&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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