-1959), calcium chloride, magnesium com-
pounds, rare earth compounds, and more recently flame retardants and indus-
trial bromides including PBB (1970-1974), HBB (1971-1976), and Tris. In
September 1978, VCC ceased production at the site and subequently has been
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systematically removing materials and equipment from the property. Any
DDT, HBB, PBB, and Tris found in Pine River sediments can be attributed to
the VCC plant site operations since this site is the only location in the
Pine River watershed where these compounds were produced.
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STUDY METHODS
During the June 2 to 6, 1980 survey, NEIC personnel collected water
and sediment samples from the Pine River at St. Louis, Michigan [Figure 1].
Water samples were collected in 1-gallon glass containers using a battery
operated vacuum pump with teflon tubing [Table 1 describes sampling sta-
tions]. All water samples were iced and shipped by common air carrier to
the NEIC laboratory in Denver, Colorado. Sediment cores [Table 2] were
collected in 2 ft long, \-\ in. I.D., acetone rinsed, stainless steel core
tubes. The cores were secured with teflon-lined caps after sediment col-
lection. The sediment samples were iced and transported to the Denver lab-
oratory by NEIC personnel where the cores were extruded from the tubes and
logged [Table 3]. NEIC Chain-of-Custody procedures were followed through-
out the investigation.
DDT, PBB, and HBB analyses in addition to a limited organic scan were
conducted on all water samples and 10 sediment samples (RSS-1 to RSS-10).
The 10 sediment samples were also analyzed for Tris. Analytical procedures
and associated quality control information are described in Appendix B. An
elutriation test to determine the relative flux rates of PBB, HBB, and DDT
from sediment to water was conducted [Appendix A] on samples collected at
two stations (RSS-12 and RSS-13).
The published literature was searched to determine the toxicity and
health effects of the identified compounds. The Registry of Toxic Effects
of Chemical Substances (RTECS) and the Toxiology Information Online (TOX-
LINE) were the primary sources of information [Appendix C].
In view of the analytical and toxicology findings, additional studies
were proposed to assess alternative remedial actions to contain or remove
contaminated sediments from the Pine River.
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PAGE NOT
AVAILABLE
DIGITALLY
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8
Table 1
RIVER WATER SAMPLING STATIONS (RWS) LOCATIONS
PINE RIVER
St. Louis, Michigan
June 2 to 6, 1980
Sampling0
Station
Date of
Sampling
Time of
Sampling
Location Description
RWS-1
01
02
RWS-2
01
02
RWS-3
01
02
RWS-4
01
02
RWS-5
01
02
RWS-6
01
02
RWS-7
01
02
6/3/80
6/5/80
6/3/80
6/5/80
6/3/80
6/5/80
6/3/80
6/5/80
6/3/80
6/5/80
6/3/80
6/5/80
6/3/80
6/5/80
1040
1040
1110
1417
1120
1124
1142
1205
1130
1210
1115
1220
1400
1440
Midstream, 12 m north of Cheese-
man Road bridge.
5 m east of Devon Road in small
stream entering the Pine River
immediately south of the Route
46 bridge.
Midstream, 12 m north of Route
46 bridge.
6 m from the end of the VCC
plant site jetty and 70 m from
the north shoreline on a tran-
sect running northwestward from
the end of the jetty.
30 m from the end of the VCC
plant site jetty and 46 m from
the north shoreline on transect
running northwestward from the
end of the jetty.
52 m from end of the VCC plant
site jetty and 24 m from the
north shoreline on transect run-
ning northwestward from the end
of the jetty.
30 m below the City of St. Louis
municipal dam spillway, 3 m from
east shore of Pine River.
All River Water Samples (RWS) were collected at a 2-ft depth except RWS-2,
collected in a small stream at a 2-in depth and RWS-7 collected in the river
rapids below the St. Louis power dam at a 6-in depth.
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Table 2
RIVER SEDIMENT SAMPLING (RSS) LOCATIONS
PINE RIVER
St. Louis, Michigan
June 2 to 6, 1980
Sampling
Station
Date of
Sampling
Time of
Sampling
Location Description
RSS-1
RSS-2
RSS-3
RSS-4
RSS-5
RSS-6
RSS-7
RSS-8
RSS-9
RSS-10
RSS-11
RSS-12
RSS-13
6/2/80
6/2/80
6/2/80
6/2/80
6/2/80
6/2/80
6/2/80
6/2/80
6/2/80
6/3/80
6/5/80
6/5/80
6/5/80
1400
1428
1518
1540
1555
1615
1715
1655
1648
1420
1100
1145
1150
Mid-river on westward extention of
Hazel Avenue, southeast of City of
St. Louis water tower.
34 m east of the mouth of the stream
entering near the intersection of Route
46 and Devon Drive south of the Route
46 bridge.
200 m north of the Route 46 bridge,
36 m west of the VCC plant site shore-
line.
37 m west of the south water intake
pump.
25 m northwest of the point of land
protruding into the Pine River next
to the disposal pit in the rotary
kilns area of the VCC plant site.
31 m from the south shore and 107 m
from the north shore on a transect
running north-south across the Pine
River at the VCC plant site east
boundary.
49 m from the south shore and 89 m
from north shore on a transect run-
ning north-south across the Pine
River at the VCC plant site east
boundary.
92 m from the south shore and 46 m
from the north shore on a transect
running north-south across the Pine
River at the VCC plant site east
boundary.
112 m from the south shore and 26 m
from the north shore on a transect
running north-south across the Pine
River at the VCC plant site east
boundary.
Downstream of the St. Louis municipal
dam, 5 m from shore directly opposite
the City of St. Louis municipal waste-
water treatment plant outfall.
Same as RSS-1.
Same as RSS-5.
Same as RSS-7.
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10
Table 3
SEDIMENT CORE DESCRIPTIONS
PINE RIVER
St. Louis, Michigan
June 2 to 6, 1980
Station Water
Depth
RSS-1 3 ft
RSS-2 1 ft
RSS-3 7 ft
RSS-4 6 ft
RSS-5 4 ft
* t
RSS-6 4 ft
RSS-7 4 ft
RSS-8 5 ft
RSS-9 6 ft
RSS-10 1 ft
RSS-11 3 ft
RSS-12 4 ft
RSS-13 4 ft
Total
Core Core
Length Segments
7 in. 0-2.5 in.
2.5-5 in.
5-7 in.
12 in. 0-6 in.
6-8 in.
8-12 in.
7 in. 0-7 in.
10 in. 0-3 in
3-9 in.
9-10 in.
11 in. 0-4 in
4-4.5 in
4.5-5 in.
5-6 in.
6-6.5 in.
6.5-9 in.
9-11 in.
23 in. 1-3 in.
3-5 in. Aa
5-7.5 in.
7.5-8 in
8-13.5 in.
13.5-18 in. Ba
18-23 in.
10 in. 0-1.5 in.
1.5-2 in.
2 in.
3-6 in.
6-8 in.
8-10 in
8 in. 1-5 in.
5-8 in.
18 in. 1-9 in. A
. 9-18 in. B
4 in."
8 in. 0-8 in.
13-!$ in. 0-4 in.
4-6 in.
6-8.5 in
8.5-12 in.
12-13.5 in.
16 in 0-8.5 in.
8.5-10.5 in.
10.5-13.5 in
13.5-15 in.
15-16 in.
Core Description
Gray-brown sludge-like material iwth fine
sand.
Hard black layer of plant detritus.
Well sorted gray sand.
Gray- brown sandy silt.
Black sludge layer.
Gray-brown sandy silt.
Well sorted gray-brown medium-grained sand.
Dark gray silty sand.
Black sludge layer.
Plant detritus and silty sand.
Gray-brown fine-grained silt.
Banded gray-brown and white layers.
Black layer fine clay-sized particles.
White layer-fine material.
Gray-black hard deposit.
White-gray sludge
Brown to black plant detritus.
Black to gray-black sludge.
Green-brown sludge.
Black sludge
White layer fine-grained material.
Gray silt with white bands.
Gray silt.
Gray-brown mixed silt and organic detritus.
Dark brown fine silt.
Gray-white band.
Black (organic) sand.
Gray silt.
Black (organic) sand.
Organic detritus and medium-grained sand
grading upward into silt
Brown medium- grained sand quite odoriferous
(petroleum smell).
Dark gray-black fine-grained sand and silt.
Black chemical sludge material with whitish-
gray bands.
Gray sludge.
Top 4 inches of sediment gray sand.
Gray-black medium-grained well sorted sand.
Dark gray-brown silty sand.
Banded zone, gray white-gray
Black sludge and plant detritus.
Dark gray-brown silt.
Black plant detritus.
Black sludge grading downward into gray
silty sand.
Gray-brown poorly sorted silty sand with
plant detritus.
Gray-black sludge with plant detritus.
Gray fine-grained sand.
Red-brown plant detritus.
a A denotes top portion and B the bottom portion of cores which were divided into sec-
tions for chemical analysis (RSS-G and RSS-9).
b Core sample was not collected at RSS-10 because of thin sediment layer in this part
of the River. A sample was scooped out of the top 4 inches of the river bed using
an acetone rinsed steel shovel.
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11
ANALYTICAL RESULTS
Fourteen river water samples (RWS) and 13 sediment samples (RSS) were
collected by NEIC personnel during the June 2 to 5, 1979, Pine River sur-
vey. All water samples and 10 sediment samples (RSS-1 to RSS-10) were ana-
lyzed for PBB, HBB, DDT, its analogs, and subjected to a limited organic
scan. Sediment samples RSS-1 to RSS-10 were also analyzed for Tris. For
analysis, sediment samples RSS-6 and RSS-9 were each divided in two sec-
tions. Three sediment cores were collected for elutriation testing of PBB,
HBB, and DDT [Appendix A], although only two of the cores (RSS-12 and 13)
were used in the test (concentration of contaminants in the upstream sample
(RSS-11) were too low for testing).
HBB, PBB, or DDT analogs were not detected in any of the river water
samples. However, the RWS-6-01 and RWS-6-02 contained 3.5 ug/1 and
2.7 ug/1 methoxychlor, respectively. The origin of this compound in the
water samples is not known.
All of the cores were contaminated to some degree by DDT and its ana-
* DC
logs with four samples containing over 2,000 ug/g (RSS-6A , 6B , 7, 9A). A
maximum DDT concentration of 44,000 ug/g (4.4%) was found in RSS-6B. PBB
levels of over 70 ug/g were found in three samples (RSS-6A, 7, and 8) with
a maximum of 270 ug/g found in RSS-6A. HBB was found in concentration ex-
ceeding 20 ug/g in four samples (6A, 7, 8, and 9A) with a maximum of
540 ug/g found in RSS-6A. Tris was identified at quantifiable level (240
ug/g) in only one sediment sample (RSS-6A). Chlorobenzene was identified
in several samples (RSS-6A, 6B, 7, 8, and 9A) with a maximum concentration
of 2,000 ug/g found in RSS-6B. Several other organic contaminants were
identified including dichlorobenzene isomers, trichlorobenzene, 4,4-dichlo-
robenzophenone, and several hydrocarbons associated with petroleum com-
pounds. As can be seen, the most highly contaminated sediment samples were
* 'A1 designates top of sediment core sample; 'B1 designates bottom.
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12
found in cores collected in the lower end of the St. Louis Reservoir adja-
cent to the VCC plant site. Sediment cores collected upstream of the Route
46 bridge were relatively uncontaminated by DDT, HBB, and PBB.
Only one sediment sample was collected below the St. Louis Reservoir
dam and, although PBB, HBB,' and DDT were identified in this sample, they
were at much lower concentrations than in the reservoir sediment. Sediment
sample analysis results are shown on Table 4.
Elutriation testing under laboratory condition showed very little de-
sorption of DDT, PBB, or HBB from the reservoir sediments. A small amount
of p.p-DDT was detected in the water from the static phase of the testing.
However, the amounts desorbed was less than 0.01% of the amount present in
the sediment.
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Table 4
RIVER SEDIMENT SAMPLES (RSS)
ORGANIC* CONTENT (ug/g)
PINE RIVER, ST. LOUIS, MICHIGAN
June 2 to 6, 1980
Station Number RSS-1 RSS-2 RSS-3 RSS-4 RRS-5 RSS-6A RSS-6B RSS-7 RSS-8 RSS-9A RSS-9B RSS-10 Detection
Limits
Chemical
Total DOT
p.p'-DDT
o,p'_DDT
p.p'-DDE
p.p'-DDD
PBB
HBB
Tns
Chlorobenzene
1,2,4-trichlorobenzene
p-dichlorobenzene
o-dichlorobenzene
4 ,4-dichlorobenzophenone
Confirmed Total
Hydrocarbons
0 06
NDC
NO
0.02
0.04
ND
ND
ND
NO
ND
ND
ND
ND
ND
0.09
0.01
ND
0.03
0.05
ND
0.01
ND
ND
ND
ND
ND
ND
ND
0 045
0 02
0.01
0.005
0.01
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.37
ND
ND
0.09
0.28
0.38
0.08
ND
ND
ND
ND
ND
NO
7
2.62
0.40
0.20
0.62
1.4
0.29
0.13
ND
ND
ND
ND
ND
ND
ND
4,700
2,000
650
260
1,800
270
540
240
40
ND
ND
ND
7
8
44,000
24,000
. 17,000
1,300
1,400
ND
ND
ND
2,000
60
100
30
ND
ND
2,210
1,200
760
11
340
7 8
190
ND
4
ND
NO
ND
ND
ND
13.3
5.5
0.59
1.4
5.8
1.4
31
ND
2
ND
ND
ND
ND
20
3,400
1,900
1,300
80
110
ND
20
ND
200
ND
NO
ND
NO
10
0.01
ND
ND
0.01
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.80
0.41
0 07
0 06
0.26
0.03
0.30
no
ND
ND
ND
ND
ND
NDb
0.008
0.008
0 004
0.004
0.02
0.01
1
0 1
0.1
0.1
0.1
0.2
a The detection limits are as given except for RSS-6B where PBB = 48 ug/g, HBB = 240 ug/g, and Tris = 15 ug/g; and for RSS-9A where PBB = 5ug/g.
b Chlorostyrene isomers were identified by their excellent match with library spectra in RSS-6A, RSS-6B, RSS-7, and RSS-9A. However, these compounds
could not be confirmed or quantified because standards were not available.
c Not detected
d Additional hydrocarbon compounds associated with the presence of petroleum compounds were found in RSS-1, RSS-2, RSS-5, RSS-6A, RSS-8, RSS-9A, and
RSS-9B. No attempt was made to confirm or quantify most of these compounds due to lack of standard or chromatographically unresolved peaks result-
ing in poor spectra.
CO
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14
TOXICITY AND HEALTH EFFECTS
Thirteen halogenated compounds and numerous hydrocarbon compounds were
identified in sediment samples from the Pine River at St. Louis, Michigan.
Of the 13 compounds, 7 are listed as priority pollutants and 4 are listed
as hazardous substances under Section 311 of the Federal Water Pollution
Control Act [Table 5].
DDT and PBB, found in high concentrations, in the sediments have ex-
hibited numerous human and animal health effects. PBB ingestion by farm
animals in Michigan caused interference with reproduction and liver func-
tion, promotion of nervous disorders, teratogenic effects, and mortality of
some livestock. DDT is classified as a human carcinogen by the USEPA Can-
cer Assessment Group (CAG) and has exhibited central nervous system, neo-
plastic, and mutagenic effects on laboratory animals. DDT is extremely
toxic to aquatic invertebrates in concentrations as low as 0.12 ug/1 . DDT
also bioaccumulates readily. Studies by the National Water Quality Lab-
oratory in Duluth, Minnesota exhibited bioaccumulation of DDT in fish of
100,000 times. Because of this bioaccumulation effect up the food chain,
DDT can quickly accumulate in concentrations rendering fish unfit for human
consumption.
Tolerance limits for human consumption of PBB or DDT in fish have not
been established. However, tolerance limits in beef for PBB (0.3 mg/kg fat
weight basis) and DDT (5.0 mg/kg fat weight basis) have been established.
Maximum concentrations of PBB and DDT found in Pine River fish collected
during a 1974 Michigan DNR survey were 0.87 mg/kg and 1.67 mg/kg, respect-
ively (wet weight basis). These concentrations would equate to 19.6 mg/kg
* Eisler, R. Acute Toxicity of Organochlorine and Organophosphorus
Insecticides to Estuarine Fishes. Bureau of Sport Fisheries and
Wildlife, U.S. Department of Interior, Technical Report No. 16, 1970.
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15
Table 5
PRIORITY POLLUTANTS
PINE RIVER SEDIMENTS
ST. LOUIS, MICHIGAN
June 2 to 6, 1980
Chlorobenzene3
o-dichlorobenzenea
p-dichlorobenzene3
1,2,4-triChlorobenzene
l,l-dichloro-2,2-bis(p-chlorophenyl)ethane (ODD)
l,l-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE)
l,l,l-trichloro-2,2-bis(p-chlorophenyl)ethane(p,p'DDT)a"
a Hazardous substances as defined by Section 311 of Federal
Water Pollution Control Act.
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16
PBB and 37.2 mg/kg DDT fat weight basis employing the wet weight to fat
ratios used by Hesse and Powers.* Both PBB and DDT fat weight concentra-
tions in the Pine River fish collected by Michigan DNR are several times
greater than the tolerance limits for human consumption of beef.
Presently a warning against human consumption of Pine River fish from
St. Louis to the Chippewa River is in effect. This ban is unlikely to be
lifted in the near future because of the extremely high levels of PBB and
DDT in the Pine River fish.
* Hesse, J. L. and Power, R. H., Polybrominated Biphenyl (PBB) Con-
tamination of the Pine River, Gratiot, and Midland Counties, Michigan.
Environmental Health Perspectives, vol. 23, pp. 19-25.
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17
EVALUATION OF FINDINGS
Analyses of sediment samples collected by NEIC personnel showed high
levels of DDT, PBB, and HBB in the St. Louis Reservoir from the Route 46
bridge to the municipal dam. Elutriation testing under laboratory con-
ditions showed these major contaminants of concern are bound tightly with
the sediment and do not desorb and solubilize readily. Water sample anal-
yses showed levels of these contaminants to be below the detectable limit,
supporting the elutriation testing data. However, fish tissue analyses
performed by Michigan DNR show high levels (over the tolerance limits for
human consumption) of PBB and DDT evoking a ban against consumption of Pine
River fish.
If the contaminated sediments are left in the Pine River, levels of
PBB and DDT in fish may remain above tolerance limits for human consumption
for an unknown period of time. However, removal of sediment may re-entrain
sediment particles with the adsorbed contaminants and have an acutely toxic
impact on aquatic invertebrates downstream of St. Louis and may spread the
contaminants further down the watershed.
Because of the chronic bioaccumulation problem of DDT and PBB in the
Pine River fish, alternatives for removing or containing the contaminated
Pine River sediments should be studied. However, the environmental impact
of any sediment containment or removal method must be considered in de-
veloping any feasible remedial action.
-------
APPENDICES
A ELUTRIATION STUDY, PINE RIVER SEDIMENTS
B SUMMARY OF ANALYTICAL METHODOLOGY
C TOXIC DATA COMPILATION METHODS
-------
APPENDIX A
ELUTRIATION STUDY
PINE RIVER SEDIMENTS
-------
A-l
PINE RIVER SEDIMENTS
ST. COUIS, MICHIGAN
To determine the extent to which organic compounds leach from sediment
ueoSs media under both static and dynamic conditions. The static conditions
ueous meoia unuer uu ^ dynamic conditions will simulate leaching
from a river.
Test Format:. , Jhe tests will closely follow the Elutriate Test Procedure of the-
Corps of Engineers (attached). j j]
a) Background Testing. Three 25 g aliquots of sediment will be analyzed in
triplicate to determine the baseline concentration of organic compounds. A
solvent blank will also be analyzed with this set.
b) Dynamic Testing. A 25 gm aliquot 6f sample will be weighed into a 500 ml
Erlenmeyer flask and 100 ml of distilled water added. The temperature of the
-
solids concentration. After centrifugation, the supernatant will be fi'tere?
throuah a 0 45u membrane filter to yield the final solution for analysis. This
sSlStiSn will be extracted and analyzed according to the NEIC Procedure for
OroanohJlorlne Pesticides in Water. -This test will be done in triplicate. In
addition a blank! consisting of-'lOO ml of distilled water, will be analyzed.
The cJ°centrat?Sn 'of organic compounds which have eluted into the aqueous phase
will be reported. ^:.
rl Static Testing The statjc testing will differ from the dynamic testing
ail
cs-imniP* tn hp Tested Three sediment samples were collected for the leaching
"study RSS- n! RSS- i 2 . and RsVl 3 . 'These correspond in location to three samples
showed mainly alkanes (probably from; petroleum products) in RSS-1 and RSS-b.
RSS-7 cMtS ned alkanes, a small amount (c.a. 8 ng of chlorobenzene) and a sig-
5lficaSl?h1gher concentration of DDT-related compounds The leaching study will
bl done only for DDT-related compounds, since those" are.the most significant com-
oonents of the sample. Since the sentivity and precision of GC/MS i0s ess than
EC/GC twhnlqSe" Snly EC/GC will be used. RSS-11 , which shows virtually no con-
t mfnatfoS w?ll not b^ subjected to the leaching study The o her wo samp e s,
R^ -\? and RSS-13 will be tested. Twenty five grams of RSS-1Z will be usen cut
due to the much higher concentration of organics in RSS-7, only five grams of this
sample w?ll be used It is anticipated that these tests will take approximately
3 weeks to complete.
d) Analytical Methodology - See Methods for Organochlorine Pesticides in
Water and Sediment [Appenaix B].
-------
Table I. Results of Triplicate Analysis of Sediment Samples
p,p'-DDT
o.p'-DDT
p.p'-DDE
p,p'-DDD
HBB
PBB
RSS-11A
ug/g
NO
ND
0.005
0.007
ND
ND
RSS-11B
ug/g
ND
ND
0.008
ND
0.03
ND
RSS-11C
ug/g
ND
ND
0.008
ND
ND
ND
ND
ND
0.007
ND
0.03
ND
p.p'-DDT
o,p'-DDT
p,p'-DDE
p,p'-DDD
HBB
PBB
RSS-12A
ug/g
0.075
0.023
0.17
0.31
0.18
0.60
RSS-12B
ug/g
0.19
0.023
0.16
0.32
0.17
0.64
RSS-12C
ug/g
0.18
0.022
0.17
0.27
0.16
0.51
0.15
0.023
0.17
0.30
0.17
0.58
p,p'-DDT
o,p'-DDT
p,p'-DDE
p,p'-DDD
HBB
PBB
RS5-13A
ug/g
8.0X10°
RSS-13B
ug/g
7.1X10"
RSS-13C
uq/g
7.0X10?
Avg.
7.4X10:
\J \J/\ 1 v»O
4.9X10
380
440
50
22
t i »» > *^ -j
4.4X10"5
320
490
51
21
5.9X10J
410
500
83
17
5.1X10
370
480
61
20
-------
PINE RIVER SEDIMENTS
ST. COUIS, MICHIGAN
: To determine the extent to which organic compounds leach fjon sediment
from a river.
Test Format: The tests will closely follow the Elutriate Test Procedure of the
Corps of Engineers (attached).
a) Background Testing. Three 25 g aliquots of sediment will be analyzed in
triplicate to determine the baseline concentration of organic compounds. A
solvent blank will also be analyzed with this set.
b) Dynamic Testing. A 25 gm aliquot of sample will be weighed into a 500 ml
a 0 45u membrane filter to yield the final solution for analysis,
sn will be extracted and analyzed according to the NEIC Procedure for
Oraanohclorlne Pesticides in Water. This test will be done in triplicate. In
addition a blank, consisting of 100 ml of distilled water, will be analyzed.
The conc^rat^Sn of organic compounds which have eluted into the aqueous phase
will be reported.
cl Static Testing. The static testing will differ from the dynamic testing
ss ss
^
^
RSS-7 contained a Kanes, a smaii amuum- \<-.». ^ » - ~ ~-» ...m
nificaStly higher concentration of DDT-related compounds. The leaching study will
£e d"e only for DDT-related compounds, since those are the most significant com-
oonents of the sample. Since the sentivity and precision of GC/MS is ess than
EC/GC tecLiSues Snly EC/GC will be used. RSS-11, whichjhows, virtual y no con-
this
HUP tn the much hiaher concenurdLiun ui uryam«-o m >^^- > "^ - a---_ ._lt,
sample win be used It is anticipated that these tests will take approximately
3 weeks to complete.
d) Analytical Methodology - See Methods for Organochlorine Pesticides in
Water and Sediment [Appendix B].
-------
RSS-12A
ug/g
0.075
0.023
0.17
0.31
0.18
0.60
RSS-12B
ug/g
0.19
0.023
0.16
0.32
0.17
0.64
RSS-12C
ug/g
0.18
0.022
0.17
0.27
0.16
0.51
Table I. Results of Triplicate Analysis of Sediment Samples
RSS-11A RSS-11B RSS-11C
uq/q uq/g ug/g
p,p'-DDT ND ND ND ND
o p'-DDT ND ND ND ND
p.S'-DDE 0.005 0.008 0.008 0.007
BirDD° °r o.s§ s
pBB ND ND ND ND
Avg.
p,p'-DDT 0.075 0.19 0.18 0.15
S:?
0.58
RSS-13A RSS-13B RSS-13C
ug/g ug/g ug/g Avg.
np'-DDT 8.0X10^ 7.1X10| 7.0X10^ 7.4X10J
Sp'-DDT 4.9X103 4.4X103 5.9X103 5 1X10J
D D'-DDE 380 320 410 370
S;g'-DBD 440 490 500 480
HBB 50 51 83 61
PBB 22 21 17 20
-------
A-3
Table II. Results of Dynamic Leaching Test
RSS-12A RSS-12B RSS-12C
leachate leachate leachate
ug ug ug
p.p'-DDT ND ND ND
o.p'-DDT ND ND ND
p.p'-DDE ND ND ND
p,p'-DDD ND ND ND
HBB ND ND ND
PBB ND ND ND
RSS-13A RSS-13B RSS-13C
leachate leachate leachate
ug ug ug
p,p'-DDT ND ND ND
o.p'-DDT ND ND ND
p,p'-DDE ND ND - ND
p,p'-DDD ND ND ND
HBB ND ND ND
PBB ND ND ND
-------
A-4
Table III. Results of Static Leaching Test
"RSS-12A RSS-12B RSS-12C
leachate leachate leachate
ug ug ug
p,p'-DDT ND NO ND
o.p'-DDT ND ND ND
p,p'-DDE ND ND ND
p.p'-DDD ND ND ND
HBB ND ND ND
PBB ' ND ND ND
RSS-13A RSS-13B RSS-13C
leachate leachate leachate
ug ug ug
p,p'-DDT 0.4 ND 1.5
o,p'-DDT ND ND ND
p,p'-DDE ND ND ND
p.p'-DDD ND ND ND
HBB ND ND ND
PBB ND ND ND
-------
A-5
Table IV. Detection Limits
p,p'-DDT
o.p'-DDT
p,p'-DDE
p,p'-DDD
HBB
PBB
Sediment
ug/g
0.008
0.008
0.004
0.004
0.01
0.02
Leachate
ug
0.2
0.1
0.1
0.1
0.2
1.0
-------
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-------
A-7
APPENDIX A: ELUTRIATE TEST PROCEDURE
Number of Samples
1. The number of sediment and water samples to be taken from the
dredging site for replicate analyses-'must be carefully considered be-
cause of the extremely heterogeneous nature of samples of this type.
Also, the necessary number of replicate analyses of composite disposal
i
site water samples must be carefully considered because of the compara-
tively low background concentrations of some constituents in samples of
this type.
Sample Collection and Preservation
Water
2. Collection should be made with appropriate noncontaminating
water-sampling devices. Collect a 2-gal representative water sample at
both the dredging site and the disposal site. If the samples are to be
analyzed for trace organics or for a large number of constituents, a
proportionately larger initial sample should be collected. The samples
must be stored in plastic bottles or in glass storage ccuxtainers if
trace organic analyses are to be performed on the samples.
3. The samples should be stored immediately at 2 to 4°C. The
samples should never be frozen. The storage period should be as short
as possible to minimize changes in the characteristics of the water.
It is recommended that samples be processed within one week of col-
lection.
Al
-------
A-8
Sediment
A. Sediment samples from the dredging site should be taken with
a grab sampler or corer in such a manner to ensure that their character-
istics are representative of the proposed dredging site. - Approximately
1 gal of sediment should be collected; if the samples are to be analyzed
for trace organics or a large number of constituents, a proportionately
larger initial sample should .be collected. The samples should be placed
in airtight plastic bags or jars or in glass storage containers if trace
organic analyses are to be performed on the samples. Care should be
taken to ensure that the containers are completely filled with sample
and that air bubbles are not trapped in the container.
5. The samples should be stored immediately at 2 to A°C. Th£
«.
samples must never be frozen. The storage period should be as short as
possible to minimize changes in the characteristics of the sediment. It
is recommended that samples be processed within one week of collection.
Apparatus
6. The following items are required. Prior to use, all glassware,
filtration equipment, and filters should be washed with 5 to 10 percent
(or stronger) hydrochloric acid (HC1) and then rinsed thoroughly with
deionized water.
a. Acid-rinsed plastic bottles for collection of water samples,
b. Plastic jars or bags ("Whirl-Pak," plastic freezer con-
tainers, etc.) for collecting dredged or fill material samples.
c. Laboratory shaker capable of shaking 2-litre flasks at
A2
-------
A-9
approximately 100 excursions/min. Box type or wrist-action shakers are
acceptable.
d. Several 1-litre graduated cylinders.
e. Large (15 cm) powder funnels.
f. Several 2-litre- large-mouth graduated Erlenmeyer flasks.
g. Vacuum ^r pressure filtration equipment, including vacuum
pump or compressed air source, and an appropriate filter holder capable
of accomodating 47, 105, or 155-mm-diameter filters.
h. Membrane filters with a 0.45p pore-size diameter should
be used. The filters should be soaked in 5M HC1 for at least 2 hr prior
to use.
i. Centrifuge capable of handling six 1- or 0.5-litre centri-
fuge bottles at 3,000 to 5,000 rpm. International Model K or Sorval
Super Speed are acceptable models.
j. Wide-mouth, 1-gal capacity glass jars with Teflon-lined
screw-top lids should be used for sample containers when samples are to
be analyzed for trace organics. (It may be necessary to purchase jars
and Teflon sheets separately; in which case, the Teflon lid liners may
be prepared by the laboratory, personnel.)
Test Procedure
7. The stepwise test procedure is given below.
a. Subsample a minimum volume of 1 litre each of dredging
site and disposal site water. If it is known in advance that a large
number of measurements are to be performed, the size of each subsample
A3
-------
A-10
should be increased to meet the anticipated needs.
b. Filter an appropriate portion of the disposal site water
through an acid-soaked 0.45y pore-size membrane filter that has been
prerinsed with approximately 100 ml of disposal site water. The filtrate
from the rinsing procedure should be discarded.
c. Analyze-the filtered disposal site sample for' the major
121
constituents as soon as possible using acceptable procedures.
If necessary, the samples may be stored at 2 to 4°C after preservatives
have been added. The filtered water samples may be frozen with no
apparent destruction of sample integrity.
d. Repeat steps a, b, and c with dredging site water.
e. Subsample approximately 1 litre of sediment from the well-
mixed original sample. Mix the sediments and unfiltered dredging site
water in a volumetric sediment-to-water ratio of 1:4 at room tempera-
ture (22 + 2 C) . This is'best done by the method of"volumetric dis-
4
placement. One hundred ml of unfiltered dredging site water is placed
into a graduated Erlenraeyer flask. The sediment subsample is then
carefully added via a powder funnel to obtain a total volume of 300 ml.
(A 200-ml volume of sediment will now be in the flask.) The flask is
then filled to the 1000-ml mark with unfiltered dredging "site water,
which produces a slurry with a final ratio of one volume sediment to
o
four volumes water. If the volume of water required for analysis
exceeds 700 to 800 ml, the initial volumes should be proportionately
increased (e.g. , mix 400 ml of sediment and 1600 ml disposal site
water). Alternately, several 1-litre dredged material/dredging site
A4
-------
A-n
water slurries may be prepared as outlined above and the filtrates
combined to provide sufficient water for analysis.
f. (1) Cap the flask tightly with a noncontaminating stoppper
and shake vigorously on an automatic shaker at about 100 excursions per
min for 30 rain. A polyfilm-covered rubber stopper is acceptable for
minimum contamination.
(2) During the mixing step given in paragraph 5f(l), the
oxygen demand of the dredged material may cause the dissolved oxygen
concentration in the elutriate to be reduced to zero. This change can
alter the release of chemical contaminants from dredged material to the
disposal site water and reduce the reproducibility of the elutriate
test. If it is known that anoxic conditions (zero dissolved oxygen)
»
will not occur at the disposal site or if reproducibility of the elu-
triate test is a potential problem, the mixing may be accomplished by
using the compressed air mixing procedure instead of the mechanical
mixing described in paragraph 5f(l). After preparation of the elutriate
slurry, an air-diffuser tube is inserted almost to the bottom of the
flask. Compressed air should be passed through a deionized water trap
and then through the diffuser tube and the slurry. The flow rate
should be adjusted to agitate the mixture vigorously for 30 min. In
addition, the flasks should be stirred manually at 10-min intervals to
ensure complete mixing.
g. After shaking or mixing with air, allow the suspension to
settle for 1 hr.
h. After settling, carefully decant the supernatant into
A5
-------
A-12
appropriate centrifuge bottles and then centrifuge. The time and rpm's
during centrifiguration should be selected to reduce the suspended
solids concentration substantially and therefore shorten the final
filtration process. After centrifugation, vacuum or pressure filter
approximately 100 ml of sample through a 0.45 u membrane filter and
discard the filtrate. Filter the remainder of the sample to give a
clear final solution (the standard elutriate) and store at 4°C in a
clean noncontaminating container in the dark.
i. Analyze as soon as possible for major constituents using
123
accepted procedures. ' '
j. Prepare and test the elutriate in triplicate and report
the average concentration of the three replicates as the concentration
in the standard elutriate.
A6
-------
ftfrc.il/uif- IT
-Kivt'll S7.
A-13
Table I. Results of Triplicate Analysis of Sediment Samples
RSS-11A RSS-11B RSS-11C
ug/g ug/g ug/g Avg.
p,p'-DDT ND ND ND ND
o n'-DDT ND ND ND ND
p p'-DDE 0.005 0.008 0.008 0.007
N
pBB
.
ND ND ND ND
RSS-12A
ug/g
0.075
0.023
0.17
0.31
0.18
0.60
RSS-12B
ug/g
0.19
0.023
0.16
0.32
0.17
0.64
RSS-12C
ug/g
0.18
0.022
0.17
0.27
0.16
0.51
Avg.
p.p'-DDT 0.075 O.iy u.10 0.15
op'-DDT 0.023 0.023 0.022 0.023
pp'-DDE 0.17 0.16 0.17 0.17
5:!?
pBB n Kn n. . 0.58
RSS-13A RSS-13B RSS-13C
ug/g ug/g ug/g Avg.
p,p'-DDT 8.0X10:? 7.1X10^ 7.0X10:* 7.4X10^
dp'-DDT 4.9X103 4.4X103 5.9X103 5.1X10J
PP'-DDE 380 320 410 370
p p'-DDD 440 490 500 480
HBB 50 51 83 61
PBB 22 21 17 20
'o
-------
A
Table II. Results of Dynamic Leaching Test
RSS-12A RSS-12B RSS-12C
leachate leachate leachate
ug ug tig
p,p'-DDT ND ND ND
o,p'-DDT ND ND ND
p,p'-DDE ND ND ND
p.p'-DDD ND ND ND
HBB ND ND ND
PBB ND ND ND
RSS-13A RSS-13B RSS-13C
leachate leachate leachate
ug ug ug
p.p'-DDT ND ND ND
0,p'-DDT ND ND ND
p.p'-DDE ND ND ND
p.p'-DDD ND ND ND
HBB ND ND ND
PBB ND ND ND
-------
Table III. Results of Static Leaching Test
RSS-12A RSS-12B RSS-12C
leachate leachate leachate
ug ug ug
p,p'-DDT ND ND ND
o.p'-DDT ND ND ND
p.p'-DDE ND ND ND
p,p'-DDD ND ND ND
HBB ND ND ND
PBB ND ND ND
RSS-13A RSS-13B RSS-13C
leachate leachate leachate
ug ug ug
p,p'-DDT 0.4 ND 1.5
o.p'-DDT ND ND ND
p.p'-DDE ND ND ND
p.p'-DDD ND ND ND
HBB ND ND ND
PBB ND ND ND
-------
June
Table IV. Detection Limits
p,p'-DDT
o.p'-DDT
p.p'-DDE
p,p'-DDD
HBB
PBB
Sediment
ug/g
0.008
0.008
0.004
0.004
0.01
0.02
Leachate
ug
0.2
0.1
0.1
0.1
0.2
1.0
-------
APPENDIX B
SUMMARY OF ANALYTICAL METHODOLOGY
-------
B-l
SUMMARY OF ANALYTICAL METHODOLOGY
I. DOT'S, DDE, ODD, HBB, PBB
A. Water Samples
SampTes were serially extracted with 15% CHpCWhexane at a neutral
pH. The extracts were dried and filtered by passing through Na^SO-
and concentrated to 10 ml in a Kuderna-Danish (K-D) apparatus. The
extracts were screened and quantitated using electron capture gas
chromatography. If necessary, the extracts were cleaned up before
quantisation using a alumina adsorption column. The procedure is
described in the NEIC "Method for Organochlorine Pesticides in
Environmental Water Samples."
B. Sediment Samples
Sediment samples were sieved through a 2 mm mesh sieve. Sieved
samples were serially extracted with acetone and hexane and the
combined extracts dried over Na^SO, and concentrated to 10 ml in a
K-D. The extracts were screened arid quantitated using electron
capture gas chromatography. If necessary, the extracts were cleaned
up before quantitation using an alumina column. The procedure is
described in the NEIC "Method for Organochlorine Pesticides in Soil
and Sediment."
II. TRIS
A. Sediments
Samples were serially extracted with acetone. The acetone extract
was combined with a large volume of water and the TRIS extracted
with CHgClp- The extracts were dried and filtered by passing
through NapSO. and then exchanged into hexane and concentrated to
10 ml in a K-D. The extract was cleaned up using a Florisil adsorption
column, exchanged into methanol and analyzed by HPLC. The procedure
is described in the NEIC "Method for TRIS (2,3-dibromopropyl)
phosphate in Soil and Sediments."
III. ORGANIC CHARACTERIZATION AND PRIORITY POLLUTANT PROCEDURES
A. Sample Preparation
1. Water Samples - Extractables:
Samples were extracted with CHpClp at a neutral pH. The extracts
were dried and concentrated with the addition of acetone to 1 ml.
The resultant extract concentrates were subjected to GC and GC/MS
analyses. This procedure is in the method "Neutral Extraction
Technique for Organics Analysis, NEIC-March 1979." To monitor the
general performance of the method, each sample was spiked with
300 pg/1 of a, a, a-Trifluoro-m-cresol and 100 ng/1 of D,0-Biphenyl.
These "surrogate" spike recoveries were monitored to show the
overall efficiency of the preparation procedures.
-------
B-2
2. Sediment Samples - Extractables:
Soil samples were sieved through a 2 mm mesh sieve. Sieved samples
were repeatedly extracted with acetone and hexane. The extracts
were dried over Na^SO, and concentrated to 10 ml in a K-D. The
extraction method is in "Method for Organochlorine Pesticides in
Soil and Sediment."
B. Analytical Procedures
1. Extractable Organics:
An aliquot of sample extracts, in acetone, was injected into a gas
chromatographic column. The eluting components were detected by a
mass spectrometer. Identifications were made by comparison of the
sample mass spectra to the mass spectra of pure compounds within
specific GC retention-time windows. Quantification was by measurement
of the area of specific ion fragments of each component. Retention
time and response references were made to the internal standard.
The detailed procedure is in "Base/Neutrals, Acids, and Pesticides -
Method 625", Federal Register, Monday, December 3, 1979. Starting
at section 11.
2. Identification of Unknowns:
The samples contained many nonpriority pollutant components. The
mass spectra of these compounds were compared to the EPA/NIH/NBS
25000 spectra library. The best "hits" were determined by computer
spectra matching programs and they were manually evaluated to
determine the best probable identification. Where standards were
available, they were analyzed under identical conditions and the
suspected components verified or denied. If no standard was available,
the best "hits" were reported as possibly present.
-------
B-3
METHOD FOR ORGANOCHLORINE PESTICIDES IN ENVIRONMENTAL WATER SAMPLES
SCOPE AND APPLICATION
1.1 This method is an adaptation of that described in ref. 1
and covers the determination of various organochlorine pesti-
cides, including some pesticidal degradation products and
related compounds in industrial effluents. Such compounds
are composed of carbon, hydrogen, and chlorine, but may
also contain oxygen, sulfur, phosphorus, nitrogen or other
halogens.
1.2 The following compounds may be-determined individually by
this method with a sensitivity of at least 1 ug/liter:
BHC, lindane, heptachlor, aldrin, heptachlor epoxide, di-
eldrin, endrin, DDE, ODD, DDT, methoxychlor, endosulfan,
mi rex, trifluralin, endrin aldehyde, and endosulfan sulfate.
Under favorable circumstances, Strobane, toxaphene, chlordane
(tech) and others may also be determined. The usefulness
of the method for other specific pesticides must be demon-
strated by the analyst before any attempt is made to apply
it to sample analysis.
1.3 When organochlorine pesticides exist as complex mixtures,
the individual compounds may be difficult to distinguish.
High, low, or otherwise unreliable results may be obtained
through misiclenti fication and/or one compound obscuring
another of lesser concentration. Provisions incorporated
in this method are intended to minimize the occurrence of
such interferences.
-------
B-4
2. SUMMARY
2.1 The method offers several analytical alternatives, dependent
on the analyst's assessment of the nature and extent of
interferences and/or the complexity of the pesticide mixtures
found. Specifically, the procedure describes the use of an
effective co-solvent for efficient sample extraction; provides,
through use of column chromatography and liquid-liquid parti-
tion, methods for elimination of non-pesticide interferences
and the pre-separation of pesticide mixtures. Identification
is made by selective gas chromatographic separations and
may be corroborated through the use of two or more unlike
columns. Detection and measurement is accomplished by elec-
tron capture, microcoulometric or electrolytic conductivity
gas chromatography. Results are reported in rnicrograms per
1 Her.
2.2 This method is recommended for use only by experienced pesti-
cide analysts or under the close supervision of such qualified
persons.
3. INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing
hardware may yield discrete artifacts and/or elevated base-
lines causing misinterpretation of gas chromatograms^. All
of these materials must be demonstrated to be free from
interferences under the conditions of the analysis. Speci-
fic selection of reagents and purification of solvents by
distillation in all-glass systems may be required.
3.2 Tho interferences in industrial effluents are high and varied-
and often pose great difficulty in obtaining accurate and
precise measurements of organochlorine pesticides. Sample
clean-up procedures are generally required and may result
-------
B-5
in the loss of certain organochlorine pesticides. Therefore,
great care should be exercised in the selection and use of
methods for eliminating or minimizing interferences. It is
not possible to describe procedures for overcoming all of
the interferences that may be encountered in industrial
effluents.
3.3 Polychlorinated Biphenyls (PCB's) - Special attention is
called to industrial plasticizers and hydraulic fluids such
as the PCB's which are a potential source of interference
in pesticide analysis. The presence of PCB's is indicated
by a large number of partially resolved or unresolved peaks
which may occur throughout the entire chromatogram. Parti-
cularly severe PCB interference will require special separa-
tion procedures (2,3).
3.4 Phthalate Esters - These compounds, widely used a plasticizers,
respond to the electron capture detector and are a source of
interference in the determination of organochlorine pesticides
using this detector. Water leaches these materials from
plastics, such as polyethylene bottles and tygon tubing.
The presence of phthalate esters is implicated in samples
that respond to electron capture but not to the microcoulo-
metric or electrolytic conductivity halogen detectors or to
the flame photometric detector.
3.5 Organophosphorus Pesticides - A number of organophosphorus
pesticides, such as those containing a nitro group, e.g.,
parathion, also respond to the electron capture detector
and may intefere with the determination of the organochlorine
pesticides. Such compounds can be identified by their res-
ponse to the alkali flame ionization or flame photometric
detectors.
3.6 Anaerobic extracts may contain gross interference due to
the presence of sulfur compounds. This interference can be
removed by reacting the extract with a small amount of metal-
-------
B-6
lie mercury to precipitate the sulfur compounds. After
alumina column cleanup, the sulfur interferences are con-
fined to the first fraction, and only this fraction need be
reacted with metallic mercury (4).
4. APPARATUS AND MATERIALS
4.1 Gas Chromatograph - Equipped with glass lined injection
port.
4.2 Detector Options:
4.2.1 Electron Capture - Radioactive (tritium or nickel
63)
4.2.2 Microcoulometric Titration
4.2.3 Electrolytic Conductivity
4.3 Recorder - Potentiometric strip chart (10 in) compatible
with the detector.
4.4 Gas Chromatographic Column Materials:
4.4.1 Tubing - Pyrex (180 cm long x 4 mm ID)
4.4.2 Glass Wool - Silanized
4.4.3 Solid Support - Gas-Chrom Q (60-80 mesh)
4.4.4 Liquid Phases - Expressed as Weight percent coated
on solid support.
4.4.4.1 OV-101, 3%
4.4.4.2 OV-210, 5%
4.4.4.3 OV-17, 3% or any column yielding equiva-
lent separation
4.5 Kuderna-Danish (K-D) Glassware (Kontes)
4.5.1. Snydcr Column - three ball (macro)
4.5.2 Evaporative Flasks - 500 ml
4.5.3 Receiver Ampuls - 10 ml, graduated
4.6 Chromatographic Column - pyrex (approximately 340 mm long
x 20 mm ID) with coarse fritted place on bottom (Kontes
-------
B-7
K422000) modified to include a reservoir for 50 ml of solvent
and fitted with a ball joint.
4.7 Micro Syringes - 10, 25, 50 and 100 pi
4.8 Separatory Funnels - 125 ml, 1000 ml and 2000 ml with
Teflon stopcock.
4.9 Graduated cylinders - 100, 250 and 1000 ml.
4.10 Florisil - PR Grade (60-100 mesh); purchase activated at
1250 F and store in dark in glass containers with glass
stoppers or foil-lined screw caps. Before use, activate
each batch overnight at 130°C in foil-covered glass container.
4.11 Alumina, Basic, Brockman Activity I; 80-200 mesh. The amount
of water needed for proper deactivation is determined by
the elution pattern for a technical chlordane standard. A
1.75% deactivation is usually sufficient to yield the correct
elution pattern (see Table IV)'.
5. REAGENTS, SOLVENTS, AND STANDARDS
5.1 Ferrous Sulfate - (ACS) 30% solution in distilled water.
5.2 Potassium Iodide - (ACS) 10% solution in distilled water.
5.3 Sodium Chloride - (ACS) Saturated solution in distilled
water (pre-rinse MaCl with hexane).
5.4 Sodium Hydroxide - (ACS) 10 N in distilled water.
5.5 Sodium Sulfate - (ACS) Granular, anhydrous (conditioned at
300 °C for 4 hours).
5.6 Sulfuric Acid - (ACS) Mix equal volumes of cone. H2S04 with
distilled water.
5.7 Diethyl Ether - Nanogro.de, redistilled in glass, if necessary.
5.7.1 Must contain 2% alcohol and be free of peroxides
by following test: To 10 ml of ether in glass-stop-
pered cylinder previously rinsed with ether, add
one ml of freshly prepared 10% KI solution. Shake
-------
B-8
and let stand one minute. No yellow color should
be observed in either layer. Alternately the
peroxide test may be done with EM Quant Ether
Peroxide - Test stacks. The peroxide level must
be less than 1.5 ppm.
5.7.2 Decompose either peroxides by adding 40 g of 30%
ferrous sulfate solution to each liter of solvent.
CAUTION: Reaction may be vigorous if the solvent
contains a high concentration of peroxides.
5.7.3 Distill deperoxidized ether in glass and add 2%
ethanol.
5.8 Acetonitrile, Hexane, Methylene Chloride, Petroleum Ether
(boiling range 30-60°C) - nanograde,redistill in glass if
necessary.
5.9 Pesticide Standards - Reference grade: sources
5.9.1 Quality Assurance Section, Environmental Toxi-
cology Division, EPA, HERL, Research Traingle
Park, N.C. 27711, MD-69
5.9.2 Pesticides Reference Standards Section, Bldg 048
Range 3 and 3rd Street, BARC, West, Beltsville,
MO 20705
5.9.3 Nanogens, P.O. Box 1025, Watsonville, CA 95076
6. CALIBRATION
6.1 Gas chromatographic operating conditions are considered
acceptable if a Standard Mix B elutes from the GC with
correct retention times and sensitivity. Standard Mix B
consists of 0.025 pg/ml lindone, 0.050 jjg/ml heptachlor,
0.075 |irj/ml aldrin, 0.100 |ig/ml y chlordane, 0.125 (.ig/ml
dieldrin, 0.250 |ig/ml o, p'-DDT and 0.250 |jg/inl p,p'-DDT
-------
B-9
in hexane. The chromatographic conditions chosen should
yield at least 30% full-scale deflection for all of the
components of Std. Mix B (see Figures 1 through 3). For
all quantitative measurements, the detector must be operated
within its linear response range and the detector noise
level should be less than 2% of full-scale.
6.2 Standards are injected frequently as a check on the stability
of operating conditions. Gas chromatograms of several stan-
dard pesticides are shown in Figures 1, 2 and 3 and provide
reference operating conditions for recommended columns.
6.3 The elution order and retention ratios of various organo-
chlorine pesticides are provided in Table I, as a guide.
The sensitivity of these compounds is given in Table II.
7. QUALITY CONTROL
7.1 Replicate and spiked sample analyses are recommended as
quality control checks. At a minimum, one replicate and
one spiked analysis should be included per 20 sample anal-
yses. If less than 20 sample analyses are required, one
duplicate and one spiked analysis should still be included.
Data for recovery of specific organochlorine pesticides
from water is given in Table III.
7.2 In addition, one method blank is required per 20 sample
analyses. If less than 20 sample analyses are required,
one method blank should still be included.
7.3 One sample should be injected in replicate into the gas
chromatograph per 20 samples analyzed. If less than 20
sample analyses are required, a replicate GC injection
should still be made.
-------
B-10
8. SAMPLE PREPARATION
8.1 Shake the sample if suspended matter is present and adjust pH
to near neutral (pH 6.5-7.5) with 50% sulfuric acid or 10 N
sodium hydroxide.
8.2 Quantitatively transfer 1 liter of sample into a two-liter
separatory funnel. Less sample may be analyzed if necessary,
with the realization that detection limits will be affected.
9. EXTRACTION
9.1 Add 60 ml of 15% methylene chloride in hexane (v:v) to the
sample in the separatory funnel and shake vigorously for two
minutes.
9.2 Allow the mixed solvent to separate from the sample, then
draw the water into a one-liter beaker. Pour the organic
layer into a 250 ml beaker. Return the water phase to the
separatory funnel. Rinse the one-liter beaker with a second
60 ml volume of solvent; add the solvent to the separatory
funnel and complete the extraction procedure a second time.
Perform a third extraction in the same manner.
9.3 Transfer the combined solvent extract to a 500 ml Kuderna-
Danish evaporative concentrator by passing it through a
funnel plugged with glass wool and filled with sodium sulfate
which has been prewashed with hexane.
9.4 Concentrate the extract to 10 ml in the K-D evaporator on a
hot water bath.
9.5 Analyze by gas chromatography unless a need for cleanup is
indicated (see Section 10).
-------
B-ll
10. CLEAN-UP AMD SEPARATION PROCEDURES
10.1 Interferences in the form of distinct peaks and/or high
background in the initial gas chromatographic analysis, as
well as the physical characteristics of the extract (color,
cloudiness, viscosity) and background knowledge of the sam-
ple will indicate whether clean-up is required. When these
interfere with measurement of the pesticides, or affect
column life or detector sensitivity, proceed as directed
below.
10.2 Acetonitrile Partition - This procedure is used to isolate
fats and oils from the sample extracts. It should be noted
that not all pesticides are quantitatively recovered by
this procedure. The analyst must be aware of this and demon-
strate the efficiency of the partitioning for specific pesti-
cides.
10.2.1 Quantitatively transfer the previously concentrated
extract to a 125 ml separatory funnel with enough
hexane to bring the final volume to 15 ml. Extract
the sample four times by shaking vigorously for
one minute with 30 ml portions of hexane-saturated
acetonitrile.
10.2.2 Combine and transfer the acetonitrile phases to a
one-liter separatory funnel and add 650 ml of dis-
tilled water and 40 ml of saturated sodium chloride
solution. Mix throughly for 30-45 seconds. Extract
with two 100 ml portions of hexane by vigorously
shaking about 15 seconds.
10.2.3 Combine the hexane extracts in a one-liter separa-
tory funnel and wash with two 100 ml portions of
distilled water. Discard the water layer and
pour the hexane layer into a 500 ml K-D flask
-------
B-12
10
through a funnel plugged with glass wool and
filled with sodium sulfate which has been pre-
washed with hexane. Rinse the separatory funnel
and column with three 10 ml portion of hexane.
10.2.4 Concentrate the extracts to 10 ml in the K-D eva-
porator in a hot water bath.
10.2.5 Analyze by gas chromatography unless a need for
further clean-up is indicated.
10.3 Florisil Column Adsorption Chromatography
10.3.1 Adjust the sample extract volume to 10 ml with
hexane.
10.3.2 Prepare a 20 mm I.D. column that contains 4 inches
(after settling) of activated Florisil topped
with 0.5 inch anhydrous sodium sulfate.
10.3.3 Pre-elute the column-with 50-60 ml of petroleum
ether. Just prior to exposure of the sulfate
layer to air, quantitatively transfer the sample
extract onto the column. Just prior to exposure
of the sodium sulfate layer to air, add the first
eluting solvent, 200 ml of 6% ethyl ether in petro-
leum ether. Collect the eluate in a 250 ml beaker.
Perform the second elution with 200 ml of 15%
ethyl ether in petroleum ether, the third elution
with 200 ml of 50% ethyl ether-petroleum ether,
and the fourth elution with 200 ml fo 100% ethyl
ether. (See Eluate Composition 10.3.6). °
10.3.4 Concentrate the e-luates to 10 ml in a K-D in a
hot water bath. Fifty mis of petroleum ether
must be added to the fourth fraction prior to
concentration to eliminate the ethyl ether from
the concentrated extract.
JO.3.5 Analyze by gas chromatography.
-------
B-13
11
10.3.6 Eluate Composition - The composition of the eluate
should be checked for each new batch of Florisil
with a standard mix consisting of gamma-BHC (lindane)
heptachlor, endosulfan A and B. If the composition
of the eluate varies from that given below, the
amount of Florisil used in the column should be
altered i.e., an increase in the amount of Florisil
will increase the amount of solvent needed to
elute compounds from the column. The majority of
the compound should elute in the fraction listed
below.
6% Eluate
Aldrin - DDT
BHC Heptachlor
Chlordane Heptachlor Epoxide
ODD Lindane
Endosulfan A Mi rex
Toxaphene PCB's
DDE Methoxychlor
15% Eluate 50% Eluate
Endrin Endosulfan B
Dieldrin
Phthalate esters
Certain thiophosphate pesticides will occur in
each of the above fractions as well as the 100%
fraction. For additional information regarding
eluate composition, refer to the FDA Pesticide
Analytical Manual (5).
10.4 Alumina Column Adsorption Chromatography (6).
10.4.1 Adjust the sample extract volume to 10 ml with
hexane.
10.4.2 Prepare a 15 cm (after settling) x 2 cm column
of properly deactivated alumina (see 4.11). The
alumina should be settled by tapping the column.
-------
;B:14
12
10.4.3 Pre-eluate the column with 40-50 ml of hexane.
Adjust the flow of the solvent through the column
to 5 ml/min with air. Just prior to exposure of
the alumina surface to air, quantitatively trans-
fer the sample extract to the column using several
hexane washes. This transfer should be done with-
out disturbing the surface of the alumina.
10.4.4 Just prior to the exposure of the alumina surface
to air, add 50 ml of a 10% ethyl ether in hexane
solution. Collect the eluate in a 50 ml beaker.
Ten 50 ml fractions are collected in like manner
and each fraction is concentrated to 10 ml on a
hot plate under a gentle stream of air.
10.4.5 Analyze by gas chromatography.
10.4.6 Eluate Composition. -The composition of the eluate
should be checked for each new batch of alumina
with a technical chlordane standard. If the composv
tion of the eluate varies from that given in Table
IV, the amount of water added to the alumina should
be altered, i.e., an increase in the amount of
water will decrease the amount of solvent needed
to elute compounds from the column.
11. CALCULATION OF RESULTS
11.1 Determine the pesticide concentration by using the absolute
calibration procedure described below:
(1) Micrograms/liter = (A) (B) (V
(V ) (V )
ng standard
Standard area
B = Sample aliquot area
V. = Volume of extract injected (ul)
V = Volume of total extract (|jl)
V = Volume of water extracted (ml)
-------
12. REPORTING RESULTS
12.1 Report results in micrograms per liter without correction
for recovery data. When duplicate and spiked samples are
analyzed, all data obtained should be reported.
B-15
13
-------
B-16
14
REFERENCES
1.
2.
3.
4.
5.
6.
"Method for Organochlorine Pesticides in Industrial Effluents",
Natinal Pollutant Discharge Elimination System, Appendix A, Federal
Register, 38, No. 75, Pt. II.
Monsanto Methodology for Arochlors - Analysis of Environmental
Materials for Biphenyls, Analytical Chemistry Method 71-35, Mon-
santo Company, St. Louis, Missouri, 63166, 1970.
"Method for Polychlorinated Biphenyls in Industrial Effluents,"
Environmental Protection Agency, National Environmental Research
Center, Cincinnati, Ohio, 45268, 1973. (Also NPDES, Appendix A,
Fed. Reg., 38, No. 75, Pt. II.)
Goerlitz, D.F. and Law, L.M., "Notes on the Removal of Sulfur
Interferences from Sediment Extracts for Pesticide Analysis,"
Bulletin of Environmental Contamination and Toxicology, Vol. 6,
No. 1, 1971.
"Pesticide Analytical Manual," U.S. Dept. of Health, Education
and Welfare, Food and Drug Administration, Washington, D.C.,
Vol. I, 211.14 (d).
Boyle, H.W., Burttschell, R.H., and Rosen, A.A., "Infrared Iden-
tification of Chlorinated Insecticides in Tissues of Poisoned
Fish," Organic Pesticides in the Environment, Advances in Chemistry
Series, No. 60, A.C.S., Washington, D.C., 1966.
-------
Table I
Retention Times of Organochlorine Pesticides
Relative to Aldrin
Liquid Phase
Solid Support 2
Column Temperature
Flow Ratea (ml/inin)
32 OV-101
nrm x 6' glass
on 60/80 GCQ
180°C
25
3% OV-17
4 mm x 6' glass
on 60/80 GCQ
200°C
60
5% OV-210
2 mm x 6' glass
on 60/80 GCQ
200°C
37
3% OV-225
2 mm x 6' glass
on 80/100 GCQ
200°C
32
Pesticide
o-BHC
B-BHC
Y-BHC (lindane)
6-BHC
heptoclilor
heptachlor epoxide
T chlordane
Endosulfen A
a chlordane
dieldnn
p.p1 DDE
endrin
endosulfan B
o.p1 DOT
p,p' DUD
endrin aldehyde
endosulfan sulfate
p,p' DOT
methoxychlor
aldrin (min absolute)
RRT
0.40
0.44
0.48
0.50
0.80
1.25
1.44
1.60
1.62
1.88
1.96
2.11
2.20
2.64
2.52
2.52
2.99
3.37
5.31
3.80
RRT
0.45
0.49
0.53
0.54
0.82
1.19
1.38
1.47
1.50
1.73
1.68
1.89
1.93
2.25
2.10
2.10
2.46
2.77
4.01
Z.28
RRT
0.68
0.96
0.83
1.54
0.88
1.71
1.64
2.16
; 1 .64
2.55
1.78
2.97
3.72
2.22
2.94
5.76
8.42
3.18
4.60
1.74
RRT
0.87
2.94
1.24
0.53
0.90
2.11
2.52
2.40K
wflb
MA
3.24
2.79
3.82
6.82
3.92
6.70
5.39
15.03
6.38
12.96
4.92
3 Argon 10% methane. RRT for other columns are given in reference 1, Table I,
flA - Value not available.
OO
I
-------
B-18
16
Table II
SENSITIVITY OF ORGANOCHLORINE PESTICIDES USING
ELECTRON CAPTURE (EC) DETECTOR
Instrument
Liquid Phase
Solid Support
Column Temperature
Flow Rate
Injection Size
Tracor MT-220
3% OV-17
4 mm x 6' glass
60/80 GCQ
200°C
81.6 ml/min
2 pi
Pesticide
cone.
(ug/ml)
att.
peak height
(mm)
Lindane 0.025 8
Heptachlor 0.05 8
Aldrin 0.075 8
y-Chlordane 0.10 8
Dieldrin 0.125 8
o.p1 DDT 0.250 8
p,p' DDT 0.250 8
a-BHC 0.05 8
endosulfan A 0.10 8
p,p' DDE 0.10 8
endosulfan B 0.10 8
DDD 0.10 8
endosulfan sulfate 0.50 8
(5-BHC 0.050 8
Heptachlor Epoxide 0.100 8
Endrin 0.100 8
Endrin Aldehyde 0.100 8
79
113
140
132
136
95
92H
256
77
104
60
46
215
79
134
58
31
-------
B-19
17
Table III
RECOVERY DATA FOR SELECTED ORGANOCHLORINE PESTICIDES
(EXTRACTION FROM WATER ONLY)
Spiking Number of Average % Standard
Compound Level ((jg) Determinations Recovery Deviation
lindane 0.25
heptachlor 0.50
aldrin 0.75
y-chlordane 1.00
dieldrin 1.25
o.p1 DDT 2.50
p.p1 DDT 2.50
ODD 1.00
Endosulfan A 1.00
Endosulfan B 1.00
a-BHC 0.50
p,p' DDE 1.00
Endosulfan sulfate 5.00
p-BHC 0.50
heptachlor epoxide 1.00
endrin 1.00
endrin aldehyde 1.00
12
12
12
12
12
12
11
11
12
12
9
12
11
8
9
7
8
110
89
91
97
100
98
109
100
99
95
102
98
107
103
99
115
89
8.3
7.6
12.4
2.5
3.8
6.4
5.5
14.8
4.3
6.0
3.8
4.1
11.6
5.2
6.2
12.2
7.2
-------
B-20
18
Table IV
ORDER OF ELUTION OF CHLORINATED INSECTICIDES
FROM ALUMINA ADSORPTION COLUMN3 (6)
Insecticide
DDE
Aldrin
Heptachlor
Tech. Chlordane
Toxaphene
DDT
y-Chlordane
orChlordane
DDD
Lindane
Endrin
Heptachlor Epoxide
Dieldrin
.Methoxyclor
'Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Lindane
Lindane
50 ml Eluate
123
95 5
93 7
75 25
30 30 35
15 55 30
5 95
2 80
95
60
35
100
98 2
95 5
95 5
(Acid Alumina)
(Neutral Alumina)
Fractions - % of Total Recovered
4 5 6 7 8 9 10
5
Trace
18
5
40
65
45 55
35 50 15
20 40 20 15 5
5 30 50 10 5
25 60 15
3 75 20 2
% Recovery
94
97
96
99
93
94
99
97
93
40
95
95
96
96
100
100
100
100
100
91
a 9/1 Hexane/Ethyl Ether Eluting Solvent.
-------
B-21
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PAGE J? OF
ANALYTICAL DATA REPORTING SHEET
PROJECT 624, VELSICOL, ST. LOUIS, MICHIGAN
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B-26
METHOD FOR ORGANOCHLORINE PESTICIDES IN SOIL AND SEDIMENT
1. SCOPE AND APPLICATION
1.1 This method is an adaptation of that described'in reference 1
and covers the determination of various organochlorine pesti-
cides, including some pesticidal degradation products and
related compounds in soil. Such compounds are composed of
carbon, hydrogen, and chlorine, but may also contain oxygen,
sulfur, phosphorus, nitrogen or other halogens.
1.2 The following compounds may be determined individually by
this method with a sensitivity of at least 0.05 ug/g: BHC,
lindane, heptachlor, aldrin, heptachlor epoxide, dieldrin,
endrin, DDE, ODD, DDT, methoxychlor, endosulfan, mirex,
trifluralin, endrin aldehyde, and endosulfan sulfate. Under
favorable circumstances, Strobane, toxaphene, chlordane
(tech.) and others may also be determined. The usefulness
of the method for other specific pesticides must be demon-
strated by the analyst before any attempt is made to apply
it to sample analysis.
1.3 When organochlorine pesticides exist as complex mixtures,
the individual compounds may be difficult to distinguish.
High, low, or otherwise unreliable results may be obtained
through misidcntification and/or one compound obscuring
another of leaser concentration. Provisions incorporated
in this method arc intended to minimize the occurrence of
sucli interferences.
-------
B-27
2. SUMMARY
2.1 The method offers several analytical alternatives, dependent
on the analyst's assessment of the nature and extent of inter-
ferences and/or the complexity of the pesticide mixtures
found. Specifically, the procedure describes the use of an
effective co-solvent for efficient sample extraction; provides,
through use of column chromatography and liquid-liquid parti-
tion, methods for the elimination of non-pesticide interferen-
ces and the pre-separation of pesticide mixtures. Identifica-
tion is made by selective gas chromatograohic separation
and may be corroborated through the use of two or more unlike
columns. Detection and measurement are best accomplished
by electron capture, microcoulometric or electrolytic conduc-
tivity gas chromatography. Results are reported in micro-
grams per gram of dry sample.
2.2 This method is recommended for use only by experienced pesti-
cide analysts or under the close supervision of such quali-
fied persons.
3. IHTERFERCHCES
3.1 Solvents, reagents, glassware, and other sample processing
hardware may yield discrete artifacts and/or elevated base-
lines causing Misinterpretation of gas chromalograms. All
of these materials must bo demonstrated to be free from
interference under the conditions of the analysis. Specific
selection of mngenLs and purification of solvents by distil-
lation in all-glass systems may be required.
3.2 The inliM-.fcmicos in soil and sediment samples arc high and
v.inecl and oflr-n pose qre.it difficulty in obtaining accurate
and p;<;cr-.o i-icnsm r-ni-iiit of organocM urine pesticides. Stinr
plu clonn-i.p prncodures arc i]on..-r,il ly required and may result
in the lose of certain orrpncchlorinc pesticides. Therefore,
-------
B-28
great, care should be exercised in the selection and use of
methods for eliminating or minimizing interferences. It is
not possible to describe procedures for overcoming all of
the interferences that may be encountered in soil and sedi-
ment samples.
3.3 Polychlorinated Biphenyls (PCB's) - Special attention is
called to industrial plasticizers and hydraulic fluids such
as the PCB's which are a potential source of interference
in pesticide analysis. The presence of PCB's is indicated
by a large number of partially resolved or unresolved peaks
which may occur throughout the entire chromatogram. Partic-
ularly severe PCB interferences will require special separa-
tion procedures (2,3).
3.4 Phthalate Esters - These compounds, widely used as plasti-
cizers , respond to the electron capture detector and are a
source of interference in the determination of organochlorine
pesticides using this detector. Water leaches these materials
from plastics, such as polyethylene bot.Lles and lygon tubing.
The presence of phthalate esters is implicated in samples
that respond to electron capture but not to the microcoulo-
metric or electrolytic conductivity halogen detectors or to
the flame photometric detector.
3.5 Oganophosphorus Pesticides - A number of organophosphorus
pesticides, such as those containing a nitro group, eg,
parathion, also respond to the electron capture detector
and may interfere- with the determination of the organochlo-
rine pesticides. Such compounds can be identified by their
response Lo tho alk.ili flame ionization or flame photometric
detectors.
3.G Anaarc^c extracts have gross ir.Lcrfarences duo to tho pros-
one? of siilfi-r ci:--ipouiiils. This interference can bo removed
Iw n.',icU'i
-------
B-29
column cleanup, the sulfur interferences are confined to
the first fraction, and only this fraction need be reacted
with metallic mercury. (4)
4. APPARATUS AND MATERIALS
4.1 Gas Chromatograph - Equipped with glass lined injection
port.
4.2 Detector Options:
4.2.1 Electron Capture - Radioactive (tritium or nickel
4.2.2 Hicrocoulometric Titration
423 Electrolytic Conductivity
4.3 Recorder - Potentio.netric strip chart (10 in) compatible
with the detector.
4.4 Gas Chromatographic Column Materials:
4.4.1 Tubing - Pyrex (180 cm long x 4 mm ID)
4 4.2 Glass Wool - Silanized
443 Solid Support - Gas-Chrom Q (60-80 mesh)
4'4.4 Liquid Phases - Expressed as weight percent coated
\
on solid support.
4.4.4.1 OV-101, 3%
4.4.4.2 OV-210, 5%
4.4.4.3 OV-17, 3% or any column yielding equiva-
lent separation.
4.5 Kuilerna-Danish (K-D) Glassware (Kontes)
4.5.1 Snyclcr Column - three ball (macro)
4.5.2 Evaporative Flasks - 500 ml
4 5 3 Receiver Ampuls - 10 ml , graduated
4 G Ch,lo,jrnuh,c Column - Pyrex (approximately 340 «. long x
20 no. ID) with coa,"* fritted plate on bottom. (Kontes
K,,:OGO) Mod.fKM. LO incl.dc a reservoir for 50 ml of solvent
4.7 M.cro Syin-J'". ' 1° z5 - 50
-------
B-30
4.3 Separatory Funnels - 125 ml and 1000 ml with Teflon stopcock.
4.9 Hicro-pipets - disposable (140 mm long x 5 mm ID).
4.10 Graduated cylinders - 500 ml.
4.11 Beakers - 50 and 250 ml.
4.12 Wrist Action shaker
4.13 Erlenmeyer flask - 500 ml.
4.14 Graduated cylinders - 100, 250 and 1000 ml.
4.15 Floris-il - PR Grade (60-100 mesh); purchase activated at
1250 F and store in the dark in glass containers with glass
stoppers or foil-lined screw caps. Before use, activate
each batch overnight at 130 C in foil-covered glass container.
4.15 Alumina, Basic; Brockman Activity I; 80-200 mesh. The
amount of water needed for proper deactivation is determined
by the elution pattern for a technical chlordane standard.
A 1.75% deactivation is usually sufficient to yield the
correct elution pattern (see Table IV).
5. REAGENTS, SOLVENTS. AMD STANDARDS
5.1 Ferrous Sulfatc - (ACS) 30% solution in distilled water.
5.2 Potassium Iodide - (ACS) 10% solution in distilled water.
5.3 Sodium Chloride - (ACS) Saturated solution in distilled water
(pre-rinsc NaCl with hexane).
5.4 Sodium Hydroxide - (ACS) 10 M in distilled water.
5.5 Sodium Sulfate - (ACS) Granular, anhydrous (conditioned @
400 C for 4 hrs.).
5.G Sullutic Acid - (ACS) Mix equal volumes of cone. II2SO., with
distilled water
5.7 Oi.-Lliyl LLhLT - Nanoijrade. red is Li 11 ud in glass, if necessary.
5.7.1 Must contain 27- alcohol and bo free of peroxides
by fn11c-.;iiK] tost: To 10 ml of ether in glass-
stop!)i:ri'(l c-yI inilor previously ringed with oilier,
Vd Di'...: ml of fn."-,hly pn:parod 10" KI solution.
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B-31
4.3 Separator" Funnels - 125 ml and 1000 ml with Teflon stopcock.
4.9 Micro-pipets - disposable (140 mm long x 5 mm ID).
4.10 Graduated cylinders - 500 ml.
4.11 Beakers - 50 and 250 ml.
4.12 Wrist Action shaker
4.13 Erlenmeyer flask - 500 ml.
4.14 Graduated cylinders - 100, 250 and 1000 ml.
4.15 Florisil - PR Grade (60-100 mesh); purchase activated at
1250 F and store in the dark in glass containers with glass
steppers or foil-lined screw caos. Before use, activate
each batch overnight at 130 C in foil-covered glass container.
4.16 Alumina, Basic; Brockman Activity I; 80-200 mesh. The
amount of water needed for proper deactivation is determined
by the elution pattern for a technical chlordane standard.
A 1.75% doactivation is usually sufficient to yield the
correct elution pattern (see Table IV).
5. REAGENTS. SOLVENTS. AMD STANDARDS
5.1 Ferrous Sulfate - (ACS) 30% solution in distilled w^ater.
5.2 Potassium Iodide - (ACS) 10% solution in distilled water.
5.3 Sodium Chloride - (ACS) Saturated solution in distilled water
(pre-rinse NaCl with hexane).
5.4 Sodium Hydroxide - (ACS) 10 H in distilled water.
5.5 Sodium Sulfato - (ACS) Granular, anhydrous (conditioned @
400 C for 4 Mrs.).
5 6 Sulluric Acid - (ACS) Mix equal volumes of cone. I1..SO.,. with
distilled w.ilur
5.7 Oiothyl CLIiur - Hanocjrade, redistilled in glass, if necessary.
5.7.L Knot contain 2% alcohol and be free of peroxides
by fnllcv.nna tost: To 10 ml of ether in glass-
stiiljiiurinl cylinder previously rinsed with ether,
ncM iir." ml of freshly prepared ID1- KI solution.
-------
B-32
consists of 0.025 |ig/ml lindane, 0.050 jjg/ml heptachlor,
0.075 pg/ml aldrin, 0.100 ug/ml 6 chlordane, 0.125 Mg/ml
dioldrin, 0.250 ug/ml o.p1 DDT and 0.250 Mg/ml p.p1 DDT in
hexane. The chromatographic conditions chosen should yield
at least 30% full scale deflection for all of the components
of Std. Mix B [see Figures 1 thru 3]. For all quantitative
measurements, the detector must be operated within its linear
response range and the detector noise level should be less
than 2% of full scale.
6 2 Standards are injected frequently as a check on the stability
of operating conditions. Gas chromatograms of several stan-
dard pesticides are shown in Figures 1, 2, and 3 and provide
reference operating conditions for the recommended columns.
G.3 The elulion order and retention ratios of various organochlo-
rine pesticiaes are provided in Table I as a guide. The
sensitivity of these compounds AO detection by EC is given
in Table II.
7. QUALITY CONTROL
7.1 Replicate and spiked sample analyses are recommended as
quality control checks. At a minimum, one replicate and
one spiked analysis should be included per 20 sample anal-
yses. If less than 20 sample analyses are required, one
duplicate and one spiked analysis should still be included.
U.ua for recovery of specific organochlorine pesticides
from soil is given in Table III
7.2 In 311.11110.1, one method Monk is required per 20 sample
a.Kily-,.::,. K less tli.in 20 sample analyses are required,
on..' milhoil l.l.inl; should sUll bo included.
7 ">, On,- ...-.i,,.!,' il"»'l«l I"1 mJ^Lcil in replicate into the gas
ch.o-:3i«U'-M'" 1'cr ^ "*"!'105 -"'^'icil. If lcSS th311 2°
..nV.!'.'- .unlv i.-s an- rc^.rc.l, -1 replicate GC injection
should -.till be r,ntk.
-------
. B-33
8. *ftMPI E PREPARATION
8 i Separate water fro, sample, If n.c«..ry. * Recantation or
clrifugation. Analyze water using the "Method for Organo-
chlorine Pesticides in Environmental Water Samples.
8 2 Sieve the ..11 and sediment sample through a 2 mm mesh ».
to remove rocks and other foreign materia,: sediment samples
may require air drying before sieving to facilitate the
3 3 -ma Sm of t*. sieved sampU into a weighed
bjer Record the weight. Place in a !05«C oven overnlght
and reweigh for moisture determination. Calculator:
iJ. x 100 = % moisture
ujir&vtfb-
A = weight of beaker + wet sample
B = weight of beaker
C = Weight of beaker + dry sample
8 4 Weigh 25-150 g. of sample into a 500 ml Erlenmeyer flask.
Add water,"if necessary, to adjust the moisture content of
the sample to a 15% minimum.
g. EXTRACTION
g 3 Add 40 ml of acetone to the saaple and shake vigorously for
20 MinUlBs using a -ist action shaLer.
and shake lor ackliLional 10 ,,,i.H,Los.
, A, ,0.1 U« 5aBPlo ^ settle and dacant the solvent ,nto a
1 l-.Lcr ccpor-il-cry funnel
-, ,vP,.,t .I." ov.rnct.on by adcli.uj 20 ml of acetone to the
Sln,lP nnd .ln..i,H, for 20 mim-Los. followed by 30 ml of
,..',!., an adJ.Lio.ul lOmnulo, of shaking.
-------
B-34
9.4 Allow the sample to settle, decant the solvent and combine
wiuii the solvent from the first extraction.
9.5 Add 500 ml of water to the separatory funnel containing the
combined extracts and gently mix for 1 minute. Collect the
organic solvent layer which contains hexane in a 250 ml
beaker. This backwashing removes the acetone and other
polar impurities from the extract.
9.5 Extract the resulting water layer with 25 ml of hexane.
Combine the hexane extract with the extract from 9.5. Discard
the water layer.
9.7 Prepare a funnel plugged with glass wool and filled with
sodium sulfate. Remove interferes from the gls3S wool and
sodium sulfate by washing with 30-50 ml of hexane. Pass
the combined hexane extracts through the funnel and into a
500 ml Kuderna-Danish evaporative concentrator.
9.8 Concentrate the extract in the K-D evaporator on a hot water
bath to a volume of 10 ml.
9.9 Analyze by gas chromatography unless a need for a cleanup
is indicated. [See Section 10",.
10. CLEAN-UP AMD SEPARATION PROCEDURES
10.1 Interferences in Hie form of distinct peaks and/or high
background in the initial gas chrornatographic analysis, as
well as the physical characteristics of the extract (color,
cloudiness, viscosity) and background knowledge of the sample
will indicate whether clean-up is required. When thuse
inlorl'ore with measurement of the pesticide's, or affect
column life or detector sensitivity, proceed as directed
be In1.'
10 > ,\ceiuni,.rili; P.irtiti.in - llns procedure is used to isolate
fato ond nil- fro:. I In- sa-.sjjl«j oxtr.icls. It should he noted
tml i-.jL .ill pi.":;tic ifk'S ,irr- qiMiitit.Ttivoly recover^! by
-------
B-35
10
this procedure. The analyst must be aware of this and demon-
strate the efficiency of the partitioning for specie
pesticides.
10 9 l Quantitatively transfer the previously concentrated
extract to a 125 ml separatory funnel with enough
hexane to bring the final volume to 15 ml. Extract
the sample four times by shaking vigorously for
one minute with 30 ml portions of hexane-saturated
acctonitrile.
10 -> 2 Combine and" transfer the acetonitrile phases to a
one- liter separatory funnel and add 650 ml of
distilled water and 40 ml of saturated sodium
chloride solution. Mix thoroughly for 30-45 seconds.
Extract with two 100 ml portions of hexane by
vigorously shaking about 15 seconds.
10 2 3 Combine the hexane extracts in a one-liter separatory
funnel and wash with two 100 ml portions of distilled
water. Discard the water layer and pour the hexane
lawer into a 500 m1 K-D flask through a funnel
plurjged with glass wool and filled with .anhydrous
sodium sulfate which has been prewashed with hexane.
Rinse the separatory funnel and column with 10 ml
portions of hexane.
10.2.4 Concentrate the extracts to 10 ml in the K-D evapora-
tor in a hot water bath.
30.2.5 Analyze by gas chromatography unless a need for
further clean-up is indicated.
Florisil Column Adsorption Chromatography
10.3.1
Acl,i.;t the sa^lo extract volume to 10 ml with
n 3 , p!',r,rQ ., 20 mm 1.0 column th-it contain, 4 inches
(..flor ^ttT.iH) o! activated Flonsil topped
,/ltl, n o rj iiu-h nnhydrour; sodium sulfato.
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B-36
11
10.3.3 Pre-elute the column with 50-60 ml of petroleum
ether. Just prior to exposure of the sodium sulfato
layer to air, quantitatively transfer the sample
extract into the column. Just prior to exposure
of the sodium sulfate layer to air, add the first
cluting solvent, 200 ml of 6% ethyl ether in petrol-
eum ether. Collect the eluate in a 250 ml beaker.
Perform the second elution with 200 ml of 15%
ethyl ether in petroleum ether, the third elution
with 200 ml of 50% ethyl ether-petroleum ether,
and the fourth eiution with 200 ml of 100% ethyl
ether. [See Eluate Composition 10.3.6].
10.3.4 Concentrate the eluates to 10 ml in a K-D in a
hot water bath. Fifty mis of petroleum ether must be
added to the fourth fraction prior to concentration
to eliminate the ethyl ether from the concentrated
extract.
10.3.5 Analyze by gas chromatography.
10. \6 Eluate Composition - The composition of th> eluate should
be checked for each new batch of Florisil with a standard
mix consisting of gramma-BHC (lindane), heptachlor, and
Endosulfan A and B. If the composition of the eluate varies
from that given below, the amount of Florisil used in the
column should be altered i.e., an increase in the amount of
Flonsil will increase the amount of solvent needed to clute
compounds from the column. The majority of the compounds
should eluLo in the fraction listed below.
Alil.-in Dl)T
£Uf Hn
Chlm -Inn- ll.^Uchlor Cpoxido
-------
B-37
DDE Methoxychlor
Endosulfan A Mi rex
Toxaphene PC3's
15% EUiate 50% Eluate
Endrin Endosulfan B
Dieldrin
Phthalate Esters
Certain thiophosphate pesticides will occur in each of the
above fractions as well as the 100% fraction. For additional
information regarding eluate composition, refer to the FDA
Pesticide Analytical Manual (5).
10.4 Alumina Column Adsorption Chromatography (6)
10.4.1 Adjust the sample extract volume to 10 ml with hexane.
10.4.2 Prepare a 15 cm (after setting) x 2 cm column of
properly deactivated alumina [see 4.16]. The alumina
should be settled by tapping the column.
10.4.3 Pre-elute the column with 40-50 ml of hexane. Just
prior to exposure of the alumina surface to air,
quantitatively transfer the sample extract to the
colu'im using several hexane washes. This transfer
should be done without disturbing the surface of the
alumina.
10.4.4 Just prior to the exposure of the alumina surface
to air, add 50 ml of a 10% ethyl ether in hexane
solution. Collect the eluate in a 50 ml beaker.
Ton 50 ml fractions are collected in like manner
and each fraction is concmitrated to 10 ml on
o hot plota under a gentle stream of air.
10.'1.5 An.ily.iu by ips clvomatogrciphy.
'') l-u tlu.iti! Cuiii!>o5i tion. The composition of the eluato
:!ionii| HI- ch-.-ckocI for each new batch of alu.nina with
-------
B-38
13
a technical chlcrdane standard. If the composition
of the eluale varies from that given in Table IV,
the amount of water added to the alumina should be
altered, i.e. an increase in the amount of water
will decrease the amount of solvent needed to elute
compounds from the column.
11. CALCULATION OF RESULTS
11.1 Determine the pesticide concentration by using the absolute
calibration procedure described below. Concentration is
reported in terms of the dry weight of the sample.
(A) (B) (V )
(1) Micrograins/grani - .i
(V.) (WX(l.OO-M)
no standard
A =
Standard area
B = Sample aliquot area
V. = Volume of extract injected
V = Volume, of total extract (|jl)
W = Weight of sample extracted (g)
,.s % moisture
M =
100
12. KEI'OKTinG Ri'Slli. FS
]2.1 UL-po.-L nisullb in i.iicrogr;,ms per gram without correction
for rucovery data. WIHMI dujjl icatu and spiked samples arc
amlzml Jl 1 <-!'t-"1 nDl^i""^ shoul-l be rcportoil.
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B-39
REFERENCES
1. Goerlitz, D.F. and Law, L.M., "Determination of Chlorinated Insecti-
cides in Suspended Sediment and Bottom Material," Journal of the
AOAC, Vol. 57, No. 1, 1974.
2. Monsanto Methodology for Arochlors - Analysis of Environmental
Materials for Biphenyls, Analytical Chemistry Method 71-35, Monsanto
Company, St. Louis, Missouri, 63165, 1970.
3. "Method for Polychlori:>ated Biphenyls in Industrial Effluents"
Environmental Protection Agency, National Environmental Research
Center, Cincinnati, Ohio, 45258, 1973 (Also NPDES, Appendix A,
Fed. Reg., 38, No. 75, Pt. II).
4. Goerlitz, D.F. and Law, L.M., "Notes on the Removal of Sulfur
Interferences from Sediment Extracts for Pesticide Analysis,"
Bulletin of Environmental Contamination and Toxicology, Vol. 6,
No. 1, 1971.
5. "Pesticide Analytical Manual," U.S. Dept. of Health, Education,
and V'r.'lfare, Food and Drug Administration, Washington, D.C.,
Vol. I, 211.14 (d).
\
6. Boyle, H.W. Burttschell, R.H., and Rosen, A.A., "Infrared
Identification of Chlorinated Insecticides in Tissues of
Poisoned Fish," Organic Pesticides in the Environment,
Advances in Chemistry Series, No. 60, A.C.S. Washington, D.C.,
19GG.
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B-40
15
TABLE I
Retention Times of Organochlorine Pesticides
Relative to Aldrin
_
Liquid Phase
Solid Support 2
Column Temperature
Flo1./ Rate* (ml /mi n)
.
Pesti cic'-2
o-BHC
B-BHC
y-DHC (lindane)
6-BHC
heptachlor
heptachlor epoxide
Y chlordane
Endosulfan A
a chlordcme
dicldrin
n n ' M fl F
p,p ljljt
endrin
endosulfan B
o.p1 OUT
v* i i
DCl)
endrin aldehyde
oiulocul fan sul Talc
1 ,."T
P , P Liu i
ir.pll.o/yclilor
-
nl.Jrm (-nn .iD'.o.u
.
3% OV-101
min x 6' glass
on 60/80 GCQ
180°C
25
'
RRT
0.40
0.44
0.43
0.50
0.80
1.26
1.44
1.60
1.62
1.88
1.96
911
£.. \ \
2.20
O -"7 "> ( L|
-f^- 31 '"" ': 1
2.52
2.52
2.09
3 37
1" T 1
b. 31
_
i?) 3.r,o
3% OV-17
4 mm x 6' glass
on 60/80 GCO
200°C
60
.
RRT
0.45
0.49
0.53
0.54
0.82
1.19
1.38
1.47
1.50
1.73
1.68
1.89
1.93
2 25
c. . C- 'J
2.10
2.10
2.46
2.77
4. 01
,
2 :'3
5% OV-210 -
2 mm x 6' glass
on 60/80 GCQ
200°C
37
RRT
0.63
0.96
On i
.83
1.54
On o
.88
1.71
1.64
r.ie
1.64
2.55
1.78
2.97
3.72
2.22
2.94
5.76
8.42
3.13
4.60
^
1.7-1
Arri0M 10-. .:..'lh.mo. KRT for oLl.-r colunn. arc yiven in reference 1,
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B-41
TABLE II
Sensitivity of Organochlorine Pesticides
Using Electron Capture (EC) Detector Tracer HT 220
Instrument
Liquid Phase
Solid Support
Cok.mn Temperature
Flow Rate (ml/min)
Injection Size
Pesticide
Lindane
Heptachlor
Aldrin
y-Chlordane
Dieldrin
o,p' DDT
P.P1 DDT
a-BHC
Endosulfan A
p,p' DDE
Endosul fan B
ODD
Endosulfan Sul fate
B-BHC
HppLachlor Epoxiclc
End rin
Endi-in Aldc-hydo
i
Cone, uo/ml
0.025
0.05
0.075
0.10
0.125
0.250
0.250
0.05
0.10
0.10
0.10
0.10
0.50
.050
.100
.100
.100
Tracer MT-220
3% OV-17
4 mm x 6' glass
on 60/30 GCQ
200°C
81 .6 ml/min
2 ul
Att
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
Peak Height
(mm)
79
113
140
132
136
94
92
256+
77
104
60
46
215
79
134
5S
31
-------
B-42
17
TA3LE III
Recovery Data for Selected Organochlorine Pesticides from Soil
Compound
Linclane
Heplachlor
Aldrin
y Chlordane
Dieldrin
o.p1 DDT
p.p1 DD1
ODD
Endosul fan A
Endosul fan B
«-BtiC
p.p1 ODE
Enciosul !~an
Sul fate
B-SHC
Heplachlor
Epox icle
Eiiflnn
Fuel i-iii
AUL'liyrio
Spiking Level
(MS)
0.25
0.25
0.75
1.00
1.25
2.5
2.5
1.0
1.0
1.0
0.50
1.0
5.0
5.0
1.0
1.0
1.0
JJ
It
Determinations
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Average
% Recovery
94
91
94
94
93
96
105
106
102
99
92
103 x
83
95
98
98
79
Standard
Deviation
0.5
1.2
O.S
1.2
0.5
1.9
2.6
4.3
3.3
5.0
2.6
3.3
2.9
1.4
0.5
2.0
1.9
-------
is
B.-43
Table IV
ORDER OF ELUTION OF CHLORINATED INSECTICIDES
FROM ALUMINA ADSORPTION COLUMN" (6)
Insecticide
ODE
Aldn'n
Heptachlor
Tech. Chlordane
Toxaphene
DOT
y-Chlordane
a-Chlordane
ODD
Lindane
Endrin
Heptachlor Epoxide
Dieldrin
Methoxyclor
Aroclor 1242
Aroclor 12-13
Aroclor 1254
Aroclor 1260
Lindane
Lindane
50 ml Eluate
123
95 5
93 7
75 25
30 30 35
15 55 30
5 95
2 80
95
60
35
100
. 98 2
95 5
95 5
(Acid Alumina)
(Neutral Alumina)
Fractions - % of Total Recovered
4 5 6 7 8 9 10
5
Trace
18
5
40
65
45 55
35 50 15
'20 40 20 15 5
5 30 50 30 5
25 GO 15
3 75 20 2
% Recovery
94
97
96
99
93
94
99
97
93
40
95
95
96
96
100
100
100
100
100
91
a 9/1 Hexane/Cthyl Ether Eluting Solvent.
-------
ANALYTICAL DATA REPORTING SHEET
PROJECT 624, VELSICOL, ST. LOUIS, MICHIGAN
TABLE j£-, GENERAL ORGAN ICS DATA, ;?,i,'g/g.
03
I
STATIONr
NUMBER
DATE
TIME
HBB
PBB
p,p'-DDT
0,p'-DDT
p,p'-DDE
p,p'-DDD
TRIS
/ess- i
0,0 t-t
K.SS-.X
o,o/
o.o/
0,0 "3
O. OS"
-3
MI)
O.OI
0.0*1
0.
^ooo
1 Si'OO
//CO
II
Wfc.
/<*<-/ 8
no
6 vl-
0, 01
0, 3o
0. 0(p
O.OI
-------
If)
I
CO
PAGE ^ OF
ANALYTICAL DATA REPORTING SHEET
PROJECT 624, VELSICOL, ST. LOUIS, MICHIGAN
TABLE JZ^, GENERAL ORGANICS DATA, £)cfli-/-r/
$>£'&/*<; £ri
STATION
NUMBER
DATE
TIME
HBB
PBB
p,p'-DDT
o,p'-DDT
p.p'-DDE
p,p'-DDD
TRIS
0,0.^
o-03
0 .OX
3-
M/V
7471
AJA
MA
-^i e>
M'ls
0.01
Mli
£xU!"V-a<-vn,.
/OA-
W/l
4-
-H
AJI>
AiA.
MA
AJ/4
w/l
A) /I
w/l
MA
MA
Alb
WA
MA
NA
AlJb
CO
0
-------
CO
I
««»** RESULT QUALIFIERS *«««»
PNQ PRESENT BUT NOT QUANTIFIED
THE SUBJECT PARAMETER WAS PRESENT IN THE SAMPLE AT A LEVEL GREATER THAN THE LOWER LIMIT
OF DETECTION FOR RELIABLE QUANTIFICATION, BUT NO QUANTIFIABLE RESULT COULD BE
DETERMINED
PGL PRESENT BELOW LOWER LIMIT OF DETECTION FOR RELIABLE QUANTIFICATION
THE SUBJECT PARAMETER WAS PRESENT IN THE SAMPLE. BUT WAS NOT QUANTIFIED
NAI NOT ANALYZED DUE TO INTERFERENCE
THIS PARAMETER WAS NOT DETERMINED BECAUSE AN UNCONTROLLABLE INTERFERNCE WAS PRESENT
NA NOT AtJALYZED
THE SAMPLE WAS NOT ANALYZED FOR THIS COMPONENT
ND NOT DETECTED
THIS COMPONENT WAS NOT DETECTED OR IDENTIFIED IN THE SAMPLE
*»**«*««« FOOTNOTES »*««««*«*
1 QUANTITATIVE MEASUREMENTS FOR VOLATILES REPRESENT SAMPLE CORRECTED FOR ANY CONTAMINATION
DETECTED IN THE FIELD BLANK
2 '/RECOVERY OUTSIDE THE RANGE OF C 7. AVERAGE RECOVERY +- 2
-------
B-47
METHOD FOR TRIS (2,3-DIBROMOPROPYL) PHOSPHATE IN SOIL AND SEDIMENTS
Extraction
1. Weigh-out a 25g portion of sample into a 250 ml erlenmeyer
flask, add 60 ml of acetone to the flask and shake vigorously
for 15 minutes using a wrist action shaker.
2. Allow the sample to settle and decant the solvent into a 1-liter
separator^ funnel containing 500 ml of distilled/deionized H20.
3. Repeat steps 1-2.
4. Mix the contents of the separatory funnel for approximately 15-
20 seconds.
b. Extract the water with 3 successive 60 ml portions of CH2C12,
combining the extracts in an erlenmeyer flask.
6. Prepare a funnel plugged with glass wool and filled with anhydrous
Na-SO.. Remove interferences from the glass wool and sodium sul-
fate By washing with 30-50 ml of CH-CU. Pass the combined
CH?CU extracts through the funnel Ind into a 500 ml Kuderna-
Danisn evporative concentrator.
7. Concentrate the extract in the K-D evaporator on a hot H,,0 bath
to a volume of 100-150 ml.
8. Add 100 ml of hexane to the K-D evaporator containing the CH2C12
extract and continue to concentrate the extract to a volume of
10 ml.
Clean-up - Separation
Florisil Column Adsorption Chromatography
1. Prepare a 20 mm I.D. column that contains 20g of activated flori-
sil topped with a 0.5 inch layer of anhydrous Na2S04-
2. Pre-Elute the column with 50-60 ml of petroleum ether. Just prior
to exposure of the Na2S04 layer to air, quantitatively transfer
the sample extract onto the column. Just prior to exposure of the
Na?SOa layer to air, add the first eluting solvent, 200 ml of -6%
etnyl ether in petroleum ether. Collect the eluate in a 250 ml
erlenmeyer flask. Perform the second elution with 200 ml of 15%
ethyl ether in petroleum ether, the third elution with 400 ml of
502 ethyl ether in petroleum ether (use a 500 ml erlenmeyer to
collect this fraction), and the fourth elution with 200 ml of 100%
ethyl ether. The Tris will elute within the 50% and 100% fractions,
so the first two fractions collected may be discarded.
-------
B-48
3 Quantitatively transfer the 50% and 100% fractions to separate
500 ml round-bottom flasks. To each flask add 40 ml of CH3OH
and a teflon boiling chip.
4 Exchange the Tris from the ethyl ether/petroleum ether extracts
into the CH,OH by evaporating off the solvents using a rotary-
evaporator under vacuum and a hot H20 bath set to 50°C. Evaporate
to a final volume of less than 5 ml.
5. Quantitatively transfer the extract to a graduated centrifuge
tube and bring up to a volume of 5 ml with CH-jOH.
6. Transfer the extract to a clean screw-cap type vial fitted with a
teflon-liner.
7. Store the extract in a refrigerator until it can be analyzed
for Tris by HPLC.
8. Eluate composition - 91-95% of the Tris will elute with the 50%
ethyl ether-petroleum ether fraction, while the remaining Tris
will elute with the 100% ethyl ether fraction. The composition
of the eluate should be checked for each new batch of Florisil
with a known amount of Tris.
-------
B-49
NEUTRAL EXTRACTION TECHNIQUE FOR ORGANICS ANALYSIS
March 1979
1.0 Scope and Application
1.1 This procedure is applicable to the analysis of water
and wastewater samples for a broad spectrum of organic
pollutants.
2.0 Summary of Method
2.1 Hater and wastewater samples are extracted with CF^Cl^
(dichloromethane) at a neutral pH. The extract is dried
and concentrated with the addition of acetone or iso-
octane to exchange solvents. The resultant extract
concentrate is subjected to GC and GC/MS analysis to
identify and quantitate the organic pollutants present.
3.0 Sample Handling and Preservation
3.1 Prior to extraction, samples are refrigerated and
extracted as soon as possible, generally within 48
hours. Samples may be held 5 days or more if necessary.
4.0 Definitions and Comments
5.0 Interferences
5.1 Solvents, glassware and reagents could be sources of
contamination. Therefore, reagent blanks must be pre-
pared contacting the solvent with all potential sources
of contamination. This blank should then be processed
through the same analytical scheme as the associated
samples.
5.2 Typical interferences from reagents are:
4-methyl-4-hydroxy-2-pentanonc (diacetone alcohol)
from acetone and phthalate esters from ^SO^ cyclo-
hcxcne from dicholormethane.
6.0 Apparatus
6.1 ScparaLory funnels: 2 1 and 4 1 glass with glass or
teflon stoppers and stopcocks. No stopcock grease used.
6.2 Drying column: All glass 3 cm x 50 cm with attached
250 ml reservoir.
-------
B-50
6 3 Concentrator: 250 or 500 ml Kuderna-Danish evaporative
concentrator equipped with a 5 or 10 ml receiver ampule
and a 3 ball Snyder column.
7.0 Reagents
7 1 Extraction solvent: Pesticide ana-lysis grade CH2C12
(dichloromethane) (Burdick and Jackson or equivalent)
7.2 Exchange solvents
721- Exchange solvent: Pesticide analysis grade
acetone (Burdick and Jackson or equivalent)
722 Exchange solvent: Iso-octane suitable for
pesticide analysis (Burdick and Jackson or
equivalent)
7.3 Drying agent: Analytical reagent grade granular
anhydrous Na2S04 (sodium sulfate). Washed with
CH2C12 prior to use.
7.4 Glass wool that has been extracted with CH2C12
prior to use.
7.5 6N NaOH for pH adjustment.
7.6 6N liCl for pH adjustment.
7.7 pH paper for pH measurement.
8.0 Procedure
8 1 If low concentrations of pollutants are expected, measure
3 1 of'sample for extraction. Otherwise, one liter is
sufficient.
3.2 Measure and record the initial pH. Adjust the pH to 6-8
if necessary, and record the adjusted pH.
8.3 Extract the sample with 3 successive extractions of 100,
50 and 50 ml of C1I2C12 for 1 liter samples and 200, 100,
100 nil of CH2C12 for 3 liter samples.
If emulsions form, use a wire or stirring rod to break it,
pass the emulsion through glass wool or centrifuge if
necessary Combine the extracts and measure the volume
rr.Cnu,v,>c! 85 percent constitutes an acceptable recovery.
-------
B-51
S 4 Place a glass wool plug in a drying column and add ca 10 cm
of Ha?S04. Wash the Na2S04 with at least 50 ml of CH2Ci2-
Pour the combined extract through the column. Follow with
100 ml of acetone. Collect the CHgC^ and acetone and
transfer to a KD assembly. Add 2 ml of iso-octane for
1 liter extracts and 5 ml iso-octane for 3 liter extracts.
8 5 Concentrate on a hot water bath at 80 - 90°C until the ex-
tract stops boiling. Quantitatively transfer the receiv-
ing tube contents to a graduated centrifuge tube. Adjust
the volume to 2 or 5 ml by either adding more iso-octane
or evaporating the excess iso-octane under a gentle stream
of carbon filtered air. Transfer to a 12 ml vial and cap
with a teflon lined cap. (Note: The final extract volume
should depend on the sample. Extracts containing high
concentrations of pollutants may only require concentra-
tions to 5 ml while cleaner samples may require a final
volume of 2 ml).
9.0 Quality Control Procedures
9 1 Reagent blanks are prepared by contacting an equivalent
amount of solvent with reagents and glassware in order
to detect contaminants.
9 2 Duplicate extractions are prepared by thoroughly mixing
a sample, splitting it into two aliquots, extracting
and analyzing each aliquot. Duplicate extractions
measure the precision of the overall analytical scheme.
9.3 Spiked samples are prepared by thoroughly mixing a sample,
splitting into two aliquots, spiking one with the com-
pounds of interest, extracting and analyzing each aliquot.
The sample should be spiked with the compounds of interest
at levels between 50 and 200S of the original concen-
tration. Spikes measure the accuracy of the method.
9.a These audits are do.ie for two samples for batches of 20
or less samples and one sample for each additional 20
samples.
10.0 Calculations
10.1 Solvent Recovery
% recovery = Volume recovered (ml)V100/volume added (m\)
10.2 PolluLint Recovery: .
','i recovery = (Concrntration nu'insurcd - initial concentration) iuu
Concentration added
-------
B-5-2"
11.0 Precision and Accuracy
11.1 Table I is a summary of the results of analysis of 4
samples of tap water spiked at 100 ug/1 with each com
ponent for each exchange solvent. Individual recoveries
reflect the accuracy of the analysis for each component.
Overall, the average bias is -19 .and -17 percent for
the acetone and iso-octane exchange solvents respectively.
11.2 The table also shows the precision of the analysis for
each component for each exchange solvent. The average
percent standard deviations for acetone and iso-octane
exchange solvents are 28 and 15 percent respectively.
These data show that use of iso-octane as an exchange
solvent improves the precision of the analysis.
The precision of the recoveries across components is
also enhanced by the use of iso-octane vs. acetone.
This is shown by the standard deviations of the-Overall
average component recoveries of 14 and 35 percent respec-
tively.
12.0 References
(1) "An EPA GC/MS Procedural Manual - Review Copy", Environ-
mental Monitoring and Support Laboratory, Cincinnati, Ohio.
-------
B-53
Table I - Recovery of organic compounds at 100 ppb from
tap water.
Data collected in February 1979.
Acetone
Exchange
Mean3 Recovery
Recovery Rel. St.
Dev.
Iso-Octane
Exchange
Mean Recovery
Recovery Rel. St.
Dev.
Bis(2-chloroethyl ) ether
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
Hexachloroethane-nitrobenzene
Isophorone
1 ,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
2-Chloronaphthalenc
Acenaphthalene
Dimethyl Phthalate
Acenaphthene
2,4-Dinitrotoluene
Fluorene
Diethyl Phthalate
n-Nitrosodiphenylamine (Diphenyl Annne)
4-Bromodiphenyl Ether
Hexachlorobenzene
Phenanthrcne
Anthracene
Di-n-Butyl Phthalate
Fluoranthene
Pyrene
Butyl benzyl Phthalate
Ethyl hexyl Phthalate
Average
^tanH.irrl dpvintinil
92
76
78
80
90
97
82
88
68
84
80
100
82
88
69
83
68
60
54
54
50
66
49
56.
230^
118"
81
35
24
21
18
18
21
17
15
19
17
20
17
26
16
29
17
23
32
21
16
16
29
53
48
44
13
83
28
95
O *)
83
82
34
103
1*1 -1
11
86
97
50
f\ O
92
89
82
92
92
fl O
88
n f\
82
90.
87b
94
o f\
80
70
76
65
68
54
67
83
14
12
17
/
11
13
l f\
10
15
^ .
16
18
1f\
2
10
33
9
22
1 r\
12
13
11
27
T O
18
1r
5
1f\
3
19
1 r
15
26
15
15
a Mean recovery is averfuje ot" 4 analyses.
b Average- determined from 3 cinolyr.cs.
c Average determined from 2 analyses.
-------
00
ORGANIC CHARACTERIZATION Table II <"
QUALITY CONTROL REPORT *
PROJECT (0auis Lu/?LJcy Tc,'t,v; d/ - IV\ ICA
DUPLICATES UNITS SPIKE UNITE
NAME FIRST SECOND '/.DIFFERENCE LFVtL '/.RECOVCRY/
/.DIFFERENCE = 2 » 100 * (SECOND - FIRST)/(SECOND + FIRST)
/.RECOVERY = 100 « RECOVERED/LEVEL
3Q
65-
/OO
_^^
_6^_
4 4 - ri i bi"^^' bi n|\ o^i.oi | _^o_ ^_Q__
f~ W-T - . T
-------
NAME
ORGANIC CHARACTERIZATION
QUALITY CONTROL REPORT
Table II (Cont.)
PROJECT t£2LjL_ STATION MiXJ Q SEQUENCE
DESCRIPTION fihv 4-pliA ^ c C4" 1^0* VrrvA WrriK 5^l\G
TIME
TACH
DUPLICATES UNITS
FIRST SECOND V.DIFFFEfENC
SPIKE UNITS
LFVEL '/.RECOVERY
fcfi.
CO
I
en
tn
/DIFFERENCE = 2 « 100 * (SECOND - FIRST) / (SECOND + FIRST)
/RECOVERY = 100 « RECOVERED/LEVEL
-------
PROJECT
DESCRIPTION
NAME
ORGANIC CHARACTERIZATION
QUALI1Y CONTROL REPORT
ftiq5b
. SEQUENCE £'rJ2
Table II (COnt.)
CO
STATION
DATE
TIME
DUPLICATES UNITS
__
FIRST SECOND V.DIFFKKENCE
i
TACit
/jr '.)^.tin
SPIKE UNITS
LFVLL 7.RECOV
_S!2.
/.DIFFERENCE = 2 « 100 » (SECOND - FIRST)/(SECOND + FIRST)
/.RECOVERY 100 * RECOVERED/LEVEL
-------
ORGANIC CHARACTERIZATION
QUALITY CONTROL REPORT Table II (COnt.)
_£____(. STATION .SS" 3 £ SEQUENCE. ^piKf DATE ^/SU TIME j
bfl -ff fdftf cf OJ(? ft" foffrjpgrt /vt/y l/l/#i l"yitrnA;
PROJECT _£____. STATION . SEQUENCE. if DATE TIME TACIt
DESCRIPTION
DUPLICATES UNITS __ SPIKE UNITS
NAME FIRST SECOND '/.DIFFERENCE LFVEL V.RECOVKRY
a/id
as dulictik /A ^cvr -|b -fcferwin^ presence w
en
XDIFFEREtJCE = 2 « 100 * (SECOND - FIRST) / (SECOND + FIRST) en
/.RECOVERY = 100 « RECOVERED/LEVEL "^
-------
co
ORGANIC CHARACTERIZATION Tahle TT I Tnnt ^ «!"
QUALITY CONTROL REPORT IOUIC 11 VV,UIH..; CO
PROJECT W(X-T STATION JJ->*T SEQUENCE (ALU}J> DATE ' f/" TIME I*> TACH
DESCRIPTION 35-fr. gtisf cf lM'1-k n^xf to i
pump
DUPLICATES UNITS SPII^E UNITS _
NAME FIRST SECOND /DIFFERENCE LFVEL '/.nECOVERY
t
/.DIFFERENCE = 2 » 100 * (SECOND - FIRST) / (SECOND + FIRST)
/.RECOVERY = 100 * RECOVERED/LCVEL
-------
«««** RESULT QUALIFIERS «*»»«
PNQ PRESENT BUT NOT QUANTIFIED
THE SUBJECT PARAMETER WAS PRESENT IN THE SAMPLE AT A LEVEL GREATER THAN THE LOWER LIMIT
OF DETECTION FOR RELIABLE QUANTIFICATION, BUT NO QUANTIFIABLE RESULT COULD BE
DETERMINED
PEL PRESENT BELOW LOWER LIMIT OF DETECTION FOR RELIABLE QUANTIFICATION
THE SUBJECT PARAMETER WAS PRESENT IN THE SAMPLE. BUT WAS NOT QUANTIFICD
NAI NOT ANALYZED DUE TO INTERFERENCE
THIS PARAMETER WAS NOT DETERMINED BECAUSE AN UNCONTROLLABLE INTERFERNCE WAS PRESENT
NA NOT ANALYZED
THE SAMPLE WAS NOT ANALYZED FOR THIS COMPONENT
ND NOT DETECTED
THIS COMPONENT WAS NOT DETECTED OR IDENTIFIED IN THE SAMPLE
«««««*»«« FOOTNOTES »«»»««*««
QUANTITATIVE MEASUREMENTS FOR VOLATILES REPRESENT SAMPLE CORRECTED FOR ANY CONTAMINATION
DETECTED IN THE FIELD BLANK
2 '/.RECOVERY OUTSIDE THE RANGE OF C 7. AVERAGE RECOVERY +- 2(STD DEV) ]
3 COMPONENT CONCENTRATION EXCEEDED LINEAR DYNAMIC RANGE OF MASS SPEC THE QUANTITATIVE
MEASUREMENT FOR THIS COMPOUND REPRESENTS THE LEAST AMOUNT OF COMPOUND PRESENT
4 NOMINAL LOWER LIMIT OF DETECTION FOR QUf 'TIFICATION OF COMPOUNDS PRESENT IN 1 LITER OF WATER EXTRACTED,
CONCENTRATED TO 1 MILLILITER (B/N/A).
5 NOMINAL LOWER LIMIT OF DETECTION FOR QUANTIFICATION OF COMPOUNDS IN 20 MILLILITERS OF LIQUID EXTRACTED
INTO 5 MILLILITERS OF ORGANIC SOLVENT (HAZ)
6 NOMINAL LOUER LIMIT OF DETECTION FOR QUANTIFICATION OF COMPOUNDS IN 20 GRAMS OF SOLID EXTRACTED, CONCENTRATED
TO 5 MILLILITERS OF ORGANIC SOLVENT (HAZ)
7 NOMINAL LOWER LIMIT OF DETECTION FOR QUANTIFICATION OF COMPOUNDS IN 5 MILLILITERS OF WATER PURGED WITH A
CONSTANT VOLUME OF HELIUM (VOA)
c.. LUl) H -. 'M li. « -'" ' f'f ''-' ''' '"">
DO
I
cn
10
X0~|
-------
TOXIC1TY OF COMPOUNDS
PINC RIVER
St. Louis, Michigan
Compound Name Molecular
Formula
Benzene, Chloro- CGHSC1
Benzene, C6H4C12
1,2-dichloro-
Chemical
Abstracts Aquatic Toxicity Route of
Service No. Entry Species
108-90-7f TLm 96: Oral-rat
100-1 ppni Subcutaneous-rat
Oral -rabbit
Intraperitoneal-rat
I ntraperi toneal -guinea
pig
Inhalation-mouse
95-50-lf Oral -human
Oral -rat.
Inhalation-rat
Intraperitoneal-rat
Intravenous-mouse
Oral-rabbit
I ntravenous- rabbi t
Oral-guinea pig
Inhalation-guinea pig
Eye- rabbit
Other Toxicitv Data
Type of
Dose
LD50:
LDLo.
LD50:
LOLo.
LOLo:
LCLo:
LDLo
LD50:
LCLo:
LD50
LDLo
LD50:
LDLo.
LDLo:
LCLo:
Dose Duration1"
2,910 nig/kg
7,000 mg/kg
2,830 mg/kg
7,400 mg/kg
4,100 mg/kg
15 gm/m3
500 mg/kg
500 mg/kg
821 ppm 7H
840 mg/kg
400 mg/kg
500 mg/kg
250 mg/kg
2,000 mg/kg
800 ppm 24H
100 mg 30 sec
iTi
O
d Exposure
Effects0 Limits6
TLV (air). 75 ppm
OSHA std (air).
TWA 75 ppm
TLV (air): 50 ppm
OSHA std (air)
Cl 50 ppm
,
Mild
Irritation
Benzene, C6H4C12
1,4-dichloro-
106-46-7'
Benzene, C6H3C13
1,2,4-trichloro-
Benzophe- C13H8C120
none, 4,4'- Dichloro-
Ethane, 1,1- C14H10C1«
Dichloro-2,2-
Bis(p-Chlorophenyl)-
[DDD]
120-82-11
90-98-2
72-54-8
f
Oral-human
Oral-human
Eye-human
Oral-rat
Intraperitoneal-rat
Oral-mouse
Subcutaneous-mouse
Oral-guinea pig
Unreported-man
TLm 96 Oral-rat
10-1 ppm Oral-mouse
Intraperitoneal-mouse
Skin-rabbit
Intraperi toneal-mouse
Oral-human
Oral-rat
Oral-rat
Oral-mouse
Skin-rabbit
Bacteria-S. Marcescens-
mouse
LDLo:
TDLo-
LD50:
LD50.
LD50
LD50.
LDLo
LDLo:
LD50:
LD50:
LDLo.
500 mg/kg
300 mg/kg
80 ppm
500 mg/kg
2,562 mg/kg
2,950 mg/kg
5,145 mg/kg
2,800 mg/kg
221 mg/kg
756 mg/kg
766 mg/kg
500 mg/kg
1,950 mg
TLV (air): 75 ppm
Systemic
Irritation OSHA std (air):
TWA 75 ppm
TLV (air):
5 ppm
13WI
Moderate
Irritation
LD50:
LDLo:
LD50.
TDLo:
TDLo:
LD50:
200 mg/kg
5,000 mg/kg
113 mg/kg
54 gm/kg
39 gm/kg
1,200 mg/kg
1,500 mg/kg
78WC
2YC
Equivocal
Tumorigenic
Agent
Neoplastic
Mutation
-------
TOXIC ITY OF COMPOUNDS
PINE RIVER
St. Louis, Michigan
Compound Name
Molecular
Formula
Chemical
Abstracts
Service No.
Aquatic Toxici
ity" Route of
Entry
Other Toxici ty Data
Species
Type of
Dose
Dose
. Exposure
Duration0 Effects Limits
Ethylene, 1,1-
Dichloro-2,2-
Bis(p-Chlorophenyl )-
[DDE]
Ethane, 2- CMH9C15
(o-Chlorophenyl)-
2-(p-Chlorophenyl)-
1,1,1-Trichloro-
[ o,p'-DDT]
CMH8C1« 72-55-9
f
789-02-6
Oral-rat
Oral-mouse
Oral-mouse
Oral-mouse
Lymphocyte-somatic
cells-mouse
Oral-mouse
Oral-mouse
LD50
LDLo
TDLo:
TD.
880 dig/kg
200 mg/kg
28 gin/ kg
17 gm/kg
40 mg/L
80WC
78WC
4H
TDLo: 9,700 mg/kg 78WC
LDLo: 1,000 mg/kg
Ethane, 1,1,1-
Trichloro-
2,2-Bis(p-Chlorophenyl)-
[p.p'-DDT]
C14H9C15 50-29-31
TLm 96 under Oral-infant
1 ppm Oral -human
Unreported-man
Oral-rat
Oral-rat
Skin-rat
I n traperi toneal - rat
Subcutaneous-rat
Intravenous-rat
Oral-mouse
Oral-mouse
I ntraperi toneal -mouse
Subcutaneous-mouse
Oral-dog
Intravenous-dog
Intravenous-monkey
Oral-cat
Intravenous-cat
Oral -rabbit
Skin-rabbit
Subcutaneous- rabbit
Intravenous- rabbit
Oral-guinea pig
Skin-guinea pig
Subcutaneous-guinea pig
Oral-chicken
Subcutaneous- frog
Oral-domestic
Lymphocyte- somat i c
cells-human
Oral-rat
Oral -monkey
Oral -mouse
LDLo.
TDLo:
LDLo:
LD50:
TDLo:
LD50:
LD50:
LD50.
LDLo.
LD50:
TDLo:
LD50:
TDLo:
LDLo:
LDLo.
LDLo-
LDLo:
LDLo:
LD50-
LD50:
LD50-
LDLo.
LD50:
LD50:
L050.
LDLo
LD50
LDLo:
LD50:
TD
150 mg/kg
6 mg/kg
221 mg/kg
113 mg/kg
14 gm/kg
1,931 mg/kg
225 mg/kg
1,500 mg/kg
30 mg/kg
135 mg/kg
73 mg/kg
280 mg/kg
200 mg/kg
300 mg/kg
75 mg/kg
50 mg/kg
250 mg/kg
40 mg/kg
250 mg/kg
300 mg/kg
250 mg/kg
50 mg/kg
150 mg/kg
1,000 mg/kg
900 mg/kg
300 mg/kg
35 mg/kg
300 mg/kg
200 ug/1
100 mg/kg
200 mg/kg
11 qm/kg
80WC
26WC
40WI
72H
78WC
Neoplastic
Carcinogenic
Mutation
Carcinogenic
Central
Nervous
System
Neoplastic
TLV (air) Img/m3
OSHA std (air)-
TWA 1 mg/m3
(skin)
Carcinogenic
Carcinogenic
Mutation
Mutation
Equivocal
Tumongenic
Agent
CD
i
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TOXIC! 1 Y Of COMI'OUNuS
PINE RIVER
St. Louis, Michigan
Chemical
Compound Name Molecular Abstracts Aquatic Toxicity" Route of
Formula Service No. Entry " Species
Methoxychlor C1CH15C1302 72-43-5
1-Propanol, 2,3,- C3HBBr20 96-13-9
Dibromo-
Styrene, chloro- C8H7C1 1331-28-8
Oral -human
Skin-human
Oral-rat
Oral-rat
Oral -rat
Intrapentoneal-vat
Oral-mouse
Intrapen toneal-mouse
Skin-rabbit
Eye- rabbit
Oral-rat
Skin- rabbit
Other
Type
Dose
LDLo-
TDLo:
TDLo
LD50:
TDLo:
LDLo
LD50.
LDLo:
LD50:
LD50-
Toxicity Data
of
Dose
6,430 mg/kg
2,414 mg/kg
2,000 mg/kg
5,000 mg/kg
2,000 mg/kg
500 mg/kg
1,850 mg/kg
125 mg/kg
10 mg
500 mg
5,200 mg/kg
20 gm/kg
Durationc
6-150
(preg)
6-150
(preg)
24H
oo
i
cn
d Exposure
Effects Limits
Teratogenic
Teratogenic
Irritation TLV (air):
Irritation 50 ppm
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TOXICITY OF COMPOUNDS
PINE RIVER
St. Louis, Michigan
a Aquatic Toxicity:
b Type of Dose
c Duration
TLm 96:
LD50 -
LCLo -
LC50 -
LDLo -
TOLo -
TCLo -
TO
H
H
D
W
Y
C
I
96-hour static or continuous flow standard protocol, in parts per million (ppm)
lethal dose 50% kill
lowest published lethal concentration
lethal concentration 50% kill
lowest published lethal dose
lowest published toxic dose
lowest published toxic concentration
toxic dose
minute.
hour
day
week
year
continuous
intermittent
d Effects
Blood - Blood effects; effect on all blood elements, electrolytes, pH, protein, oxygen carrying or releasing capacity.
Carcinogenic - Carcinogenic effects, producing cancer, a cellular tumor the nature of which is fatal, or is associated with the formation
of secondary tumors (metastasis).
Central Nervous System - Includes effects such as headaches, tremor, drowsiness, convulsions, hypnosis, anesthesia.
Eye - Irritation, diplopia, cataracts, eye ground, blindness by affecting the eye or the optic nerve.
Gastrointestinal - diarrhea, constipation, ulceration
Irritation - Any irritant effect on the skin, eye or mucous membrane.
Mutation - Transmissible changes produced in the offspring
Neoplastic - The production of tumors not clearly defined as carcinogenic.
Psychotropic - Exerting an effect upon the mind.
Pulmonary - Effects on respiration and respiratory pathology.
Systemic - Effects on the metabolic and excretory function of the liver or kidneys.
Teratogenic - Nontransmissible changes produced in the offspring.
Equivocal Tumorigenic Agent - those studies reporting uncertain, but seemingly positive results.
e Exposure Limits. NR - not reported
NIOSH - National Institute for Occupational Safety and Health
OSHA - Occupational Safety and Health Act of 1970
TWA - time-weighted average concentration
TLV - threshold limit value
Cl - ceiling
Pk - peak concentration
f This chemical has been selected for priority attention as point source water effluent discharge toxic pollutant (NRDC vs Train consent decree)
CD
i
en
CO
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APPENDIX C
TOXIC DATA COMPILATION METHODS
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C-l
TOXIC DATA COMPILATION METHODS
Fourteen compounds were identified in the water and/or sediment
samples collected during the Pine River Investigation. Seven of the
fourteen compounds are listed as priority pollutants.
To obtain toxicity and health effects information for the 14 compounds,
two main sources were used. Those compounds for which toxic information
was not located are listed in the conclusion.
REGISTRY OF TOXIC EFFECTS OF CHEMICAL SUBSTANCES (RTECS)
RTECS contains toxicity data for about 37,000 substances, but does
not presently include all chemicals for which toxic effects have been
found. Chemical substances in RTECS have been selected primarily for
the toxic effect produced by single doses, some lethal and some non-
lethal/ Substances whose principal toxic effect is from chronic exposure
are not presently included. Toxic information on each chemical substance
was compiled from published medical, biological engineering, chemical
and trade information.
The RTECS search yielded information on 12 of the 14 compounds.
TOXICOLOGY INFORMATION ONLINE (TOXLINE)
The Toxline data base, a computerized bibliographic retrieval
system for toxicology, contains 692,394 records taken from material
published in primary journals, was also searched. It is part of the
MEDLARS system from the National Library of Medicine and is composed of.
11 subfiles:
1. Chemical-Biological Activities, 1965-
(Taken from Chemical Abstracts, Section 1-5, Sections 62-64,
Section 8 - Radiation Biochemistry, Section 59 - Air Pollution
and Industrial Hygiene, and Section 60 - Sewage Wastes.)
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C-2
2. Toxicity Bibliography, 1968-
(A subset of Medline)
3. Pesticides Abstracts, 1966-
(Compiled by the Environmental Protection Agency and formerly
known as Health Aspects of Pesticides Abstracts Bulletin.)
4. International Pharmaceutical Abstracts, 1970-
(Product of the American society of Hospital Pharmacists)
5. Abstracts on Health Effects of Environmental Pollutants, 1972-
(Comprised of profiles from BIOSIS data bases only)
6. Hayes File on Pesticides, 1940-1966
(A collection of more than 10,000 citations to published
articles on the health aspects of pesticides)
7. Environmental Mutagen Information Center File, 1960-
(Prepared at the Environmental Mutagen Information Center, Oak
Ridge National Laboratory, Tennessee.)
8. Toxic Materials Information Center File, 1971-1975
(Prepared at the Oak Ridge National Laboratory, Oak Ridge,
Tennessee.)
9. Tetratology File, 1960-1974
(Closed subfile of citations on tetratology)
10. Environmental Tetratology Information Center File, 1950-
(From the Oak Ridge National Laboratory, Oake Ridge, Tennessee)
11. Toxicology/Epidemiology Research Projects, October 1978-
(Projects selected from the Smithsonian Science Information
Exchange - SSIE data base.)
The Toxline search yielded 7,539 citations from the 14 compounds,
providing support to the toxic data from RTECS.
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C-3
ADDITIONAL SOURCES
Additional sources searched to locate toxic information were:
(1) Merck Index; (2) Toxicology Data Bank (TDB) from the National Library
of Medicine, which currently contains information on 2,514 substances;
(3) Oil and Hazardous Materials Technical Assistance Data System (OHMTADS),
an EPA file containing toxic data for about 1,000 compounds.
COMPOUNDS NOT LOCATED
Specific toxic data from RTECS were not located for the following
compounds detected in the water and/or sediment samples:
HBB (Hexabromobenzene)
PBB (Polybrominated Biphenyls)
However, there is an abundance of information in the published
literature (EPA reports, laboratory animal toxicity studies, aquatic
studies and epidemiological studies) on the adverse effects of these
2 compounds.
L'£*tut O V
3 3
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