EPA-660/4-75-004
JUNE 1975
Environmental Monitoring Series
Environmental Applications of Advanced
Instrumental Analysis: .Assistance
Projects, FY 74
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Corvallis, Oregon 97330
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agencys 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 MONITORING STUDIES
series. This series describes research conducted to develop new
or improved methods and instrumentation for the identification and
quantification of environmental pollutants at the lowest conceivably
significant concentrations. It also includes studies to determine
the ambient concentrations of pollutants in the environment and/or
the variance of pollutants as a function of time or meteorological
factors.
EPA REVIEW NOTICE
This report has been reviewed by the National Environmental
Research Center—Corvallis, and approved for publication. Mention
of trade names or commercial products does not constitute endorsement
or recommendation for use.
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EPA-660/4-75-004
JUNE 1975
ENVIRONMENTAL APPLICATIONS OF ADVANCED INSTRUMENTAL
ANALYSES: ASSISTANCE PROJECTS, FY 74
By
Ann L. Alford
Southeast Environmental Research Laboratory
National Environmental Research Center
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 National Technical Information Service,
U.S. Department of Commerce, Springfield, VA 22I51
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ABSTRACT
The Analytical Chemistry Branch of the Southeast
Environmental Research Laboratory identified and measured
aquatic pollutants under seven projects in answer to
requests for assistance from other EPA organizations and other
government agencies. 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.
This report was submitted in fulfillment of Project 16020 GHZ
by the Southeast Environmental Research Laboratory, Athens,
Georgia. Projects discussed were completed during FY 1974.
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CONTENTS
Sections
I Recommendations 1
II Introduction 2
III Discussion 3
1. Elemental Analyses to Assess Environmental 3
Impact of Pesticide Plant Explosion and Fire
2. Chemical Elements in-Water from Sugar 7
Beet Wastewater Holding Ponds
3. Chemical Elements in Waste Plating 9
Solution
U. Elemental Composition of a Major Component 11
of Ore Processing Plant Tailings
5. Chemical Elements and Volatile Organic 14
Compounds in Landfill Leachate
6. Taste and Odor Problems in Well Waters 19
a. Municipal Well 19
b. Private Well 22
7. Vinyl Chloride in Water 23
a. Analytical Method 23
b. Loss Mechanisms 25
8. Dissemination of Analytical Information 26
a. Consultations 26
b. Symposium 27
IV References 28
V Glossary of Abbreviations 30
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TABLES
1 Elements Detected by SSMS in Plant Yard 4
Ash and Related Samples
2 Mercury and Arsenic in Ash Samples Analyzed g
by Neutron Activation
3 Elements Detected in Holding Pond and 8
Ground Water Samples
4 Elements Detected in Waste Plating 10
Solution
5 Major Elemental Components of Cununingtonite 12
6 Minor Elemental Components of Cummingtonite 13
7 Volatile Organic Material in Well Water 17
Samples
8 Volatile Organic compounds identitied in 19
Well Water Samples from Landfill Area
9 Elements Detected in Well water Samples 20
from Landfill Area
10 Vinyl Chloride in Industrial Effluent 24
Samples
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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. C. E. Taylor and R. V. Moore
2. C. E. Taylor
3. C. E. Taylor
4. C. E. Taylor
5. R. G. Webb and C. E. Taylor
6. R. G. Webb
7. A. D. Thruston, R. G. Webb, and A. W. Garrison
8. Analytical chemistry Branch Staff
The assistance of M. H. Carter, 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.
v
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SECTION I
RECOMMENDATION S
Existing analytical techniques should be continually 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 Analytical Chemistry Branch* (ACB) 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 ACB has analyzed many samples
related to a variety of specific pollution problems.
Analytical results were reported only to the persons who
requested the analyses and therefore had limited
distribution. Earlier problems studied by the ACB have been
summarized in annual reports1f2/3 to acquaint other
researchers and administrators with the type of information
that can be obtained and to inform environmental chemists of
technique applications and developments. This report
summarizes fiscal year 1974 projects.
*Formerly the National Water Contaminants Characterization
Research Program.
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SECTION III
DISCUSSION
1. ELEMENTAL ANALYSES TO ASSESS ENVIRONMENTAL IMPACT OF
PESTICIDE PLANT EXPLOSION AND FIRE
An explosion and ensuing fire that completely destroyed a
pesticide formulation plant and warehouse in Oklahoma
prompted the EPA's investigation of the environmental impact
of the incident on the area receiving ash and debris.
Samples of ash, water, and grass were obtained by state
officials who requested analyses by EPA laboratories. The
plant and warehouse contained several toxic materials when
the explosion occurred, and a large area received ash and
debris that could have contaminated receiving water and
soil. Information from the Oklahoma State Health Department
indicated that arsenic, mercury, and phosphorus compounds
were among the pesticides in the plant.
The EPA's Region VT Surveillance and Analysis Division,
which was responsible for assessing the environmental
effects, requested the SERL's assistance. The SERL provided
analytical standards of pesticides, advice on analytical
methodology, and elemental analyses by spark source mass
spectrometry (SSMS) and neutron activation (NAA).
Five samples were collected and shipped to the SERL:
• ash from the plant yard,
• airborne ash from an area 3.3 miles northeast
(downwind) of the plant,
• grass from an area 0.25 mile northeast of the plant,
• roadside water from an area one mile northeast of
the plant, and
• control water from Lake Lugert, 12 miles northeast
of the plant.
All five samples were analyzed by SSMS (Table 1); each of
the three sample types (ash, water, and grass) required a
different preparation technique. The two ash samples, which
were black, oily substances of relatively low density, were
weighed and heated in a muffle furnace at 500° C for six
hours to remove the organic components. The residue was
dissolved in nitric acid, and yttrium was added as an
internal standard. The two water samples were spiked with
yttrium and dried onto graphite electrodes. The grass
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Table 1. ELEMENTS DETECTED BY SSMS IN PLANT YARD ASH AND RELATED SAMPLES
Element
Ca
P
Si
K
AS
Na
Al
Zn
Fe
Cl
Mg
S
Mn
La
I
Ash From Plant
Yard, wg/g
22,000
7,000
7,000
2,000
1,400
900
800
500
300
90
90
70
30
15
13
Airborne Ash Found
Northeast of Plant uq/q
1,000
140
800
230
1,000
500
100
76
250
70
18
16
8
N.D.C
N.D.C
Roadside Water Collected
Northeast of Plant, uq/la
23,000
50
N.R.b
700
2
19,000
12
0.7
48
650
250
19
6
N.D.C
0.5
Lake Lugert
Water Sample, uq/la
30,000
2
N.R.b
3,000
2
21,000
2
4
50
4,000
900
90
4
N.D.C
0.4
Grass
Leachate , ua/q
5,000
200
N.R.b
1,500
0.5
200
100
9
60
300
200
N.D.C
17
1
0.3
Ashed
Grass. L.Q/I
90
3
40
20
0.1
N.D.C
3
0.2
6
1
N.D.C
16
2
N.D.C
N.D.6
Average of duplicate analyses
Not reported; glassware used in sanple preparation
Not detected; less than 0.1 ug/g
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sample was leached with acetone and with nitric acid;
combined leachates were spiked with yttrium, dried onto
graphite, and heated at 500° C for six hours. Leached grass
blades were ashed at 500° C for six hours; the residue was
dissolved in nitric acid/ spiked with yttrium, and dried
onto g ra phi te.
Both ash samples contained high concentrations of arsenic
and phosphorus (Table 1). All 15 elements detected in the
plant yard ash were also found in the airborne ash, except
lanthanum and iodine, which were the two elements present in
lowest concentrations in the yard ash. Several elements
(Sb, Ba, F, V, Br, Cu) were found in the airborne ash but
not in the plant yard ash; the only one of these present in
significant concentration in the airborne ash was antimony
(130 yg/g). Its presence in the airborne ash could be
explained because of its use in paints and enamels as a
flame-proofing agent, but its absence in plant yard ash was
puzzling.
SSMS analysis of the grass and water samples did not reveal
appreciable contamination that could be directly related to
the pesticide plant explosion and fire. The phosphorus and
aluminum contents of these samples could possibly have been
related to the incident, but none of the samples contained
appreciable amounts of arsenic. The roadside water sample
contained some black oily material that appeared to be the
same as the ash samples, but not enough was present to cause
significant water contamination. Mercury was not detected
by SSMS, but it could have been lost during sample
preparation procedures.
Ash samples were also analyzed by neutron activation to
confirm arsenic concentrations determined by SSMS and to
determine mercury concentrations. NAA confirmed high
concentrations of arsenic in both ash samples; mercury was
detected in the plant yard ash but not in the airborne ash
(Table 2}. Appreciable amounts of phosphorus in the ash
samples produced energetic beta emissions that interfered
with determination of 197Hg. Therefore, values for the
2O3Hg isotope, which has a lower relative activity, were
also reported. The interference of antimony with the
primary photon of 76As dictated acquisition of data for both
its primary photon with an energy of 559.1 keV and its 657.1
keV photon.
Results of SSMS and NAA analyses were reported to the EPA's
Region VI Surveillance and Analysis Division, who included
these data in a report that included results of mercury
analysis by flameless atomic absorption and organic
pesticide residue analyses by gas chromatography (GC) and
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Table 2. MERCURY AND ARSENIC IN ASH
SAMPLES ANALYZED BY NEUTRON
ACTIVATION
Element
197
Hg
203Hg
As(559.1 keV)
As (657.1 keV)
Ash From
Plan£ Yard,
yg/g
8
11.3
1160
1280
Airborne Ash Found .
Northeast of Plant, yg/gc
N.D.b
N.D.b
775
628
Average of duplicate determinations
Not detected; less than 0.1 yg/g
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combined gas chromatography-mass spectrometry (GC-MS). in
their report to the Oklahoma State Health Department, they
concluded that ash and debris from the plant fire did not
cause a critical environmental hazard. Although ash
collected from the plant yard contained potentially
dangerous amounts of toxic substances, most ash was confined
to the yard. This ash was collected and buried in a clay
formation where leaching into surface and ground water was
unlikely to occur. The airborne ash also contained
significant quantities of arsenic but the low density of the
material reduced its environmental hazard. Evidence for
this conclusion was the low arsenic content (2 yg/1) of an
obviously ash-contaminated water.sample (the roadside
sample). This is well below the proposed maximum acceptable
arsenic concentration of 100 yg/1 in drinking water.*
2. CHEMICAL ELEMENTS IN WATER FROM SUGAR BEET WASTEWATER
HOLDING PONDS
As part of a study of possible ground water contamination
from wastewater holding ponds, the SERL was asked to analyze
several water samples by SSMS. The EPA1s National Field
Investigations Center (NFIC) in Denver, Colorado, needed
elemental analyses to determine the extent of ground water
contamination by sugar beet processing plant wastes. To
conform to pollution control guidelines, by 1977 the
industry must use holding ponds for all liquid wastes and
discharge no liquids to receiving waters. Some holding pond
liquids percolate through the soil and into ground water,
constituting a potential source of pollution. The SERL was
asked to analyze samples from holding ponds and ground water
sources to determine whether significant differences in
trace metal content existed. If such differences exist,
characteristic elements could be monitored to enforce
pollution guidelines.
Seven samples (three holding pond water samples, three
upstream ground water samples, and one downstream ground
water sample) from Colorado, Kansas, and Nebraska were
collected, preserved with nitric acid, and shipped in
nitric-acid cleaned glass bottles. For SSMS analysis, an
aliquot of each filtered sample was dried onto graphite
electrodes.
SSMS data (Table 3) indicated that phosphorus was the
element most likely to be characteristic of ground water
pollution by sugar beet wastes in holding ponds, but more
data are needed to justify this hypothesis. Only two
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Table 3. EIJSMENTS DETECTED IN HOLDING POND AND GROUND WATER SAMPLES
Element
Ca
K
Sr
Ba
Fe
Mg
Mn
P
Al
I
Sn
Ce
Pb
Cr
Ni
Cu
S
Zn
La
Ag
Br
Co
Ga
V
Se
Zr
Kansas E
Holding Pond
Water, pg/la
50,000
10,000
9,000
4,800
3,400
1,600
1,300
1,000
500
400
250
200
160
160
100
60
50
40
30
2
N.D.b
N.D.b
N.D.b
N.D.b
N.D.b
M.D.b
amples
Upstream Ground
Water, iig/la
1,000
100
180
20
1
2,000
0.5
1
1
1
N.D.b
N.D.b
0.5
N.D.b
2
0.1
1
20
K
N.D.
1
N.D.b
N.D."
N.D.b
N.D.b
N.D.b
N.D.b
Colorado
Holding Pond
Water, pg/la
>10,000
> 3,000
400
60
2,300
1,100
250
160
500
h
N.D.
N.D.b
N.D.b
150
N.D.b
b
N.D.
20
N.D.b
20
b
N.D.
4
40
10
6
4
N.D.b
N.D.b
samples
Upstream Ground
Water, pg/la
3,000
300
400
40
400
900
16
1
140
b
N.D.
N.D.b
N.D.b
200
N.D.b
K
N.D.
200
N.D.b
30
K
N.D.
2
90
2
N.D.b
2
N.D.b
N.D.b
Holding Pond
Water, )ig/la
>10,000
>_ 2,000
106
30
60
>_ 900
220
> 2,000
310
.
N.D.
0.6
N.D.b
50
N.D.b
25
5
N.D.b
35
b
N.D.
1
10
N.D/b
N.D.b
3
1
0.7
Nebraska Samples
Upstream Ground
Water, vg/la
>40,000
1,000
1,600
1,200
160
2,000
2
1
30
K
N.D.
N.D.b
N.D.b
70
N.D.b
X
N.D.
1,400
N.D.b
250
b
N.D.
N.D.b
25
N.D.b
N.D.b
4
N.D.b
N.D.b
Downstream Ground
Water, yg/la
j>10,000
>_ 1,000
250
400
12,000
800
1,400
4
2
b
N.D.
0.
N.D.b
30
N.D.b
b
N.D.
5
N.D.b
ISO
N.D.
0.
10
N.D.b
N.D.b
N.D.b
N.D.b
Average of duplicate analyses
bM.,-_ . 1 • A e
CO
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elements, phosphorus and aluminum, were present in higher
concentrations in all three holding pond samples than in
upstream and downstream samples. Differences in phosphorus
concentrations were more significant than those for
aluminum.
In Kansas samples, all elements detected, except magnesium,
were present in the holding pond sample in greater
concentrations than in the upstream ground water sample.
Magnesium concentrations were approximately equal in both
samples. However, the Nebraska upstream water sample
contained larger amounts of calcium, strontium, barium,
magnesium, zinc, and copper than either holding pond water
or downstream water. In Colorado samples, more copper was
present in upstream water than in wastewater.
These data were reported to NFIC officials who compared them
with results of other analyses performed by other
laboratories. Analytical data indicated that no serious
pollution problem had resulted from holding pond seepage.
3. CHEMICAL ELEMENTS IN WASTE PLATING SOLUTION
To plan a safe disposal method, the United States Army
Medical Laboratory at Fort McPherson, Georgia, requested
elemental analysis of a waste liquid that was thought to be
a metal-plating solution. For about 20 years, approximately
600 gallons of this solution had been stored at Fort
Stewart, Georgia, but information as to its former use and
its contents was no longer available. The SERL was
requested to analyze the solution for its elemental content
and to determine if the suspected high concentrations of
cyanide were present.
SSMS analysis revealed that the solution contained very high
concentrations of cadmium along with significant amounts of
iron and copper (Table 4). Relatively small 1-ml samples
were spiked with yttrium as an internal standard and
evaporated onto graphite electrodes. The small sample size
was dictated by the high salt content of the solution. The
use of a small sample raised the lower limit of detection to
approximately 1 mg/1, but eliminated the need for extensive
salt removal procedures.
At the SERL's reguest, personnel from the EPA1s Region IV
Surveillance and Analysis Division determined the cyanide
concentration in the solution. Using colorimetric analysis
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Table 4. ELEMENTS DETECTED IN WASTE PLATING SOLUTION
Concentration,
Element rog/£a
Na 50,000
Cl 50,000
Cd 40,000
Fe 1,200
Cu 140
Mg 40
Mn 3
Average of duplicate analyses
10
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of the acidified sample, they found the cyanide
concentration to be 28.5 g/1.
The high concentration of cyanide and cadmium dictated that
careful disposal methods be devised to avoid hazardous
environmental contamination. Fort Stewart officials decided
that such a toxic solution required expert attention, and an
experienced waste reclamation firm was hired to handle the
disposal.
H. ELEMENTAL COMPOSITION OF A MAJOR COMPONENT OF ORE
PROCESSING PLANT TAILINGS
Spark source mass spectrometric analysis provided
information about the elemental composition of a silicate
mineral thought to be the majcr component of tailings
discharged from a Minnesota iron-ore processing plant. The
EPA's National Water Quality Laboratory in Duluth,
Minnesota, requested this analysis to assist in its
investigation of the ecological effects of mine wastes
dumped into Lake Superior. Each day the plant discharges a
slurry containing approximately 60,000 long tons of taconite
wastes; half of this is thought to be cummingtonite, a
magnesium-iron silicate that comprises about 3Q% of the
mine's raw ore. Since cummingtonite is discharged in such
large quantities, even its trace metal components could be
quite significant.
A pure sample of cummingtonite can be obtained only with
extremely tedious procedures, and the literature contains
conflicting reports of its composition. The cummingtonite
sample sent to the SERL for analysis was a composite of
hand-picked crystals that had been collected for use as a
standard for X-ray analysis of lake water and sediment.
To obtain the best possible composite for SSMS analysis, the
hand-picked crystals were combined and ground into a powder.
A portion of the powder was spiked with yttrium as an
internal standard. Two aliquots of this spiked sample were
analyzed to provide quantitative data for the major
elemental components. The aliquots were then diluted with
unspiked cummingtonite to obtain quantitative data for minor
components.
The cummingtonite sample contained so much silicon that no
attempt was made to quantify it, but quantitative data were
obtained for seven other major components (Table 5) and 15
minor components (Table 6).
11
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Table 5. MAJOR ELEMENTAL COMPONENTS OF CDMMINGTONITE
Concentration
Element Weight Percent3
Fe 1.6
Ca 1.6
Mn 0.4
Mg 0.1
Na 0.1
Cl 0.03
F 0.01
Average of duplicate analyses
12
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Table 6. MINOR ELEMENTAL COMPONENTS OF CUMMINGTONITE
Element Concentration, yg/gc
K 100
Al 30
P 10
Cr 10
Sb 10
Cu 10
La 10
Ba 4
V 4
Br 2
Tm 2
Pr 2
Cs 2
Pb 1
Co 2
a Average of duplicate analyses
13
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These data were reported to the National Water Quality
Laboratory for use in the continuing evaluation of
environmental effects of the mineral processing wastes.
5. CHEMICAL ELEMENTS AND VOLATILE ORGANIC COMPOUNDS IN
LANDFILL LEACHATE
To determine a practical treatment for water containing
pollutants leached from an abandoned landfill, Delaware's
Department of Natural Resources requested analyses of
several water samples.
In a residential and light-industrial area of Newcastle
County, Delaware, a resident complained about a persistent,
unpleasant odor in his drinking water. Although the water
was supplied by a private company, various governmental
agencies became involved when the obnoxious odors were
traced to contaminants leached from an abandoned landfill
near the commercial wells.
For about 13 years, Newcastle County had used an abandoned
sandpit as a receptacle for municipal and industrial
garbage. In 1968, the landfill was closed after an area
three miles long and varying from 0.25 to 0.5 mile wide was
filled with refuse estimated to be 30 to 50 feet deep.
Within one mile of the outer edge of the landfill is the
Artesian Water Company's Well field, from which three to
five million gallons of water are pumped daily.
Newcastle County hired a consulting firm to determine the
pollution source and to propose a remedy to prevent further
ground water contamination. The consulting engineers
concluded that landfill leachate had polluted the aquifer.
To prevent further contamination of the well field, the
consulting firm proposed drilling recovery and blocking
wells. Blocking wells would be located to remove water that
would normally flow into the landfill area and be
contaminated. Recovery wells would be drilled in or near
the landfill area to remove the leachate-containing water,
which could then be treated and returned to the aquifer.
Only treated water would then reach the private well field.
To monitor aquifer pollution and to devise an effective
treatment, state and county officials needed knowledge of
the chemical composition of the leachate. Therefore,
Delaware's Department of Natural Resources requested through
the EPA's Region III office in Philadelphia, Pennsylvania,
that the SERL identify organic and inorganic pollutants in
four water samples: water from a well inside the landfill,
14
-------
water from two recovery veils between the landfill and the
well field, and finished water from the Artesian Well
Company (Figure 1).
Volatile organic components were identified and measured by
gas chromatography and combined gas chromatography-mass
spectrometry. Each sample was extracted by a procedure
designed to separate it into neutral, acid, and basic
fractions.6 Preliminary examination by GC showed which
fractions contained significant amounts of organic
components, and mass spectral data were acquired for these
fractions. Preliminary identifications of several compounds
were obtained by computer-matching of unknown mass spectra
with standard mass spectra in a data bank. When standard
samples were available, these identifications were confirmed
by comparing mass spectra obtained under the same
conditions. Further confirmation was obtained by comparing
GC retention times of standards and unknowns. Quantitative
data were calculated from GC peak area measurements.
The relative contamination in each well was shown by
comparison of the total amount of organic materials
indicated by peak areas from the gas chromatograms. These
data (Table 7) showed that the landfill well contained
approximately 100 times more volatile organic matter than
the recovery wells.
Thirty compounds were positively identified and quantitated
in the landfill well sample (Table 8). Major components
were short-chain (
-------
LANDFILL AREA SAMPLING SITES
Recovery
Well #3
Artesian Water
® Company Well
-1000 FT-
1/4" = 200'
Figure 1. Sampling sites for landfill leachate analyses
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Table 7. VOLATILE ORGANIC MATERIAL IN WELL WATER SAMPLES
Sample Concentration, mg/£c
Landfill Well 89.3
Recovery Well #3 1.5
Recovery Well #29 0.4
Artesian Water Co. Well 0.005
Calculated from area of major portion of gas
ch romat o gr am.
17
-------
Table 8. VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN WELL WATER SAMPLES PROM LANDFILL AREA
Compound
n-butanol
camphor
caprolactam
chlorobenzene
o-cresol
o-cresol
cyclohe xanol
diacetone alcohol
2 , 3-dibromo-l-propanol
dichlorobenzene
diethyl phthalate
2-ethyl hexanol
fenchone
l-methoxy-2-propanol
phenol
1,4-thioxane
triethyl phosphate
g-xylene
acetic acid
benzoic acid
butyric acid
heptanoic acid
hexanoic acid
isobutyric acid
isovaleric acid
octanoic acid
phenylacetic acid
propionic acid
toluic acid
valeric acid
Landfill Well Extract
Concentration, mg/2.a
5.4
3.0
2.9
23.8
1.2
0.2C
0.2C
0.3=
9.9
O.lc
4.7
2.4
39
5.9
1.3
0.6
2.6
6.5
0.1
0.5
Recovery Well f3 Extract
Concentration , rag/£a
0.007
0.03°
0.03
0.16
0.005C
0.005C
0.3
0.02=
0.004
0.03
0.07
0.24
0.07C
0.09
0.03
Recovery Well |29 Extract
Concentration , mg/ia
0.03C
0.07
0.01
0.19
0.03
0.005
0.01
0.005
0.005
0.005
O.OOS
Detection Thresholds
in Water , mg/ib
Taste
0.5
1.9
20-40
6.2-6.4
2.5-50
1.6
5.8
Odor
2.5
0.07- 0.65
3.5
270
0.02- 0.03
2.2
2.4
<17
3
3
8.1
0.7
3
20
3
Because extraction efficiencies are unknown, reported concentrations are minimum values.
From Compilation of Odor and Taste Threshold Values Data, Edited by W. H. Stahl, Aror. Soc. for Testing and Materials,
Philadelphia, PA, 1973.
Estimated value; not as accurate as unqualified concentrations.
-------
The Artesian Well Company water extract did not contain
volatile organic contaminants in quantities that could be
detected by GC or GC-MS, and no organic compounds were
identified. The neutral-fraction chromatogram showed only a
few ill-defined humps with no sharp peaks; the acid-fraction
chromatogram had no peaks. Compounds present in this
finished water at concentrations >0.001 mg/1 should have
been detected, because the finished water extract
represented a larger sample volume than the well water
extracts.
SSMS analysis produced quantitative data for the 21 elements
detected (Table 9) in these four samples and supported the
volatile organic component analyses. The landfill well
sample was the most contaminated; well 129 was less
contaminated than well f3. Several elements were present in
considerably higher concentrations in the landfill well
water than in other water samples, but the most significant
differences were observed for concentrations of bromine and
barium. The high concentration of bromine in the landfill
well supported the identification of 2,3-dibromo-1-propanol
as the major organic contaminant. Comparison of SSMS data
from all four samples indicated that magnesium, iron,
manganese, cobalt, and boron would be other useful elements
to trace the movement of contaminants from the landfill
toward the well field.
Analytical data were reported to the Delaware Department of
Natural Resources. A series of recovery wells has been
completed. Water from these wells is presently discharged
into small creeks in the area, but the county is constructing
aeration tanks that will permit effluent discharge into a
tidal area beyond the freshwater zone.
6. TASTE AND ODOR PROBLEMS IN WELL WATERS
a. Municipal Well
For over a year, citizens of the small town of Milner,
Georgia, complained about an unpleasant odor in their
drinking water. The odor was similar to that of natural gas
to which an odorous material has been added to permit rapid
detection of leaks during shipping or use. Townspeople
suspected that the source of the odor was a nearby cavern
that was used for propane storage. Leachate from the
storage cavern could have contaminated the aquifer feeding
19
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Table 9. ELEMENTS DETECTED IN WELL WATER
SAMPLES FROM LANDFILL AREA
Element
Mg
Br
Fe
Ca
Cl
K
Ba
S
Mn
Sn
Rb
B
F
P
Al
Zn
Cr
Cu
Co
Pb
I
Concentration, yg/la
Landfill Well
28,000
10,700
8,800
7,200
5,200
3,300
2,600
1,800
1,400
900
327
256
182
145
116
68
60
39
30
4
N.D.
Recovery Well
#3
11,000
66
8,800
4,900
2,000
2,100
366
1,400
1,800
106
22
36
84
74
168
38
23
2
139
N.D.
2
Recovery Well
*29
4,800
26
2,500
1,400
2,000
900
340
120
490
22
6
28
66
5
70
14
8
0.3
26
N.D.
N.D.
Artesian Water
Company Well
155
6
139
2,200
1,900
1,200
42
48
10
.26
4
0.2
8
7
26
6
N.D.
8
0.4
2
N.D.
Average of duplicate analyses
20
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the deep well that supplies the town's water. However, the
cavern had been used for propane storage for ten years, and
pipeline company officials reported that ethyl mercaptan is
added to the propane when it is shipped,. not before or
during storage.
The Georgia State Department of Natural Resources requested
assistance in locating the contamination source. The SERL
examined samples of water from the cavern, from the town
well, from a well located between the cavern and the town,
and from a well located several miles on the opposite side
of town. The town well water and cavern water samples had
similar odors, but the cavern water odor was stronger.
Town well and cavern water both contained some sulfur
compounds and other organic impurities, but different
compounds were present in each sample. None of the samples
contained ethyl mercaptan at >50 V»g/l, the detection limit
with the analytical method used. The odor component of each
sample was concentrated in a steam distillate, which was
placed in a sealed vial from which the headspace gas could
be sampled with a syringe. Headspace gases were analyzed
with a gas chromatograph equipped with a flame photometric
detector (FPD) that responds almost exclusively to sulfur-
containing compounds. The cavern water sample contained
four sulfur compounds. The concentration of the major one
was estimated to be 4 mg/1; the other three were present at
much lower concentrations. Water from the town well and
from the well between the town and the cavern contained the
same single sulfur compound, which was not present in the
cavern water.
The steam distillates were also examined by direct injection
into a combined GC-MS. The town water sample contained at
least one organic contaminant and the cavern sample
contained more than two. None of these contaminants
contained sulfur, and the town well contaminant was not
present in the cavern sample. These compounds could not be
specifically identified from their weak mass spectra.
Methylene chloride and tetradecane extracts of the town
water sample did not contain any impurities detectable with
the GC (FPD), and the odor remained in the water after the
attempted extraction. In a control experiment, the
mercaptan odor was easily discernible in a solution
containing 15 ug ethyl mercaptan per liter water, but
attempts to remove the mercaptan by conventional methods
were unsuccessful.
Hydrogen sulfide was eliminated as a possible odor-causing
pollutant; a sulfide specific-ion electrode showed clearly
21
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•that hydrogen sulfide concentration was less than 1 ng/1 (1
ppt) .
No evidence was found to link the town water contamination
to leachate from the storage cavern. Both samples could
have contained ethyl mercaptan at a level that could have
caused an objectionable odor but would not have been
detected. However, the lack of similarity in other organic
compounds found in the two samples led to the conclusion
that the source of contamination was probably not the
cavern.
Later, independent analyses supported the lack of evidence
connecting the cavern with town well contamination. Town
well and cavern water samples were collected and shipped to
the EPA1s Methods Development and Quality Assurance Research
Laboratory in Cincinnati, Ohio, for analysis. Volatile
organics were removed by bubbling nitrogen gas through each
sample and into a small column packed with a porous polymer
that trapped the organics.7 The trapping column was placed
in a GC injection port where the volatile organics eluted
into a standard column for GC and GC-MS analysis. Dimethyl
ether, acetone, methanol, and isopropanol were present in
high concentrations in the cavern water but were absent from
the town water. This strongly indicated that the cavern was
not the contamination source. If contaminated water moving
from the cavern to the town well were causing the odor
problem, these four very water-soluble compounds should be
present in town well water. No ethyl mercaptan was
detected, but its detection limit with this purging-trap
method was judged to be as high as 100 yg/1.
After these analyses and other tests performed by the
Georgia state Water Laboratory and by a private consulting
laboratory failed to identify the odorous contaminant or its
source, the townspeople decided to abandon their inadequate
and odorous well and obtain water from a nearby town's water
system.
b- Private Well
A similar problem involved the unpleasant taste of water
from a 300-ft deep sealed well in a non-industrial and
lightly populated area in Georgia. Industrial contamination
of the aquifer seemed unlikely, and no probable pollution
source could be located.
Examination of well water extracts (carbon tetrachloride) by
GC and GC-MS revealed the presence of long-chain, normal
hydrocarbons (C 21-^3 a)- since such long-chain materials are
22
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not found in fuel or lubricating oils, the pollutant was
suspected to be a lubricating wax leaking from the submerged
pump. Indeed, the taste problem disappeared when the pump
was replaced.
7. VINYL CHLORIDE IN WATER
a- Analytical Method
A cursory investigation of the behavior of vinyl chloride
in water solutions revealed that the volatility of vinyl
chloride makes it a much greater threat as 3n air pollutant
than as a water pollutant. The occurrence of a rare type of
tumor in certain industrial workers was thought to be
related to their occupational exposure to vinyl chloride.
The EPA Administrator appointed a task force to"advise him
of the Agency's best course of action to determine the
significance of vinyl chloride as an environmental
pollutant. To assist this task force, the EPA's Office of
Monitoring Systems requested assistance from several EPA
laboratories. The SERL's Analytical Chemistry Branch was
asked to provide information about methods for quantitative
analysis of vinyl chloride in water. Assessment of existing
methods and, if necessary, development of new methods were
needed within the month before the first task force meeting.
Two gas chromatographic methods for analysis of vinyl
chloride in aqueous solutions were shown to be reproducible
and quantitative at mg/1 concentrations. The detection
level with the previously-developed method of direct aqueous
injection (2 yl) varied from 0.05 to 2 mg/1, depending on
the condition of the particular gas chromatograph used.
Samples containing lower vinyl chloride concentrations
required solvent (carbon tetrachloride) extraction. A
detection level of approximately 2 ng/1 was attained with a
2-pl injection of carbon tetrachloride extract. Four
effluent samples from a plastics manufacturing plant were
analyzed with both techniques; data indicated that either
method was applicable for the concentrations (0.2-9.3 mg/1)
of vinyl chloride found in these samples (Table 10) .
The presence of vinyl chloride in the effluent samples was
confirmed by GC-MS analysis. A 2- 1 (4 ng) direct aqueous
injection of the 0.2 mg/1 samples-produced a good mass
spectrum, and an acceptable spectrum was obtained from a 2-
liL injection of a carbon tetrachloride extract containing
0.14 ng of vinyl chloride.
23
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Table 10. VINYL CHLORIDE IN INDUSTRIAL
EFFLUENT SAMPLES
Sample
Primary Clarifier Effluent3
Primary Clarifier Effluent3
Primary Clarifier Scum*3
Plant Storm Sewer Effluent
Vinyl Chloride Concentration , mg/&
Direct. Aqueous
Injection
2.8
2.8
9.3
0.2
CCl^ Extraction
3.0
2.9
6.8
0.2
Samples taken on two different days.
Sample contained large amount of suspended particulates.
24
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A major problem with analysis of vinyl chloride in aqueous
solutions is its volatility. Because aqueous solutions are
not stable, carbon tetrachloride solutions were used to
calibrate the flame ionization detector in both GC methods.
This volatility also necessitates careful sample collection,
shipment, and storage. However, it does permit headspace-
gas analysis8, which is a rapid and sensitive method for
screening water samples for vinyl chloride.
b. Losjs Mechanisms
A brief study of the behavior of vinyl chloride in aqueous
solutions indicated that the most important loss mechanism
is volatilization rather than hydrolysis or photolysis. The
volatilization rate varied with agitation rate. During two
hours of rapid stirring at 22° C, a 16 mg/1 solution of
vinyl chloride in distilled water lost 96% of the solute; a
quiescent solution of the same concentration lost 25% under
the same conditions. No significant rate differences were
observed for vinyl chloride loss from distilled water, river
water, or industrial plant effluent, indicating negliglible
adsorption of vinyl chloride by particulate matter. When
the industrial plant's clarifier effluent was spiked with
110 mg vinyl chloride/1 effluent and stirred rapidly for
three hours, the vinyl chloride concentration decreased to
21.8 mg/1. Under the same conditions, river water and
distilled water solutions decreased from 105 mg/1 to 2.2
mg/1 and 1.8 mg/1, respectively.
The loss of vinyl chloride from clarifier effluent samples
was not affected by pH variations. During 57 hours at 50°
C, vinyl chloride concentrations decreased at the same rate
in solutions of pH (».3, 8.0, and 9.U. This lack of pH
dependence suggested loss by volatilization rather than by
hydrolysis.
Another experiment eliminated sunlight-induced photolysis as
an important mechanism for vinyl chloride loss from aqueous
solutions. Relative to a shielded blank, vinyl chloride
concentration did not decrease in industrial plant effluent
exposed to sunlight during a 57-hour period (approximately
25 hours of sunlight).
This information was presented to the EPA Vinyl Chloride
Task Force. After receiving data from several laboratories,
the task force recommended that the EPA's concern and action
should be directed at vinyl chloride as an air pollutant.
Data indicated that no further laboratory studies of vinyl
chloride were justified at that time.
25
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8. DISSEMINATION OF ANALYTICAL INFORMATION
The ACB'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, monitoring procedures, and
information about previously identified wastewater
components.
a. Consultations
• Continued interest in the GC method9 for
identification and quantitation of polychlorinated
biphenyl (PCB) isomers prompted more than a dozen
requests for standard samples in FY 1974. Standards
were provided to various analysts quantitating
individual components of complex PCB mixtures in
industrial effluents.
• A computer program10, developed at Battelle Columbus
Laboratories under an EPA grant, was provided to
various people involved with GO-MS analysis of
organic compounds. This program is used for
selected-ion monitoring of organic compounds by
computer-controlled GC-MS (quadrupole) systems. It
enhances detection of specific compounds in complex
mixtures and alleviates background interferences.
Current applications range from effluent monitoring
to detecting drug residues and metabolites in
overdose victims,
• The ACB's knowledge of various industrial
wastewaters was invaluable to contractors who are
compiling industrial effluent guidelines and
performing effluent analyses to support these
guidelines'. ACB personnel provided advice about
advanced analytical instrumentation and techniques
for analysis of water pollutants.
• To evaluate proposed textile effluent guidelines and
grant proposals to study wastewater treatment
methods, the SERL's Industrial Pollution Branch
utilized the ACB's knowledge of textile industrial
effluents. The ACB provided information about water
consumption by various dyeing processes and advice
about proposed treatment facilities for printing
wastewaters.
26
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b. Symposium
In April, 1974, the Symposium on the Identification and
Transformation of Aquatic Pollutants, was planned and
coordinated by SERL personnel from the ACB and the
Freshwater Ecosystems Branch. This symposium was designed
to provide a forum for chemists to learn about pollutant
transformation processes and products and for biologists to
learn of recent developments' in analytical techniques,
instrumentation, and methods. Invited speakers presented
technical talks equally balanced between biological and
chemical aspects of water pollution. Emphasis was placed on
state-of-the-art discussions including examples of recent
research results that had not been published or might not
have attracted the attention of workers not involved in that
particular field.
The symposium, held in Athens, Georgia, was jointly
sponsored by the EPA, the American Chemical Society, the
American Society for Microbiology, and the University of
Georgia. Industrial, academic, and governmental
institutions were equally represented by the 303
participants from 41 states and 4 foreign counties.
27
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SECTION IV
REFERENCES
1. Keith, L. H. and S. H. Hercules. Environmental
Applications of Advanced Instrumental Analyses:
Assistance Projects, FY 69-71.. U. S. Environmental
Protection Agency, Athens, Georgia. Publication Number
EPA-R2-73-155. May 1973. 82 p.
2. Alford, A. L. Environmental Applications of Advanced
Instrumental Analyses: Assistance Projects, FY 72. U.
S. Environmental Protection Agency, Athens, Georgia.
Publication Number EPA-660/2-73-013. September 1973.
46 p.
3. Alford, A. L. Environmental Applications of Advanced
Instrumental Analyses: Assistance Projects, FY 73. D.
S. Environmental Protection Agency, Athens, Georgia.
Publication Number EPA-660/2-74-078. August 1974.
31 p.
4. Water Quality Criteria 1972. U. S. Environmental
Protection Agency, Washington, DC. Publication Number
EPA-R3-73-033. March 1973. p. 56.
5. 1972 Annual Book of ASTM Standards, Part 23. Water;
Atmospheric Analysis. Philadelphia, Pensylvania,
American Society for Testing and Materials, 1972. p.
556-558.
6. Webb, R. G., A. W. Garrison, L. H. Keith, and J. M.
McGuire. Current Practices in GC-MS Analysis of
Organics in Water. U. S. Environmental Protection
Agency, Athens, Georgia. Publication Number EPA-R2-73-
277. August 1973. p. 5-13.
7. Bellar, T. A. and J. J. Lichtenburg. The Determination
of Volatile Organic Compounds at the g/1 Level in
Water by Gas Chromatography. U. S. Environmental
Protection Agency, Cincinnati, Ohio. Publication
Number EPA-670/4-74-009. November 1974. 27 p.
8. Kepner, R. E., H. Maarse, and J. Strating. Gas
Chromatographic Head Space Techniques for the
Qualitative Determination of Volatile Components in
Multiconponent Aqueous Solutions. Analytical
Chemistry. 36; 77-82, January 1974.
28
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9. Webb, R. G. and A. C. McCall. Quantitative PCB
Standards for Electron Capture Gas Chromatography.
Journal of Chromatographic Science. 11.: 356-373, July
1973.
10. Neher, M. B. and J. R. Hoyland. Specific Ion Mass
Spectrometric Detection for Gas Chromatographic
Pesticide Analysis. Battelle Columbus Laboratories,
Columbus, Ohio. Washington, D. C. EPA-660/2-74-004.
U. S. Environmental Protection Agency. January 1974.
32 p. and Appendices.
29
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SECTION V
GLOSSARY OF ABBREVIATION
ACS - Analytical Chemistry Branch
EPA - U. S. Environmental Protection Agency
GC - gas chromatography
GC-MS- combined gas chromatography and mass spectrometry
MS - mass spectrometry
NAA - neutron activation analysis
NFIC - National Field Investigations Center of the
Environmental Protection Agency
PCB - polychlorinated biphenyl
SSMS - spark source mass spectrometry
30
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TECHNICAL REPORT DATA
(Please read Inxructions on the reverse before completing)
1. REPORT NO.
EPA-660/4-75-004
3. RECIPIENT'S ACCESSION'NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
ENVIRONMENTAL APPLICATIONS OF ADVANCED
INSTRUMENTAL ANALYSIS: ASSISTANCE PROJECTS,
FY 74
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Ann L. Alford
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORG '\NIZATION NAME AND ADDRESS
U.S. Environmental Protection Agency
Southeast Environmental Research Laboratory
College Station Road
Athens, Georgia 30601
10. PROGRAM ELEMENT NO.
1BA027
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 Analytical Chemistry Branch of the Southeast Environmental
Research Laboratory identified and measured aquatic pollutants
under seven projects in answer to requests for assistance from
other EPA organizations and other government agencies. 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.
This report was submitted in fulfillment of Project 16020 GHZ by
the Southeast Environmental Research Laboratory, Athens, Georgia,
Projects discussed were completed during FY 1974.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Water pollution sources, pollutant
identification, analytical tech-
niques, industrial wastes, gas
chromatography mass spectrometry,
neutron activation analysis, ele-
ments (chemical)
spark source mass
spectrometry, GC-MS,
multi-element analysis
05 A
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