MONITORING TO DETECT
PREVIOUSLY UNRECOGNIZED POLLUTANTS
IN SURFACE WATER
July 1977
Office of Toxic Substances
Environmental Protection Agency
Washington, D.C. 20460
-------
EPA-560/7-77-001
MONITORING TO DETECT PREVIOUSLY UNRECOGNIZED
POLLUTANTS IN SURFACE WATERS
INSTITUTE FOR ENVIRONMENTAL STUDIES
University of Illinois at Urbana-Champaign
B. B. Ewing Principal
E. S. K. Chian Investigators
J. C. Cook J. C. Means
F. B. DeWalle R. Milberg
C. A. Evans E. G. Perkins
P. K. Hopke J. D. Sherwood
J. H. Kim W. H. Wadlin
Final Report
Contract No. 68-01-3234
July 1977
Project Officer—Vincent J. DeCarlo
Prepared for
Office of Toxic Substances
U.S. Environmental Protection Agency
Hashington, D.C. 20460
Document is available to the public through the National Technical Information
Service, Springfield, Virginia 22151
-------
NOTICE
This report has been reviewed by the Office of Toxic Substances, EPA,
and approved for publication. Aprroval does not signify that the contents
necessarily reflect the views and policies of the Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
n
-------
CONTENTS
LIST OF ILLUSTRATIONS iv
LIST OF TABLES v
ACKNOWLEDGMENTS vii
INTRODUCTION 1
Background and Objectives 1
Organization 1
Sample Collection and Analysis Schedule 3
SITE SELECTION, SAMPLE COLLECTION, AND GROSS ANALYSIS
Site Selection 6
Sample Collection 29
Gross Analysis 32
SAMPLE PREPARATION
Stripping Procedures 35
Liquid-liquid Extraction 37
Sorptive Extraction Technique 39
INORGANIC ANALYSIS 42
Spark-source Mass Spectral Analysis 44
Instrumental Neutron Activation Analysis 46
Energy-dispersive X-ray Fluorescence Analysis 49
ORGANIC ANALYSIS
Identification of Organics 52
Quantitation of Organics 54
Summary of the Organic Compounds Found 63
REFERENCES 75
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ILLUSTRATIONS
1. Industrialized Areas Sampled 2
2. Sample Collection and Analysis Schedule 4
3. Sites Sampled in the Chicago Metropolitan Area 8
4. Sites Sampled in the Illinois River Basin 9
5. Sites Sampled in the Delaware River Basin 11
6. Sites Sampled in the Hudson River Basin 13
7. Sites Sampled on the Upper and Middle Mississippi River 15
8. Sites Sampled on the Lower Mississippi River 16
9. Sites Sampled in the Houston Area 17
10. Sites Sampled in Alabama 18
11. Sites Sampled in the Ohio River Basin 20
12. Sites Sampled in the Great Lakes and Their Tributaries 22
13. Sites Sampled in the Tennessee River Basin 23
14. Sites Sampled in the Greater Los Angeles Area 25
15. Sites Sampled in the San Francisco Bay Area 26
16. Sites Sampled on the Willamette River and in the Greater Portland Area 27
17. Sites Sampled in the Seattle-Tacoma Area 28
18. Rate of Water Inflow into a Sample Bottle Suspended at Constant Depths 30
19. Rate of Water Inflow into a Sample Bottle Released at Different Heights 31
20. Procedure for Stripping Volatile Organic Compounds 36
21. Procedure for the Extraction of the Less-volatile Organics 38
22. Flow Diagram of Experimental Setup for Sorptive Studies 41
23. Schematic Diagram of Volatile Organic Elution System 55
24. Gas-chromatographic Trace of a Representative System Blank 59
IV
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TABLES
1. Sampling Sites in the Chicago Area and the Illinois River Basin 7
2. Sampling Sites in the Delaware River Basin 10
3. Sampling Sites in the Hudson River Basin 12
4. Sampling Sites in the Mississippi River Basin, in Alabama, and in Texas 14
5. Sampling Sites in the Ohio River Basin 19
6. Sampling Sites in the Great Lakes and the Tennessee River Basin 21
7. Sampling Sites on the West Coast 24
8. Location of Gross Analysis Data for All Samples 33
9. Summary of Gross Analysis Data 34
10. Directory of Inorganic Analyses 43
11. Gas Chromatograph Column Conditions 56
12. Extraction Efficiencies of Selected Amines 61
13. Relative Retention Times and Relative
Response Factors for Selected Amines on 3% OV-17 62
14. Relative Retention Times and Relative Response
Factors for Selected Amines on 10% Apiezon L/2% KOH 62
15. Acid-extractable Compounds and Their Frequency of Occurrence 65
16. Base-extractable Compounds and Their Frequency of Occurrence 69
17. Volatile Compounds and Their Frequency of Occurrence 72
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ACKNOWLEDGMENTS
The Institute for Environmental Studies and the project team members
express their appreciation to Dr. Larry Keith, formerly of the USEPA laboratory
in Athens, Georgia, to Dr. John McGuire of the Athens laboratory, and to Dr.
Billy Fairless of the USEPA Region V office for valuable advice on the refine-
ment of sample preparation and analysis techniques. Gratitude is also expressed
to the many local, state, and federal officials whose cooperation greatly
facilitated the process of locating sampling sites and collecting samples.
-------
1, INTRODUCTION
This report summarizes the activities and accomplishments of a
research project conducted to detect previously unrecognized pollutants in
surface waters. The work was supported by the U. S. Environmental Protection
Agency under Contract No. 68-01-3234.
BACKGROUND AND OBJECTIVES
The heavy concentration of industry in certain areas of the United
States has caused increasing concern about the introduction of contaminants
into our surface waters, especially since some constituents of industrial
waste discharges have proven to be carcinogenic or toxic at trace levels.
With the proliferation of new chemical substances it is likely that some
potentially harmful pollutants in our surface waters have gone undetected.
At the same time as waste discharges to our waterways have increased, we have
come to rely more heavily on those water resources not only for industrial but
also for municipal water supplies. It was therefore deemed vital to detect
contaminants wherever they may be present.
The purpose of the present study was to undertake a sampling and ana-
lytical survey to determine, insofar as possible, the identities and semi quan-
titative concentrations of organic compounds and inorganic elements present in
the waterways around industrial centers in the United States.
A total of 204 water samples were collected from fourteen heavily
industrialized river basins. These areas and the number of samples taken from
each are indicated in Figure 1. Each sample was analyzed using state-of-the-
art techniques for detecting trace contaminants.
ORGANIZATION
This interdisciplinary project, conducted at the University of Illinois
at Urbana-Champaign, was administered by the Institute for Environmental Studies.
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CHATTANOOGA
MEMPHIS —v^/x"~
Encircled numbers indicate quantity of
samples to be collected in each area.
ro
Figure 1. Industrialized areas sampled.
-------
It involved the personnel and facilities of five university units. The pro-
ject was directed by the co-principal investigators, Professor E. S. K. Chian,
Department of Civil Engineering, and Professor B. B. Ewing, Director of the
Institute. The participating units and principal research personnel were:
Department of Civil Engineering
Site Selection—E. S. K. Chian and F. B. DeWalle
Sample Collection—F. B. DeWalle
Sample Preparation—E. S. K. Chian and J. H. Kim
Department of Chemistry
Identification of Organics—K. L. Rinehart, J. C. Cook, and
R. Milberg
Department of Food Science
Quantification of Organics—E. G. Perkins and J. C. Means
Materials Research Laboratory
Inorganic Analysis (SSMS)—C. A. Evans and W. H. Wadlin
Institute for Environmental Studies
Inorganic Analysis (INAA and XRF)—P. K. Hopke and J. D. Sherwood
Editing and Publication—T. W. Knecht
SAMPLE COLLECTION AND ANALYSIS SCHEDULE
The research contract was executed for initiation on July 1, 1975, for
an 18-month period to terminate December 31, 1976. The first six samples were
collected in the Chicago area in August 1975. The initial six months of the
project were devoted to staffing, development of methods, and the analysis of
these six samples. The sampling rate was then increased so that all sampling
would be completed by September 1976 and was adjusted as necessary to keep
sample collections only moderately in advance of the analysis process. The
sampling schedule for the entire project is shown in Figure 2. All samples
were numbered in the chronological sequence of collection.
-------
220
200
180
160
(/>
£ 140
5>
120
.a
E
100
80
60
40
20
0
E - Extractable Organic Analyses
VOA - Volatile Organic Analyses
SSMS - Spark-Source Mass Spectral Analyses
INAA - Instrumental Neutron Activation Analyses
Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan
1975 1976
Date
Figure 2. Sample collection and analysis schedule.
-------
Inorganic analyses by x-ray fluorescence and spark-source mass spec-
trometry were completed at a rate of approximately 20 samples per month,
closely following the delivery of the samples to the University of Illinois
campus. It was intended that instrumental neutron activation analysis be
performed at the same rate, but after processing 28 samples the schedule was
delayed for about three months because of an equipment failure.
Analysis for volatile organics was delayed a few months after pro-
cessing the initial six samples so that the methodology could be revised to
improve detection limits. Thereafter, the rate of analysis was increased to
about 30 samples per month until the backlog was reduced, after which it
followed the sampling schedule closely. The preparation and analysis of
extractable organics generally followed the collection schedule throughout
the last 12 months of the project. The organic and inorganic analysis
schedules are also shown in Figure 2.
-------
2, SITE SELECTION, SAMPLE
COLLECTION, AND GROSS ANALYSIS
SITE SELECTION
E. S. K. Chian
F. B. DeWalle
During the study, water samples were collected from 204 sites across
the continental United States. The areas sampled and the number of samples
collected in each are indicated in Figure 1. The sites were chosen in such a
way that the concentration of organic and inorganic contaminants in the col-
lected water samples would be affected by industrial pollutants and so that all
principal types of industry would be represented. So that the impact of indus-
trial discharges on water quality could be assessed, a limited number of samples
were generally taken upstream from industrial sources in the less polluted
reaches of rivers while the majority of the samples were collected from the
waterways near major industrial areas. Several downstream sites were also
sampled to indicate the extent to which contaminant concentrations were atten-
uated.
The samples were generally taken at sampling locations established
by state or federal water pollution regulatory agencies. The sites are listed
in Tables 1 through 7 along with the coordinates and description of their
locations. The maps presented in Figures 3 through 17 show the general position
of each site along the waterways sampled.
Ninety-one of the sites were located along major rivers such as the
Hudson, the Delaware, the Mississippi, the Ohio, and the Tennessee. Fifty-seven
samples were collected in tidal areas and estuaries, such as the Hudson River
estuary, the Delaware River estuary, Mobile Bay, Galveston Bay, Los Angeles
Harbor, San Francisco Bay, and Puget Sound. Twelve sites were located in manmade
canals and three in major lakes. Since industrial wastewater is often treated
at municipal sewage treatment plants, four samples were taken from effluent
discharge structures.
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Table 1
Sampling Sites in the Chicago Area and the Illinois River Basin
Sample
Number
Waterway
Station
Latitude
Longitude
Nearest
Bridge,
Point, River
or Highway
Nearest
Town
Remarks
WSW Sewage Treatment Plant 41.48.51 87.46.11
Chicago Central Water Wks
Calumet-Sag Channel Highway 83 Bridge
Calumet-Sag Channel Ashland Avenue Bridge
Chicago Sanitary Lockport Powerhouse
& Ship Canal
Chicago Sanitary
& Ship Canal
41.53.45
41.41.53
41.39.22
41.34.08
87.36.20
87.56.12
87.39.39
88.04.41
Highway 83 Bridge
41.42,02 87.56.22
Pershing & Austin Roads
Lake Shore Drive & Ohio St.
U.S. Highway 83
Ashland Avenue
U.S. Highway 83
Stickney, IL
Chicago, IL
Lemont, IL
Blue Island, IL
Lockport, IL
Lemont, IL
Final effluent after sec.
sedimentation & chlorination
Final tap water
Midstream
Midstream
From sideline of large
water tunnel.
Midstream
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Chicago Sanitary
& Ship Canal
—
—
Indiana Harbor Cnl .
Calumet River
Calumet-Sag Channel
Calumet-Sag Channel
—
Chicago Sanitary
& Ship Canal
Calumet River
Calumet-Sag Channel
Des Plaines River
Illinois River
Illinois River
Illinois River
Illinois River
Illinois River
Illinois River
Illinois River
Illinois River
Chicago Central Water Wks
Chicago Central Water Wks
Lockport Powerhouse
North Side Sewage
Treatment Plant
West Side Sewage
Treatment Plant
Calumet Sewage
Treatment Plant
South West Filtration Plant
Indiana Harbor
Calumet River
Ashland Avenue Bridge
Highway 83 Bridge
Chicago Central Water Wks
Lockport Powerhouse
Highway 41 Bridge
Ashland Avenue Bridge
Des Plaines River
Dresden Island Lock & Dam
Utica, Illinois
Hennepin, Illinois
Peoria Water Works
Peoria Water Works
Pekin, Illinois
Havana, Illinois
Meredosia, Illinois
Hardin, Illinois
41.53.45
41.53.45
41.34.08
42.01.11
41.48.51
41.39.36
41.47.10
41.39.19
41.39.36
41.39.22
41.41.53
41.53.45
41.34.08
41.43.37
41.39.22
41.25.25
41.23.53
41.19.29
41.15.00
40.43.30
40.43.30
40.34.25
40.18.00
39.50.00
39.10.00
87.36.20
87.36.20
88.04.41
87.42.42
87.46.11
87.44.23
87.32.00
87.27.34
87.44.23
87.39.39
87.56.12
87.36.20
88.04.41
87.42.30
87.39.39
88.11.35
88.16.45
89.02.00
89.23.00
89.33.10
89.33.10
89.39.15
90.04.00
90.34.00
90.37.00
Lake Shore Drive & Ohio St.
Lake Shore Drive 8 Ohio St.
-.-
Howard and McCormick Blvd.
Pershing and Austin Roads
130th St. & Lawrence Ave.
South Shore Dr. & Chattenham
Dickey Road
130th Street Bridge
Ashland Avenue
U.S. Highway 83
Lake Shore Drive » Ohio St.
...
U.S. Highway 83
Ashland Avenue
U.S. Highway 55
—
U. S. Highway 178
U. S. Highway 26
—
—
U. S. Highway 9
U. S. Hiahway 97
U. S. Highway 104
U. S. Highway 100
Chicago, IL
Chicago, IL
Lockport, IL
Lincolnwood, IL
Stickney, IL
Chicago, IL
Chicago, IL
E. Chicago, IN
Chicago, IL
Blue Island.'IL
Lemont, IL
Chicago, IL
Lockport, IL
Chicago, IL
Blue Island, IL
El wood, IL
Dresden, IL
Utica, IL
Hennepin, IL
Peoria, IL
Peoria, IL
Pekin, IL
Havana, IL
Meredosia, IL
Hardin, IL
Untreated L. Michigan V'tr.
Final tap water after
chlorination
Tunnel water (field
extracted & stripped)
Final effluent after
chlorination
Final effluent after
chlorination
Final effluent after
chlorination
Final tap water after
chlorination
Midstream
Midstream
Midstream
Midstream
Final tap water (XAD,
carbon extractions)
Tunnel water (XAS,
carbon extractions)
Near mouth, midstream
Midstream
Midstream
Midstream
Midstream
Midstream
Untreated river water
Finished water
Midstream
Midstream
Midstream
Midstream
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LAKE MICHIGAN
Sampling locations shown
within concentric circles
Figure 3. Sites sampled in the Chicago metropolitan area.
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((Sampling Locations
1 .inch = 38 miles
Figure 4. Sites sampled in the Illinois River basin.
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Table 2
Sampling Sites in the Delaware River Basin
Sample
Number Waterway
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Delaware River
Schuylkill River
Schuylkill River
Schuylkill River
Delaware River
Delaware River
Lehigh River
Lehigh River
Lehigh River
Lehigh River
Delaware River
Delaware River
Delaware River
Delaware River
Station
St. John
Reedy Island
D. Memorial Bridge
Marcus Hook
Paulsboro
Navy Yard
B. Franklin Bridge
Five Mile Point
Torresdale Range
Bristol
D. Memorial Bridge
Mouth
Mouth
Mouth
Mouth
Margaretville
St. John
Mouth
Queens Lane
Queens Lane
Torresdale
Torresdale
Allentown
Hill to Hill
Bethlehem
Easton
Easton
Trenton
Trenton
Frenchtown
Latitude
39.
39.
18.
30.
39.42.
39.
39.
39.
39.
39.
40.
40.
39.
38.
38.
39.
39.
42.
39,
39.
39.
39.
40.
40.
47.
.50.
52.
57.
53.
.02.
05.
42.
,49.
.58.
14
46
35
55
54
39
10
40
00
13
35
60
53
03.03
.10.
50
22.42
,18.
53.
,58.
58.
02.
02.
40.37.
40.
40.
40.
40.
40.
40.
40.
36.
37.
.41.
.42.
.13.
,13.
,31.
14
24
00
00
24
24
22
58
11
13
43
17
17
40
Longitude
75.22.57
75.33.12
75.32.13
75.25.48
75.15.53
75.11.45
75.08.10
75.04.35
74.59.20
74.51.12
75.32.13
75.01.40
75.07.42
75.10.00
75.16.24
74.32.18
75.22.57
75.11.45
75.11.05
75.11.05
74.59.40
74.59.40
75.28.57
75.22.40
75.20.11
75.12.32
75.11.48
74.46.44
74 . 46 . 44
75.04.00
Nearest Point, River
Bridge, or Highway
Bombay Hook Pt.
—
U.S. Highway 295
Blue Ball Avenue
Little Tinicum Island
West Horseshoe Range
U.S. Highway 676
Frankford Creek
Pennypack Creek
Otter Creek
U.S. Highway 295
Cape Henlopen
Brandywine Shoal
Fourteen Foot Bank
Elbow of Cross Ledge
McGregor Mnt. on U.S. Hwy 30
Bombay Hook Point
Reserve Basin
U.S. Hwy 1 to U.S. Hwy 76
U.S. Hwy 1 to U.S. Hwy 76
City Water Treatment Plant
City Water Treatment Plant
Tilghman Street
Wyandelle Ave. , P.S. Hwy 378
Freemonsburg Bridge
S. Delaware St., P.S. Hwy 611
N. Delaware Drive, City WTP
City WTP, P.S. Hwy 29
City WTP, P.S. Hwy 29
N.J.S. Hwy 12
Nearest
Town
Woodland Beach, DE
Port Penn, DE
Pigeon Point, DE
Marcus Hook, PA
Paulsboro, NJ
Philadelphia, PA
Philadelphia, PA
Brides burg, PA
Torresdale, PA
Bristol , PA
Pigeon Point, DE
Lewes, DE
Fowlers Beach, DE
Big Stone Beach, DE
Pickering Beach, DE
Margaretville, DE
Woodland Beach, DE
Philadelphia, PA
Philadelphia, PA
Philadelphia, PA
Torresdale, PA
Torresdale, PA
Allentown, PA
Bethlehem, PA
Bethlehem, PA
Easton, PA
Easton, PA
Trenton, NJ
Trenton, NJ
Frenchtown, NJ
Remarks
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
mid
channel ;
channel;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel ;
channel;
channel ;
channel ;
channel ;
channel ;
low slack tide
low slack tide
low slack tide
low slack tide
low si ack tide
low slack tide
low slack tide
low slack tide
low slack tide
low slack tide
high slack tide
high slack tide
high slack tide
hiqh slack tide
high slack tide
high slack tide
high slack tide
low slack tide
non tidal
finished water
high slack tide
finished water
non tidal
non tidal
non tidal
non tidal
non tidal
non tidal
finished water
non tidal
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11
LEHIGH
RIVER
57(
61
SCHUYLKILL
RIVER
60
Figure 5. Sites sampled in the Delaware River basin.
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Table 3
Sampling Sites in the Hudson River Basin
Sample
Number
62
63
64
65
66
57
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
Waterway
Raritan Bay
Raritan Bay
Arthur Kill
Arthur Kill
Arthur Kill
Arthur Kill
Arthur Kill
Newark Bay
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Hudson River
Mohawk River
Mohawk River
Passaic River
Hackensack River
Hudson River
Hudson River
Hudson River
Station
Perth Amboy
Perth Amboy
Perth Amboy
Sewaren
Tufts Point
Tremley Point
Port Elizabeth
Newark
Bayonne
Narrows
Lower Bay
Beacon
Poughkeepsie
Poughkeepsie
Kingston
Catskill
Glenmont
Waterford
Thomson
Glens Falls
Corinth
Schenectady
Waterford
Mouth
Mouth
Fort Lee
Piermont
lona
Latitude
40.29.12
40.29.46
40.30.44
40.33.05
40.34.42
40.36.17
40.38.47
40.39.17
40.39.11
40.36.20
40.32.10
41.30.18
41.44.05
41.44.05
41.55.40
42.12.36
42.35.43
42.47.50
43.07.36
43.18.20
43.14.53
42.49.07
42.49.07
40.43.54
40.43.39
40.50.37
41.02.34
41.18.51
Lonai tude
74.14.21
74.16.52
74.15.34
74.15.00
74.13.00
74.12.08
74.10.42
74.08.47
74.03.43
74.02.45
74.01.35
74.59.21
73.56.15
73.56.15
73.57.44
73.51.12
73.45.43
73.40.33
73.35.16
73.36.58
73.49.49
73.56.59
73.56.59
74.07.04
74.05.57
73.58.03
73.53.48
73.59.08
Nearest Point, River
Bridge, or Highway
Hard Point Bent
CRR of N.J. RRB at Sandy Pt.
Ferry Dock
Smith Creek
Fresh Kills
Pralls Island
North of Shooter's Range -
CRR of N.J. RRB, Bergen Pt.
Robbins Reef
Verrazano Bridge, U.S. 278
Romer Shoal
Main Street
City Water Treatment Plant
City Water Treatment Plant
N.Y.S. Hwy 30
N.Y.S. Hwy 385
Elect. Power & Light Co.
N.Y.S. Hwy 32
U.S. Hwy 4
N.Y.S. Hwy 32
N.Y.S. Hwy 9N
fl.Y.S. Hwy 50
N.Y.S. Hwy 32
Lincoln Hwy, U.S. Hwy 1/9
Lincoln Hwy, U.S. Hwy 1/9
N.Y.S. Hwy 505
Continental Can Dock
Bear Mountain Bridge
Nearest
Town
Tottenville, NY
Perth Amboy, NO
Perth Amboy, NJ
Sewaren, NJ
Chrome, NJ
Graselli, NJ
Port Elizabeth, NJ
Newark, NJ
Bayonne, NJ
Rosebank, NY
Sandy Hook, NJ
Beacon, MY
Poughkeepsie, NY
Poughkeepsie, NY
Kingston, NY
Catskill , NY
Glenmont, NY
Waterford, NY
Thomson, NY
Glens Falls, NY
Corinth, NY
Schenectady, NY
Waterford, NY
Newark, NJ
Jersey City, NJ
Fort Lee, NJ
Piermont, MY
Ft. Montgomery, NY
Remarks
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
mid channel; low slack tide
shore sample; low slack tide
shore sample; low slack tide
finished water
shore sample; low slack tide
shore sample; low slack tide
shore sample; low slack tide
mid channel; non tidal
mid channel; non tidal
mid channel; non tidal
mid channel; non tidal
shore samole; non tidal
mid channel; non tidal
mid channel; low slack tide
mid channel; low slack tide
shore sample; low slack tide
shore sample; low slack tide
shore sample; low slack tide
ro
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13
ARTHUR 68.
KILL
RARITAN
RIVER
RARITAN BAY
LOWER BAY
MOHAWK
RIVER
82
HUDSON
RIVER
76
NEW YORK AREA
HUDSON AREA
Figure 6. Sites sampled in the Hudson River basin.
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Table 4
Sampling Sites in the Mississippi River Basin, in Alabama, and in Texas
Sample
Number
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
Waterway
Mississippi River
"
11
11
11
11
11
"
11
Wisconsin River
11
"
Buffalo Bayou
Houston Ship Channel
11
11
"
11
Galveston Bay
"
Mississippi River
"
11
11
11
11
11
11
Mobile Bay
"
Mobile River
Black Warrior River
"
11
11
Mississippi River
"
"
"
"
"
Illinois River
Mississippi River
11
11
Station
State Highway 6
Fourth St., Minneapolis
Wabash St., Minneapolis
St. Paul Intake
St. Paul Finished Water
Lock and Dam 3
Reads Landing
Weaver Bottom
Lower Weaver Bottom
Wausau
Nekoosa
Bridgeport
Shepard Dr.
Morgan Point
Lynchburg Ferry
Tuckers Bayou
North Shaver Road
Turning Basin
Pelican Island
Red Fish Bay
Head of Passes
Port Sulphur
Lul ing
Lutcher
New Orleans
Finished Water
Plaquemine
St. Francisville
Dauphin Island
Fowl River Pt.
McDuffie Island
Demopolis
Tuscaloosa
Bankhead L.D.
Atwood Ferry
Vicksburg
Memphis
Ensley Plantation
St. Louis
Finished Water
Lock and Dam 26
Highway 100
Jefferson Barracks
Lock and Oam 14
Lock and Dam 16
Latitude
46.32.40
44.51.12
44.56.40
45.07.33
45.00.10
44.36.40
44.24.45
44.12.29
44.12.26
44.56.55
44.17.46
43.00.00
29.45.30
29.40.24
29.45.39
29.44.30
29.43.24
29.44.54
29.21.54
29.29.37
29.09.08
29.28.39
29.56.19
30.01.55
29.57.03
29.57.55
30.17.38
30.45.30
30.06.35
30.29.30
30.39.25
32.32.30
33.06.05
33.27.36
33.35.12
32.19.36
35.12.42
35.03.50
38.42.06
38.42.06
38.53.48
39.09.24
38.29.10
41.32.36
41.27.24
Longitude
93.57.09
93.00.35
93.05.19
93.16.36
93.10.50
92.36.42
92.06.47
91.47.45
91.47.43
89.37.34
89.53.97
91.03.00
95.22.36
94.58.42
95.04.25
95.11.18
95.13.12
95.17.12
94.47.46
94.51.52
89.15.06
89.41.21
90.21.40
90.41.45
90.08.17
90.07.40
91.13.59
91.23.45
38.02.11
88.01.06
88.01.55
87.49.30
87.39.12
87.21.12
87.06.48
90.53.49
90.04.18
90.10.45
90.15.00
90.15.00
90.14.36
90.41.36
90.16.28
90.24.30
91.00.00
Nearest Point, River
Bridge, or Highway
M.S. Hwy 6
4th Ave. and County Hwy 24
Wabash St.
Talraadge Lane
Roselawn
U.S. Hwy 63
U.S. Hwy 61
U.S. Hwy 61
U.S. Hwy 61
W.S. Hwy 52
Above Munic. STP
U.S. Hwy 18
—
Main Street
T.S. Hwy 134
Tidal Road
N. Shaver Rd., County 526
75th Street
T.S. Hwy 87
Eagle Point
—
M.S. Hwy 23
Ferry Crossing M.S. Hwy 18 & 44
Ferry Crossing M.S. Hwy 18 & 44
Eagle/Spruce
Eagle/Spruce
Ferry Crossing, M.S. Hwy 1 & 75
Ferry Crossing, M.S. Hwy 10
Middle Ground
Fowl River Point
McDuffie Island
U.S. Hwy 43/SL.SF RRB
U.S. Hwy 11 and 43
Lock and Dam
Atwood Ferry Bridge
U.S. Hwy 80
Loosahatchie River
Arvid Power Line Crossing
Chain of Rocks Br.U.S. 270
Chain of Rocks Br.U.S. 270
U.S. Hwy 67
I.S. Hwy 100
U.S. Hwy 50
I.S. Hwy 92
U.S. Hwy 80
Nearest
Town Remarks
Crosby, MN
Inver Grove Heights, MM
St. Paul , MN
Fridley, MN
Maplewood, MN
Red Wing, MN
Reeds Landing, MM
Weaver, MN
Weaver, MN
Uausau, WI
Nekoosa, WI
Bridgeport, WI
Houston, TX
Morgan Point, TX
Lynchburg, TX
Deer Park, TX
Pasadena Gardens, TX
Magnolia Park, TX
Galveston, TX
San Leon, TX
Venice, LA
Port Sulphur, LA
Lul ing, LA
Lutcher, LA
New Orleans, LA
New Orleans, LA
Plaquemine, LA
St. Francisville, LA
Dauphin Island, AL
Fowl River, AL
Mobile, AL
Demopolis, AL
Tuscaloosa, AL
Fosters, AL
Birmingham, AL
Vicksburg, MS
Memphis, TN
Ensley Plantation, TN
St. Louis, MO
St. Louis, MO
Alton, IL
Hardin, IL
Mehlville, MO
Muscatine, IA
Davenport, I A
Midchannel
Midchannel
Midchannel
Shore
Roseville
Midchannel
Midchannel
Midchannel
Near shore
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Shore
Shore
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Shore
liore
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
-------
15
90
MINNEAPOLIS
WISCONSIN
RIVER
MADISON
MISSOURI
RIVER,
Figure 7. Sites sampled on the upper and middle Mississippi River.
-------
16
ARKANSAS
RIVER
MISSISSIPPI
RIVER
RLEANS
Figure 8. Sites sampled on the lower Mississippi River.
-------
GULF OF
MEXICO
Figure 9. Sites sampled in the Houston area.
-------
18
MULBERRY FORK/
123)
VALLEY CREEK
TOMBIGBEE
RIVER
LOCUST FORK
xFIVE MILE CREEK
'VILLAGE CREEK
'BIRMINGHAM
TOMBIGBEE
RIVER
Figure 10. Sites sampled in Alabama.
-------
Table 5
Sampling Sites in the Ohio River Basin
Sample
Number Waterway
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
Ohio River
Tennessee River
Wabash River
Ohio River
Ohio River
Ohio River
Ohio River
Kanawha River
Ohio River
Ohio River
Ohio River
Ohio River
Ohio River
Ohio River
Ohio River
Monongahela River
Monongahela River
Allegheny River
Monongahela River
Monongahela River
Allegheny River
Beaver River
Beaver River
Ohio River
Ohio River
Ohio River
Ohio River
Station
Joppa
Calvert City
New Harmony
Evansville WTP
Evansville WTP
Cannelton LD
Louisville WTP
Winfield
Markland UD
Cincinnati WTP
Cincinnati WTP
Huntington WTP
Huntington WTP
Belleville LD
Joppa
Point Marion
Charlerni
Freeport LD
S. Pittsburgh WTP
S. Pittsburgh WTP
Oakmont WTP
Beaver Falls WTP
Beaver Falls WTP
South Heights
E. Liverpool WTP
E. Liverpool WTP
Wheeling WTP
Latitude
37.12,00
37.02.16
38.07.55
37.58.20
37.58.20
37.53.53
38.16.52
38.31.32
38.46.29
39.04.11
39.04.11
38.25.57
38.25.57
39.07.07
37.12.00
39.43.57
40.08.30
40.42.41
40.24.36
40.24.36
40.31.51
40.45.48
40.45.48
40.34.12
40.38.20
40.38.20
40.06.54
Longitude
88.51.00
88.31.46
87.56.25
87.34.35
87.34.35
86.42.20
85.42.08
81.54.40
84.57.52
84.25.57
84.25.57
82.25.57
82.25.57
81.44.32
88.51.00
79.54.42
79.53.35
79.34.59
79.57.15
79.57.15
79.50.12
80.18.55
80.18.55
80.13.47
80.31.15
80.31 .15
80.42.21
Nearest Point, River
Bridge, or Highway
Joppa Steam Plant
G.R. Clark Br., K.S. Hwy 60
U.S. Hwy 460
Inland Marina Y.C.
Inland Marina Y.C.
Lock and Dam
Falls City Boat Company
Lock and Dam
Lock and Dam
South of U.S. Hwy 275
South of U.S. Hwy 275
Tristate Materials Corp.
Tri state Materials Corp.
Lock and Dam
Joppa Steam Plant
Upstream from Lock & Dam 8
Belle Vernon Hwy Bridge
Above Lock & Dam 5
Bedes Run
Bedes Run
Twelve Mile Island
U.S. Hwy 18
U.S. Hwy 18
Duquesne Light Co. Intake
Mill Creek
Mill Creek
U.S. Army Base
Nearest
Town
Joppa, IL
Paducah, KY
New Harmony, IN
Evansville, IN
Evansyille, IN
Cannelton, IN
Louisville, KY
Winfield, WV
Markland
Cincinnati, OH
Cincinnati, OH
Huntington, WV
Huntington, WV
Belleville, IL
Joppa, IL
Point Marion, PA
Charleroi, PA
Freeport, PA
Pittsburgh, PA
Pittsburgh, PA
Oakmont, PA
Beaver Falls, PA
Beaver Falls, PA
South Heights, PA
E. Liverpool , OH
E. Liverpool , OH
Wheeling, WV
Remarks
Midstream
Midstream
Midstream
Raw water
Finished water
Midstream
Raw water
Midstream
Midstream
Raw water
Finished water
Raw water
Finished water
Midstream
Midstream
Midstream
Midstream
Midstream
Finished water
Raw water
Raw water
Finished water
Raw water
Midstream
Finished water
Raw water
Raw water
-------
WABASH
RIVER
137
TENNESSEE
RIVER
BEAVER
RIVER
ALLEGHENY
RIVER
KANAWHA
RIVER
150
MONONGAHELA
RIVER
ro
CD
Figure 11. Sites sampled in the Ohio River basin,
-------
Table 6
Sampling Sites in the Great Lakes and the Tennessee River Basin
Sample
Number
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
Waterway
St. Lawrence Seaway
Black River
Oswego River
Genessee River
Niagara River
Lake Erie
Fields Brook
Cuyahoga River
Maumee River
Detroit River
Detroit River
St. Clair River
St. Clair River
Grand River
Saginaw River
Lake Michigan
St. Mary's River
St. Louis River
Lake Superior
Fox River
Milwaukee River
Indiana Harbor Canal
French Broad
Holston River
Hiwassee River
Ocoee River
Chattanooga Creek
Tennessee River
Station
Cape Vincent
Dexter
Oswego
Rochester
Fort Niagara
Buffalo
Ashtabula
Cleveland
Toledo
Maple Beach
Detroit
Port Huron
Algonac
Grand Haven
Bay City
Cecil Bay
Brush Point
Duluth
Beaver Bay
Green Bay
Milwaukee
Chicago
Asheville, N.C.
Church Hill, Tenn.
Brittsville, Tenn.
Ducktown, Tenn.
Chattanooga, Tenn.
Paducah, Ky.
Latitude
44.07.58
44.00.15
43.27.23
43.13.59
43.14.14
42.52.47
41.53.28
41.29.15
41.41.35
42.03.20
42.16.21
43.00.11
42.37.15
43.03.35
43.38.10
43.45.35
46.28.46
46.44.58
47.16.00
44.32.12
43.01.29
41.39.19
35.36.32
36.31.00
35.22.03
35.00.13
35.01.08
37.02.16
Longitude
76.20.40
76.02.39
76.30.35
77.37.06
79.03.20
78.54.45
80.47.52
81.41.11
83.28.09
83.11.35
33.06.32
82.25.06
82.31.00
86.14.36
83.50.42
84.45.00
84.26.58
92.06.02
91.16.42
88.00.21
87.54.01
87.27.34
82.34.43
82.43.22
84.54.35
84.24.22
85.19.35
88.31.46
Nearest Point, River
Bridge, or Highway
Ferry to Alexandria
N.Y. S. Hwy 180
U.S. Hwy 104
Turning Basin, Rattlesnake Pt.
St. Catheriens Boat Club
Middle Reefs Crib Intake
Riverside Yacht Club
W. 3rd St. near U.S. 71 & 90
U.S. Hwy 65 Gage
Lee Rd. & Rockwood Drive
Ft. Gratiot Light
Ferry to Ualpole Isl .
Corps of Engineers Boatyard
Corps of Engrs. Field Office
One mile north of shore
Point aux Pins
West Gate Basin, U.S. 535
Near munic. ramp, Pellet Isl.
Green Bay Yacht Club
U.S. 794, Evinrude Exp. St.
Dickey Place, Cty Hwy 912
USGS Gaging Station, Rm* 144
Patterson Hill Br., Rm 131.5
I.S. Hwy 58 at Chickamonga L.
Rogers Bridge
L & N RR Bridge
Ashland Oil Terminal
Nearest
Town
Cape Vincent, NY
Dexter, NY
Oswego, NY
Rochester, NY
Youngstown, NY
Buffalo, NY
Ashtabula, OH
Cleveland, OH
Toledo, OH
Gibraltar, MI
Detroit, MI
Port Huron, MI
Algonac, MI
Grand Haven, MI
Bay City, MI
Mackinaw City, MI
Sault Ste. Marie,
Duluth, MN
Beaver Bay, HI
Green Bay, WI
Milwaukee, WI
East Chicago, IN
Asheville, NC
Church Hill, TN
Brittsville, TN
Ducktown, TN
Chattanooga, TN
Paducah, KY
Remarks
Midstream
Midstream
Midstream
Midstream
Midstream
Raw water
Midstream
Midstream
Midstream
1/6 from shore
1/6 from shore
Midstream
Midstream
Midstream
Midstream
Midstream
MI Midstream
Midstream
Near shore
Midstream
Midstream
Midstream
Midstream
Midstream
Midstream
Midstream
Midstream
Midstream
*Rm = Rivermile
-------
Figure 12. Sites sampled in the Great Lakes and their tributaries.
-------
MISSISSIPPI
RIVER
OHIO
RIVER
CLINCH
RIVER
CHATTANOOGA
CREEK
OCOEE
RIVER
HOLSTON
RIVER
WATAUGA
RIVER
NOLICHUCKY
RIVER
FRENCH
BROAD
RIVER
ro
CO
Figure 13. Sites sampled in the Tennessee River basin.
-------
Table 7
Sampling Sites on the West Coast
Sample
Number Waterway
190 Burbank Western Wash
191 Los Angeles River
192 Los Angeles River
193 Los Angeles Harbor
194 Dominguez Channel
195 Ballona Creek
196 San Pablo Strait
197 San Pablo Bay
198 Carquinez Strait
199 Carquinez Strait
200 Willamette River
201 Willamette River
202 Willamette River
203 Commencement Bay
204 Duwamish River
Station
Glendale
South Gate
Long Beach
Los Angeles
Carson
Playa Del Rey
San Pablo Point
San Pablo
Valona
Port Costa
Portland
Oregon City
Wheatland Ferry
Taconia
Seattle
Latitude
34.09.39
33.57.10
33.46.02
33.45.00
33.48.22
33.58.03
37.59.04
38.01.47
38.03.38
38.02.50
45.34.28
45.21.54
45.05.06
47.14.13
47.34.00
Longitude
118.18.14
118.10.20
118.12.16
118.16.14
118.13.37
118.19.09
122.25.43
122.22.19
122.15.41
122.10.18
122.37.49
122.36.03
123.00.55
122.30.58
122.21.10
Nearest Point, River
Bridge, or Highway
Stanton Ave.
Firestone Blvd.
Ocean Blvd.
Vincent Thomas Bridge
Sepulveda Ave.
Lincoln Blvd.
San Pablo Point
Point Pinole
Davis Point
Port Costa
SPS RR Bridge
Sportscraft Marina
Wheatland Ferry
Commercial Street
Spokane Street
Nearest
Town
Glendale, CA
South Gate, CA
Long Beach, CA
Los Angeles, CA
Carson, CA
Playa Del Rey, CA
San Pablo, CA
San Pablo, CA
Valona, CA
Port Costa, CA
Portland, OR
Oregon City, OR
Uheatland, OR
Tacoma, WA
Seattle, WA
Remarks
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
Midchannel
"R2"*
"5"*
"5"*
"5"*
"5"*
Shore
Shore
Shore
Midchannel
-------
25
BUR BANK
WESTERN
WASH
190
LOS ANGELES
RIVER
RIO. HONDO
SANTA
MONICA
BAY
SANTA
ANNA
RIVER
Figure 14. Sites sampled in the Greater Los Angeles area.
-------
26
Figure 15. Sites sampled in the San Francisco Bay area,
-------
27
COLUMBIA RIVER
OREGON CITY
200%. PORTLAND
Figure 16. Sites sampled on the Willamette River
and in the Greater Portland area.
-------
28
GREEN
RIVER
PAYALLUP
RIVER
Figure 17. Sites sampled in the Seattle-Tacoma area,
-------
29
Most of the samples from major rivers and canals were collected in
midstream or at the location of greatest river depth. In some instances,
shore samples were taken when the established sampling sites were located on
the shore instead of in the middle of the waterway. Midstream samples were
generally taken from a boat or from bridges and spillways.
The sequence of sampling generally followed the flow of the river.
Estuarine samples were generally taken during low slack tide, which at a given
location is the time just before the outgoing tide reverses to an incoming tide.
No flow occurs in the estuary at that location and time, and collected pollutants
therefore generally reflect the discharge at the location. Since the low slack
tide starts at the mouth of the estuary and subsequently travels upstream,
samples were collected in a corresponding sequence.
SAMPLE COLLECTION
The waterway samples were collected with a 3.8-liter (1-gallon) glass
bottle clipped into a metal frame. Depth-integrated samples were obtained by
dropping the bottle from a heightof 63 centimeters above the surface and allow-
ing it to fall freely through the water. When it reached the bottom, the bottle
was pulled up rapidly. During ascent, the remaining air in the bottle expanded
and left the bottle, preventing additional water from entering.
Prior to sampling, tests were conducted to study the water inflow rate
versus time. The sampling bottle was suspended at two different depths, 1.5
meters and 3.5 meters, and allowed to fill. As Figure 18 shows, the inflow rate
is nearly linear with time at both depths. Further experiments were conducted
to determine the rate at which such a bottle fills when lowered through the
water column. It was found that releasing the bottle at the water surface and
allowing it to fall freely through the water resulted in a disproportionately
large amount of water entering the bottle in the first meter below the surface.
Allowing the bottle to drop from a heightof 63 centimeters above the surface,
however, minimized this nonlinearity, as shown in Figure 19.
-------
30
10 -
20 -
30
o
01
10
O)
,10 -
20 -
30
1.0 2.0 3.0
Water Volume in Glass Bottle (liters)
Figure 18. Rate of water inflow into a sample bottle suspended
at constant depths of (a) 1.5 m and (b) 3.5 m.
-------
o.
O)
o
0>
o
0
1.0
2.0
3.0
4.0
Water Volume In Glass Bottle (I)
0.5 1.0 1.5
2.0
I I
O Sample Bottle Released at Water
Surface
A Sample Bottle Released 15cm Above
Water Surface
D Sample Bottle Released 32cm Above
Water Surface
V Sample Bottle Released 63cm Above
Water Surface
Figure 19. Rate of water inflow into a sample bottle released at different heights
above the water surface and allowed to fall freely through the water column.
CO
-------
32
The sample was divided among eight different storage containers:
1. a 3.8-liter (1-gallon) glass bottle for analysis of
extractable organics
2. a 3.8-liter (1-gallon) glass bottle for a reserve
sample
3. a 1.9-liter (0.5-gallon) polyethylene container for
inorganic analysis
4. a 1.9-liter (0.5-gallon) polyethylene container for
gross analysis
5. four 120-ml vials for analysis of volatile organics
Both the sampling bottle and the storage containers were thoroughly
cleaned prior to sample collection. The glass bottles were new or baked at 350° C
overnight to remove any traces of organics, while the polyethylene containers
were rinsed first with nitric acid and then with distilled water to remove any
heavy metals which might be attached to the container wall. Immediately prior
to filling, the containers were rinsed three times with portions of the sample.
The sample was poured into the eight containers in rotation, each being only
partially filled at each pass to insure uniform division of the sample. The
sampling process was repeated until all storage bottles were filled. The
samples for inorganic analysis were stabilized by acidifying them with three
ml per liter of ultrapure nitric acid supplied by the U. S. Bureau of Standards.
The containers were closed with teflon-lined caps, refrigerated immediately, and
transported to the analytical laboratories by surface courier or air freight.
GROSS ANALYSIS
In addition to advanced analyses for trace organic and inorganic con-
taminants, each sample was subjected toan analysis for gross pollutants for
comparison with data collected previously at the same sampling sites. The para-
meters examined were:
1. total chemical oxygen demand (COD)
2. turbidity
-------
33
3. conductivity
4. pH
5. color
6. oxidation reduction potential (ORP)
7. suspended solids
8. volatile suspended solids
The results of these analyses have been presented in the quarterly reports.
Table 8 gives the location of the results for each sample.
TABLE 8
Location of Gross Analysis Data for All Samples
Sample
Number
1-6
7-31
32-61
62-89
90-134
135-173
174-204
Report
Number
PR 1
PR 2
PR 3
PR 3
PR 4
PR 5
PR 5
Table
Number
2
3
4
5
3
5
6
Page
13
10
11
12
12
16
17
-------
34
To indicate the range of water quality exhibited by the 204 water
samples collected, the results of the gross analyses are summarized in Table
9. Mean values are presented only for the COD and suspended solids measure-
ments because the other parameters are not linear functions of concentration
and mean values would therefore have no significance.
Table 9
Summary of Gross Analysis Data
Parameter
PH
Turbidity, JTU
Total COD, mg/1
Suspended Solids, mg/1
Color (absorbance at
400 nm)
ORP, +mv
Minimum
5.21
0.1
1.3
0
.000
100
Mean Maximum
9.80
92.5
33.0 78.5
31.1 194
.690
458
The lowest COD was encountered in the Delaware River at Torresdale
and the highest at Burbank Western Wash near Glendale, California. The sus-
pended solids concentration was lowest in the Hudson River at Corinth and
highest in the Mississippi'River at New Orleans. Turbidity, on the other
hand, was lowest in the water flowing out of Lake Superior through St. Mary's
River and highest in the Houston Ship Channel near Shaver Road. Color was
maximum in the Wisconsin River at Nekoosa, Wisconsin. The pH varied from
5.21 in the Hudson River at Bayonne, N.J., to 9.80 in the Saginaw River at
Bay City, Michigan. The ORP was minimum in the Ohio River at the Belleville
Lock and Dam and maximum at the mouth of the Schuylkill River at Philadelphia.
-------
3, SAMPLE PREPARATION
E. S. K. Chian
J. H. Kim
Samples to be analyzed for volatile organic contaminants were prepared by
a stripping procedure; those for the less-volatile organics were prepared by
liquid-liquid extraction techniques. They were then forwarded to the labora-
tories which performed the quantification and identification procedures described
in Chapter 5.
STRIPPING PROCEDURES
The volatile organic compounds were stripped from the incoming samples
by a technique similar to that described by Chian and Kuo (1975) and illustrated
in Figure 20. The compounds were stripped from a 120-ml sample at a temperature
of 60° C by passing nitrogen through the sample at a rate of 200 ml per minute.
The compounds were adsorbed in a Tenax GC trap, which was then sealed in a
glass tube and transmitted to the appropriate laboratories for analysis. All
glassware was baked at 450° C overnight prior to use. The stripping efficiency
of this method was in the range from 12 to 100 percent, depending on the
initial concentrations and the physical properties of the compounds present.
The stripping procedure of Bellar and Lichtenberg (1974) was used
initially for this project, the sample being held at 98° C during the stripping
operation. It was found, however, that at that temperature excessive moisture
accumulated in the Tenax traps, interfering with later analysis by gas chromato-
graphy-mass spectrometry (GC/MS). Stripping tests conducted at various temperatures
indicated that the moisture content in the trap decreased with temperature. Below
65° C, however, the stripping efficiency for compounds with a relatively high
boiling point and those that are less polar (such as hexane and toluene) de-
creased appreciably. Recovery of polar compounds was optimum at about 65° C.
The temperature ultimately selected, 60° C, represented the best compromise
between these variables. Problems with background contamination from the Tenax
traps and from the Carbowax 1500 GC columns provided another impetus for changing
35
-------
36
120-ml sample in 120 ml glass bottle sealed
with Teflon-lined septum and aluminum seal*
Transfer to 1-liter stripping vessel
Strip at 60 with 200 ml/min N2 gas for 20
minutes. Collect sample on TenaxGCtrap.
[Seal Tenax GC trap in glass tube for later analysis
*Kopfler e-t al. , 1976
Figure 20. Procedure for stripping volatile organic compounds,
-------
37
the stripping procedure. Initially, the volume of sample stripped was 5 ml.
Increasing it to 125 ml made it possible to exceed the background contamination
level by a significantly greater margin. The level of background contamination
from the stripping flask, Carbowax 1500 GC column, and the Tenax traps was mea-
sured at less than the 0.03 ppb level.
A number of other tests of the stripping procedure were also conducted
using prepared samples containing selected concentrations of 12 model compounds.
Specifically, the following parameters were examined:
1. techniques for transferring the samples from the storage
bottles to the stripping flask
2. reproducibility of the stripping procedure
3. variation in stripping efficiency (recovery rate) with
stripping gas flow rate
4. variation in stripping efficiency with stripping time
5. variation in stripping efficiency with stripping flask size
6. variation in stripping efficiency with the concentration of
compounds in the original sample
7. the effects of storing the Tenax traps for periods of 5 and
28 days in sealed glass tubes after stripping
The results, presented in Progress Report Number 3, were used in establishing
the stripping procedure ultimately adopted.
LIQUID-LIQUID EXTRACTION
The less-volatile organic compounds were extracted from the water sam-
ples using the procedure shown in Figure 21. Each sample was first spiked with
camphor, which served as an internal standard. The pH was adjusted to approxi-
mately 12, and the sample was extracted using nanograde chloroform. The solvent
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38
3.8-1iter water sample in 1-gallon glass container
Spike with 15 yg of camphor from 30 yl of
methanol solution. Stir for 15 minutes.
Adjust pH to M2 with NaOH pellets.
Extract three times with 200 ml of chloroform in 100/50/50 ml portions
under mechanical agitation using Teflon-coated magnetic bar.
Base Extract
Acid Extract
160 to 185 ml of solvent extract
concentrated to 2 ml with Kuderna-
Danish (K-D) evaporator.
Concentrate to 0.4 ml with Micro-
K-D evaporator.
Adjust aqueous layer pH to
with concentrated HC1.
Spike with 40 yg of 2-ethyl
hexanoic acid from 80 yl of
methanol solution.
Store in vials with Teflon-coated
septum in 100/100/200 yl portions
in refrigerator.
Extract three times with 200 ml
of chloroform in 100/50/50 ml
portions.
Concentrate to 5 ml with K-D
evaporator.
Concentrate to dryness wi th
Micro-K-D evaporator followed
by helium blowing, then dilute
back to 0.4 ml with methylene
chloride.
DAM (diazomethane) treatment in
methylene chloride.
Fix final volume to 0.4 ml in
vials for analysis.
Figure 21. Procedure for extraction of the less-volatile organics.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA DCO/7
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Monitoring to Detect Previously Unrecognized
Pollutants in Surface Waters
5. REPORT DATE
July 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
B. B. Ewing, E. S. K. Chian, J. C. Cook, C. A. Evans,
P. K. Hooke. and E. G. Perkins
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Institute for Environmental Studies
408 S. Goodwin Avenue
University of Illinois at Urbana-Champaign
Urbana, Illinois 61801
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-3234
12. SPONSORING AGENCY NAME AND ADDRESS
United States Environmental
Office of Toxic Substances
Washington, D. C. 20460
Protection Agency
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Samples of surface waters were collected from 204 sites near heavily industrialized
areas across the United States. The samples were analyzed for all contaminants
present at concentrations greater than one part per billion. Each water sample
was preconcentrated for analysis of organics in three fractions: volatile
organics by nitrogen-gas stripping and the less-volatile organics by extraction
with chloroform under both basic and acidic conditions. Organic constituents
were identified by gas chromatography/mass spectrometry and quantified by gas-
chromatographic techniques. Inorganic constituents were determined by spark-
source mass spectrometry, energy-dispersive x-ray fluorescence analysis, and
instrumental neutron activation analysis. For comparison with previous data from
the same sites, the samples were also analyzed for total chemical oxygen demand,
turbidity, conductivity, pH, color, oxidation-reduction potential, suspended
solids, and volatile suspended solids. Results of the inorganic analyses were
presented in previous quarterly progress reports. Final results of the organic
analyses are presented in the appendix to this report.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Water quality
Water pollution
Water analysis
Water chemistry
Surface waters
Trace contaminants
Organic compounds
Volatile organic
compounds
Industrial pollution
Nationwide survey
8h
7b, 7c, 7e
18. DISTRIBUTION STATEMENT
Unrestricted
Available from National Technical Infor-
mation Sprvirp. Springfield. VA 22151
19. SECURITY CLASS (ThisReport)'
Unclassified
21. NO. OF PAGES
86
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
-------
39
and aqueous layers were then separated. The solvent was concentrated to 0.4 ml
in evaporators, and the resulting base extract was stored in three vials, one
containing 200 pi and two containing 100 yl each. The latter two vials were
transferred to the appropriate laboratories for analysis.
The remaining aqueous layer was then adjusted to a pH of between 2 and
3 and spiked with 2-ethyl hexanoic acid as an internal standard. It was extracted
with chloroform and the solvent was concentrated to 5 ml in an evaporator. The
chloroform was then exchanged with a different solvent, methylene chloride, by
evaporating the sample to dryness and then diluting it to a 0.4-ml volume with
the latter compound. The resulting acid extract was methylated with diazomethane.
The final volume was adjusted to 0.4 ml and the sample was transmitted to the
analytical laboratories in the same volumes as for the base extracts.
In the process used initially for preparing the acid extracts, the
chloroform was not exchanged with methylene chloride. A high level of sample
contamination was observed, however. Because the level of impurities in the
nanograde chloroform used was found to be less than 0.01 ppb, the contamination
of the sample was attributed to impurities in the diazomethane used as a methyl -
ating agent. Further tests revealed that the interfering contaminants were not
present in the diazomethane but were formed as side-reaction products between
the diazomethane and the chloroform solvent. This problem did not arise when
methylene chloride was used as the solvent. The recovery of organic compounds
was better when the sample was extracted with chloroform, however. Therefore,
chloroform was used for the initial extraction but replaced with methylene
chloride prior to the methylation step.
SORPTIVE EXTRACTION TECHNIQUE
Adsorption onto a sorptive medium was evaluated as a possible alternative
to the liquid-liquid extraction process for preconcentrating the less-volatile
organic compounds. XAD-4 resin (Rohm and Haas, Philadelphia, Pennsylvania) and
six types of activated charcoal were evaluated for their effectiveness as sorptive
media. Of these, the XAD-4 resin and Widco activated carbon (Widco Chemical Corp,
N.Y.) exhibited the lowest levels of background contamination and were therefore
chosen for further testing.
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40
Samples number 18 and 19 were used to compare the effectiveness of
the sorptive technique with the liquid-liquid extraction method. These samples
were processed both by the normal procedure in the laboratory and by the sorp-
tive method at the sample collection site using the experimental setup shown in
Figure 22. Several different methods for processing the resulting resin and
carbon samples were evaluated. The analytical procedures applied to sample 18
were described in Progress Report Number 2. Based on the results, the process
was modified somewhat for sample number 19, as described in Progress Report
Number 4.
The activated carbon was found to be better for sampling neutral
organics than was the XAD-4 resin,.as indicated by the number of peaks observed.
For acidic organics, the number of peaks for the two sorptive materials were
comparable, but the carbon column exhibited some impurities.
The data indicate that preconcentration by the use of sorptive materials
in columns is superior to liquid-liquid extraction for neutral organic compounds,
0
while the two methods produce comparable results for acidic organics.
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41
HC1
Spi ked
Sample
Neu-
tral
Acti-
vated
Car-
bon
or
Resin
Col-
umn
Acid i fy
to pH 2
Meter ing
Pumping
Bypass
Valves
•M-
Acidic
Column
Vacuum
Seal
Effluent
Col lector
Amount of Sample Used:
Spiking Compound and Amount:
Flow Rate:
Period of Experiment:
200 1iters
0.253 m9 °f camphor and 1.51 mg
of 2-ethyl hexanoic acid dissolved
in 3.5 mg CH OH per 200-liter sample
^60 ml/min
4 to 5 days
Figure 22. Flow diagram of experimental setup for sorptive studies.
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4, INORGANIC ANALYSIS
Inorganic multielemental analysis was performed by three separate and
independent techniques: spark-source mass spectrometry (SSMS), instrumental
neutron activation analysis (INAA), and energy-dispersive x-ray fluorescence
(XRF) analysis. The results of the analyses have been presented in the five
quarterly progress reports. Table 10 lists the location of the SSMS data for
all samples.
The SSMS technique is capable of detecting or establishing detection
limits for approximately 80 elements in the type of water sample analyzed for
this project. For 44 of these elements the semi quantitative determination
is confirmed by either a multiply charged or second isotopic spectral line.
For the remaining 36 elements the analysis is based on a single spectral line.
For 22 of those 36 elements the INAA and XRF methods are able either to provide
a quantitative confirmation of the SSMS estimates (for Sc, Co, Ni, Se, Sb, and
Hg) or to establish a better detection limit than SSMS (for Mo, Ru, Ag, Cd, Cs,
Ce, Sm, Eu, Tb, Yb, La, Hf, Ta, Re, Ir, and U). The combined use of these
techniques provided two significant benefits. The number of unconfirmed anal-
yses was reduced from 36 to 14, and confirmed analyses were obtained on six of
the seven environmentally important elements: Pb, Tl, Cd, Hg, Se, and As.
(Three were confirmed by INAA and three by XRF). Only the Be determination
depended on a single analytical technique.
The analyses by the three different techniques agreed within the
limits of detection and experimental error for almost all elements. INAA
determinations (44 elements) are quantitative within the stated limits, as
are the XRF determinations. SSMS determinations are semiquantitative; the
true concentration is expected to be within the range from one-third to three
times the stated value. SSMS values obtained for the alkali metals and alkaline-
earth metals appear to be somewhat higher than the INAA and XRF results.
It can be concluded that the three complementary techniques yield a
complete elemental analysis of this type of water sample. Limitations assoc-
iated with one method are usually compensated by high sensitivities of the
other methods.
42
-------
43
Table 10
Directory of Inorganic Analyses
Sample
Number
1 - 6
7
8, 9
10, 11
12
13
14
15 - 17
18 - 31
32 - 38
39 - 41
42
43
44 - 46
47
48, 49
50 - 61
62-73
74 - 84
85, 86
87 - 89
90 - 102
103, 104
105 - 107
108 - 110
111 - 117
118 - 120
121 - 134
135 - 204
Progress
SSMS
PR1
PR2
PR2
PR2
PR2
PR2
PR2
PR2
PR2
PR3
PR3
PR3
PR3
PR3
PR3
PR3
PR3
PR3
PR3
PR3
PR4
PR4
PR4
PR4
PR4
PR4
PR4
PR4
PR5
Report
INAA
PR1
PR2
PR5f
PR2
PR5f
PR2
PR5
PR2
PR51"
PR5
PR4
PR5
PR5
PR5
PR4
PR5
PR4
PR5
PR4
PR5
PR5
PR4
PR5
PR4
PR5
PR4
PR5
•PR4
PR5
Number
XRF
PR!
PR2
PR2.5*
PR2
PR2,5
PR2
PR2,5
PR2
PR2,5
PR3.5
PR3,4
PR3.5
PR5
PR3.5
PR3,4
PR3.5
PR3,4
PR3,5
PR3,4
PR3,5
PR3,5
PR4
PR5
PR4
PR5
PR4
PR5
PR4
PR5
*Where two progress report numbers are listed, complete XRF data
are presented in both reports.
^Partial INAA results for these samples were presented in Progress
Report No. 2; the complete data were presented in Progress Report No. 5
-------
44
SPARK-SOURCE MASS SPECTRAL ANALYSIS
C. A, Evans
W. H. Wadlin
Most of the samples analyzed by SSMS were composited,consisting of
from two to five individual samples. Samples analyzed as composites were
grouped according to geographic origin and expected composition. For example,
composite XXIII comprised three consecutive samples which represent the upper
Hudson River, and composite LXV comprised waters from three tributaries to
Lake Erie. Of the eighty composites, fourteen consisted of only one component
sample. Also, the first six samples were analyzed individually and were not
assigned composite numbers. In addition to these 86 samples which constitute
the reported SSMS results, an additional 62 samples consisting of standards,
blanks, replicates, and research samples were processed during the course of
the project.
Procedure
The samples were evaporated in the presence of a suitable matrix ma-
terial and the residues formed into electrodes. A laboratory study indicated
that the loss of trace elements by volatilization during the bulk evaporation
process was insignificant when a silver matrix was used. A total volume of
100ml of sample per composite was nominally used. There was no advantage to
using more sample, since the detection limits for most elements were limited
by the appearance of organic interferences in the spectra. Thus, detection
limits become lower as the sample size is increased up to the point at which
the electrodes are so heavily loaded with sample that enough organics are pre-
sent to appear in the longest exposures, interfering with element identification.
For saltwater samples, only 25 ml could.be used because of interferences from
inorganic molecular ions. The samples were doped with 50 yg of yttrium as an
internal standard and evaporated nearly to dryness in Pyrex evaporating dishes
with 1.0 g of matrix material at 80°C. The drying was completed in an oven at
105°C. Silver powder was used as the matrix material in preference to graphite,
as it resulted in fewer matrix interferences and higher sensitivity. The residue
was then transferred to a plastic ball mill for mixing. Since the dried residues
-------
45
were frequently quite hygroscopic, it was found necessary to make the transfer
quickly while the material was still warm and to store it immediately in a
dessicator. After mixing, the powder was pressed into electrodes in a poly-
ethylene slug.
The electrodes were mounted in the AEI MS-7 mass spectrometer for
analysis using photographic detection. The samples were presparked for the
equivalent of a 30 nC exposure at 30 pulses per second. This process removed
surface contamination and the abnormally high initial sensitivity caused by
the adsorption of trace elements contained in the sample on the surface of
matrix particles. Although it was considered possible that some elements
could be lost by thermal vaporization from the electrodes during the sparking
process, tests conducted using a sample containing model elements indicated
that selective volatilization was not a problem.
In obtaining the analytical exposures the pulse repetition rate was
kept as low as was practical for obtaining the exposure in a reasonable amount
of time. The maximum pulse repetition rate used was 100 pulses per second
regardless of the time required to obtain the exposure. Higher rates caused
sufficient heating of the electrode bulk to drive organic materials out from
the interior, giving rise to severe interferences and unacceptably high detec-
tion limits. Three exposures per decade of exposure magnitude were obtained
over the range from .001 to 300 nC.
Concentrations of trace elements were determined by comparing the
exposures required for their spectral lines to be just detectable with
the equivalent exposure for the internal standard. Elemental sensitivities
were assumed to be equal. The results were presented in the appendices of
the five quarterly progress reports. If an element was confirmed by the pre-
sence of either a multiply charged ion or multiple isotopes of the correct
relative intensities, the value for that element was given without a prefix
symbol. If the value was prefixed by the symbol "<" (meaning "less than or
equal to") it indicates that a line corresponding to the +1 ion of that element
was observed, but its presence could not be confirmed by the procedures above.
-------
46
That is, either the element was present at the concentration stated or there
was an interference. The symbol "*<" (meaning "definitely less than") was
applied if no lines were observed which could be attributed to this element
or if there was a definite, known interference. In cases where no line was
observed, the number given was calculated on the basis of what the concentration
would be had the element been just detectable in the longest exposure. In the
case of a known interference, the value given was the concentration at which
the element would have had to be present to appear with an intensity equal to
that observed for the interference.
Discussion of Results
Considering that the data were taken with three exposures per decade
and that there are some differences in elemental sensitivity, the results
reported should generally be accurate to within one-third to three times the
actual concentration. Detection limits are generally in the range from 0.2 to
2 yg/1 for freshwater samples. For saltwater samples, inorganic molecular
interferences and a general loss of sensitivity raise the detection limits to
the range from 20 to 200 yg/1.
Comparison of SSMS results with the INAA and XRF results for these
samples shows general agreement within the expected range of errors given above.
Notable exceptions are the concentrations determined for K, Mg, and Ca. The
SSMS results for K and Mg are consistently higher by about a factor of 3 and for
Ca are higher by a factor of 5 to 10. Analysis of standards indicates that
the error is in the SSMS determination and results from unusually large differ-
ences in sensitivity for these elements, a factor not compensated for in the
calculations.
INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS
P. K. Hopke
J. D. Sherwood
Procedure
The sensitivity of instrumental neutron activation analysis (INAA) is
governed by the number of neutrons with which a sample is irradiated, the delay
time between irradiation and the start of the count, and the counting time
-------
47
intervals. Other investigators (Clemente and Mastinu, 1974; Salbu et al.,
1975) have used various methods of applying INAA to obtain determinations of
trace elements in water samples. In some studies where a small number of
samples were processed, long irradiation intervals (up to 72 hours) were used.
For the large number of samples involved in the present project, however, long
intervals become economically unfeasible because of reactor costs. Therefore,
a relatively short interval was used, compensated for by using larger sample
volumes, counting the irradiated samples for comparatively longer intervals, and
using a more efficient gamma counting system. The following procedures were
used for freshwater and saltwater samples through number 94.
Freshwater Samples
1. The quartz ampoules used to hold the samples during
irradiation were pretreated in a bath of dilute
nitric acid at 85°C for four hours to remove any
contaminants
2. A 15-ml sample was loaded into each ampoule, which
was then heat-sealed
3. The sealed ampoules were tested to insure that they
would not break from thermal stress during irradiation
4. The samples were irradiated for 30 minutes at 500 kW
5. After a decay period of three days, the samples were
transferred to standard polyethylene counting vials.
The ampoules were rinsed with two 1-ml portions of
dilute hydrochloric acid to recover any adsorbed
molecular or ionic species and the rinse was added to
the contents of the counting vial
6. The emitted radiation was counted for 1,000 seconds
using a 10% Ge(Li) detector in conjunction with a
4096-channel analyzer system
7. The samples were repackaged and irradiated for eight
hours at 1.5 MW
8. After a decay period of 14 days, the samples were
transferred to counting vials as before and the
emitted radiation was counted for 4,000 seconds
-------
48
Saltwater Samples
1. The ampoules were pretreated as for freshwater
samples
2. Each ampoule was loaded with a 10-ml sample and
heat-sealed
3. The ampoules were tested for thermal stress resistance
4. The samples were irradiated for eight hours at 1.5 MW
5. After a decay period of seven to ten days the samples
and acid rinse were transferred to polyethylene
counting vials
6. The emitted radiation was counted for 1,000 seconds
7. After an additional 7-day decay period, the sample
radiation was counted for 20,000 seconds
Data obtained from the multichannel analyzer system were transferred
to magnetic tape for computerized peak analysis. Two computer programs were
written which combine peak identification and quantitative calculations in
a single computer run. The results have been presented in the five quarterly
reports. Table 10 lists the location of INAA data for all samples.
A preconcentration procedure was adopted for freshwater samples
above number 94 in order to achieve a higher rate of sample analysis. Pre-
concentration permits the use of larger sample volumes with a proportionate
decrease in the required counting time. The samples were preconcentrated by
evaporation in the presence of AVICEL, a microcrystalline cellulose, which acts
as an adsorption medium for the inorganic constituents. A 500-ml sample is
evaporated with 100 mg of AVICEL at 50°C in a polyethylene beaker and quanti-
tatively transferred to an irradiation container. In addition to faster sample
analysis, this technique provides lower detection limits and reduces the
hazards of handling the samples after irradiation. The disadvantages are the
increased possibilities of contamination and errors resulting from loss of
sample during the transfer.
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49
ENERGY-DISPERSIVE X-RAY FLUORESCENCE ANALYSIS
P. K. Hopke
J. D. Sherwood
Samples analyzed by energy-dispersive x-ray fluorescence were precon-
centrated by three methods:
1. Precipitation with ammoniurn-1-pyrrolidine dithiocarbomate
(APDC) at a pH of 4 and filtration through a 25-mm
0.2 y-pore Nuclepore filter
2. Precipitation of cyanide complexes at a pH of 12.0 followed
by filtration twice through Reeve Angel SB-2 anion-exchange
paper
3. Filtration twice through Reeve Angel SA-2 cation-exchange
filter paper at a pH of 2.0
Each sample was divided into two aliquots, each of which was analyzed
separately. For samples through number 89, one sample was preconcentrated by
the first (APDC) method while the other portion was preconcentrated by one of
the other two methods. For later samples, both portions were preconcentrated
by the APDC technique, since it was found to yield the most consistent recovery
rate for the elements analyzed in both freshwater and saltwater samples.
The basic procedure used for analyzing samples by the XRF method was
as follows:
1. A 1% w/v APDC solution was prepared daily and filtered
through a 0.2 y Nuclepore filter.
2. The water sample was shaken sufficiently to resuspend
particulate matter.
3. Two 50-ml aliquots were removed and the pH was adjusted
to 4.0.
4. 5 ml of APDC solution was added and the precipitation
process was allowed to develop for approximately 15 minutes..
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50
5. The precipitate was filtered through a 25-mm, 0.2 y
Nuclepore filter.
6. After the filter dried, it was mounted between 0.00010-in.
Mylar film on a polyethylene XRF sample cup.
7. The sample was positioned under the source exciter system.
4
8. Each sample was counted for 10 seconds for each secondary
target (Mo and Dy).
9. The accumulated spectrum was transferred to magnetic tape
for processing.
10. Treating the filter as a thin sample, the results were
calculated by a method identical to that used by Bonner,
Bazan, and Camp (1975), except that all of the material
was assumed to be on the top of the filter. With the
Nuclepore filters used in this study it is believed that
there was very little penetration of precipitate into the
filter.
To determine the net area of each peak in the spectra produced, it
was necessary to subtract the background level from the region of interest.
For the early samples through number 89, a background-stripping computer pro-
gram similar to that of Bonner, Bazan, and Camp (1975) was used. Discrepancies
between the results of XRF analyses and those obtained by the INAA and SSMS
techniques were traced to problems with this program. Consequently, for samples
after number 89, the background was subtracted manually, resulting in much greater
consistency between the three techniques.
The results of the XRF analyses have been presented in the quarterly
reports. The location of the XRF data for all samples is listed in Table 10.
-------
5, ORGANIC ANALYSIS
Samples prepared for the determination of organic constituents
were divided and sent to two separate laboratories for analysis. For ex-
tractable organics, one 100-pl aliquot was sent to the gas chromatography-
mass spectrometry (GC/MS) laboratory in the Department of Chemistry for the
identification of constituents, and another 100-yl aliquot was analyzed by
gas chromatography (GC) in the Department of Food Science to establish the
quantity of each contaminant present. Similarly, separate Tenax traps were
prepared and sent to the two laboratories for the analysis of volatile organics.
Identical gas chromatographic operating parameters were used in the two labora-
tories, making it possible to use the relative retention times for each compound
to correlate the identification and quantification of each peak observed.
In some samples a comparatively large number of compounds were detected
at levels below 1 ppb. Because identifying and quantifying all of these com-
pounds would have been excessively time consuming, it was determined in consul-
tation with the sponsor that only those organic substances present at or above
the 1 ppb level would be reported.
Preliminary results of the organic analyses were presented in the
quarterly reports. Upon completion of sample analysis, the data were reexamined
and corrected or adjusted as necessary. The final results are presented in the
appendix of this report. In particular, the quantisations were revised on the
basis of the relative GC response factors determined for selected compounds,
with the result that some compounds formerly determined to be present at concen-
trations below 1 ppb are now known to be at a higher level and are therefore in-
cluded in the updated listings. Conversely, some compounds previously listed
have been found to be present at concentrations less than 1 ppb and have hence
been deleted. In addition, the relative retention times have been rechecked,
resulting in corrections to some of the identifications. Compounds which could
not be identified were not listed in the previous reports, but their presence is
indicated in the final results presented here.
51
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52
IDENTIFICATION OF ORGANICS
J. C. Cook, Jr.
R. M. Milberg
All of the samples processed by the organic identification laboratory
were analyzed on a Varian-MAT 311A combined gas chromatagraph-mass spectrometer
with a Varian-Aerograph 2700 gas chromatagraph using a 2-stage Watson-Biemann
sample enricher. The system is of all-glass construction from column inlet to
source inlet.
Procedures
The Tenax traps for analysis of volatile organic compounds were received
from the sample preparation laboratory in sealed glass tubes. The traps were
removed from the tubes, connected to the gas chromatagraph, and flushed for two
minutes at ambient temperature with helium gas. A tubular furnace with an in-
terior temperature of 250°C was then slipped over the trap and allowed to pre-
heat the trap for two minutes, after which the volatiles were flushed from the
trap onto the GC column for four minutes with a helium flow rate of 40 ml per
minute. The column was held at ambient temperature during this period. The
outside diameter of the glass column used was 6 mm, the inside diameter was 2
mm, and the length was 12 ft. The column was packed with 0.2% Carbowax 1500 on
60/80-mesh Carbopack C (Supelco, Inc., Bellefonte, Pa.). After the volatiles
were flushed onto the column, the temperature of the column was programmed to
increase at a rate of 8°C per minute from 30°C to 200°C. It was held at the
latter temperature for the remainder of the run.
For the analysis of base and acid extracts, 1 yl of the sample was in-
jected onto a glass column of the same dimensions as above but packed with 3%
OV-17 on 80/100-mesh Gas Chrom-Q (Applied Science, State College, Pa.). The
column temperature was held at 50°C during injection and was then programmed to
increase to 300°C at a rate of 8°C per minute.
The mass spectrometer was scanned continuously from an m/e of 33 to an
m/e of 350 for volatiles and from m/e 33 to m/e 600 for extractable organics.
The scan rate was 2.3 seconds per mass decade, and the ionization potential was
-------
53
70 eV. Data were acquired on a Varian-MAT SSI00 data system and stored on a
disk cartridge.
Identification
Mass spectra were identified by inspection, manual searches, and
computer searches using the ADP-Cyphernetics Mass Spectral Search System (MSSS).
The usefulness of the MSSS was limited by the fact that the spectra for many
compounds found in the samples were not in the computer file, nor were there any
compounds of similar type. Also, spectra for most of the compounds in the file
were obtained by direct-probe mass spectrometry under ideal conditions with the
result that many of the spectra were different from those obtained by the GC/MS
technique at the 1 ppb level.
The volatile compounds were the easiest to identify because of their
low molecular weights and simple spectra and because many of them were halogen-
ated, giving excellent isotope cluster patterns. Compounds in the acid extracts
were the most difficult to identify because of the large number of peaks and the
fact that the methyl ester spectra for many of the compounds were not present in
the MSSS file.
A computer program was developed to calculate the relative retention
times of the observed peaks. These relative retention times provided a second
confirmation of the identifications and, as discussed above, were used to
correlate the identifications of the compounds with their quantisations.
Results .
All compounds identified in the samples were listed along with their
relative retention times in the quarterly reports. The final adjusted data for
those compounds present at concentrations of 1 ppb or greater are presented in
appendix B of this report.
-------
54
QUANTITATION OF ORGANICS
E. G. Perkins
J. C. Means
The work of the quantitation laboratory focused on several areas:
(1) quantitative analysis of the stripped volatile, acid extractable, and base
extractable organic compounds contained in the 204 surface water samples col-
lected, (2) the optimization of the chromatographic conditions used to separate
the organic constituents of each sample fraction, (3) the investigation of con-
ditions affecting the purity of blanks, (4) the investigation of parameters
related to the selection of internal standards for the acid and base extract-
able fractions, and (5) the investigation of parameters related to the sepa-
ration and quantition of selected amines.
Quantitative Analysis of Purgeable and Extractable Organics
As mentioned previously, the gas chromatographic conditions used in
the quantitation laboratory and in the identification laboratory were coordi-
nated during all stages of the project. Initially, base and acid extract
samples were run routinely on a Hewlett-Packard 5830A programmable gas chroma-
tograph. One-microliter samples were injected onto a 12-foot by 1/4-inch
(2 mm ID) all-glass column packed with 3% OV-17 on Gas-Chrom Q (60-80 mesh).
Other pertinent instrument conditions are given in Table 11. These conditions
corresponded exactly to those used by the mass spectrometry laboratory and the
sample preparation team, making it possible to compare relative retention times.
Peaks exceeding the 1 ppb level in water ('v-lO ng/yl in extracts) were identified
by peak integration values. Once these peaks were identified, quantitation was
accomplished by converting the integration units to ng/yl and then calculating
the concentration in the original water samples on the basis of the known
extraction efficiencies in the sample preparation step.
-------
VENT TO
ATMOSPHERE
TUBE
FURNACE
CONTAINING
TENAX
TRAP
AUX
GAS CYLINDER
GAS CHROMATOGRAPH
CARRIER
GAS CYLINDER
01
01
Figure 23. Schematic diagram of volatile organic elution system.
-------
56
Table 11
Gas Chromatograph Column Conditions*
Initial temperature 35° C
Initial time 5.0 min.
Programming rate 10° C/min
Final temperature 300° C
Injector temperature 275° C
Detector temperature 350° C
Carrier gas flow 40 ml/min
*12 ft. x 1/4 in. (2 mm ID) all-glass column packed with
3% OV-17 on Gas-Chrom Q (60-80 mesh).
After two months, all quantisations were performed on a new Hewlett-
Packard-Model 5711 gas Chromatograph equipped with a Model 3380A reporting
integrator. This instrument was used routinely to quantitate the balance of
the samples collected. The procedure was modified slightly to make the best
use of this new instrument and to shorten analysis times. The initial five-
minute isothermal hold at 35° C was reduced to four minutes and the initial
temperature was increased to 50° C. These changes reduced the tailing of the
solvent peak and generally improved the characteristics of the total chroma-
togram. The temperature programming rate was decreased from 10° C/min to
8° C/min to improve resolution of peak clusters in the chromatograms. All
other conditions remained unchanged.
Volatile samples were chromatographed on a 12-foot, all-glass column
(2 mm ID) packed with 0.4% Carbowax 1500 on Carbopack C (Supelco, Inc.,
Bellefonte, Pa.). This column was determined to have resolution, capacity, and
thermal stability (bleed) characteristics superior to the other column packings
traditionally used for volatiles (e.g., Porapacks, Chromasorbs, etc.). For
quantitation purposes, the Tenax trap was heated to 250° C and stripped for six
minutes with a nitrogen carrier gas flow of 40 ml/min onto the Carbowax column
held at 30° C (Figure 23). After purging, the trap was isolated from the column
by changing the position of the valve. The column temperature was programmed to
increase from 30° C to 200° C at 8° C/min and then held at 200° C for an addi-
tional 6 minutes. The injector and detector temperatures were maintained at
250° C.
-------
57
Because of early problems encountered in the other laboratories with
contamination from the gas valving system, the possibility of using a high-
temperature valve when analyzing the stripped samples was investigated.
Initially, the traps were heated to 250° C while the valve remained at 30
to 70° C. This temperature difference affected the purity of the stripping
blanks and could have been a potential source of cross-contamination of vola-
tiles from one run to the next. A new Valvco two-position, six-port valve
which can be heated to 200° C was therefore substituted, making it possible
to heat both the Tenax GC trap and the valve during analysis. The new valve
had other advantages as well in that the carrier flow to the GC column was not
interrupted and the column was never exposed to the atmosphere. Also, traps
could be swept with carrier gas before connecting them to the GC column, again
eliminating exposure of the column to the atmosphere. Finally, the valve
material was stable at high temperatures, which helped to eliminate some of
the peaks in the stripping blanks believed to originate in the Teflon gaskets
of the original valves used.
The only difference between the procedures used by the quantisation
and identification laboratories was in the method of heating the traps. In
the quantisation laboratory, a combustion-tube furnace comrnercially available
from A. H. Thomas was used rather than a hand-made tube heater. Evaluation of
the tube furnace showed that it had several advantages: (1) the dimensions of
the furnace accommodated the entire length of the trap in the heated zone; (2)
the temperature of the furnace at a given potentiometer setting was highly
reproducible; (3) the temperature variation along the length of the heated
zone was negligible; (4) traps could be inserted and removed for cooling in
seconds; and (5) the internal temperature of room-temperature traps inserted
into the furnace rose to 250° C in two minutes or less.
Increasing the quantity of water sample stripped from 5 ml to 125 ml
also simplified the analysis of the volatile samples by eliminating many of
the significant contamination problems encountered in the early stages of this
project. None of the fluorinated hydrocarbon species believed to have come
-------
58
from the sampling valve were identified in any of the samples at the equiv-
alent 1 ppb level or above after increasing the volume of sample stripped.
The quality of the system blanks, which include bleed peaks from the Tenax
GC trap matrix, was also improved. Figure 24 is a reproduction of a typical
system blank. All of the peaks observed in the blank are well below the 1
ppb level. The first two peaks are methanol and ethanol. These substances
are observed in every volatile sample by gas chromatography but are not seen
in the GC/MS runs because they are vented out with the water. Peaks 3 through
5 are acetone, benzene, and toluene, respectively. Peak 6 is due to column
bleed.
Quantisation of the volatile organics was accomplished by determining
individual relative response factors for each of the commonly occurring vola-
tile substances observed in the samples collected. The estimated concentrations
of these compounds were corrected for these factors prior to the preparation of
this report.
Selection of Internal Standards for the Acid- and Base-Extractable Fractions
To increase the accuracy of the quantitative data obtained on the acid-
and base-extractable organics and to maintain consistent control of laboratory
extraction procedures, internal standards were sought for both the acid and
base extraction steps. The criteria used in selection were (1) gas chromato-
graphic retention time, (2) purity, (3) mass spectral characteristics, (4)
extraction efficiency at pH ^12 or pH^2 with chloroform, (5) chemical and bio-
logical stability, and (6) occurrence in surface water samples.
Since it was known that hydrocarbon-type materials extract readily at
basic pH, the cyclic hydrocarbon camphor was selected for the base extraction
step. Likewise, fatty-acid-type compounds were known to be characteristic of
the pH 2 extractables. Therefore, a branched-chain Cg fatty acid (2-ethyl
hexanoic acid) was selected for the acid internal standard. Both camphor and
2-ethyl hexanoic acid extraction efficiencies were determined on each group of
samples processed. The average extraction efficiencies observed were 67% and 69%,
respectively. These factors were used in correcting the quantitative data for the
corresponding fractions. The 2-ethyl hexanoic acid served the added function of
providing a check on the efficiency of the methylation step as well.
-------
CJ1
ID
Figure 24. Gas-chromatographic trace of a representative system blank.
-------
60
Since both camphor and napthalene, another compound considered as an
internal standard, had previously been reported as constituents of certain
surface water samples, an investigation was begun to find an alternative com-
pound which would not be expected in nature and which would meet the criteria
listed above. Several brominated compounds were evaluated:
Bromobenzene
Bromocyclohexane
Bromoheptane
Bromopentane
Bromononane
Bromodecane
Bromotetradecane
p-Bromo-Anisole
a-Bromo-Toluene
a-Bromo-p-Xylene
A number of the compounds were determined to be unsatisfactory based
on the selection criteria above. The last three compounds in the list all had
retention times in a good range, were of high purity, gave distinctive mass
spectra, and had extraction efficiencies in a satisfactory range. When these
compounds were tested for chemical stability in chloroform and surface water,
however, the bromo compounds decomposed or reacted with compounds in the water.
Other brominated compounds were considered, but none was found which met the
criteria.
Investigation of Gas Chromatographic Methods for Monitoring Amines
Pure samples of six selected amines were obtained for analysis:
Aniline
Benzidine
3-Naphthylamine
o-Tolidine
o-Toluidine
Phenyl Hydrazine
The initial work was directed toward determining whether the ex-
traction and separation techniques being used for this project would be able
to detect these amines if they were present in any of the water samples.
A liter of ultrapure water was spiked with a pure amine compound at
a level of 100 ppm, 1 ppm, or 50 ppb. Samples were prepared in triplicate.
Once the amine was dissolved completely, the pH was adjusted to between 11
-------
61
and 12. The sample was then extracted with a total of 200 ml of chloroform in
three portions (100, 50, and 50 ml). The amount of the amine recovered in the
chloroform was then determined either by direct weighing of the residue after
removal of the solvent or by quantisation of the amine by gas chromatography.
The extraction efficiencies determined are reported in Table 12.
Table 12
Extraction Efficiencies of Selected Amines
Ami ne
Aniline
Benzidine
3-Naphthyl amine
0-Tolidine
Phenyl Hydrazine
o-Toluidine
100 ppm
85.3
99.9
47.7
82.2
73.2
87.5
% Recovery*
1 ppm
83.7
99.9
46.8
83.1
75.1
87.2
50 ppb
84.0
99.8
46.7
82.7
74.8
86.8
*Average of triplicate determinations.
Next, the relative retention times of these six amines were determined
against the retention time of camphor using the gas chromatographic conditions
routinely used for this project. Relative response factors for each amine
(integrator counts/ng of amine divided by integrator counts/ng of camphor)
were also determined using solutions of known concentration on the OV-17
column used for this project. The values are reported in Table 13.
Five other gas chromatographic column packings for the analysis of
amines were evaluated using the six selected amines. Chromasorb 103, 4% Carbo-
wax 20M +0.8% KOH on Carbopack B, 4% Carbowax 20M + 1% Polypropyleneimine on
Carbopack B, and 0.1% SP-1000 on Carbopack C columns were tested. In each case,
the retention times of all of the amines being studied were too long or the
compounds were not eluted at all. Relative retention times of the six amines
selected for study were determined against the retention time of camphor using
10% Apiezon L/2% KOH on 80/100 mesh Chromasorb WAW. Relative response factors
were also determined using solutions of known concentration. The results are
presented in Table 14.
-------
62
Table 13
Relative Retention Times and Relative Response Factors
For Selected Amines on 3% OV-17
Amine
Aniline
Benzidine
B-Naphthylamine
o-Tolidine
Phenyl Hydrazine
o-Toluidine
Relative
Retention Time1
0.77
2.48
1.72
2.65
1.38
0.93
Relative
Response Factor2
0.96
0.75
1.45
1.39
0.36
0.96
2 Calculated relative to the retention time of camphor (10.84 min).
Calculated relative to the response per nanogram of camphor (1650/ng),
Table 14
Relative Retention Times and Relative Response Factors
For Selected Amines on 10% Apiezon 1/2% KOH
Amine
Aniline
Benzidine
3-Naphthylamine
o-Tolidine
o-Toluidine
Phenyl Hydrazine
Relative
Retention Time1
0.746
2.425
1.638
3.180
0.919
1.500
Relative
Response Factor2
0.695
0.693
0.655
0.715
0.761
0.0143
Calculated relative to the retention time of camphor (14.19 min).
Calculated relative to the response per nanogram of camphor (3409/ng)
3Coloration of sample and multiple peaks in chromatogram suggest some
chemical and/or thermal degradation.
-------
63
Both the OV-17 column and the Apiezon L/KOH column gave very satis-
factory separation of the amines selected. The response per nanogram of
material injected on column, however, was significantly higher using the
deactivated Apiezon packing, indicating that some of the amine material was
adsorbed to the OV-17 column packing. In survey studies such as the one just
completed, a good approach may be to use the deactivated packings for quanti-
tation and the OV-17 packing for mass spectrometry, since the bleed character-
istics of the latter are more favorable than those of Apiezon L.
A major effort was directed toward evaluating the potential of a
nitrogen-specific flame ionization detector (NFID) for amine analysis. A
prototype conversion kit NFID detector was installed in the Hewlett-Packard
5710 gas chromatograph. The detector specifications state that a response
discrimination factor of 5000 to 1 for nitrogen-containing vs. nonnitrogen-
containing compounds can be achieved. This selectivity makes the NFID detector
system ideal for screening water sample extracts (which may contain hundreds of
organic compounds) for those that contain nitrogen. In practice, the NFID device
was variable in response and had to be tuned and checked with standards frequently.
When the device was operating properly, however, 0.1 ng of an amine (aniline)
could be detected reproducibly at a relatively insensitive attenuation. New
devices which are easier to maintain and which are more sensitive are avail-
able and should be evaluated.
Studies of the recovery of selected amines on ion exchange resins
using purified XAD-4 and Biorex 70 resins were initiated. The selective
recovery of amines on ion-exchange resins and subsequent elution showed some
promise as a technique for the analysis of amines as an alternative to ex-
traction. Limited access to liquid chromatographic facilities, however,
prevented any detailed studies in this area.
SUMMARY OF THE ORGANIC COMPOUNDS FOUND
J. C. Means
A comprehensive listing of all of the organic compounds identified in
the 204 samples collected and analyzed during the project is presented in
Tables 15 through 17.
-------
64
In the acid-extractable fraction (Table 15) 110 compounds were
identified. These compounds generally fell into the classes of alcohols,
fatty acid methyl esters, phthalate esters, polycyclic and polyunsaturated
hydrocarbons, hydrocarbons, substituted phenolics, and halogenated hydro-
carbons. The compounds appearing the most frequently in the acid extracts
were: methyl palmitate (183), methyl stearate (165), diethyl hexyl phthalate
(132), C,r terpineol (56), and methyl myristate (47). Of these compounds, only
the phthalate ester is a synthetic organic compound. The others are believed
to be products of the decay of natural materials. The majority of the com-
pounds identified, however, were of synthetic origin and many have been iden-
tified as toxic or carcinogenic.
In the base extractable fraction (Table 16), 89 compounds were iden-
tified. These compounds fell into the general classes of: phthalate esters,
hydrocarbons, halogenated hydrocarbons, and polycyclic and polyunsaturated
hydrocarbons. The compounds appearing the most frequently in the base ex-
tracts were: diethyl hexyl phthalate (132), dibutyl phthalate (84), C15
terpineol (55) and C-.Q terpineol (36). Of these, the two phthalate esters
are widely used synthetic organics while the terpineols are believed to be
natural products. Many of the compounds identified in the base extracts were
of synthetic origin and many of these have been identified as toxic.
Eighty-one purgeable organic compounds were identified in the 204
samples collected (Table 17). The majority of the compounds were halogenated
hydrocarbons from C-, to Cg. The compounds appearing the most frequently in
the purgeable fraction were: chloroform (178), trichloroethylene (88), tetra-
chloroethylene (77), 1,2 dichloroethane (53), benzene (40), acetone (33),
dichloromethane (32), toluene (31), and bromo-dichloromethane (24). It is
significant that chloroform and many of the other chlorinated and brominated
hydrocarbons appeared in almost every sample but at levels below 1 ppb. These
compounds are now suspected carcinogens or are known to be toxic. Their wide-
spread occurrence in surface waters emphasizes the need for further study of
the origin and impact of these highly mobile substances in the environment.
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65
Table 15
List of Acid-Extractable Compounds Found in 204 Water Samples
and Their Frequency of Occurrence
Compound Name
Cc Alcohol
0
Cj Alcohol
Cg Alcohol
Cg Alcohol
C,Q Alcohol
C-j-j Alcohol
C12 Alcohol
C, ~ Alcohol
C14 Alcohol
C,5 Alcohol
C16 Alcohol
C-iy Alcohol
C. Alcohol
'19
Alcohol
C2Q Alcohol
C2, Alcohol
C22 Alcohol
C23 Alcohol
Alcohol
Alcohol
Alcohol
74
"26
Alkyl Benzene
(C-,gH, 2) Benzoanthrene
Butyl benzyl Phthalate
Butyl Phthalyl Butyl Glycolate
Caffeine
CvHvC17 ' x - 4, z - 5 Isomers
A y L
CgH,,- Isomer
C10H10 Isomer
C15H24
Frequency
.1
2
3
5
6
7
7
8
9
9
9
9
9
6
7
6
6
4
3
1
1
3
1
3
23
1
12
1
1
1
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66
Table 15, cont.
Compound Name Frequency
C, ,Hin Isomer 1
ID I u
ci6Hio (pyrene) 3
^21^2^2 Methyl Pimarate Isomer 8
Dibutyl Phthalate 15
Di chlorinated Hydrocarbon C - 5 2
Dichlorobutane 11
Dichloroheptane 1
Di ethyl Hexyl Phthalate 132
Diisobutyl Phthalate 2
Dioctyl Adi pate 6
Dioctyl Phthalate 1
Diphenyl Dulfone 1
Fatty Acid Methyl Ester C - 10 1
Fatty Acid Methyl Ester C - 12 7
Fatty Acid Methyl Ester C - 13 1
Fatty Acid Methyl Ester C = 14 3
Fatty Acid Methyl Ester C - 14 15
Fatty Acid Methyl Ester C - 15 7
Fatty Acid Methyl Ester C - 16 11
Fatty Acid Methyl Ester C - 17 2
Fatty Acid Methyl Ester C - 18 5
Fatty Acid Methyl Ester C - 19 2
Fatty Acid Methyl Ester C - 20 14
Fatty Acid Methyl Ester C - 21 1
Fatty Acid -Methyl Ester C - 22 18
Fatty Acid Methyl Ester C - 23 1
Fatty Acid Methyl Ester C - 24 11
Fatty Acid Methyl Ester C - 26 3
Hexachlorobenzene 2
Hexachlorobutadiene 2
Hexachlorobutene 2
Hexachloroethane 1
Hexachloro-hexafluoropentane 1
-------
67
Table 15, cont.
Compound Name Frequency
Hydrocarbon C - 8 3
Hydrocarbon C - 10 4
Hydrocarbon > 12 3
Hydrocarbon C - 14 4
C, 5 Hydrocarbon 2
Hydrocarbon C - 16 7
C-|g Hydrocarbon 2
C, 7 Hydrocarbon 2
Hydrocarbon C - 18 11
Hydrocarbon C - 20 7
Hydrocarbon C - 22 10
Hydrocarbon C - 24 4
Hydrocarbon C - 26 5
Hydrocarbon C - 28 4
Hydrocarbon C - 30 5
Methoxy Carbonyl Benzophenone 1
Methyl Arachidate 2
Methyl-2(4-chlorophenoxy) Butanoate 13
Methyl Dehydroabietate 11
Methyl Dichlorophenoxy Acetate 4
Methyl Dichlorophenyl Ether 1
Methyl-2, 2-Dichloro-3-Methyl Butanoate 1
Methyl Laurate 7
Methyl Myristate 47
Methyl Naphthoate 1
Methyl Palmitate 183
Methyl Pentachlorophenyl Ether 12
Methyl Pentachlorophenoxy Ether 2
Methyl Stearate 165
Methyl Tetrachlorophenyl Ether 1
2-Methyl Thiobenzothiazole 1
Methyl-Trichlorophenoxy Acetate 1
Methyl Trichlorophenyl Ether 5
Pentachloroanisole 10
-------
68
Table 15 , cont.
Compound Name Frequency
Pentachlorobutadiene 2
Pentachlorobutene 3
Pentachloroethane 3
Tetrachlorobutadienne 3
C,5 Terpene 37
CIQ Terpineol 27
C-|5 Terpineol 56
Tetrachloroanisole 4
Trichloroanisole 3
Trichloroheptane 1
Trichlorohexane 3
Trichloropentane 4
Unidentified Phthalate 2
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69
Table 16
List of Base-Extractable Compounds Found in 204 Water Samples and
Their Frequency of Occurrence
Compound Name Frequency
Alkyl Acid Ester (R + R1 - 8) 3
Alkyl Phenyl Ether 1
Anthracene 1
Atrazine 5
Benzothiazole 2
Biphenyl 1
Bromopropyl Benzene 1
Butyl benzyl Phthalate 2
Butyl Phthalyl Butyl Glycolate 17
Caffeine 9
C-|Q Camphenol 2
CXH Clz, x - 4, z - 5 (series of isomers) 5
C5H10C12 1
CgH-|6 Isomer 1
ci6Hio (pyrene) 7
C18H12 3
C22 H14 ]
Chloro-Nitrobenzene 3
Chloroprene Dimer 1
Chloroprene 1
Dibromo-chloroethane 1
Dibromoethane 1
Di butyl Nonanedioate 1
Dibutyl Phthalate 84
Dichlorobenzene 9
Dichlorobutane 19
Dicyclohexyl Phthalate 1
Diethoxyethane 4
N,N-Di ethyl aniline 1
-------
70
Table 16, cont.
Compound Name
Di ethyl Hexyl Phthalate
Diethyl Phthalate
Diisobutyl Nonanedioate
Diisobutyl Phthalate
Dimethyl Biphenyl
Dimethyl Naphthalene
Dimethyl Styrene
Dinitrotoluene
Dioctyl Adi pate
Diphenyl Benzene
Diphenyl Ethane
Diterpene C,gH,g
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorobutene
Hexachloroethane
Hydrocarbon C-8
Hydrocarbon C ^ 10
Hydrocarbon C - 12
Hydrocarbon C - 14
C-.,- Hydrocarbon
C,g Hydrocarbon
Hydrocarbon C - 16
Cig Hydrocarbon
Hydrocarbon C - 18
Hydrocarbon C - 20
Hydrocarbon
Hydrocarbon
Hydrocarbon
Hydrocarbon
Hydrocarbon
Hydrocarbon
Hydrocarbon
C - 22
C - 24
C - 26
C - 28
C - 29
C - 30
C - 31
Frequency
132
6
1
5
1
2
1
2
2
1
1
4
1
2
2
2
1
1
5
10
1
2
16
3
8
16
13
11
7
7
1
7
1
-------
71
Table 16, cont.
Compound Name
Hydrocarbon C - 32
Hydrocarbon C - 33
Hydrocarbon C - 34
Hydrocarbon C - 35
Hydroxy-borneol
Indole
Methyl Acenaphthene
Methyl Naphthalene
2-Methyl Thiobenzothiazole
Nitro toluene
Pentachlorethane
Pentachlorobutadiene
Pentachlorobutene
Phenanthrene
Terpene C^
Terpineol C,Q
Terpineol C,5
Tetrachlorobutadiene
Tetrachloroethane
Tetrach1oroethy1ene
Tri chloroethylene
Tritepene C,5H-.
Unidentified Phthalate
Xylene
Frequency
1
1
1
1
1
1
1
2
1
3
2
3
2
1
1
36
55
3
2
4
1
3
6
1
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72
Table 17
List of Volatile Compounds Found in 204 Water Samples and
Their Frequency of Occurrence
Compound Name Frequency
Acetone 33
Acetophenone 6
Benzaldehyde 1
Benzene 40
Bromobenzene 9
1-Bromo-l-Chloroethane 2
l-Bromo-2-Chloroethane 1
l-Bromo-2-Chloropropane 1
Bromo-Dichloroethane 2
Bromo-dichloromethane 24
Bromo-Trichloropropane 1
Butadiene 1
Butanal 1
Butane 3
Butene 5
C5HgO or CgH120 11
C5H1Q0 or C6H120 2
C8H17 ]
Carbon Tetrachloride 6
Chlorobenzene 11
l-Chloro-2-Bromoe.thane 1
l-Chloro-2-Bromopropane 1
Chloroform 178
Chloroprene 1
Cyclohexane 13
Cyclopentane 1
Dibromo-Chloromethane 10
Dibromoethane 2
Dichlorobenzene 23
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73
Table 17, cont.
Compound Name
1,2-Dichloroethane
Dichloroethylene
Di chloro-lodomethane
Dichloromethane
1,2-Dichloropropane
Die thy 1 Ether
Diisopropyl Ether
Dimethoxymethane
Dimethyl Sulfide
Dimethyl Disulfide
Dime thy Iformamide
Dioxane
Dioxolane
Ethanethiol
Ethyl Acetate
Ethyl benzene
Ethyl Methyl Dioxolane
Fluoro-dichloro-bromomethane
Freon
Furfural
Heptene
Hexane
Hexanol
Hexene Isomers
Methacrylonitrile
Methyl-t-Butyl Ketone
Methyl Ethyl Ketone
Methyl-isobutyl Ketone
Methyl Methacrylate
2-Methyl Propanal
Methylal
4 Methyl-2-Ethyl-l,3-Dioxolane
Methyl -tetrahydrofyran
Neopentane
Frequency
53
19
1
32
8
9
2
10
1
5
1
4
1
1
1
5
5
1
1
1
1
14
1
5
1
1
1
2
1
1
1
2
2
1
-------
74
Table 17, cont.
Compound Name Frequency
Nonene 1
Pen tane 18
Pentene Isomer 4
C,g Terpene 2
1,1,2,2-Tetrachloroethane 12
Tetrachloroethylene 77
Tetrahydrofuran 29
Tetrahydropyran 4
Toluene 31
Tribromomethane 5
Trichlorobutane 1
Trichloroethane 11
1,1,1-Trichloroethane 18
Trichloroethylene 88
Trichloropropane 6
Trichloro-fluoromethane 11
Trichloro-trifluoroethane 8
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75
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