EPA-660/2-74-078
August 1974
Environmental Protection Technology Series
nvironmental Applications of Advanced
Instrumental Analyses: Assistance
Projects, FY '73
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Corvallis , Oregon 97330
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology .
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY ; series. This series
describes research performed to develop and
demonstrate instrumentation* equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
EPA REVIEW NOTICE
The Office of Research and Development has reviewed this report
and approved its publication. Mention of trade names or
commercial products does not constitute endorsement or recommen-
dation for use.
-------
EPA-660/2-74-078
August 1974
ENVIRONMENTAL APPLICATIONS OF ADVANCED INSTRUMENTAL
ANALYSES: ASSISTANCE PROJECTS, FY 73
By
Ann L. Alford
Southeast Environmental Research Laboratory
College Station Road
Athens, Georgia 30601
Project #16020 GHZ
Program Element #1BA027
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
CORVALLIS, OREGON 97330
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, B.C. 20402 - Price $1
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ABSTRACT
The National Water Contaminants Characterization Research
Program (now the Analytical Chemistry Branch) of the
Southeast Environmental Research Laboratory identified
and measured aquatic pollutants under eight projects in
answer to requests for assistance. In most cases these
analyses helped to solve, or at least to understand more
clearly, the related pollution incident and in some cases
provided evidence for enforcement of regulatory legislation.
Under an additional project, analytical consultations were
held as requested by various organizations concerned with
pollution incidents.
11
-------
CONTENTS
Page
Abstract ii
List of Figures v
List of Tables vi
Acknowledgments vii
Sections
I Recommendations 1
II Introduction 2
III Discussion 3
1. Terpenes in Paper Mill Effluents and 3
Mississippi River Samples
2. Organic Components of Pesticide Plant 4
Effluents
3. Organic Compounds Formed During Chlori- 10
nation of Municipal Waste Sludge
4. Organic Components of Dye Plant Effluent 11
5. Organic and Elemental Components of Coal- 14
Gasification Pilot Plant Effluent
6. Elemental Analysis of Lake Ontario Water 19
7. Elemental Analysis of Patio Debris 22
8. Elemental Analysis of Mineral Processing 22
Plant Wastes
9. Dissemination of Analytical Information 25
a. Consultations 25
b. Industrial Organic Pollutant List 27
111
-------
CONTENTS (cont'd)
Page
c. Symposia 2o
IV References 2g
V Glossary of Abbreviations 31
IV
-------
FIGURES
No. Page
1 Diagram of sampling sites for paper mill 4
effluent analyses.
2 Computer-reconstructed gas chromatogram of 16
coal-gasification plant effluent extract
3 Lake Ontario sampling sites for IFYGL elemental 20
survey
v
-------
TABLES
No. Page
II.I.I.IIII-IIII. .! ITUH-
1 Organic Compounds Identified in Paper Mill 5
Effluents and Mississippi River Samples
2 Compounds Tentatively Identified in Pesticide 8
Plant Effluent
3 Organic Components of Dye Plant Effluent 13
4 Organic Components of Coal-Gasification Pilot 17
Plant Effluent
5 Elemental Composition of Coal-Gasification 18
Pilot Plant Effluent
6 Elemental Composition of Lake Ontario Water 21
Samples
7 Elements Detected in Ore Processing Plant Waste 24
Slurry
VI
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ACKNOWLEDGMENTS
The following Southeast Environmental Research Laboratory
staff were the principal investigators of the projects
listed in Section IV:
Project
1. L. H. Keith
2. J. M. McGuire
3. A. W. Garrison
4. A. W. Garrison
5. J. M. McGuire and C. E. Taylor
6. C. E. Taylor
\
7. C. E. Taylor
8. C. E. Taylor and R. V. Moore
9. National Water Contaminants Characterization Research
Program staff
The assistance of F. R. Allen, M. H. Carter, T. L. Floyd,
A. C. McCall, O. W. Propheter, W. J. Taylor, and G. D.
Yager in preparing samples for analysis, performing data
acquisition procedures, and interpreting analytical data is
gratefully acknowledged.
VI1
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SECTION I
RECOMMENDATIONS
Analytical data about specific past and present pollutant
sources should be used to establish and enforce effluent
water quality standards for the industrial permit program
and to update these standards as information is obtained.
More laboratories concerned with environmental quality should
be equipped to perform analyses such as those described in
this report. Existing analytical techniques should be con-
tinually improved, and new techniques should be investigated
for applicability to pollutant analysis. Information about
specific pollution incidents should be widely disseminated
to help solve and perhaps prevent future environmental
problems.
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SECTION II
INTRODUCTION
The National Water Contaminants Characterization Research
Program (NWCCRP)* at the Southeast Environmental Research
Laboratory (SERL) develops techniques for identifying and
quantifying chemical pollutants and identifies specific
compounds associated with various pollution sources. The
NWCCRP has analyzed many samples related to a variety of
specific pollution problems. Analytical results were repor-
ted only to the persons who requested the analyses and
therefore had limited distribution. The problems studied
1 2
by the NWCCRP are briefly summarized in annual reports '
to acquaint other researchers and administrators with the
type of information that can be obtained and to inform
environmental chemists of technique applications and develop-
ments. This report summarizes fiscal year 1973 projects.
*In late 1973 this group's name was changed to the Analytical
Chemistry Branch/ but the projects described in this report
were performed under the NWCCRP designation.
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SECTION III
DISCUSSION
1. Terpenes in Paper Mill Effluents and Mississippi River
Samples
The NWCCRP was requested by the Environmental Protection
Agency's (EPA) Region VI Lower Mississippi River Field
Facility in Slidell, Louisiana, to identify specific com-
pounds in two paper mill effluents and in three river
water samples. Organic pollution of the Mississippi River
near New Orleans, Louisiana, was indicated by taste and
odor problems in fish from the area. When six terpenes
were identified in the New Orleans finished drinking water,
paper mills near St. Francisville, Louisiana, were suspected
as possible sources.
Three-day composite samples (1800 ml total volume each) were
taken from the effluents of two paper mills, which were
located approximately eight miles apart, and from three
nearby Mississippi River sites (Figure 1). Each sample
^
was extracted with chloroform, concentrated, and analyzed
with gas chromatography (GC). The extracts' gas chromato-
grams were compared to determine which paper mill effluent
components might also be present in the river water.
Each sample was then analyzed with a combined gas chromato-
graph-mass spectrometer (GC-MS) interfaced with a small
dedicated computer. Appropriate mass spectra were plotted
after the computer-reconstructed chromatograms were compared
to previously obtained gas chromatograms. Specific com-
pounds were identified by comparison of their mass spectra
with standard spectra in the SERL's files or in the litera-
ture , by computer matching ' with standard spectra in a
data bank containing more than 11,000 spectra, or by a com-
bination of these methods.
3
-------
Paper
Mill
A
River
Sample
#2
Paper
Mill
B
River
Sample
#3
.25 mi-*-->-»-'--»-»-0.25 mi->-> -»-»-> 8 mi-»-->->»->-»"»-0.25 mi-»-»»
River
Sample
#1
Figure 1. Diagram of sampling sites for paper mill effluent
analyses
Twenty-one compounds that were absent from the solvent blank
and from the sample taken upstream from both mills were
identified in the two mill effluents (Table 1). Of these
compounds, five identified in paper mill A effluent were
also found in river sample #3. None of the six terpenes
previously identified in the New Orleans finished drinking
water were found in any of these samples. Absolute
concentrations of identified compounds were not determined.
However, low concentrations were indicated by the large
concentration factor (2 X 10 ) required to identify river
water contaminants.
Mass spectral identifications were reported to the EPA
Region VI Enforcement Division Office and were compiled
with other analytical data. All data were then sent to the
U. S. Attorney in Dallas, Texas, who concluded that insuf-
ficient evidence existed for litigation.
2. Organic Components of Pesticide Plant Effluent
The EPA1s Lower Mississippi Field Facility in Slidell,
Louisiana, requested the identification of specific organic
components in a pesticide plant effluent to permit develop-
ment of efficient monitoring techniques.
The effluent of the pesticide manufacturing plant, located
near Memphis, Tennessee, was included in industrial effluents
-------
Table 1. ORGANIC COMPOUNDS IDENTIFIED IN PAPER MILL EFFLUENTS AND MISSISSIPPI RIVER
SAMPLES
Compound
bis (2-ethylhexyl) azalate
dichloropropene
1 , 1-diethoxypropane
n-nonyl aldehyde
3 , 5 , 5-trimethylhexanol
hexachloroe thane
guaiacol
camphor
fenchyl alcohol
terpinene-4-ol
a-terpineol
3-pinene
limonene
fenchone
anethole isomer "a"
anethole isomer "b"
anethole isomer "c"
2- formy Ithiophene
2 -acety Ithiophene
2 -propiony Ithiophene
dime thylsulf one
n-undecane
n-dodecane
n-tridecane
n-tetradecane
n-pentadecane
Solvent
Blank
(Cone.
Factor
2xl05)
X
X
X
X
X
River
Sample
#1
(Cone.
Factor
2xl05)
X
X
X
X
Paper
Mill
#1
(cone.
Factor
6xl05)
X
X
X
X
X
X
X
X
X
X
X
X
River
Sample
#2
(Cone.
Factor '
2xl05)
X
X
X
X
X
X
X
X
X
X
X
X
Paper
Mill
#2
(Cone.
Factor
6xl05)
X
X
X
X
X
X
X
X
X
X
X
River
Sample
#3
(Cone.
Factor
2xl05)
X
X
X
X
X
X
X
X
X
X
X
X
-------
Table 1. (Continued)
Compound
n-hexadecane
ethylidenecyclopentane
methyl trisulfide
noreamphor
diphenyle thane
4-methyl-2-pentanol
syringaldehyde
Solvent
Blank
(Cone.
Factor
5
2x10 )
River
Sample
#1
(Cone.
Factor
5
2x10 )
Paper
Mill
#1
(Cone.
Factor
5
6x10 )
River
Sample
#2
(Cone.
Factor
5
2x10 )
X
Paper
Mill
#2
(Cone.
Factor
5
6x10 )
X
X
X
X
River
Sample
#3
(Cone.
Factor
5
2x10 )
X
X
X
-------
monitored during an EPA Mississippi River water quality
survey. The plant's effluent was sampled bi-weekly for six
months. Gas chromatographic analyses showed the pesticides
endrin, dieldrin, aldrin, and heptachlor and other chlori-
nated compounds with relative retention times different
from those of known pesticides.
Extracts of a solvent blank and of twelve samples of the
pesticide plant's effluent were sent to the NWCCRP for GC-MS
analysis. An aliquot of each extract was injected into a
gas chromatograph to establish optimum separation conditions.
A computer-controlled GC-MS was used to record mass spectra.
As GC peaks eluted, mass spectra were collected continually
and stored in the computer for later output with appropriate
background spectra subtracted.
3 4
Computer matching ' of effluent component mass spectra with
standard spectra in a central data bank was unsuccessful in
most cases. Each spectrum was inspected and compared to
standard spectra in the literature. A combination of
methods produced tentative identifications of 44 effluent
components that were not found in the solvent blank (Table 2);
30 of these were chlorinated compounds. Many were pesticide
by-products whose spectra were not included in the data bank.
Few standards were available for confirmation, and many
identifications were based on literature spectra of related
compounds and on the analyst's knowledge of the principles
of mass spectrometry.
The identifications were reported to the Administrator of
Region VI for correlation with other analytical data
acquired during the survey. The analyses indicated that
monitoring of the plant's effluent should be continued with
-------
Table 2. COMPOUNDS TENTATIVELY IDENTIFIED IN PESTICIDE PLANT EFFLUENT
oo
Sample Number
Compound Name
1
1 . Acenaphthene
2. Aldrin
3. Chlordane
4 . Chlordene
5 . Cymene
6. Dicyclopentadiene
7. Dieldrin
8. Dimethyl naphthalene isomer
9. Diphenylether
10. Endrin
11. Endrin isomer
12. l,2-Epoxy-4,5, 6, 7, 8, 8a-hexachloro-a-
dicyclopentadiene (hexachlor
epoxide)
13. Ethylnapthalene isomer
14. Heptachlor
15. Heptachloronorbornene isomer
16. Heptachlornorbornene isomer
17 . Hexachlorobutadiene
18. Hexachlorocyclopentadiene
19. Hexachloronorbornadiene isomer
20. Hexachloronorbornadiene isomer
21. Hexadienal
22. Hydroxybiphenyl isomer
23. Isodrin
24. Jasmone
25. Methylnapthalene isomer |||
Itlllll
1
X
X
X
X
X
X
X
X
X
2
X
X
X
X
X
X
X
X
X
X
3
X
X
X
X
X
X
4
X
X
X
X
X
X
X
X
X
X
X
X
X
X
5
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
6
X
X
-X
X
X
X
X
X
X
X
X
7
X
X
X
X
X
X
X
X
X
X
X
9
X
X
X
X
X
X
10
X
X
X
X
X
X
X
X
11
X
X
X
X
X
12
X
X
X
X
X
X
X
X
X
-------
Table 2. CONTINUED
Compound Name
Sample Number
II
26. Naphthalene 1
27. Nonachlor 1
28. Octachlorocyclopentene |
29. Pentachlorocyclopentadiene ||
30. Pentachloronorbornadiene isomer I V
31. Pentachloronorbornene isomer
32 . Pentachloronorbornadiene epoxide 1
isomer |||||
33. Pentachloronorbornene isomer 1
34. Phthalate ester ||
35. Tetrachlorocyclopentene isomer | A
36. Tetramethylbenzene isomer ||||
37. Trichlorocyclopentene isomer ||
38. Trichlorocyclopentene isomer |||||
39. Trichlorocyclopentene isomer |||
40. Trichlorocyclopentene isomer I
41. Xylene ||
42. C10H7OC17
43. C12H9C15 (related to Endrin) I
44. Cl2H10ci6 II
1
X
X
2
X
X
3
X
4
X
X
X
X
X
X
5
X
X
X
X
X
X
X
6
7
X
X
9
X
10
X
X
X
X
X
X
X
11
X
12
X
X
-------
emphasis on total effluent content rather than on GC
analysis for only a few specific pesticides.
3. Organic Compounds Formed During Chlorination of Munici-
pal Waste Sludge
Intensive chlorination to disinfect sludges from sewage
treatment plants and septic tanks prompted the EPA1 s
investigation of the possibility that toxic compounds are
formed during this treatment. The NWCCRP was requested by
the EPA1s advanced Waste Treatment Laboratory in Cincinnati,
Ohio, to identify specific chlorinated compounds formed
during Purifax treatment of sludge from a municipal waste
treatment plant. The Purifax process, which involves
mixing the sludge with large amounts of chlorine (2 g Cl2/£
sludge), deodorizes and stabilizes the sludge against
petrefaction for up to six months. Therefore, it must
produce sludge components that are toxic to bacteria and
that may be toxic to other organisms.
Two sludge samples from the Fairlawn, New Jersey, municipal
waste plant, one taken before and one after Purifax treat-
ment, were extracted to give acid, basic and neutral
fractions. The acid fraction was esterified with diazo-
methane. Aliquots of all fractions were analyzed with gas
chromatography. The Coulson conductivity GC detector
showed that chlorine- and/or sulfur-containing compounds
were present in all samples taken before and after Purifax
treatment.
The acid fraction of the after-treatment sample contained
several GC peaks not present in the before-treatment sample.
This suggested that some compounds were formed during the
Purifax process. GC analysis with a flame ionization
10
-------
detector established the necessary conditions for combined
GC-MS analysis of the additional peaks in the after-
treatment sample. Mass spectral data indicated the presence
of several fatty acid esters and other non-chlorinated
organics. Only four minor components appeared to be
chlorinated compounds. Two were specifically identified and
confirmed as the methyl esters of 274-dichlorophenol and
2,4,6-trichlorophenol; the concentration of each was
estimated to be 10 yg/£. Two other chlorinated aromatic
compounds were not specifically identified.
These analyses indicated the need for further investigations
to determine the specific compounds synthesized during
Purifax sterilization and their environmental implications.
An EPA grant is currently funding such investigations at
North Texas State University. Information obtained will be
used to evaluate Purifax chlorination and to establish
guidelines for final disposition of Purifax-processed
sludges and supernatant liquors.
4. Organic Components of Dye Plant Effluent
The EPA1s Region IV Research and Development Program
Representative requested analyses to determine if a sulfur
black dye plant's wastewaters could be used as a dechlorin-
ating agent. A Charlotte, North Carolina, dye manufacturing
plant was developing (under an EPA Demonstration Grant) a
treatment process for sulfur black dye wastewaters. About
25% of the plant's effluent is sodium thiosulfate, which is
an excellent dechlorinating agent and is used in production
of the dye Sulfur Black 1^. The effluent had been proposed
as a dechlorinating agent for treated sewage, but organic
components of the effluent could make it undesirable for
this purpose.
11
-------
The NWCCRP's routine organic extraction techniques were
used to separate volatile organics into acid, basic, and
neutral fractions. GC analysis showed no significant peaks
in basic or neutral fractions; about 45 components were
detected in the acid fraction after its esterification with
diazomethane. Combined GC-MS analysis provided tentative
identifications for 16 compounds, including 7 chlorinated
benzoic acid derivatives (Table 3). Standard samples were
available for only three of the identified compounds.
Their presence was confirmed by comparison of GC retention
times and mass spectra of effluent components to those of
the standard samples. Wastewater component concentrations
were estimated from GC peak height comparisons (Table 3).
Mass spectral data for six effluent components, five of the
tentatively identified chlorinated benzoic acid derivatives
and one unidentified component, were sent to Cornell Univer-
sity for computer interpretation with the Self-Training
Interpretive and Retrieval System (STIRS) program. If the
reference file includes mass spectra of related compounds,
this program provides extensive, if not complete, structural
information. The STIRS system provided additional evidence
for the five preliminary identifications but did not distin-
guish between isomers. The remaining compound was apparently
a non-chlorinated aromatic and was not specifically identi-
fied.
3 4
Computer matching ' of these six effluent component mass
spectra to standard spectra in the Battelle reference
library confirmed one identification and provided supporting
evidence for another. No reliable matches were obtained for
the remaining four spectra.
12
-------
Table 3. ORGANIC COMPONENTS OF DYE PLANT EFFLUENT
Compound Name3
benzoic acid
p-chlorobenzoic acid
2 , 4-dichlorobenzoic
acid
amino-chlorobenzoic
ac id i somer
amino-chlorobenzoic
acid isomer
amino-chlorobenzoic
acid isomer
dichloromethoxy ben-
zoic acid
tr ich loromethoxy-
benzoic acid
myristic acid
pentadecanoic acid
palmitic acid
margaric acid
stearic acid
sulfur
dioctyl adipate
ethyl palmitate
GC-MS
Identification
^
/
/
^
/
/
/
/
/
i/
/
/
/
/
/
'
Confirmation
GC Retention
Time of Standard
/
/
/
Mass Spectrum
of Standard
/
/
y/
STIRSb
Evidence
,/
/
j
/
J
Battelle
Match
Excellent
Good
No
No
No
Estimated
Cone.
(ua/A)
110
20
12
25-30
25-30
25-30
<5
<5
U)
Acids actually identified as methyl esters
STIRSSelf-Training Interpretive and Retrieval System computer program, Cornell University.
-------
A black solid that precipitated from the acidified waste-
water sample was identified as a sulfur black dye. Its
solubility and color matched those of several sulfur black
g
dyes. The properties of a cotton swatch dyed with a
sodium sulfide solution of the precipitate matched those of
cotton dyed with sulfur black.
Identifications were reported to the requester, who will
use bioassay and toxicity data for these compounds to
determine if the effluent should be used as a dechlorinating
agent. If this is not feasible, the data will be used by
dye plant officials who must plan appropriate waste treat-
ment.
5. Organic and Elemental Components of Coal-Gasification
Pilot Plant Effluent
The U. S. Bureau of Mines requested mass spectrometric
analysis of trace elements and specific organic components
in effluent from a coal-gasification pilot plant. The
Pittsburgh Energy Research Center designed and constructed
the pilot plant to determine the feasibility of the Synthane
coal gasification process. Coal is heated to expel gases
from which synthetic natural gas is produced. The Synthane
process requires large volumes of water, approximately
190 gal. for each ton of coal. Plant effluent component
data were needed to develop disposal methods that could
ultimately be used in full-scale operation.
The pilot plant effluent samples was shaken well to mix the
relatively clear water with the oily scum floating on the
surface. A 100-ml sample portion was extracted with 200 ml
of chloroform, dried with sodium sulfate, and concentrated
to approximately 25 ml.
14
-------
Combined GC-MS analysis showed a mixture of five major and
several minor volatile organic components (Figure 2) .
Computer matching of seven sample mass spectra with refer-
ence spectra in the Battelle data bank provided good matches
for all five major GC peaks and one minor peak (Table 4) .
Each match's reliability was indicated by the similarity
index (SI) , a number between 0 and 1 that showed how well
the unknown spectrum matched the selected reference spectrum.
Experience has shown that a good match produces a similarity
iridex >_ 0 . 5 .
Spark source mass spectrometric (SSMS) analysis of duplicate
100-ml sample portions spiked with yttrium and zirconium as
internal standards showed the presence of 26 elements in
varying quantities (Table 5) . The most significant detected
element was selenium at a concentration of 360
9
The importance of selenium is well documented. Selenium is
believed to be highly toxic to humans and produces symptoms
similar to arsenic poisoning. In 1962, the U. S. Public
Health Service Drinking Water Standards set the mandatory
limit at 10 ug Se/£. Selenium poisoning (both chronic and
acute) of livestock has been associated with consumption of
selenium-containing foodstuffs. Irrigation waters containing
selenium at concentrations of 210-500 yg/£ cause toxic
accumulations in plants, and waters containing over 500 yg/£
cannot be used for irrigation.
The NWCCRP's analytical data will be used by the Pittsburgh
Energy Research Center's personnel to design pollution
control facilities for Synthane coal-gasification plants.
A technical progress report currently in preparation will
include these data.
15
-------
Figure 2. Computer-reconstructed gas chromatogram of coal-gasification plant
effluent extract
10 20 30 10 S3 60 70 00 90 100 110 120 130 1% ISO 160 170 180 ISO 200
SPECTRUM NUMBER
-------
Table 4. ORGANIC COMPONENTS OF COAL-GASIFICATION PILOT PLANT
EFFLUENT
RGC
Peak
1
2
3
4
5
6
7
Best Match
Phenol
o-Cresol
m-Cresol
2, 5-Dimethylphenol
3, 4-Dimethylphenol
2 , 4 -Dimethy Iphenol
a-Naphthol
S.I.
0.834
0.846
0.867
0.839
0.700
0-653
0.245
Second Best
Match
Phenol
m-Cresol
o-Cresol
2, 6-Dimethylphenol
3, 4-Dimethylphenol
3, 4-Dimethylphenol
1 , 2-dihydroxy-
1 , 2-dihydronaph-
thalene
S.I.
0.795
0.741
0.842
0.804
0.692
0.637
0.232
17
-------
Table 5. ELEMENTAL COMPOSITION OF COAL-GASIFICATION PILOT
PLANT EFFLUENT
Element
Detected
sib
Ca
Nab
Fe
SB
Al
Se
K
Ba
P
Zn,
Clb
Mn
Ge
As
Ni
Sr
Sn,
Brb
Cu
I*3
Nb
Cr
V
Co
Concentr at ion
yg/£a
Aliquot #1
4000
4400
4000
2600
1500
700
800
401
117
109
82
44
48
36
32
44
23
33
25
25
16
10
7
4
4
1
Aliquot #2
5000
3600
2000
2900
1800
900
700
323
204
155
92
83
54
38
61
28
34
24
26
20
20
9
5
8
2
2
Average
4500
4000
3000
2750
1650
800
750
360
160
130
90
60
50
40
40
30
30
30
20
20
20
10
6
6
3
2
Minimum detection limit for most elements was approxi-
mately 1 yg/& effluent.
Concentration estimated using calculated relative
sensitivity.
18
-------
6. Elemental Analysis of Lake Ontario Water
The elemental components of 12 Lake Ontario water samples
were determined with SSMS analysis as part of the Hazardous
Materials Survey during the International Field Year for
the Great Lakes (IFYGL). This joint United States-Canadian
study was conducted to develop a sound scientific basis for
water resource management. The sampling program involved
universities, private institutions, and several United
States Government agencies, including the EPA. Lake Ontario
and the Ontario Basin were selected for intensive study
because their physical characteristics were typical of the
Great Lakes. Analytical data were needed to compile a
quantitative description of hazardous materials entering,
inhabiting, and leaving Lake Ontario.
The Hazardous Material Study Coordinator requested an
elemental study of 12 water samples collected at three
depths from four Lake Ontario sites (Figure 3). The 1-gal.
samples were collected during a four-day period in late
June 1972 and shipped to the SERL in glass containers. A
100-ml aliquot of each sample was evaporated onto a
graphite electrode for analysis with the computerized spark
source mass spectrometer, which provided quantitative data
for 72 elements.
Only 24 elements were detected, and only nine were found in
concentrations greater than 1 ug/A (Table 6). Low signal
intensities prevented quantitation of elements present at
concentrations less than 1 yg/£. Silicon and boron were
detected in all samples, but because samples were stored in
glass containers, analyses for these elements were invalid.
Nitrogen, hydrogen, and oxygen were present in the vacuum
system's residual gases and were therefore not determined.
19
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Figure 3. Lake Ontario sampling sites for IFYGL elemental survey
to
o
LAKE ONTARIO
SAMPLING STATIONS
Toronto
LAKE
MILES
-------
Table 6. Elemental Composition of Lake Ontario Water Samples
Element
Ca
Na
Sr
Mg
Cl
Ba
K
F
Al
Br
As
Ga
Cr
Cu
Mn
Fe
S
P
Zn
Ni
Ba
Rb
Sc
Co
Station 10 Sample
Components, yg/£
DEPTH
1m
100
300
200
100
500
100
10
10
2
<1
<1
<1
<1
<1
<1
<1
DEPTH
60m
2000
1000
200
200
300
100
10
10
4
<1
<1
<1
<1
<1
<:L
BOTTOM
119m
3000
1000
200
200
100
50
40
10
2
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
Station 45 Sample
Components, yg/£
DEPTH
1m
2000
2000
100
300
200
100
50
1
1
<1
<1
<1
<1
<1
<1
DEPTH
90m
3000
2000
200
300
200
50
30
1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
BOTTOM
183m
2000
1000
100
200
100
100
40
10
1
<1
<1
<1
<1
<1
<1
<1
<1
Station 75 Sample
Components, yg/£
DEPTH
1m
2000
1000
200
200
200
100
40
20
1
<1
<1
<1
<1
<1
<1
-------
Mercury and inert gases were pumped away too quickly and
were ignored.
Results of the elemental survey were reported to the
Hazardous Materials Study Coordinator for inclusion in
formal documentation of the IFYGL Study.
7. Elemental Analysis of Patio Debris
A concerned citizen's complaint to the EPA Administrator
prompted the SERL's elemental analysis of floor sweepings
from a patio in Tell City/ Indiana. The citizen stated
that air pollution was caused by black soot emissions from
industrial plants in the area. His letter was accompanied
by material swept from his home patio. The EPA1s Office of
Research and Monitoring requested the SERL to determine the
sample's elemental components.
The SSMS analysis did not indicate an air pollution problem.
Meaningful data acquisition was severely hampered by the
sample's content of extraneous debris, leaf fragments, and
brown straw components. The sample was ashed at 600 C in
air for one hour and leached with boiling aqua regia.
Quantitative SSMS analysis showed that silicon was the major
elemental component of the soluble portion.
The SERL's report to the EPA's Office of Research and
Monitoring listed quantitative data for all elements detected
and stated the need for appropriate collection techniques for
samples that reflect air pollution problems.
8. Elemental Analysis of Mineral Processing Plant Wastes
Spark source mass spectrometric elemental analysis provided
quantitative data for the EPA1s investigation of the ecolo-
gical effects of taconite tailings discharged from a
22
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Minnesota iron ore processing plant into Lake Superior.
Each day the plant discharges a slurry containing approxi-
mately 60,000 long tons of taconite wastes, including 5,400
long tons of particles less than four microns in diameter.
These small particles remain suspended in water and are
transported by water currents. Evidence of taconite-
related materials has been found in the municipal water
systems of Beaver Bay, Two Harbors, and Duluth, Minnesota.
Elemental analyses were requested by the EPA's National
Water Quality Laboratory (NWQL) in Duluth.
The NWQL prepared a composite of the plant's discharge by
combining smaller samples taken hourly for ten days. Parti-
cles larger than five microns in diameter were filtered from
the composite sample, and aliquots were used for various
ecological studies. One 6-ml aliquot was shipped to the
SERL for elemental analysis by SSMS. The slurry was centri-
fuged to separate liquid and sediment. Two 1-ml liquid
samples were spiked with the internal standard yttrium and
evaporated onto graphite electrodes. Four sediment samples
were dried and spiked with yttrium and indium for internal
standards.
The SSMS method provided quantitative data for 12 elements
in the liquid portion and for 28 elements in the sediment
portion (Table 7). Concentrations were estimated for four
other elements detected in both liquid and sediment (Table 7)
'Electronic detection provided ah absolute sensitivity of
about 0.1 yg for most elements.
At another time, the EPA's National Coastal Pollution
Research Program in Corvallis', Oregon, requested the SERL
to analyze for mercury and arsenic in waste tailings from
the iron ore processing plant in Minnesota. Neutron
23
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Table 7. ELEMENTS DETECTED IN ORE PROCESSING PLANT WASTE
SLURRY
Element
Si
Fe
Mg
Ca
Na
Mn
K
Al
P
S
Cl
Sr
Ba
Ti
Zn
Zr
Ce
Y
Co
Er
Nd
Sc
La
Sm
Cu
V
Pb
Nb
Rb
As
Pr
Cs
Sediment Portion
Concentration
yg/g
100,000a
98,000
30,000
18,000
7,000a
6,000
3,000
3,000
2,000
300a
200a
45
40
14
i 11
8
6
5
5
3
3
3
2
2
2
2
1
1
1
1
1
0.5
Liquid Portion
Concentration
yg/mfi,
4a
7
20
10
0.5a
0.3
9
7
16
2a
0.5a
0.2
0.5
0.1
0.6
0.6
Concentrations estimated with calculated relative
sensitivity.
24
-------
activation analysis was used to provide an estimate of the
quantities of these elements being dumped into Lake Superior.
Mercury concentrations did not vary significantly in 47
samples of ore and tailings samples. In most samples, the
mercury content was close to the detection limit of 10 ng/g
and in no case greater than typical U. S. Geological Survey
values for sediments and rocks in that area. Arsenic
values,-.which varied from 10 to 30 ug/g, were well above
the detection limit but were not uncharacteristic of
natural sediments.
These data were reported to the National Coastal Pollution
Research Program for compilation with other analytical data.
The EPA1s investigation of the ecological effects of the
ore processing plant's effluent has not been completed.
9. Dissemination of Analytical Information
The NWCCRP's analytical expertise was utilized by scientists
in industry, universities, and state and federal agencies.
Requests were answered for publication reprints, standard
samples, analytical methods and monitoring procedures, and
information about previously identified wastewater compo-
nents .
a. Consultations
Several requests concerned polychlorinated biphenyls (PCB's),
A publication and several oral presentations
about identification and quantitation of PCB isomers in
Aroclors documented the NWCCRP's knowledge and prompted
more than 40 requests for samples of individual isomers and
analytical information.
12
A compilation of tentative EPA methods included
25
-------
the NWCCRP's procedure as the chosen PCB-guantitation
method for samples containing mixtures of more than one
Aroclor.
The author of a book on PCB's was granted permission
to include melting points and infrared spectra of individual
isomers synthesized at the SERL.
Instructions for quantitative analysis of PCB's in
chicken tissue were given to the South Carolina Board of
Health.
Two sewage sludge extracts were quantitatively
analyzed for PCB's by the SERL method as requested by the
Midwest Research Institute of Kansas City, Missouri.
South Dakota State University personnel requested
and obtained information for application of the SERL PCB
method to the analyses of several hundred samples of wild
birds.
The Amarillo, Texas Municipal Water Authority
received assistance with evaluation of the impact of low
concentrations of PCB's in sediments and waters of streams
feeding their reservoir.
The EPA1s Region IV Surveillance and Analysis Division was
provided immediate information about monitoring and clean-
up procedures after 1400 gallons of transformer fluid con-
taining Aroclor 1254 were spilled near Kingston, Tennessee.
The immediate environmental problems were magnified by
heavy rains that spread the PCB's over several acres. The
contaminated area included a farm well, a dairy cattle
watering pond, and a large recreational lake's draining
area. Public concern demanded immediate action. Federal,
state, and local resources were utilized for clean-up and
26
-------
restoration of the contaminated site. The transformer
manufacturer removed 11,531 drums of contaminated soil at
a cost of more than $300,000 and monitored the area for
several months to assure that no further water supply con-
tamination had occurred.
The NWCCRP's knowledge of specific components of paper mill
and domestic wastewaters helped to determine the sources of
pollution incidents. The Montana State Board of Health
requested this information to locate the cause of foam
downstream from a paper mill, in Denver, Colorado, the
EPA1s Region VIII Surveillance and Analysis Division sus-
pected a paper mill holding pond as the source of private
well contamination. The NWCCRP provided standard samples
of suspected pollutants and detailed information about
sample extraction, concentration, GC analysis, and probable
components.
b. Industrial Organic Pollutant List
At the request of the EPA1s Effluent Guidelines Division,
the NWCCRP compiled a list of organic compounds identified
by combined GC-MS in industrial effluents. A list was
needed to compare specific identified pollutants with com-
pounds in reports from consultants chosen by the EPA to
recommend effluent guidelines.
The list contained 257 compounds (from 22 industries) that
were identified by the NWCCRP and the Region IV Surveillance
and Analysis Division. The difference in compounds detected
for plants within the same industries indicated that each
plant is unique. Concentration, toxicity, taste, and odor
information were included when available.
The report was distributed to various EPA officials for
27
-------
planning research in pollutant identification, treatment,
c
and control and was included in an EPA Research Report.
An expanded and updated list will be prepared periodically
/
and will include data obtained at other EPA laboratories.
c. Symposia
During FY 73 two symposia were sponsored by the SERL and
coordinated by NWCCRP personnel. In November 1972 the
two-day symposium on Applications of Mass Spectrometry to
Environmental Problems, which was sponsored jointly by the
EPA and the University of Georgia Chemistry Department,
dealt with the present and potential applications of mass
spectrometry to the identification and measurement of
environmental pollutants, both organic and inorganic. The
twelve invited speakers presented a wide range of ideas and
experiences to the 242 symposium registrants from government,
university, and industrial laboratories.
The Third Symposium on Recent Advances in the Analytical
Chemistry of Pollutants was held on May 14-16, 1973, in
Athens, Georgia. The SERL and the University of Georgia
were host sponsors. Other sponsors were the Chemical
Institute of Canada, the National Research Council of
Canada, and the American Chemical Society. The symposium's
purpose was to bring together applied environmental
analytical chemists and experts in advanced techniques with
environmental applications. The 268 registrants represented
diverse analytical interests and were evenly distributed
from industry or research institutes, academic institutions,
and government facilities.
28
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SECTION V
REFERENCES
Keith, L. H., and S. H. Hercules. Environmental Appli-
cations of Advanced Instrumental Analyses: Assistance
Projects, FY 69-71. Environmental Protection Agency,
Athens, Georgia. Publication Number EPA-R2-73-155.
May 1973. 82 p.
Alford, A. L. Environmental Applications of Advanced
Instrumental Analyses: Assistance Projects, FY 72.
Environmental Protection Agency, Athens, Georgia.
Publication Number EPA-660/2-73-013. September 1973.
46 p.
Hoyland, J. R., and M. B. Neher. Implementation of a
Computer-Based Information System for Mass Spectral
Identification of Pesticides. Battelle Columbus
Laboratories, Columbus, Ohio. EPA Grant #16020 HGD.
Quarterly Report. January 1972.
McGuire, J. M., A. L. Alford, and M. H. Carter. Organic
Pollutant Identification Utilizing Mass Spectrometry.
Environmental Protection Agency, Athens, Georgia.
Publication Number EPA-R2-73-234. July 1973. 48 p.
Glaze, W. H. Identification of Chlorinated Organic
Compounds Formed During Wastewater Chlorination.
North Texas State University, Denton, Texas, EPA
Grant #R80300701. Research in progress.
Webb, R. G., A. W. Garrison, L. H. Keith, and J. M.
McGuire. Current Practices in GC-MS Analysis of
Organics in Water. Environmental Protection Agency,
Athens, Georgia. Publication Number EPA-R2-73-277.
August 1973. p. 5-13.
Kwok, K. S., R. Venkataraghavan, and F. W. McLafferty.
Computer-Aided Interpretation of Mass Spectra. III. A
Self-Training Interpretive and Retrieval System.
Journal of the American Chemical Society. 94(13):
4185-4195, June 1973.
Colour Index. 2nd ed. The Society of Dyers and Colou-
rists and The American Association of Textile Chemists
and Colorists. London, Percy Lund, Humphries and Co.,
Ltd., 1.956. Vol. 3, p. 3445-3447.
29
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9. Water Quality Criteria. 2nd ed. California State
Water Resources Control Board, Sacramento, California.
Publication Number 3-A. April 1971. p. 253-254.
10. Forney, A. J. Analysis of Tars, Chars and Gases from
the Synthane Process. U. S. Bureau of Mines Technical
Progress Report. In preparation.
11. Webb, R. G., and A. C. McCall. Quantitative PCB Stan-
dards for Electron Capture Gas Chromatography. Journal
of Chromatographic Science. 11:366-373, July 1973.
12. Method for Polychlorinated Biphenyls (PCB's) in Indus-
trial Effluents. National Pollutant Discharge Elimina-
tion System. The Federal Register. Vol. 38, No. 75,
Part II, Appendix A, Section 3.
30
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SECTION VI
GLOSSARY OF ABBREVIATIONS
EPA - Environmental Protection Agency
GC - gas chromatography
GC-MS - combined gas chroma tography and mass spectrometry
IFYGL - International Field Year for the Great Lakes
MS - mass spectrometry
NWCCRP - National Water Contaminants Characterization
Research Program at the Southeast Environmental Research
Laboratory
NWQL - National Water Quality Laboratory
PCB's - polychlorinated biphenyls
RGC - computer-reconstructed gas chromatogram
SERL - Southeast Environmental Research Laboratory
SI - similarity index (for comparison of organic mass
spectra)
SSMS - spark source mass spectrometric analysis
STIRS - Self-Training Interpretive and Retrieval System (for
organic mass spectrometry)
31
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
EPA-660/2-74-078
3. RECIPIENT'S ACCESSION-NO.
rt-E AND SUBTITLE
Environmental Applications of Advanced
Instrumental Analyses: Assistance Projects,
FY 73
IEPORT DATE. .
August 1974
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Ann L. Alford
9. PERFORMING ORG \NIZATION NAME AND ADDRESS
Environmental Protection Agency
Southeast Environmental Research Laboratory
College Station Road
Athens, Ga. 30601
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The National Water Contaminants Characterization Research
Program (now the Analytical Chemistry Branch) of the Southeast
Environmental Research Laboratory identified and measured
aquatic pollutants under eight projects in answer to requests
for assistance. In most cases these analyses helped to solve,
or at least to understand more clearly, the related pollution
incident and in some cases provided evidence for enforcement of
regulatory legislation. Under an additional project, analytical
consultations were held as requested by various organizations
concerned with pollution incidents.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
water pollution sources, pollutant
identification, analytical
techniques, industrial wastes, gas
chromatography, mass spectrometry,
neutron activation analysis
GC-MS, spark source
mass spectrometry,
mass spectra compute3
matching, municipal
wastes
05 A
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3G
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