&EPA
United States
Environmental Protection
Agency
Environmental Research
Laboratory
Athens GA 30613
Research and Development
EPA-600/S3-82-058 August 1982
Project Summary
Components Identified in
Energy-Related Wastes and
Effluents
J. E. Gebhart and M. M. McKown
The results of an analysis of effluent
samples obtained from seven energy-
related activities are presented. The
energy-related processes included
coal strip mining, oil refineries, oil
shale operations, coal-fired power
plants, coal liquefaction operations,
coal gasification processes, and geo-
thermal energy production. Chemical
analyses were performed on solid and
liquid effluents associated with each
of these activities to identify organic
and inorganic components. Organic
compounds were identified and quan-
tified by gas chromatography/mass
spectrometry/data system techniques.
Sample preparation methods permitted
determination of purgeable (volatile)
and extractable (semivolatile) organics.
Samples were analyzed for mercury
using a cold vapor atomic absorption
spectrophotometric procedure. Ap-
proximately 70 other elements were
determined in the samples by spark
source mass spectrometry.
Because much relevant data were
being generated concurrently with this
research effort, a state-of-the-art
review,* was updated regularly. The
reliability of the data reviewed was
evaluated according to preselected
criteria of sample source, sampling and
analytical methodology, and data
source. Information gathered during
''Gebhart, J.E. and M.M. MEKown. Research to
Identify Components of Energy-Related Wastes:
A State of-the-Art Report. EPA-600/7-79-255,
U.S. Environmental Protection Agency, Athens,
GA, 1979. 526 pp.
the review was used to identify gaps in
existing data on characterization of
energy-related wastes and effluents
and thereby serves as a guide to
selection of sites for the samples
analyzed in this research effort.
This Project Summary was developed
by EPA's Environmental Research
Laboratory, Athens. GA. to announce
key findings of the research project that
is fully documented in a separate report
of the same title (see Project Report
ordering information at back).
Introduction
The need for energy sources that are
both reliable and safe, coupled with the
national goal of energy independence,
has generated increasing activity in the
technology of energy production. Tech-
nologies are being developed and used
to exploit this country's reserves of oil,
coal, and geothermal fluids and gases.
Energy production processes must be
assessed from the standpoint of cost
effectiveness and of potential health
and environmental effects.
Use of domestic oil supplies is
increasing as a matter of policy and
economics. Fuel generated from refining
conventional crude oil feed stocks will
continue to be an important source of
energy for some years to come. Much
emphasis, however, has been placed on
coal conversion processes because
United States coal reservesare estimated
to comprise more than 80 percent of the
total available coal, oil, and gas. Further-
more, these supplies are sufficient to
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support production of a large amount of
synthetic fuels. Over 230 billion tons of
coal are accessible to conventional
mining techniques. Technological ad-
vances are increasing the total amount
of usable coal and making additional
reserves available in the form of oil
shale and tar sands. Development of
geothermal resource areas offers the
potential for the extraction of thermal
and electrical energy.
The nature and extent of the controls
that may be required for energy-related
production processes are based on a
knowledge of the constituents in the
crude fuel feedstocks, an understanding
of the conditions and chemical reactions
involved in the finished fuel producing
processes, and a knowledge of the
components in the process streams
from these activities. Generation of
such data could also result in identifica-
tion of potentially useful by-products of
the fuel producing technologies.
Sample Site Selection
Although the state-of-the-art review
and site selection for sample collection
were conducted concurrently, informa-
tion gathered during the review was
used to identify gaps in existing data on
characterization of energy-related
wastes and effluents and to identify
operations from which solid and liquid
waste samples might be obtained. In
choosing sites for sample collection,
priority was given to the energy-related
activities of the Western Energy Resource
Development (WERD) sector of the
United States. Attempts were also made
to obtain samples from operations on
which some data had been generated by
other research efforts. In this manner,
those investigations would be comple-
mented by this program.
Difficulties were encountered in
obtaining solid samples from several of
the energy-related activities. Some of
the processes simply did not generate
significant quantities of solid wastes
(e.g., geothermal sources), and some
operations were not equipped with a
mechanism for collecting samples of
this type (e.g., in situ gasification).
When these problems arose, additional
liquid samples were obtained. It was not
always possible to arrange cooperative
agreements to obtain samples from
commercial operations. Therefore, most
of the analyses carried out were
samples collected from operations
supported or sponsored by a govern-
mental agency.
All samples were collected in a
manner to insure that they were
representative of the process stream or
effluent being characterized. Precautions
were taken in preserving and shipping
the samples to guarantee their integrity.
Results
Table 1 presents an overview of the
classes of organic compounds identified
in the effluents of each energy-related
activity surveyed in this program.
Coal Strip Mining
The mercury levels in the aqueous
effluent obtained from coal mining
operations were, in general, fairly low.
Of the 20 mines whose wastes were
sampled and analyzed, only one was
shown to contain mercury at a level
higher than 10 ppb. This mine is located
in West Virginia. The effluents of other
mines located in this area contained
smaller amounts of this metal. Other
metals determined to be present in
these samples at moderate or high (>1
ppm) concentrations included the alkali
and alkali earth metals. In some
samples, calcium and magnesium
concentrations exceeded 10 ppm. Sig-
nificant levels of strontium, sulfur, sili-
con, chlorine and fluorine, were also
present in most of these samples. The
concentrations of toxic metals (e.g..lead,
arsenic, selenium, and calcium) in
general were less than 10 ppm.
The most significant component of
the purgeable fraction of the coal
mining effluents was methylene chloride,
usually present at the parts-per-million
level. The identification of other halo-
genated volatile materials such as
chloroform, 1,1,1-trichloroethane, and
1,1,2,2-tetrachloroethane suggests
either that these effluents had been
chlorinated as a treatment procedure
prior to discharge or that a chlorinating
agent was used in some phase of the
coal mining process. The compounds
most frequently detected in the semi-
volatile fractions of these samples were
phthalates.
Oil Refineries
In general, concentrations of mercury
and other elements determined in the
oil refinery effluents were low. Major
components (>1 ppm) in these samples
included calcium, chlorine, fluorine,
magnesium, phosphorus, potassium,
strontium, and sulfur. None of these
materials, however, was determined to
be present at levels that constituted an
environmental hazard.
Organic compounds identified in the
purgeable fractions of these effluent
samples were present at relatively low
levels. Among them were trihalo-
methanes, cyclohexane, benzene, and
toluene. Several sulfur-containing
compounds were tentatively identified.
However, standards were not available
to confirm these identifications. The
major semivolatile organic components
identified in these effluents included
phenols and normal alkanes. With the
exception of phenol and p-cresol in one
sample, all extractable organic com-
pounds were determined to be present
at levels less than 100 ppb.
Oil Shale Operations
Mercury levels determined in effluents
from the Paraho oil shale retorting
process were less than 1 ppb, with the
exception of one sample of process
water that was less than 5 ppb. Other
elements detected at moderate to high
levels in these samples included sodium,
potassium, calcium, magnesium, iron,
sulfur, and strontium. It is of interest
that the three samples of this set that
were most representative of the process
discharge also contained arsenic, at
concentrations approaching or exceed-
ing 1 ppm. The levels of the other toxic
metals, however, were fairly low.
Organic compounds identified in the
purgeable fractions of these samples
included significant levels of halcgenated
compounds including methylene chloride,
chloroform, carbon tetrachloride, bro-
modichloromethane, dibromochloro-
methane, and trichloroethane. The
presence of these compounds may be
due to the use of chlorination as a
treatment method for the wastes or
because the process water had already
been chlorinated in the retorting process.
The product water samples contained
thiophene, alkyl-substituted thiophenes,
benzene, and alkyl-substituted benzenes.
The recycle gas condensate sample
contained a number of compounds at
levels greater than 1 ppm including
nitriles, thiophene and alkyl-substituted
thiophenes, benzene and substituted
benzenes, ketones and substituted
pyridines. The semivolatile fractions of
these samples were found to contain
carboxylic acids and alkyl substituted
pyridines in the acid and base/neutral
extracts, respectively. Components of
the product water also included the
homologous series of normal alkanes
from n-undecane (Cn) to pentacosane
(Czs) at levels in the parts-per-million
range.
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Table 1. Organic Compounds Identified in Effluents from Energy-Related Activities
Alkanes
Alkenes & Alkynes
Benzene & Alkyl Benzenes
Polynuclear Aromatic
Hydrocarbons
Ethers & Heterocyclic
Oxygen Compounds
Amines
Alcohols
Esters
Aldehydes
Ketones
Nitro Compounds
Amines
Phenols & Naphthols
Car boxy lie A cids
Nitrogen Compounds
Sulfur Compounds
Coal
Strip
Mining
X
X
X
X
X
Oil
Oils Shale
Refineries Processing
X X
X
X X
X
X
X
X
X
X X
X
X
X
Coal-Fired
Power
Plants
X
X
X
X
X
Coal Coal
Liquefaction Gasification
X X
X
X X
X
X X
X
X
Geothermal
X
X
X
In the samples collected during the
operation of the oil shale retort of
Lawrence Livermore Laboratory, the
mercury levels increased with time into
experiment (TIE). The concentration of
this metal determined in the earlier
samples was approximately 1 ppb. As
the retorting process proceeded, the
amount of mercury in the effluent
increased until, in the final sample
collected, it reached 58 ppb. Although
the concentration of the other elements
in these samples, as determined by
spark source mass spectrometry, was
somewhat higher than in the effluents
of other energy-related activities, there
was no obvious trend of concentration
increasing with TIE.
The results of the analysis of the latter
samples for organics indicated that they
were heavily contaminated with volatile
compounds. Among the purgeable
organic components identified were
normal alkanes, thiophene and alkyl-
substituted thiophene, benzene and
alkyl-substituted benzenes, ketones,
substituted pyridines, substituted pyr-
roles, and, possibly, substituted cycloal-
kanes. In general, levels of these
components increased as retorting pro-
ceeded. These effluents also contained
a wide variety of semivolatile organic
compounds including substituted phe-
nols, a homologous series of alkanoic
acids, substituted pyridines, and alkane
series up to dotriacontane (Caa), an
alkene series up to heptacosene (Cn),
and a variety of ketones. Again, the
number of components in these efflu-
ents and their concentrations increased
with retort progress.
It is probable that the increase in all
types of contaminants in these samples
as a retorting experiment progressed
was in part due to leaching of contami-
nants from spent shale and subsequent
transport of these materials down the
retort. In assessing data generated by
analyses of these effluent samples, it
must be noted that these wastes were
sampled prior to any clean-up or
pollution abatement treatment, this is
in contrast to many other samples
analyzed under this program that were
final effluents collected after treatment.
Coal-Fired Power Plants
The levels of mercury determined in
the aqueous effluents from coal-fired
power plants were generally low. There
was no apparent difference in the
mercury concentration in these samples
from one geographical area to another.
In these samples the alkali and alkali
earth metals were shown to be present
at concentrations exceeding 1 ppm.
Strontium and sulfur were also found at
significant levels in many of these
samples.
The purgeable fractions of many of
these aqueous waste samples contained
very high levels of methylene chloride.
Other volatile components identified in
the coal-fired power plant effluents
included chloroform, benzene, toluene,
trichloroethylene, and bromoform.
Organic compounds identified in the
extractable fractions of these samples
primarily included phthalates and
alkanes.
The concentrations of mercury deter-
mined in the fly ash and scrubber sludge
samples obtained from coal-fired power
plants were also determined to be
relatively low. Other elements, however,
were determined to be present at very
high levels. Antimony, arsenic, cadmium,
lead, copper, manganese, and sulfur
were present at levels exceeding 10
ppm in all cases and greater than 100
ppm in several of the samples.
A wide variety of organic compounds
were thermally desorbed from the solid
waste samples. These compounds
included a number of ketones, alcohols,
and ethers. Only phthalates were
determined to be present in the semivola-
tile fractions at significant levels, however,
probably because these samples were
collected from the final discharge of a
treatment process.
Coal Liquefaction
The purgeable fractions of the effluents
obtained from the coal liquefaction
operation contained a number of organic
compounds at relatively high concentra-
tions, including alkyl benzenes, a variety
of unsaturated hydrocarbons, and
chlorinated materials including methy-
lene chloride, chloroform, and trichloro-
ethylene. Many of these materials were
determined to be present at levels
exceeding 100 ppb; some at concentra-
tions greater than 1000 ppb.
These samples were also found to be
highly contaminated with extractable
organic compounds, the major compo-
nents being alkyl phenols. Alkyl phenols
from phenol through isomers of Cs alkyl
phenol were determined to be present at
concentrations exceeding 1000 ppb.
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Several higher molecular weight normal
alkanes were also present.
Coal Gasification
The gasifier solid samples obtained
from Pittsburgh Energy Technology
Center were found to contain only low
levels of mercury. Other elements
including cerium, chromium, copper,
and zirconium were determined to be
present, however, at concentrations
exceeding 100 ppm. Major organic
components identified in these samples
included methylene chloride, chloroform,
isopropyl alcohol, carbon tetrachloride,
ethyl acetate, and several low molecular
weight alkanes.
The concentrations of mercury in the
samples obtained from the underground
coal gasification process operated by
the Laramie Energy Technology Center
were also quite low. • Elements in
significant concentrations in these
samples included calcium, iron, mag-
nesium, phosphorus, potassium, sulfur,
and, in some cases, strontium.
In the samples obtained from wells in
the Hanna III site prior to gasification,
the number of organic components and
their concentrations were relatively
low Compounds identified in the
purgeable fractions of these samples
included methylene chloride, dichloro-
ethylene, and traces of benzene and
toluene Semivolatile compounds that
were present included low levels of
phthalates and normal hydrocarbons.
Samples obtained from the same wells
during the gasification contained more
purgeable organic components than
the pre-burn samples, including thiols,
ethers, and substituted amines. Organic
compounds identified in extractable
fractions were primarily phthalates and
normal hydrocarbons. Samples of the
product water obtained from the Hanna
III test during gasification contained a
large number of organic compounds in
very high concentrations. Among the
components identified in the purgeable
fractions were nitriles, ketones, thio-
phenes, pyridines, and alkyl benzenes.
Extractable organic components included
a variety of alkyl phenols, alkyl naph-
thalenes, and normal alkanes at concen
trations exceeding 10 ppm.
In the samples obtained from wells in
the Hanna III site some time after the
gasification operation had been com-
pleted, both the number and concentra-
tion of organic components were
significantly lower. In the purgeable
fractions of many of these samples only
traces of benzene, carbon disulfide, and
toluene were determined. In the extract-
able fractions, alkyl phenols, carboxylic
acids, and normal alkanes were identified.
Mercury levels determined in the
product tar and product liquor samples
obtained from the lignite gasification
operation of Grand Forks Energy Research
were less than 1 ppm. High concentra-
tions of a number of other elements
were determined in these samples,
particularly in the product tar. Very high
levels of a number of organic compounds
were detected. Among the organic
components identified were alkyl phe-
nols, carboxylic acids, normal alkanes,
and phthalates. The product tar was the
more heavily contaminated of the two
samples and also contained a number of
alkenes and polynuclear aromatics.
In the aqueous samples obtained
from wells in the Hoe Creek II experi-
mental site prior to gasification, the
number of components identified and
the concentrations at which they were
determined were quite low. After the
experimental burn was conducted, the
number and amount of material found
in these samples increased significantly.
Immediately after the gasification
experiment, samples obtained from
wells closest to the burn zone showed
the greatest increase in types and levels
of contaminant. As time passed, wells
further from the burn zone began to
show the effect of leaching of the spent
fuel by the natural movement of
groundwater. Prior to gasification,
calcium and magnesium were the only
elements found in these samples at
concentrations exceeding 10 ppm. After
gasification, iron, potassium, sulfur,
titanium, and strontium were also
determined to be major components of
these effluents. Of the organics, only
alkanes and phthalates were determined
in the samples collected before the test
burn. After gasification, however, the
classes of compounds identified in these
samples included alkanes, alkenes, alkyl
phenols, alkyl benzenes, alkyl thio-
phenes, alkyl anilines, alkyl pyridines,
and polynuclear aromatics.
Several aspects of this research effort
should be continued in an effort to
characterize the components of energy-
related wastes and effluents. First, the
state-of-the-art summary of completed
programs and research in progress
should be continued. The collection of
this information provides a valuable
data base for researchers to use in the
design of additional analytical studies.
Second, there should be continued and
expanded efforts to characterize effluents
and wastes from energy-related pro-
cesses. The inclusion of nonvolatile and
nonextractable materials in these
characterization schemes should be
considered. Specifically, it would be of
interest to sample and analyze the
process streams and final effluents of
those technologies that are approaching
commercial scale-up. This would provide
valuable information on the efficacy of
the waste treatment procedures. Finally,
there is need for the involvement of the
life sciences, particularly toxicology, in
these programs. Total characterization
of the wastes and effluents from
energy-related activities is an important
effort when very little is known about
the nature of these liquid and solid
byproducts. As more information is
generated, however, it should be
possible to identify specific compounds
or classes of compounds related to
certain energy producing activities that,
because of their stability or toxicity,
represent a potential threat to the
environment and/or the health of a
given population. Then, monitoring the
effluents of a certain process for only
important materials known to result
from that process could be accomplished
in a timely and cost-effective manner.
Geothermal Energy
Production
Because the samples obtained from
geothermal energy production activities
were collected as part of a round-robin
analytical effort, additional data were
available on the characterization of
these samples. The levels of mercury
and most other elements were relatively
low. Elements found to be present at
concentrations exceeding 1 ppm included
arsenic, barium, calcium, cesium,
chlorine, fluorine, iron, lead, lithium,
magnesium, manganese, molybdenum,
phosphorus, potassium, rubidium,
silicon, sodium, strontium, sulfur,
titanium, and zinc.
Few organic compounds were identified
in either the purgeable or the semivola-
tile fractions of these samples. Low
levels of methylene chloride, chloroform,
benzene, and toluene were determined
in the purgeable fractions. Small
amounts of phenol were found in the
semivolatile fractions.
Conclusions and
Recommendations
The data collected during the state-of-
the-art review were evaluated according
to the following criteria: 1) sample
source, 2) completeness of sampling
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design, 3) sampling procedures, 4)
sample preparation procedures, 5)
analytical procedures, and 6) complete-
ness of analysis. Information gathered
in this review indicates that character-
ization of the inorganic components of
energy-related wastes has 'received
more attention than the identification of
the organic components. The research
conducted to date on the analysis of
these effluents, however, is insufficient
to assess the efficiency of these energy-
related processes or the potential
environmental impact.
Analysis of the waste and effluent
samples collected from the seven
energy-related activities surveyed in
this program revealed their extreme
complexity. It became evident that
analysis of these samples required high
resolution glass capillary gas chroma-
tography/mass spectrometry/data sys-
tem analysis. In some cases derivatization
techniques were required to obtain
acceptable separation of the individual
organic compounds.
J. E. Gebhart and M. M. McKown are with Gulf South Research Institute. New
Orleans, LA 70126.
A. L. Alford was the EPA Project Officer (see present contact belowj.
The complete report, entitled "Components Identified in Energy-Related Wastes
and Effluents," (Order No. PB 82-236 985; Cost: $49.50, subject to change)
will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
For information contact A. W. Garrison at:
Environmental Research Laboratory
U.S. Environmental Protection Agency
Athens, GA 30613
U. S. GOVERNMENT PRINTING OFFICE: I982/559-092/0467
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