v>EPA
United States
Environmental Protection
Agency
Office of Environmental Engineering EPA-600/7-80-125
and Technology June 1980
Washington DC 20460
Research and Development
A Summary of Oil
Shale Activities at the
National Bureau of
Standards 1975-1979
Interagency
Energy/Environment
R&D Program
Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
t
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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A SUMMARY OF OIL SHALE ACTIVITIES AT
THE NATIONAL BUREAU OF STANDARDS
1975 - 1979
Edited by
Lottie T. McClendon
Office of Environmental Measurements
National Bureau of Standards
U. S. Department of Commerce
Washington, DC 20234
EPA-IAG-D5-E684
This study was conducted
as part of the Federal
Interagency Energy/Environment
Research and Development Program
Prepared for
OFFICE OF ENERGY, MINERALS, AND INDUSTRY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, DC 20460
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
Chicago, Illinois 60604
-------
DISCLAIMER
This report has been prepared Dy tne Office of Environmental
Measurements of the National Bureau of Standards, and reviewed by the
National Bureau of Standards and the U.S. Environmental Protection
Agency, and approved for publication. Approval does not signify that
the contents necessarily reflect the views and policies of the U.S.
Environmental Protection Agency. In order to adequately describe
materials and experimental procedures, it was occasionally necessary to
identify commerical products by manufacturer's name or label. In no
instance does such identification imply endorsement by the National
Bureau of Standards or the U.S. Environmental Protection Agency nor does
it imply that the particular products or equipment is necessarily the
best available for that purpose.
-------
CONTENTS
Foreword 1-
Abstract ! .'ii
Acknowledgment
m
1. Introduction 1
2. Summary 2
3. Summary of Workshop on Standard Reference Materials for
Oil Shale Processing 4
a. Introduction 4
b. Purpose of Workshop 4
c. Workshop Summary 5
d. Workshop Program 7
e. List of Attendees g
4. Status of Oil Shale Research and Development at NBS ... .11
a. Introduction Tl
b. Raw Oil Shale H
c. Shale Oil 14
d. Methods for the Quantitative Determination of
Individual Organic Compounds in Shale Oil 15
e. Existing NBS-SRM's Useful in Characterizing Oil
Shale and Oil Shale Products 43
5. Recommendations for Future Oil Shale Projects 45
Appendix A - Manuscripts presented during Workshop 47
Preparation of Standard Oil Shale Samples
OS-1, SS-1, and SS-2 - T. Wilderman 48
Minor Elements in Oil Shale and Oil Shale Products -
R. E. Poulson, et.al 67
Low-Temperature Spectroscopic Analysis of Polycyclic
Aromatic Hydrocarbons - E.L. Wehry, et.al 96
Appendix B - Information of NBS Standard Reference
Materials Applicable to Oil Shale 114
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FOREWORD
The role of the National Bureau of Standards (NBS) in the Interagency
Energy/Environment R&D program, coordinated by the Office of Research
and Development, U. S. Environmental Protection Agency, is to provide
those services necessary to assure data quality in measurements being
made by a wide variety of Federal, State, local, and private industry
participants in the entire program. The work at NBS is under the di-
rection of the Office of Environmental Measurements and is conducted in
the Center for Analytical Chemistry, The Center for Radiation Research
and the Center for Thermodynamics and Molecular Science. NBS activities
are in the Characterization, Measurement, and Monitoring Program category
and address data quality assurance needs in the areas of air and water
measurement methods, standards, and instrumentation. NBS outputs in
support of this program consist of the development and description of
new or improved methods of measurement, studies of the feasibility of
production of Standard Reference Materials for the calibration of both
field and laboratory instruments, and the development of data on the
physical and chemical properties of materials of environmental importance
in energy production. This report is one of the Interagency Energy/En-
vironment Research and Development Series reports prepared to provide
detailed information on the NBS measurement methods and standards development
pertaining to Oil Shale activities. To provide a complete report on NBS
Oil Shale activities this document contains summaries of research and
development performed by NBS (parts of which were supported by the
Interagency Energy/Environment Program and parts of which were supported
by NBS directly appropriated funds and also funds obtained from other
Federal agencies). The source of the funding used to support the
various activities is so indicated in the appropriate places in this
document. It is hoped that this document will provide those researchers
involved in evaluating the environmental impact of increased Oil Shale
production with information on measurement methods and Standard Reference
Materials pertaining to data quality assurance in all aspects of their
studies.
C. C. Gravatt, Chief
Office of Environmental Measurements
National Bureau of Standards
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ABSTRACT
This report provides a summary of NBS Oil Shale activities covering
the period 1975 to 1979. At the start of this period a Workshop on
Standard Reference Materials (SRM's) needed for Oil Shale Processing was
held at NBS and served to provide the priority guidance for the future
of this program. A summary of the recommendations of that Workshop, the
manuscripts presented during the Workshop, and the list of attendees is
included in this report. The status of the Oil Shale Research at NBS is
also presented consisting of developmental work on the feasibility of
producing an Oil Shale and a Shale Oil Standard Reference Materials
characterized for both trace inorganic and trace organic constituents.
Additionally, information is given dealing with the development of
measurement methods appropriate for Oil Shale and Shale Oil trace in-
organic and trace organic analysis. Several papers are also included
giving additional details on these matters. Other NBS Standard Reference
Materials, which may be appropriate for the use by the Oil Shale community,
are described briefly within this document. Finally, recommendations
for future Oil Shale projects dealing with the development of measurement
methods and Standard Reference Materials at NBS are presented.
ii
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ACKNOWLEDGMENT
The Office of Environmental Measurements, the National Bureau of
Standards gratefully acknowledges the partial support of this work from
the U.S. Environmental Protection Agency under the Interagency Energy/
Environmental Agreement EPA-IAG-D5-E684. The Center for Analytical
Chemistry of NBS gratefully acknowledges the support of the Department
of Energy (Office of Health and Environmental Research) for the work
described dealing with the development of methods for the quantitative
determination of individual organic compounds in Shale Oil. Additionally,
we acknowledge the considerable work of Mr. Donald Becker of NBS who was
responsible for the initial planning and conduct of the Workshop on the
needs for Standard Reference Materials for Oil Shale Processing.
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SECTION 1
INTRODUCTION
The purpose of this report is to summarize the National Bureau of
Standards' (NBS) activities in oil shale and oil-shale products. The
role of NBS in oil shale research and development, is to provide those
services necessary to assure data quality in measurements being made by
a wide variety of Federal, state, local, and private industry participants
in oil shale technology. Development of a compatible data base to
assess the total effect of oil shale development upon our environment is
a necessity if rational and logical decisions are to prevail in planning
and developing this energy resource in an environmentally and economically
acceptable manner.
A series of eight Workshops were conducted during 1975-1976 by the
NBS and the Environmental Protection Agency to assess the needs and
kinds of chemical standards and reference materials required for mon-
itoring the environmental effects associated with energy development.
The second workshop of the series was held November 24-25, 1975 at NBS.
The objective of this workshop was to obtain input to NBS from pertinent
experts on Standard Reference Materials, homogeneous intercomparison
materials, and analytical methodology needed for the accurate analysis
of environmental samples associated with oil shale processing. A
summary of this workshop, recommendations made by the participants, as
well as some of the papers presented on oil shale activities during the
workshop are included as part 3 of this report. Part 4 of this report
provides a summary of the oil shale research and development efforts
performed at NBS over the past five years. The scope of work for on-
going and future oil shale projects are summarized in part 5.
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SECTION 2
SUMMARY
The assessment of the environmental Implication and Impact of new
and expanding energy techniques requires that an effective multimedia
monitoring and measurement assurance system be maintained. Development
of a compatible data base to determine the source, transport, and fate
of environmental pollutants is a necessity 1f rational and logical
decisions are to prevail in planning the types, pattern, and magnitude
of energy developments which are environmentally acceptable. In rec-
ognition of this need, the Office of Management and Budget and the U.S.
Congress established an Interagency Energy/Environment Research and
Development Program in 1975 under the direction of the U.S. Environmental
Protection Agency. This program established a mechanism for the planning,
coordination, and allocation of research and development funds for
environmental pollution control technologies associated with energy
development.
As part of the Interagency Energy/Environment Program, an EPA/NBS
interagency program was initiated in 1975. The overall objective of
this program is to provide quality assurance for environmental baseline
data in those geographical areas where the impact on the environment of
energy development is or is projected to be of major magnitude. NBS
activities within this program concern the development of measurement
methods, Standard Reference Materials (SRM's) and instrumentation in
support of programs for evaluating environmental effects of increased
energy development. The measurement methods and SRM's developed at NBS
will help to ensure comparability and compatibility among energy related
measurements made in the laboratory and in field monitoring.
The 1973 Oil embargo spurred the National government to focus on
the development of new energy technologies to meet our Nation's Increased
energy demands. One of the industries activated and spotlighted for
technology development was the oil shale Industry. By 1975, planning,
design and environmental study efforts were underway on several oil
shale tracts and the EPA had established a high priority Oil Shale
program with two primary objectives: (1) support the regulatory goals
of the Agency and (2) support and conduct research directed towards
ensuring the oil shale industry develop in the most environmentally
acceptable manner that was reasonably possible. However, with a short-
lived oil embargo and very high construction costs, Interest in developing
the oil shale industry slackened 1n 1976 and 1977 and many Agencies
reduced and/or directed priorities and funds from oil shale research and
development to other areas and environmental issues. The NBS activity
in oil shale has been in support of the objectives of other Agencies'
oil shale programs (i.e. EPA, DoE) and as such, the NBS activity over
the past five years has been impacted by the priorities and funding
directives from such agencies.
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The first major accomplishment of the NBS Oil Shale Program for the
period 1975 to 1979 was a Workshop on Standard Reference Materials
and Measurement Methods required for Oil Shale processing to develop
priorities for the NBS activities in this program. It was concluded by
that Workshop that raw Oil Shale, (the approximately 25 gallon per ton
minus 200 mesh type) characterized for trace inorganic and trace organic
constituents was the highest priority. Second priority was a processed
shale material characterized for trace inorganic and organic constituents.
The third priority was a research material shale oil, and forth priority
was a research material process water. The second major accomplishment
was the analysis of trace elements in oil shale from one pilot plant
sample material. The third accomplishment was a comparison of gas
chromatographic profiles before and after radiation sterilization of
oil shale materials to ascertain the long-term stability of oil shale
samples. The fourth was the development of measurement methods for
an analysis of consent decree organics in shale oil based on high
performance liquid chromatography techniques. Finally, feasibility
studies were conducted on both the oil shale and shale oil materials
in order to assess the production of these two materials as SRM's.
The shale oil SRM material has been characterized for five trace organic
constitutents and is expected to be available as SRM 1580 by April
198Q. More work, as well as a shift in funds and priorities will be
needed to characterize the shale oil for trace inorganic elements.
The oil shale SRM is still under investigation due to the difficulty
at the present time of certifying the complete extraction of organic
compounds from the oil shale starting materials.
Future work at NBS is Oil Shale related activities will consist of
the completion of the development of measurement methods required for
certifying trace organic compounds in oil shale, thereby permitting
the production of an oil shale SRM certified for trace organic con-
stituents. Additionally, all commercial shale operations will be
required to preserve water resources and to control effluent discharges.
In order to meet those requirements, measurement methods and Standard
Reference Materials will be needed for water discharge from oil shale
operations. Similarly, process and fugitive emissions into the ambient
air will require a variety of reference methods and Standard Reference
Materials. The specific materials required will need to be determined
after a careful analysis of the type of emissions found in pilot oil
shale activities.
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SECTION 3
SUMMARY OF WORKSHOP ON STANDARD REFERENCE MATERIALS FOR
OIL SHALE PROCESSING
a. Introduction
On November 24-25, 1975, a workshop (sponsored by EPA and NBS) was
held at the National Bureau of Standards, Gaithersburg to determine the
needs and types of Standard Reference Materials which could be used for
monitoring the environmental effects of oil shale processing. Since the
adequate evaluation of environmental pollution is based largely upon the
results from chemical analysis, adequate reference materials are es-
sential for quality assurance and inter-laboratory comparison purposes.
Thus, the objective of this workshop was to obtain input to NBS from
pertinent experts on certified reference materials, homogenous inter-
comparison materials, and analytical methodology needed for the accurate
analysis of environmental samples associated with oil shale processing.
Several papers were presented during the workshop and many fruitful
discussions took place on a variety of subject areas related to the
environmental aspects of oil shale processing (e.g., trace inorganic,
trace organic and gaseous pollutants, overview of environmental studies
to that date and the significance thereof, etc.). As a result of a
number of obstacles, the Proceedings of this Workshop were not published.
Thus, three of the papers prepared for and presented during the Workshop
are attached as Appendix A of the report (with author's permission).
b. Purpose of Workshop - D. A. Becker
One of the purposes for this workshop involves what we can do to
help you and how you can get information to us so we can miximize our
return to you.
Accurate measurements in environmental monitoring is important
since a 100% deviation in measurement can mean either over controlling
or under controlling the process being monitored, both of which are
undesirable.
NBS has three divisions involved in this program, the Office of
Air and Water Measurement, The Office of Standard Reference Materials and
The Analytical Chemistry Division.
What this workshop needs to discuss and determine includes the
needs of the oil shale industry for reference materials, the elements
needed and concentration levels involved, the requirement for organic
analyses, the suitability of current methods and how best such needs
can be met.
Priorities are needed from this workshop to determine what is to
be done realizing that NBS had limitations on funds, people, and time.
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c. Workshop Summary
The following summary on the Oil Shale Processing Workshop covers
the major recommendations made under four main material types considered
as possible SRM's for oil shale operations: Raw Oil Shale; Spent Shale;
Shale Oil; and Process Water.
Raw Oil Shale:
The priority requirement for an SRM, to be used in the oil shale
processing field, was a powdered raw oil shale. Complete analysis of a
raw oil shale SRM is needed to provide the foundation for batch production
analyses and to assess the environmental impact, and the immediate focus
would be. trace elements. This material should come from the Mahogany
zone oil shale, preferably Anvil Point, and contain approximately 25
gallons oil/ton. The material should be sterilized by Cobalt-60 radi-
ation for stablility.
As in all grinding operations, the contamination by the grinding
materials can be severe. After due consideration, it was recommended
that alumina grinding balls be used if possible. The next best material
would be hardened steel rather than tungsten carbide which would cause
cobalt contamination. It was also pointed out that there was a need for
care in shale grinding due to the possible degradation of the hydrocarbon
components caused by the heating and oxidation that occurs during the
grinding process. To minimize this problem, the material should be
ground in an inert atmosphere.
A final SRM sample size of 80 to 100 grams would be sufficient for
trace element use. Trace elements certified should include arsenic,
selenium, boron, molybdenum, lead, zinc, mercury, flourine, antimony,
cadmium, vanadium, cobalt, nickel, iron, uranium, thorium, chromium,
lithium, and beryllium. Calcium, magnesium and other major elements
should also be certified. In addition, carbon, hydrogen, nitrogen,
sulfur, and total and organic carbon should be certified along with the
moisture content. It was suggested that information on storage under
refrigeration be included since organic decomposition would be minimized.
Storage under refrigeration would also prevent the sample being left on
the shelf where heat and light would speed up the decomposition process.
Due to the usefulness of the Fischer Assay determination, it was suggested
that an amount of the original material be split off at 60 mesh and used
as a Research Material for Fischer Assay determinations.
Although not of the same matrix, the currently available SRM's for
Coal (1632) and Fly Ash (1633) should be very useful in instrumental
procedure development.
Spent Shale
The second priority requirement was for a spent shale SRM. To
cover the present processes, two types of spent shale SRM's would be
needed. One material from the oxidative process (Paraho) and the other
from the reductive process (TOSCO II). The certification required for
these materials would be the same as that described for the raw shale
material. However, no information on Fischer Assay would be needed.
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Shale Oil
The third priority material was shale oil. Four source possi-
bilities exist for a shale oil standard: TOSCO II, Paraho, Occidental
and "in-situ." It is expected that considerable compositional differ-
ences would occur among these four types due to the differences in
manufacture. The main analyses needed for shale oil could be confined
to those elements that are catalyst poisons.
It is expected that the shale oil will go through a refining
process to become standard petroleum products. As a result, the shale
oil did not carry a high priority as a needed SRM, but it was recommended
the oil be available as a Research Material.
Process, Water
The fourth priority material recommended in the workshop was
process water. Since techniques are presently not available for cer-
tification analysis of organics in water, the production of a process
water SRM was felt to be impossible at the time of the workshop.
However, considerable need existed for the development of methods for
trace organic analysis in effluents from shale oil processing.
Although the process water is alkaline, the soon to be released
water SRM (At the time of this workshop, the Trace Element in Water SRM,
1643 was not available. Since that time, SRM 1643 was sold out and SRM
1643a is ready for re-issue) should suffice for trace element analysis.
Individual laboratories would be required to modify the water SRM and
test procedures for their elements of interest.
It was recognized that the determination of trace organics in
water would become a serious problem as production increased and analytical
methods would need to be developed in order to characterize process
waters for organic constituents.
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d. Workshop Program
ENERGY/ENVIRONMENT WORKSHOP
SRM's FOR OIL SHALE PROCESSING
NOVEMBER 24-25, 1975
NATIONAL BUREAU OF STANDARDS
GAITHERSBURG, MARYLAND
November 24, 1975
Welcome - D. A. Becker, NBS
Introductory Remarks -
G. D'Alessio, EPA
Statement of Purpose -
D. A. Becker, NBS
Session I -
A. "Oil Shale Overview"
B. "Preparation of Standard Oil-Shale Samples
OS-1, SS-1, and SS-2"
T. R. Wildeman
Colorado School of Mines
Session II -
C. "Environmental Studies"
T. R. Wildeman
Colorado School of Mines
»
"Determination of Trace Metals in Oil Shale, Materials
Balance Studies"
M. T. Atwood
TOSCO
Session III -
"Environmental Effects of Organic Trace Elements in
Oil Shale and Waste Products."
J. J. Schmidt-Collerus
Denver Research Institute
"Trace Elements in Oil Shale Liquid Products"
R. E. Poulson
ERDA, Laramie, WY
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Session IV -
Open Discussion
Address
"NBS and Pollution"
J. R. McNesby
Office of Air and Water Measurements, NBS
November 25, 1979
Session V
"High Resolution Techniques for Analysis of Polycyclic
Hydrocarbons"
E. L. Wehry
University of Tennessee
"Speciation"
J. Fruchter
Battelle Northwest Laboratories
Session VI - Brief Remarks
"ERDA's Role in Energy and Environment"
G. J. Rotariu
ERDA
"Use of Standard Reference Materials"
J. P. Cali
Office of Standard Reference Materials, NBS
Discussion
Session VII - Closing Discussion
8
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e. LIST OF ATTENDEES
Energy/Environment Workshop
SRM's for Oil Shale Processing
Mark Atwood
The Oil Shale Corporation (TOSCO)
18200 West Highway 72
Golden, Colorado 80401
I. Lynus Barnes
Analytical Spectrometry
National Bureau of Standards
Washington, DC 20234
Donald A. Becker
Analytical Chemistry Division
National Bureau of Standards
Washington, DC 20234
Francis Bonomo
Denver Research Institute
2390 So. University Boulevard
Denver, Colorado 80206
Irving Breger
Office of Energy
U. S. Geological
National Center,
Reston, Virginia
Resources
Survey
Stop 923
22092
J. Paul Cali
Office of Standard Reference
Materials
National Bureau of Standards
Washington, DC 20234
Stephen Chesler
Bioorganic Standards
National Bureau of Standards
Washington, DC 20234
Bruce R. Clark
Analytical Chemistry Division
Holifield-Oak Ridge National
Laboratory
P. 0. Box X
Oak Ridge, Tennessee 37831
Jack Clarkson, L-404
Lawrence Livermore Laboratories
P. 0. Box 808
Livermore, California 94550
Richard H. Coe
Shell Development Co.
Westhollow Research Center
P. 0. Box 1380
Houston, Texas 77001
Gregory D'Alessio
Office of Research & Development
Environmental Protection Agency
Waterside Mall - R/D 681
401 M Street, SW
Washington, DC 20460
Jon Fruchter
Batten e Northwest Laboratories
P. 0. Box 999
Rich!and, Washington 99352
Donald B. Gilmore
Environmental Monitoring and Support
Laboratory
Environmental Protection Agency
P. 0. Box 15027
Las Vegas, Nevada 89114
Barry H. Gump
Bioorganic Standards
National Bureau of Standards
Washington, DC 20234
Harry S. Hertz
Bioorganic Standards
National Bureau of Standards
Washington, DC 20234
David Jones
Radian Corporation
Box 9948
Austin, Texas 78766
James R. McNesby
Office of Air and Water Measurement
National Bureau of Standards
Washington, DC 20234
Thomas W. Mears
Office of Standard Reference Materials
National Bureau of Standards
Washington, DC 20234
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John A. Norn's
Analytical Chemistry Division
National Bureau of Standards
Washington, DC 20234
Richard E. Poulson
ERDA-Laramie
Box 3395
University Station
Laramie, Wyoming 82070
Harry L. Rook
Activation Analysis
National Bureau of Standards
Washington, DC 20234
George J. Rotariu
Energy Research & Development
Administration
Washington, DC 20540
Robert Schaffer
Bioorganic Standards
National Bureau of Standards
Washington, DC 20234
Josef J. Schmidt-Collerus
Denver Research Institute
University of Denver
University Park
Denver, Colorado 80206
Haven Skogen
Occidental Oil Shale
P. 0. Box 2999
Grand Junction, Colorado
Howard Taylor
Accu-Labs Research, Inc.
11485 West 48th Avenue
Wheat Ridge, Colorado 80033
Earl L. Wehry
University of Tennessee
W. Cumberland Avenue, SW
Knoxville, Tennessee 37916
Thomas R. Wildeman
Department of Chemistry
Colorado School of Mines
Golden, Colorado 80401
81501
Charles Taylor
Southeast Environmental Research
Laboratory
Environmental Protection Agency
College Station Road
Athens, Georgia 30601
John K. Taylor
Air and Water Pollution Analysis
National Bureau of Standards
Washington, DC 20234
10
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SECTION 4
STATUS OF OIL SHALE RESEARCH AND DEVELOPMENT AT NBS
a. Introduction
It has been long recognized that accurate baseline data and
effective and meaningful monitoring programs are essential to under-
standing the environmental impact of an industry. Thus, NBS efforts
in oil shale technology have been focused on developing measurement
methods and standards to help ensure accuracy, comparability and
compatibility among related measurements in the oil shale industry.
The following discussion describe NBS activities on powdered oil shale
and shale oil.
b. Raw Oil Shale
As a result of the recommendation from the workshop on "SRM's
for Oil Shale Processing" (Section 3 of the report), NBS obtained
samples of oil shale from TOSCO (originated from Parachute Creek
Area) and oil shale from the Energy Research Center at Laramie,
Wyoming (originated at Anvil Points Area) in early 1976. In addition
to the workshop recommendation, the experience obtained in producing the
Coal and Fly Ash materials (i.e. SRM 1632 and 1633) for trace element
certification provided the basis for NBS's initial focus on trace
elements in the raw oil shale. The two oil shale materials were ground
according to recommendations set forth at the workshop and prepared for
the preliminary assessments required of a potential Standards Reference
Materials (e.g., homogeneity, elemental profile, suitability.
Instrumental Neutron Activiation Analysis (INAA) was used to
provide a preliminary assessment of the trace element concentration
of minus 200-mesh TOSCO oil shale. The elemental concentrations
observed are listed in Table 4-1 with the estimated analytical un-
certainties which could be obtained. To conduct this study, the NBS
SRM 1632 (coal) was used as the reference material. The NBS SRM 1633
(Fly Ash) was treated as an unknown sample material along with the oil
shale material during the study for comparison purposes. Several oil
shale samples have been semi-quantitatively analyzed using emission
spectroscopy by NBS scientists in conjunction with work being performed
for another NBS program. While the results are very preliminary using
this technique some of the elemental concentrations obtained agree
favorably with those obtained using INAA (e.g. Na,K, Fe, Cr).
A portion of the oil shale material was radiation-sterilized,
analyzed for its trace element content by INAA, and the results obtained
compared to the trace element concentration of the unsterilized oil
shale to determine if there were changes in the elemental concentration
of volatile elements. A preliminary interpretation of the results,
indicated there were no significant elemental concentration differences
in the two materials.
Additionally, high resolution gas chromatography was conducted on
the unsterilized and the radiation sterilized oil shale. Extracts of the
oil shale analyzed with or without cobalt-60 irradiation sterilization of
the oil shale gave identical chromatograms. Evaluation of the organic
11
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extraction efficiency is needed to quantify organics present in the oil
shale.
As a result of the trace element assessment, the TOSCO oil shale
was chosen as the material to be used for production of the first trace
element oil shale SRM. In June, 1978, NBS received a batch of processed
TOSCO oil shale (about 1200 Ibs.) to begin the certification process.
However, by that time, the other agencies had directed its resources
be used by NBS to support their other priority programs, The certification
program for trace elements in oil shale is currently at a standstill.
Method development for trace organic analysis is currently in progress
and preliminary studies will be conducted on the TOSCO oil shale to assess
the feasibility for its use as a trace organic SRM.
12
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TABLE 4-1
Elemental Concentrations (yg/g unless indicated) and
Estimated Uncertainties Attainable
Na (%)
K (%)
Rb
Cs
Ba
Sc
Cr
Fe (%)
Co
As
Se
Sb
La
Ce
Sm
Eu
Yb
Lu
Hf
Ta
Th
Oil
1.6
1.0
63
3.4
540
4.6
32
1.8
9.0
64
3.5
2.8
20
34
2.5
0.52
0.85
0.18
1.5
0.30
4.7
Shale
5%
5%
5%
5%
5-10%
5%
5%
5%
B%
5%
5-10%
5-10%
5%
5%
5%
5%
5%
5%
5-10%
10-15%
5%
SRM 1632*
Coal
0.040
0.27
20
1.4
330
3.7
20.2
0.87
5.6
5.9
2.9
4.3
11.3
20.4
1.83
0.38
0.70
0.14
0.95
0.21
3.0
SRM 1633
Fly Ash
0.34
1.6
120
7.9
3100
27
120
6.4
40
62
11
6.9
89
160
14
3.0
4.9
1.0
7.8
1.5
25
* Reference Material Used for Calculation of the Oil Shale Values.
13
-------
c. Shale Oil
The potential carcinogenicity of processed oil shale and Us products
has received widespread attention in the press and is presently a primary
concern of environmentalists. The determination of trace elements and
trace organic compounds in very complex mixtures (e.g. processed oil
shale, feedstock, process streams, plant effluents) is very difficult.
Many of the analytical techniques that have been used 1n the past to
characterize oils and effluents from petroleum technology are Inadequate
or cannot be applied to the characterization of oil shale materials. As
a result, NBS's efforts have focused on developing measurement methods
to accurately identify and quantify individual organic compounds in
complex matrices. The certification of trace organic Standard Reference
Materials for shale oil, liquified coal, etc. are contingent upon the
development of accurate methods for quantifying individual toxic and/or
carcinogenic compounds in such complex matrices.
NBS obtained a quantity of shale oil from Oak Ridge National
Laboratory in 1978, to apply NBS developed methods and assess the fea-
sibility of preparing a trace organic Shale Oil SRM. The results of
these efforts are described (Sec. 4.d of this report) in the draft,
"Methods for the Quantitative Determination of Individual Orgnalc
Compounds in Shale 011." In addition to the financial support from
the EPA Interagency Energy/Environment Research and Development
Program, the work described in this draft was performed with partial
financial support from the Office of Health and Environmental Research
of the Department of Energy. The authors of this draft are In the
process of finalizing their work for publication. A Shale Oil SRM,
1580, certified for five polycyclic aromatic hydrocarbons (PAH.)—
pyrene, fluoranthene, benzo(a)pyrene, benzo(e)pyrene, o-cresol--
will be available from the NBS Office of Standard Reference Materials
by April 1980.
14
-------
d. Methods for the Quantitative Determination of
Individual Organic Compounds in Shale Oil*
H. S. Hertz, J. M. Brown, S. N. Chesler, F. R. Guenther,
L. R. Hilpert, W. E. May, R. M. Parris, and S. A. Wise
Organic Analytical Research Division
National Bureau of Standards
Washington, DC 20234
* This paper is being submitted to the Journal of Analytical Chemistry
for publication in
15
-------
Brief
Acid-base extraction and high performance liquid chroma-
tography are used to fractionate shale oil. Capillary gas
chromatography, high performance liquid chromatography and gas
chromatography-mass spectrometry are used to identify and
quantify individual compounds in the shale oil fractions.
16
-------
Abstract
Several techniques have been investigated for quantitating
individual organic compounds in shale oil. Emphasis was focused
on acid-base extraction and high performance liquid chromatography
as independent methods of shale oil fractionation. Gas chroma-
tography, gas chromatography-mass spectrometry and high perfor-
mance liquid chromatography were used for individual compound
quantitation utilizing external and/or internal standards or
standard addition techniques. The following compounds were
measured in the shale oil: pyrene, fluoranthene, benzo(e)pyrene,
benzo(a)pyrene, phenol, p_-cresol, acridine, and 2,4,6-trimethyl-
pyridine. Comparable results were obtained by the various
methods for extraction and quantitation.
17
-------
Increasing energy demand in the United States and reliance
on foreign sources of petroleum have resulted in a national
program designed to develop new sources of energy. The con-
version of coal to gaseous or liquid fuels and the utilization
of oil shale and tar sands are some of the energy sources that
appear promising. In terms of energy, it is estimated that
domestic coal and oil shale reserves are 8000x10 and 400x10
BTU, respectively, while petroleum reserves are only 200x10
BTU (1). However a serious and still largely unknown compli-
cation of developing these alternate fuels is their potentially
deleterious impact on man and the environment. To evaluate this
impact properly, it will be necessary to analyze the feedstock,
process streams, plant effluents and final product for their
trace element and organic compound content. The accurate quan-
titative analysis of individual organic compounds will become
increasingly important as mutagenicity testing on chromato-
graphic fractions generated from various fuels and effluents
expands. These tests should eventually allow scientists to
relate health effects to known amounts of specific compounds.
One method for assuring the accuracy of the necessary
quantitative analyses is the use of suitable quality assurance
standards or Standard Reference Materials (SRM's). The certifi-
cation of such trace organic SRM's is contingent upon the develop-
ment of the analytical expertise to achieve individual compound
quantitation in complex matrices such as shale oil, liquified
coal, or petroleum. In the past many of the analytical techni-
18
-------
ques that have been used for the evaluation of synthetic oils
have been taken from petroleum technology (2-4). These analyses
generally involve an initial separation of the mixture into
compound classes by solvent extraction techniques followed by
various methods of further characterization. The procedures
that have been used for further characterization were usually
designed for the determination of physical and chemical prop-
erties of distillate fractions which are important to product
characteristics but are not designed for individual compound
identification and quantitation.
Recently several methods for the analysis of specific
classes of compounds in samples of petroleum, shale oil and
synthetic coal liquids have been reported. Jackson et al (5)
determined hydrocarbon types in shale oil distillates by use of
a hydroboration-acid adsorption technique; McKay and coworkers
(6) utilized a chromatographic-infrared technique to charac-
terize nitrogen bases in high boiling petroleum distillates.
Uden e_t al^ (7) have characterized the acidic and basic fractions
of shale oil by gas chromatography-Fourier transform infrared
spectroscopy Popl et^ aJL^ (8) have used frontal elution on silica
gel followed by adsorption chromatography on alumina and gel
permeation chromatography to characterize polynuclear aromatic
hydrocarbons (PAH) in white petroleum products. Suatoni and
Swab (9) developed a "back-flush" high performance liquid
chromatographic technique for the determination of total saturated
and aromatic hydrocarbons from crude oils and synthetic crudes
19
-------
derived from coal. Several workers (e.g. 10) have recently
applied mass spectrometry to class specific analysis of coal
liquids. Dark and McFadden (11) employed HPLC and liquid
chromatographymass spectrometry for the characterization of
coal liquefaction products; and, Clark et. al (12) have used
both solvent extraction and chromatographic techniques for the
isolation of alkanes and PAHs from shale oil. However, none of
these methods was developed for the accurate quantitative
analysis of individual compounds.
To enhance the accuracy of environmental measurements, we
have developed methods for quantitating individual toxic and/or
carcinogenic compounds in alternate fuels. In particular,
methods for determining the concentrations of several phenols,
N-heteroaromatic compounds (aza-arenes) and PAH in shale oil
are reported in this paper. Initial emphasis has focused on
the evaluation of an acid-base extraction scheme and a preparative
HPLC procedure as independent methods for shale oil fractionation.
Various gas chromatographic (GC), gas chromatographic-mass
spectrometric (GC-MS), and high performance liquid chromatographic
methods have been investigated as means of individual compound
identification and quantitation.
Experimental
Shale Oil Sample. The shale oil analyzed in this work is
from a 150-ton retort for in-situ simulated combustion operated
by the Laramie Energy Research Center, Laramie, Wyoming. The
shale is from the Mahogany zone of the Colorado Green River forma-
tion. An 8 L sample of this shale oil was obtained by NBS
20
-------
from Bruce R. Clark at Oak Ridge National Laboratory, Oak Ridge,
Tennessee. The shale oil underwent centrifugation at Oak Ridge
to separate water O40!) and sludge from the oil. This shale
oil has been utilized for analytical methods development at Oak
Ridge (13). A subsample of 1 liter was removed from the 8 liter
bulk sample. Aliquots of ^5 mL each were sealed in amber glass
ampoules for subsequent analyses. The samples were analyzed to
measure the concentration (yg/g) of pyrene, fluoranthene, benzo(a)
pyrene, benzo(e)pyrene, phenol, o-cresol, 2,4,6-trimethylpyridine,
and acridine.
Extraction
Acid-base extraction. The shale oil sample was separated
into three fractions (acids, bases, and neutrals) using an
extraction procedure adapted from Schmeltz (14) . This procedure
is shown schematically in Figure 1 for a 0.5g sample. For the
determination of the PAHs an additional liquid-liquid partition
step using dimethylformamide (DMF)/water was utilized to separate
the aliphatic hydrocarbons from the PAHs. This procedure for
the isolation of PAHs in complex mixtures has been previously
reported by Bjorseth (15).
HPLC extraction ffractionation) The shale oil sample was
diluted (^O.lg/mL in methylene chloride) prior to fractionation
on a preparative scale aminosilane column (yBondapak N^, 30 cm
x 8 mm i.d.). A sample containing approximately 14 mg of shale
oil was injected onto the column using a loop injector. A
mobile phase flow rate of approximately 5 mL/min was employed.
21
-------
Standards of the compounds to be determined and the compounds
utilized as internal standards for quantitation were injected
to determine the appropriate caution volumes for fraction
collection. The fractions were collected in centrifuge tubes
and reduced to 50-500 yL by passing nitrogen over the sample.
Chromatographic conditions for the HPLC fractionations are
presented in Tables I, II, and III.
Quantitation
HPLC Quantitation. Analytical liquid chromatographic
analyses were performed on an instrument equipped with a gradient
pumping system, loop injector and spectrophotometric and spectro-
fluorimetric detectors. A digital integrator and strip chart
recorder were used for data acquisition.
A determination of the volume of the sample loops for both
the fractionation and analytical HPLC system was accomplished
through use of a gravimetric procedure. The loops were initially
filled with mercury. The mercury was swept from the loops into
a tared weighing dish with approximately 1 ml of pentane. The
bulk of the pentane was decanted and the remainder was allowed
to evaporate. This process was repeated five times for each
loop. The mass of mercury displaced from the loop was deter-
mined gravimetrically. The volumes of the loops were calculated
using the density of mercury and were 137.7±1.2 and 12.98±.06
yL, respectively.
As shown in Table I, one of the methods for quantifying
phenol and o-cresol was a sequential HPLC procedure. Phenol and
o-cresol were separated from the shale oil matrix and collected
22
-------
in separate fractions. The concentration of each of these
compounds in the collected fractions was determined by use of
an internal standard method. A known amount of phenol (as an
internal standard) was added to the fraction containing o^-cresol
and o_-cresol was added as an internal standard to the fraction
containing phenol. Both fractions were reduced in volume to
approximately 100 yL with a stream of nitrogen. These fractions
were then chromatographed on an octadecylsilane (C1g) column
using 40% acetonitrile in water as the mobile phase, and ultra-
violet detection at 270 nm. The concentration of phenol and
-------
of these columns is illustrated in Figure 2 which is a chromato-
gram of shale oil bases. It would have been impossible to
quantitate these complex mixtures using gas chromatographic
methods without these high efficiency columns.
Quantitation by GC was always performed using an internal
standard method with peak areas determined using a digital
integrator. Internal standard compounds were chosen which pos-
sessed similar chemical properties to that of the analyte and
were never obscured by measurable chromatographic interferences
(co-eluting compounds). The internal standards were added to
the shale oil at the earliest possible point in the analysis
scheme. Standards containing accurately known amounts of
standard and analyte were taken through the entire quantitation
procedure to determine response factors. These response factors
thereby reflect not only differences in detector response but
also chemical and physical properties such as extraction effi-
ciencies and volatility losses which might occur during extract
concentration. Details concerning the sample preparation and
GC conditions used in the determination of the selected shale
oil constituents are summarized in Table II.
GC/MS quantitation. Gas chromatographic-mass spectrometric
analyses were performed on a standard gas chromatograph, modified
for use with WCOT columns, interfaced to a quadropole mass
spectrometer with dual disk data system. Chromatographic columns
were interfaced to the mass spectrometer either through a gold
jet molecular separator, or an 'open split' (16) constructed
24
-------
of Ni tubing (1/16" OD x 0.010" ID) which was deactivated (17)
and restricted to allow a flow rate of 1.5 mL/min into the ion
source. The operating pressure in the ion source manifold was
1.0 x 10 torr. The mass spectrometer was operated in the
electron impact mode under the following conditions: interface
temperature 250-275°C, ion source 200°C, analyzer 100°C, electron
energy 70 eV. Gas chromatographic separations were carried out
on the columns and under the conditions noted in Table III.
A standard addition technique was generally used for
individual species quantitation (see Table III). For each
compound to be determined, four shale oil samples, with different
known amounts of the analyte added, were fractionated. The
standard additions were made over a range of zero to three times
the approximate concentration of the analyte, based on a prelim-
inary quantitative determination of the compound in the shale
oil using an external standard method. The 'spiked1 shale oil
samples were subjected to either an acid/base solvent extraction
or an HPLC fractionation. The samples were reduced to 100 yL
under a stream of nitrogen, and suitable aliquots analyzed by
GC/MS with selected ion monitoring. To circumvent the
need for accurately measuring volumes during the extraction or
fractionation, and to compensate for variable injection volumes
onto the GC column, a second compound natively present in the
shale oil, and in the same compound class as the compound being
determined, was monitored as a volume correction standard. The
specific compounds used as volume correction standards for each
25
-------
analyte are listed in Table III. Selected ion monitoring was
chosen as the means of analysis for its sensitivity and selec-
tivity. The ions (generally the molecular ions) for the analytes
and the internal standards (volume correction standards) were
monitored in real time in 0.1 amu increments to insure that the
signal was sampled at the top of the mass peak. Dwell times of
either 50 or 100 ms were used to insure at least 20 data points
across a chromatographic peak. Single ion records were inte-
grated after each run, and a ratio of the peak area for the
analyte to the peak area of the internal standard (volume
correction standard) was computed. This ratio was plotted
against the concentration of the analyte (in ppm) added to the
shale oil. The concentration of the analyte natively present in
the shale oil was determined from the intercept with the abscissa,
using a linear- least squares program.
Fluoranthene and pyrene were also determined in the shale
oil without any prior acid/base extraction or HPLC fractiona-
tion. Approximately 0.5g of shale oil was diluted to 10 mL with
methylene chloride. A known amount of 9,10-dimethylanthracene
(^50 yg) was added to the solution as an internal standard. One
to two yL aliquots of this solution were analyzed by GC/MS using
selected ion monitoring. The chromatographic conditions were as
noted in Table III. Single ion records for the m/z 202 ion (for
fluoranthene and pyrene) and the m/z 206 ion (for 9,10-dimethylan-
thracene) were clean enough to allow integration of peak areas
Response factors for fluoranthene and pyrene relative to the
26
-------
9,10-dimethylanthracene were determined under identical GC/MS
conditions from gravimetrically prepared solutions of these
compounds. Concentrations of fluoranthene and pyrene were
determined from these response factors and ratios of the area
of the compound being determined to that of the internal standard,
Results and Discussion
The major aim of this study was to develop independent
analytical methods for the quantitative determination of indi-
vidual toxic and/or carcinogenic compounds in an alternate fuel.
The development of a minimum of two such independent methods is
a necessary prerequisite to the certification of a Standard
Reference Material needed as a quality assurance standard in the
rapidly expanding fields of energy, environmental and trace
organic analytical research. We have shown that individual
organic compounds can be quantitated in a shale oil matrix and
that diverse methodology will, if properly applied, yield com-
parable results. In addition we have reported a new HPLC method
for preliminary shale oil fractionation, a novel GC/MS quantita-
tion technique which has been shown to greatly enhance analytical
selectivity relative to conventional GC techniques, and finally
an HPLC fluorescence method which allows individual PAHs to be
measured in the presence of other PAHs. The success of the
HPLC fluorescence method can be attributed to: 1) the chromato-
graphic selectivity obtained by reverse phase HPLC, and 2) the
detection selectivity obtained through use of fluorometric
monitoring of the chromatographic effluent. (PAHs have very
27
-------
characteristic excitation and emission spectroscopic properties
which can be used both for identification and selective detection.)
The results obtained by the two independent methods of sample
extraction (classical acid/base solvent extraction and HPLC
fractionation) and three methods of quantitation (high performance
liquid chromatography, gas chromatography with flame ionization
detection and gas chromatography-mass spectrometry using single
ion monitoring) are summarized in Table IV.
Many laboratories are now involved in qualitative examina-
tions of pilot run alternate fuels, and an increasing number of
laboratories are becoming involved in the quantitative analysis
of constituents of alternate fuels. However, the accuracy base
needed to compare quantitative analyses performed by different
investigators is not now available. As part of a preliminary
assessment of the environmental impact of oil shale development,
researchers at the TRW Environmental Engineering Division and
the Denver Research Institute summarized the available quanti-
tative data on the presence of benzo(a)pyrene in various fuels
and natural materials (18). In addition several researchers
have determined the concentrations of various PAHs in a limited
number of coal-derived liquefaction products (19,20). However,
even in these limited studies the basis for intercomparison of
data is lacking.
In simultaneously developing independent analytical methods
as presented in this paper, one is afforded a unique opportunity
for comparative evaluation of efficiency and precision of the
28
-------
methods. The greatest improvement in efficiency noted during
this study was the incorporation of HPLC fractionation as a
replacement for classical extraction techniques. The acid/base
extraction (Fig. 1) is a laborious procedure which requires
several days to generate the acidic, basic and neutral frac-
tions. Furthermore, once the extraction has been completed, the
samples must be subjected to a high resolution chromatographic
separation to allow individual components to be sufficiently
separated for quantitation free from interferences. On the
other hand, the HPLC fractionation procedure provides a rapid
(less than 1 h) method of preparing shale oil fractions which
are considerably less complex than the three initial fractions
generated by the acid/base extraction scheme. Using a prepara-
tive scale aminosilane column and modifying the mobile phase
composition from 100 percent hexane to 100 percent methylene
chloride, it is possible to elute a wide range of compounds from
non-polar PAHs to the more polar phenols and aza-arenes. Figure
3 is an ultraviolet detection recording at 270 nm of the liquid
chromatography to generate the phenolic fractions. The upper
trace is a chromatogram of shale oil and the lower trace is a
chromatogram of various compounds used to determine retention
volumes for the phenols of interest. As one can see the PAHs are
eluted unretained when using 100 percent methylene chloride as
the mobile phase. (The PAHs are isolated according to the number of
Condensed rings using n-hexane as the mobile phase [21]). One
should also note in comparing results obtained on the small
29
-------
Kpolar compounds, phenol, p_-cresol, and 2,4,6-trimethylpyridine,
that there is an indication of greater precision in any single
method of quantitation when using HPLC fractionation rather than
the acid/base extraction.
As mentioned above, in addition to the two methods of
sample preparation, three methods of individual compound quanti-
tation were utilized. The gas and liquid chromatographic methods
of quantitation, which utilized either internal or external
standards, required some assumptions and/or prior analyses. For
the internal standard methods one had to assume that the stan-
dard behaved similarly to the component of interest and one had
to show that its native level in the sample was insignificant
relative to the amount added (which should be added to approxi-
mate the concentration of the analyte). When all appropriate
internal standards were natively present at a significant con-
centration (the phenols in this study), the internal standard
had to be added after HPLC fractionation had segregated the
analyte, thereby requiring the assumption that no losses ocurred
during fractionation. Where only an external standard was used
an assumption of instrument (detector) stability was required,
as well as an assumption that no losses occurred during sample
preparation. The gas chromatography-mass spectrometry with
single ion monitoring and standard addition techniques required
none of these assumptions and provided further selectivity by
lack of interference from co-eluting compounds in the gas
chromatography due to the mass selectivity. To the extent
30
-------
that values generated by GC-MS with standard addition agreed
with the HPLC and GC only values, the assumptions discussed
above were valid.
The use of GC/MS single ion monitoring in conjunction with
standard addition techniques provides a novel, accurate and ex-
tremely selective means for individual compound quantitation.
The only possible interference in this mode of operation is a
co-eluting compound with a peak at the same m/z ratio in its
mass spectrum. To minimize this possibility, several other ions
in the spectrum of the component of interest are periodically
monitored to assure that the relative peak areas for these ions
are in the same ratio as for an authentic sample of the pure
analyte.
To assure maximum sensitivity the ion to be used for quan-
titation was monitored at several 0.1 amu intervals to confirm
that the signal of maximum intensity was used for peak area
calculations. This principle is demonstrated in Figure 4 which
contains single ion records for 2,4,6-trimethylpyridine (M , m/z
121) and for a dimethylethylpyridine [(M-l)+, m/z 134], the
volume correction standard. Three independent area determina-
tions were made at each peak maximum (m/z 121.2 and m/z 134.2).
These numbers were averaged and the area ratio was then used for
one data point in the standard addition determination (see
Figure 5). Despite the mass specificity, a small shoulder which
represented about 21 of the total peak area was observed on
the m/z 134 peak. As can be seen in Figure 5, several GC-MS
31
-------
determinations were made at each concentration of added 2,4,6-
trimethylpyridine and the x-intercept of the least squares fit
of the data indicated a native concentration of 1214±64 ppm
2,4,6-trimethylpyridine in the shale oil sample.
As can be seen from Table IV the overall agreement between
the various methods of quantitation and extraction was quite
good, even at the 95% confidence level. The poorest between-
method precision was obtained in the determination of 2,4,6-
trimethylpyridine. This imprecision was probably related to the
sample preparation aspects o'f the work, due to the volatility of
the compound. An indication of this is the fact that the GC-MS
standard addition value is the highest and should be independent
of volatility losses.
This shale oil sample has been analyzed by various national
and university*laboratories, to evaluate interlaboratory precision
in the determination of trace organic compounds in alternate
fuels. The results of this intercomparison study are being
compiled for publication.
Acknowledgements
Partial financial support from the Office of Health and
Environmental Research of the Department of Energy and from the
Office of Energy, Minerals, and Industry within the Office of
Research and Development of the U.S. Environmental Protection
Agency under the Interagency Energy/Environment Research and
Development Program, is gratefully acknowledged.
32
-------
In order to specify procedures adequately, it has been
necessary to identify some commercial materials in this report.
In no case does such identification imply recommendation or
endorsement by the National Bureau of Standards, nor does it
imply that the material identified is necessarily the best
available for the purpose.
33
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Literature Cited
1. J. C. Davis, Chem. Eng. , 81^ (7), 30 (1974).
2. G. P. Wilson, and C. H. Jewett, "Comparative Characteriza-
tion and Hydrotreating Response of Coal, Shale and Petroleum
Liquids," ACS Div. of Petroleum Chemistry, presented ACS
National Meeting, March 1977.
3. Y. Sanadu, Sekiyu Gakkai Shi., 17. (10) » 835 (1974).
4. J. E. Dooley, G. P. Sturm, P. W. Woodward, J. W. Vogh,
and C. J. Thompson, "Analyzing Syncrude of Utah Coal",
(DOE, ERDA BERC, Bartlesville, OK) BERC/RI 75:7 (1975).
5. L. P. Jackson, C. S. Allbright, and H. B. Jensen,
"Characteristics of Synthetic Crude Oil Produced by In-
Situ Combustion Retorting," ACS Preprints, Div of Fuel
Chem., 1^9 (2), 175 (1974).
6. J. F. McKay, J. H. Weber, and D. R. Latham, Anal. Chem.,
48, 891 (1976).
•
7. P. C. Uden, A. P. Carpenter, H. M. Hackett, D. E.
Henderson, and S. Siggia, Anal. Chem., 51, 38 (1979).
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8. M. Popl, M. Stejskal, and S. Mostechy, Anal. Chem., 47,
1947 (1975).
9. J. C. Suatoni, and R. E. Swab, J_._ Chromatog. Sci., 15,
361 (1975).
10. J. T. Swansiger, F. E. Dickson, and H. T. Best, Anal. Chem.,
,4£, 730 (1974).
11. W. A. Dark, and W. H. McFadden, J_._ Chromatog. Sci., 16, 289
(1978).
12. B. R. Clark, C-H. Ho, and A. R. Jones, "Approaches to
Chemical Class Analyses of Fossil Derived Materials", ACS
Div. of Petroleum Chemistry, ACS National Meeting, March,
1977.
13. A. R. Jones, M. R. Guerin, and B. R. Clark, Anal. Chem.,
49, 1766 (1977).
14. I. Schmeltz, Phytochem. , 16, 33 (1967).
15. A. Bjorseth, Anal. Chim. Acta, 94, 21 (1977).
16. D., Henneberg, V., Henrichs, G., Schomburg, Chromatographia,
£, 449 (1975).
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17. D. C. Fenimore, J. H. Whitford, C. M. Davis, and A. Zlatkis,
J. Chromatog., 140, 9 (1977).
18. K. W. Crawford, C. H. Prien, L. B. Baboolal, C. C. Shih, and
A. A. Lee, A Preliminary Assessment of the Environmental
Impacts from Oil Shale Developments, EPA Report-600/7-77-069,
p. 92 (1977).
19. M. R. Guerin, W. H. Griest, C-H. Ho and W. D. Shults, "Chemical
Characterization of Coal Conversion Pilot Plant Material".
in Proceedings of the 3rd Environmental Protection Conference,
Chicago, 111., ERDA-92, p. 670 (1975); M. R. Guerin, J. L. Epler,
W. H. Griest, B. R. Clark, and T. K. Rao, in Carcinogenesis
3_, Polynuclear Aromatic Hydrocarbons, P. W. Jones, and
R. I. Freudenthal, eds., Raven Press, N. Y., pp. 21-33 (1978).
20. M. R. Peterson and J. S. Fruchter, "Studies of Materials
Found in Products and Wastes from Coal-Conversion Processes"
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36
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Compound
Determined
Pyrene
Fluoranthene
Table I. HPLC Methods for the Analysis of Shale Oil
Sample Preparation Internal or External Chromatographic Conditions for Analysis
Standard
HPLC fractionation - 2% CH2C12 External standards of
in hexane, collect pyrene/fluor- pyrene and fluoranthene
anthene fraction. to determine fluorescence
response.
Reverse phase C-18 column, 70/30% CH-CN/H-O,
Fluorescence detection: pyrene (excitation -
337 nm, emission - 370 nm), fluoranthene
(excitation - 295 nm, emission - 463 nm).
Benzo(a)pyrene
HPLC fractionation - 2% CH2C
in hexane, collect benzo(a)-
pyrene fraction.
External standard of
benzo(a)pyrene.
Reverse phase C-18 column, 40-100% linear
gradient CH»CN in H.O in 30 min., Fluores-
cence detection: benzo(a)pyrene (excitation
295 nm, emission - 403 nm).
Phenol
HPLC fractionation - CH.Cl- as
mobile phase - baseline resolu-
tion of o_-cresol, _p_-cresol, and
phenol standards, collect phenol
fraction only.
o-Cresol added after
fractionation.
Reverse phase C-18 column, 40/60% CH3CN/H20,
UV absorption detection at 270 nm.
o-Cresol
HPLC fractionation - CH2C1_ as
mobile phase, collect ^-cresol
fraction only.
Phenol added after
fractionation.
Reverse phase C-18 column, 40/60% CH3CN/H20-,
UV absorption detection at 270 nm.
Acridine
HPLC fractionation -
in hexane, collect acridine
fraction.
CH2C12
External standard of
acridine to determine UV
response.
Reverse phase C-18 column, 0-50% linear grad-
ient CH3CN in H20 in 20 min.
UV absorption detection at 254 nm.
-------
Compound
Determined
Sample Preparation
Table II. GC Methods for the Analysis of Shale Oil
Internal Standard Chromatographic
Column
Operating Conditions
Pyrene HPLC fractionation - 2% CH,C1, in 3-raethylpyrene added Carbowax 20 M T = 220 °C, T. = 300 °C, T, = 300 °C
£ Lt C X G
Fluoranthene hexane, pyrene/fluoranthene frac- prior to fractiona- WCOT, 30 m x
tion collected. tion. 0.30 mm i.d.
Pyrene Acid/base extraction - neutral 9,10-dimethylanthra- SE-52 WCOT,
fraction isolated, DMF partition cene added prior to 30 m x 0.25 mm
Fluoranthene to isolate PAHs extraction i.d.
T = 190 °C, T. = 300 °C, T, = 300 °C
c 1 d
Phenol
HPLC fractionation - CKJCl- as
mobile phase, collect phenol frac-
tion only (baseline resolution of
Oj-cresol, j£-cresol, and phenol
standards).
_p_-cresol added after
fractionation.
SP 1000 WCOT,
30 m x 0.25 mm
i.d.
T - 180 °C,
- 300 °C, T = 300 °C
Oj-Cresol HPLC fractionation - CH-Cl- as
mobile phase, collect o_-cresol
fraction only.
p-cresol added after
•*-
fractionation.
Carbowax 20 M
WCOT, 30 m x
0.30 mm i.d.
T - 150 °C, T. = 250 °C, T.
c 1 a
250 8C
2,4,6-tri- HPLC fractionation - CH2C12 as
methylpyridine mobile phase, collect 2,4,6,-
trimethylpyridine fraction.
4-ethylpyridine added
after fractionation.
SP 1000 WCOT,
30 m x 0.25 mm
i.d.
100 8C, T± - 200 °C,
250
2,4,6-tri- Acid/base extraction - base frac-
methylpyridlne tion isolated.
*T = Column temperature
Tc
i = Injector temperature
4-ethylpyridine added SP 1000 WCOT,
prior to extraction. 30 m x 0.25 mm
i.d.
100 °C, T± = 350 °C, Td = 350 °C
-------
Compound
Determined
Pyrene
Fluoranthene
Pyrene
Fluoranthene
Benzo(a)pyrene
Benzo( e)pyrene
Benzo(a)pyrene
Benzo(e)pyrene
Table III. GC/MS Methods for the Analysis of Shale Oil
Internal Standard Ions Chromatographic
Sample Preparation (Volume Correction) Monitored Column Operating Conditions
HPLC fractionation-
2% CH2C12 in hexane
collect anthracene
through fluoranthene
fraction.
O.OSg shale oil/mL
CH2C1_ solution -
direct inection
HPLC
3.5%
fractionation-
CH-Cl-in hexane
collect fraction
containing benzo(o)
pyrene, benzo(e)
pyrene, and perylene
Acid/base extrac-
tion - DMF parti-
tion of neutral
fraction
phenanthrene +
anthracene for
volume correction
9,10-dimethylan-
thracene added
202 SE-30 WCOT
178 30m x 0.50mm
i.d.
202 SE-52 WCOT
206 30m x 0.25mm
i.d.
perylene added 252
prior to fractiona-
tion
perylene added 252
prior to extraction
SE-52 WCOT
30m x 0.25mm
i.d.
SE-52 WCOT
30m x 0.25mm
i.d.
150°C for 8 min,
at 2°C /min.
220°C
200°C for 2 min, 260°C
at 2°C/min.
200°C for 2 min, 260°C
at 2°C/min.
200°C for 2 min, 260°C
at 2°C/min.
GC/MS
Interface
single stage
gold jet
Ni, open
split
Ni, open
split
Ni, open
split
Phenol
o-Cresol
(1) HPLC fractiona-
tion - CH2C12 as
mobile phasef collect
_o_-cresol through
phenol fraction
(2) Acid/base ex-
traction-isolate
acid fraction.
m- + jpj-cresol for
volume correction
94
108
0.1%SP-1000
on 80/100
Carbopak C
170°C isothermal
single stage
gold jet
2,4,6-Tri-
methylpyridine
HPLC fractionation-
CH2C12 as mobile
phase, collect
quinoline through
2,4,6-trimethyl-
pyridine fraction
a dimethylethyl-
pyrldine isomer
for volume cor-
reaction
121 SP-2100 WCOT,
134 30m x 0.25mm
i.d.
90°C for 4 min,
at 2°C/min
200°C
Ni, open
split
-------
Table III. GC/MS Methods for the Analysis of Shale Oil
Compound Internal Standard Ions Chromatographic GC/MS
Determined Sample Preparation (Volume Correction) Monitored Column Operating Conditions Interface
Acridine HPLC fractionation- benzoquinoline for 179 SE-52 WCOT, 160°C for 2 min, 250°C Ni, open
10% CH2C12 in
hexane, collect
acridine fraction
10% CH Cl_ in volume correction 17m x 0.25mm at 2°/min split
hexane, collect i.d.
-------
Table IV. Shale Oil Analysis
(ppm, 95% confidence level)
HPLC Extraction
Acid/Base Extraction
No Extraction
Compound
Pyrene
Fluoranthene
Benzo (a) pyrene
Benzo (e) pyrene
Phenol
o-Cresol
2,4,6-trimethyl-
pyridine
Acridine
Quantitation by
LC GC
108 + 16 101 ± 4
53 ± 6 55 ± 6
21 ± 3
-
383 ± 50 387 ± 26
330 ± 34 334 ± 86
912 ± 26
6.0 ± 2.4
Quantitation by Quantitation bjr
GC/MS GC GC/MS GC/MS
102 ±9 94 ± 10 - 104 ± 8
62 ± 5 75 ± 5 - 58+5
21 ± 5 - 24+2
20 ± 6 - 22 ± 5
416 ±28 - 334 ± 63
350 ±16 - 322 ±45
1214 +64 988 + 56 -
4.4 ±0.3
-------
Figure Captions
Solvent extraction scheme for the preparation of shale oil
sample, adapted from Schmeltz (14).
Capillary gas chromatogram of shale oil bases. Conditions:
30m SP-1000 column, 100 °C for 4 min and then temperature
programmed to 220 °C at 2°/min, flame ionization detection.
Preparative scale liquid chromatogram of shale oil. The
upper trace is a chromatogram of shale oil and the lower
trace is a chromatogram of a mixture of pure compounds used
to determine retention volumes of phenolic compounds.
(2,4,6-trime^OH = 2,4,6-trfmethylphenol). Conditions: semi-
preparative aminosilane column, methylene chloride mobile
phase and'ultraviolet detection at 254 nm.
Single ion records for 2,4,6-trimethylpyridine (IMP) and a
dimethylethylpyridine (DMEP). Three area determinations for
each peak are shown at the m/z value of maximum intensity.
The area of a small shoulder on the DMEP peak is also
indicated.
Linear least squares fit for the data point obtained in the
determination of 2,4,6-trimethylpyridine (2,4,6-TMP) by the
standard addition method. The absolute value of the x-
intercept represents the negative of the concentration of
the analyte in the sample.
42
-------
e. Existing NBS-SRM's Useful in Characterizing Oil Shale and Oil
Shale Products"
Over eighty SRM's are now being used to assure measurement com-
patibility in air and water pollution analyses. Some of these materials
could be useful and provide a common reference base for those mea-
surements being made in on-going oil shale projects. Those materials
currently available from NBS which could be useful in trace element
measurements in oil shale and oil shale products are given in Table 4-2.
It should be noted that several standards are available for the same
element, but indicated in the table by different numbers (e.g. SRM 1621
and 1622). This occurs because the same element has been certified at
varying concentrations in the same matrix. Additional information on
the materials listed in the above Table can be found in Appendix B.
43
-------
TABLE 4-2
Existing NBS-SRM's Applicable to Characterization of
Oil Shale/Oil Shale Products
(Liquids)
SRM Number Type
1621 Sulfur in Residual Fuel Oil
1622 Sulfur in Residual Fuel Oil
1623 Sulfur in Residual Fuel Oil
1624 Sulfur in Distillate Fuel Oil
1634 Trace Elements in Residual Oil
1636 Lead in Reference Fuel
1637 Lead in Reference Fuel
1638 Lead in Reference Fuel
(Solids)
1630 Mercury in Coal
1631 a Sulfur in Coal
1632a Trace Elements in Bituminous Coal
1633a Trace Elements in Coal Fly Ash
1635 Trace Elements in Sub-bituminous Coal
1648 Trace Elements in Urban Particulate Matter
44
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SECTION 5
RECOMMENDATIONS FOR FUTURE OIL SHALE PROJECTS
The environmental impact associated with commercial oil shale
operations can be expected to produce air and water pollutants, in
addition to other potential adverse impacts on the environment. Dev-
elopment of measurement methods and/or standards to ensure quality
baseline data and effective monitoring systems is a necessity if
logical and rational policy decisions are to prevail in developing
mitigation strategies for adverse environmental impacts caused by the
oil shale industry.
All commercial shale operations will be required to preserve
water resources and control effluent discharges. To meet these re-
quirements, effluents will need to be characterized, controlled, and
monitored. Similarly, process and fugitive emission into the ambient
air may arise from a variety of sources related to oil shale processing
and a monitoring program for these emissions will also be required.
Thus, appropriate standards must be available to provide data quality
assurance for measurements made on oil shale effluents as well as
emissions into the atmosphere. More importantly, accurate measurement
methods must be in place to identify, quantify and certify individual
pollutants in a variety of complex matrices which will serve as
standards/SRM's for the oil shale industry.
Recommendations for further work at NBS in oil shale products is
summarized in Table 5-1. These recommendations reflect suggestions/input
obtained during conversations with scientists involved with the char-
acterization of oil shale products.
45
-------
Table 5-1
Recommendations for Further NBS Work
Produce a Raw Oil Shale SRM, certified for all trace elements
of potential environmental or product development concern
Develop methods needed to produce a Raw Oil Shale SRM, certified
for trace organic pollutants (with focus on criteria organic
pollutants)
Develop/modify methodologies necessary to certify al] trace
elements of potential environmental or product development
concern in: 1) Shale Oil; 2) Oil Shale retort water; 3) and/or
other associated aqueous phases
Extend the trace organic certification program on shale oil to
include more criteria pollutants (specifics to be determined
through negotiations with interested parties)
Assist responsible monitoring agencies in developing protocols
for "traceability" in oil shale (and associated products) mea-
surements
46
-------
APPENDIX A
Manuscripts Prepared for/Presented During Workshop
47
-------
PREPARATION OF STANDARD OIL-SHALE SAMPLES
OS-1, SS-1, and SS-2
Thomas Wildeman
Chemistry Department
Colorado School of Mines
Golden, Colorado 80401
Work performed tinder a grant from the Colorado Energy Research Institute
48
-------
This report provides background on the standard oil shale
samplef OS-1, and the two standard spent shale samples, SS-1 and
SS-2. It describes the geology of the site, the mining and re-
torting processes used, the manner of preparation of the samples,
possible sources of contamination, and suggestions on further
preparation of standard samples. References to more detailed
discussion are also included.
Site Description, Geology, and Chemistry
The shale samples came from the Dow mine of Colony Development
Co., so named because it was purchased from the Dow Chemical Co..
The Colony Development Oper.is a consortium of energy corporations
with fhe Oil Shale Corp. (TOSCO) and the Atlantic Richfield Co.
(ARCO) being the primary participants (1, 2). The location of the
Dow Property (shown in Figure 1) is at the head of Parachute Creek
in the Piceance Creek Basin, Colorado, 17 miles north of Grand
Valley, Colorado (1).
The actual mining operation is on two 30 foot vertical sections
called the Upper Bench and Lower Bench which start at 10 feet below
the Mahogany Marker and proceed down for 60 feet. This places the
samples in the Mahogany Zone of the Parachute Creek Member of the
Green River Formation as shown in figure 2 (3, 4). Oil-shale
reserve experts call this the Mahogany Zone of the Upper Oil-Shale
zone and consider it to be one of the richest oil zones in the
Piceance Creek Basin with yields ranging from 28 to 79 gallons/
ton (4). Assays conducted by TOSCO show the Upper Bench shale as
yielding 37-39 gal/ton and the Lower Bench shale 33 gal/ton.
Roehler (3) describes the depositional environment as saline
49
-------
MINE BENCH
MINE BENCH ROAfl
LOCATI9N OF DOW PROPERTY AND
AREAS OF MAJOR DEVELOPMENT WITHIN
THE PARACHUTE CREEK BASIN
Figure 1. Taken from Reference (1).
50
-------
Uoufc *llo» Dwk USBM-AEC Ohio OH Company SMI OH Campony Thurmw G«lly Oil Company
Sect 9,10 and B, Yiltow Creek CorehoM I Ryan* Crtek I Greeno I Govl I Corehote 2
T.2M.R.98W. See 13, T. I &, R. 99 « Sec. 34, T.IS..R.9BW See. 4, T 3 S., R.97 W. Set (ft, T.4S.R.97*. Sec 30,T.5S,R97W.
T.6S.R.MW.
WH.Bra4toy.l9?!!
(FORMERLY EVACUATE
OF GREEN RIVER FORMATION!
(uHoctom iand»toiie. «IH»lam. ihoU ond »l thai*
_ -"— -—-_ Sf.-=Solint locullnnt oi|
_OF OS-1
PARACHUTE CREEK MEMBER OF GREEN RIVER FORMATION
j--~fT7- --.-«t
Ewporltet, nohcoIKe, holite, etc., and oil ihole\\N>
\
-------
lacustrine (saltwater lake) in which organic muds were deposited
and saline waters enhanced the growth of planktonic algae. The
brines settled to deeper parts of the lake so that evaporite-
deposit minerals are not as prevalent in these shales.
Although there is no published drill core information on the
Dow Property, Union Oil Co. has released information on its property
which lies to the south and west of the Dow Property (5). The
drill core data published in Donnell's report (4) contain no in-
formation on this area. Perhaps the most significant study relating
to these samples is that by Desborough's group (6, 7) on a sample
from a drill core which lies on the Dow Property. The approximate
site of this hole labeled C-230 is shown in figure 1. Even though
the vertical variation in the Green River Formation can be con-
siderable, the proximity of this sample to the standard oil-shales
described here will make for interesting comparisons.
Table I lists the composition information on this sample. The
four samples Desborough (6) analyzed from the Mahogany Zone in
Colorado are chemically and mineralogically quite similar; however,
the range in oil yield was 48 to 71 gal/ton which is higher than
the 33-39 gal/ton range of the Dow mine. It appears that shales
with lower oil yields have greater concentrations of dolomite and
smaller concentrations of quartz and pyrite. Other data available
on this C-230 sample include the chemical composition of carbonate
grains, electron microprobe images, and information on arsenic
(6, 7).
Mining and Retorting Procedures
The mining and retorting processes to be used on the Dow Property
are considered to be the closest to immediate industrical scale-up and
52
-------
y&v
^ftp'SiN.
iJiV.' '->>&..
:«
*vfa ;|*"'^SCN «>^
"jN^fel'^.v -s JMJ
^;^y^-i% • - :KX-^
ffr^py^|"y^ / ^
.}r-m;.!' "?A • PI ilk ?' / 7 f
:!!%•• ^'ter^/4 X ••>• ./
• ^f^w- - •• !•»• ' ."'. '.CSi"t ' /T.'— -i^
:y;.«;^l^!-;:^-- - -^- _ ._^
h.".. {T ,>.».- Ky; ->- -jo, ;vyj-y a
V CMMHU 4 CMWMM NOUM • »MMM» • CM.VCMT
Figure 3. Colony
mining operation
in the Middle Fork
Canyon.
Figures taken from
Reference 8.
tt^S.
-------
FMX ME *HO
FUEL PRODUCTS
LOW SULFUR FUEL OIL
LK SPECIAL
BY PRODUCTS
COKE
AMMONIA • SULFUR
Figure 5. A schematic of Colony's mining and oil-shale
processing procedure taken from reference 8.
FLUE 6AS TO ATMOSPHERE
Figure 6. A flow diagram of the TOSCO II process taken from
reference 2.
54
-------
hence have been well studied and described. Figure 3 shows the layout
of the mining operation in the canyon of the Middle Fork of
Parachute Creek and figure 4 shows the function of the Upper and
Lower Benches in the mine (1, 8). If operating today, this would
be the largest room-and-pillar mine in the world.
The TOSCO II retorting process has also been described in
detail (1, 2, 9). Figure 5 schematically shows the whole process
and figure 6 is a flowsheet of the retorting operation. This
process has some unique characteristics that should be kept in
mind. First, it uses recycled hot solids (%" ceramic balls) as
a heating agent as opposed to internal combustion of gases with-
in the retort or external fuel-fired retorting. This allows
better control of the retort temperature and the TOSCO II process
probably keeps the temperature lower (482°C, 900°F) than other
retorting methods. Second, the feed stock is crushed to a smaller
size (-35n mesh/ including fines) than other processes which exclude
feed stock below 1/8" and crush to 3 in. pieces. Furthermore, the
pyrolysis drum crushes the shale still further so that the bulk of
the spent shale is less than 200 mesh; other processes, can end up
with clinkers. Finally, the oil recovery in. the TOSCO II process
appears to be better, typically 100% of Fischer Assay, than other
processes, about 80-90% of Fischer assay.
Preparation of Standard Samples
All the samples were mined from fresh faces in the Dow mine
in 1974, crushed to -% mesh and delivered in 100 ton lots to the
TOSCO research facility in Golden, Colorado. OS-1 was taken from
a residual pile of approximately 3 tons of -% mesh feed stock
which was mined from the Upper Bench and assayed at 37 gal/ton.
SS-2 is spent shale resulting from the retort operations at TOSCO's
55
-------
Denver pilot plant on Nov. 11, 1974 on the same feed stock from
which OS-1 was taken. SS-1 is spent shale resulting from retort
operations at the pilot plant on August 23, 1974 on feed stock
from the Lower Bench which assayed at 33 gal/ton. The amounts
collected were 31 Ib. of SS-1, 24 Ib. of SS-2, and 60 Ib. of OS-1.
The spent shale samples were wet with tap water and
so were air dried at room temperature for two weeks.
Ninety percent of the spent shale was -200 mesh njateria,!
the other 10% was partially retorted stock which was greater than
10 mesh. These pieces were hand ground in a porcelain mortar and
added to the sample. Approximately 5% of SS-1 and SS-2 will not
pass through a 100 mesh sieve. No other processing of the spent
shale samples was done prior to blending and splitting.
The raw shale required extensive crushing and grinding to
prepare it for blending and splitting. The objective here is to
grind to minus 65 mesh since the analysts at TOSCO have shown that
this will provide a more representative sample of the bulk feed
stock when 100 gm is used for Fischer assay (10), First, the half
inch feed stock was crushed in a hardened steel jaw mill to minus
4 mesh particles and then in a hardened steel roller mill to minus
10 mesh particles. Grinding was then attempted using a ceramic
ball mill but the shale particles are surprisingly hard and resinous
and the ceramic balls just bounced off the particles. Grinding
to minus 65 mesh would have taken at least one day for each charge,
so this method of grinding was abandoned. Instead a "shatterbox"
was used. This was quite effective, but the action of the grinding
rings generated some heat. Charges were ground for no more than
30 sec. so the loss of volatiles would be kept to a minimum. The
56
-------
BLENDING & SPLITTING OF OS-1
25. kg
5 MIXES
5 MIXES
C71
4 MIXES
BATCH 1
SPLIT 5
700 g
BATCH 2
SPLITS
9 & 10
75 g EACH
7- 100 g
FISCHER
ASSAY
SAMPLES
BATCH 1
SPLIT 12
700 g
BATCH 2
SPLITS
23 & 24
75 g EACH
7 • 100 g
FISCHER
ASSAY
SAMPLES
Figure 7. Splitting and blending scheme for OS-1.
-------
ground shale was sized by passing thrdugh a 70 mesh stainless steel
mechanical sieve. The full 60 Ib. of shale feed stock was pro-
cessed in this fashion. The crushing and grinding operations
also blended the bulk sample to some extent. All the crushers
and griners were cleaned and portions of shale were processed and
discarded before processing the sample.
For each of the three samples, blending and splitting were
performed simultaneously by taking each split and recombining and
mixing and then splitting again. This was done 5 times on the
first two splits and 4 times on the subsequent two splits. The
16 fractions resulting from the splitting were then blended by
hand on a polyethylene sheet and two 75 gm samples were taken from
each fraction. In the case of the raw shale, 7-100 gm Fischer
assay charges were also taken from each 1/16 fraction. What re-
mained of each sixteenth fraction was placed in a polyethylene
bottle and labeled Batch 1, split 1-16. The 75g samples were pack-
aged in glass bottles and labeled Batch 2, split 1-32. All bottles
were rinsed with 1-1 HNO^ and deionized water and dried before
use . The bottled samples have been stored in a sealed polyethylen*
container in a vault at a constant temperature of 10°C. Figure 7
is a diagram of the splitting scheme for OS-1.
Comments Concerning Contamination
The steel crushers , grinders and sieves used to process OS-1
can all be a source of contamination to various degrees. A U.S.
Geological Survey group, in a study of contamination by steel crushers
and grinders, found that Fe can be increased by as much as 1.5 %
Ni - 60 ppm, Mo - 20 ppm, V - 10 ppm, Cu - 30 ppm, and Mn - 1000 ppm
(11). The main source of contamination appeared to be disc-type
58
-------
metal grinders. Another study on the grinding and sieving of small
samples showed that contamination will most likely be inhomogeneous
and cause a widely abherrent result.in a trace element analysis (12).
Stainless steel sieves can contribute about 3 ppm Ni, 3 ppm Mn, and
20 ppm Fe to a sample. Flannagan, in the preparation of the U.S.G.S.
standard rocks (13), could detect no contamination from the use of
jaw crushers and rollers in those samples. The following is an
assessment of the level of contamination introduced during the prepa-
ration of OS-1.
First, all implements used were previously used for crushing
and grinding oil-shale and were cleaned with some of the sample
which was discarded so there is little possibility of cross contam-
ination from previous samples. Processing by the jaw crusher and
roller crusher may have added bits of steel in an inhomogeneous
fashion but this could be eliminated by passage of a magnet over the
powder. The shatterbox actually grinds the sample against itself
and when the steel rings are touching, the sound changed and the
grinder was stopped and a new charge added. Thus, contamination
will be much less severe than that by using steel plates. Con-
tamination could come from the stainless steel sieve. Comparing
the levels of contamination mentioned above with those abundances
listed in Table I, it is likely that grinding added up to 10% of
Ni and Mn to OS-1, up to 5% of Fe, Cu, and Mo, and up to 1% V to the
sample.
Homogeneity Tests
A simple test of the homogeneity of the standard samples has
been made using an x-ray fluorescence analysis method for Rb and Sr
devised by Doering (14). This method uses rock powder ground to
59
-------
minus 200 mesh packed in a small nylon planchet. The analysis has
been calibrated using standards in which the Rb and Sr contents have
been analyzed by isotope dilution and yields the Rb/Sr to +3% at the
95% confidence level and the abundances of Rb and Sr to +6% at the
67% confidence level.
Eight samples of about 10 g were randomly chosen from eight
different 75 g splits of each standard and were ground in Spex
Mixer/Mill using a tungsten carbide chamber to -200 mesh. The 24
samples were all analyzed on the same day to eliminate instrument
drift and bias in packing the charges in the planchets. The results
are summarized on Table II. The mean, range, standard deviation,
and relative standard deviation are used according to the definitions
prescribed in Analytical Chemistry, 46, p. 2258, 1974. The mass
absorption coefficients were determined by making a count of the
compton scattered photons at a 28 angle of 21 .
The range and trend in the values for the mass absorption
coefficient directly correlate with the Rb and Sr abundances.
Coarser material won't pack as densely into the planchet thus
yielding a lower mass absorption coefficient and also a lower value
for the abundance of Rb or Sr. Thus, the deviations in the results
appear to be caused by grinding and packing and not by true differences
in the abundances of the two trace elements in the different splits.
The conclusion is corroborated by the fact that the results for the
spent shales, which are much finer in grain size, exhibit better
precision. The conclusion is that the different splits of all three
standard samples are homogeneous to within +5%.
60
-------
Suggestions for Next Tine
Grinding the raw shale using the shatterbox is definitely
the best procedure unless a large supply of ceramic ball mills
are available. Grinding chambers for the shatterbox are also
available in tungsten carbide and alumina ceramic. The tungsten
carbide would add appreciable Co and a trace of Ti, but it is
quite expensive (12). The alumina adds appreciable Al, Co, Ga,
and Li and may take longer for grinding (12). Unless money is
no problem, contamination by grinding will have to be tolerated.
The contamination by sieving can be eliminated by testing
how long it takes to grind a uniform charge to less than 65 mesh
in the shatterbox and then grinding for that period of time.
Pulverizing the samples to a smaller grain size such as -200
mesh may release volatile organic fractions and inorganic species
such as Hg, AsH,, and I^Se. This possibility increases because of
the dusty character of oil-shale, because of the larger surface
area of the smaller grains, and because heating of the sample may
occur during the longer grinding periods. In any event, tests
should be performed on some scrap oil-shale to determine the
amount of dust producing and the amount of heating that occurs
upon grinding.
61
-------
REFERENCES
1. Kilburn, P.D., Atwood, M.T., and Broman, W.M., (1974), Oil
shale development in Colorado: Processing technology and
environmental impact. In: Guidebook to the Energy Resources
of Piceance Creek Basin Colorado, D.K. Murray ed., Rocky
Mountain Assoc. of Geol., Denver, Colo., pp. 151-164.
2. Hendrickson, I.A., (1974), Oil shale processing methods.
In: Proceedings of the Seventh Oil Shale Symposium, Quart.
of Colo. Sch. Mines, v. 69, no. 2, pp. 45-69.
3. Roehler, H.W., (1974), Depositional environments of rocks in
the Piceance Creek Basin, Colorado. In: Guidebook to the
Energy Resources of Piceance Creek Basin, Colorado, pp. 57-64.
4. Donnell, J.R., (1961), Tertiary geology and oil-shale resources
of the Piceance Creek Basin between the Colorado and White
Rivers Northwestern Colorado, U.S. Geol. Survey Bull. 1082-L,
pp. 835-891.
5. Stanfield, K.E., Rose, C.K., McAuley, W.S., and Tesch, W.J.,
(1957), Oil yields of sections of Green River Oil Shale in
Colorado 1952-54, U.S. Bur. Mines Rept. Inv. 5321, 132 pp.
6. Desborough, G.A., Pitman, J.K., and Hoffman, C., (1974),
Concentration and mineralogical residence of elements in rich
oil shales of the Green River Formation, Piceance Creek Basin,
Colorado and the Uinta Basin Utah - a preliminary report,
U.S. Geol. Survey open file rept. 74-77, 14 pp.
7. Desborough, G.A. and Pitman, J.K., (1974), Significance of
applied mineralogy to oil shale in the upper part of the
Parachute Member of the Green River Formation, Piceance Creek
Basin, Colorado. In: Guidebook to the Energy Resources of
Piceance Creek Basin, Colorado, pp. 81-89.
8. Marshall, P.W.r (1974), Colony development operation room-
and-pillar oil shale mining. In: Proceedings of the Seventh
Oil Shale Symposium, Quart. Colo. Schoool of Mines, v. 69,
no. 2, pp. 171-184.
9. Prien, C.H., (1974) Current oil shale technology: A summary.
In; Guidebook to the Energy Resources of Piceance Creek Basin,
Colorado, pp. 141-150.
10. Goodfellow, L., and Atwood, M.T. (1974), Fischer assay of oil
shale procedures of The oil Shale Corporation. In: Proceedings
of the Seventh Annual Oil Shale Symposium, Quart. Colo. Sch.
Mines, v. 69, no. 2, pp. 205-219.
11. Myers, A.T., and Burnett, P.R., (1953), Contamination of rock
samples during grinding as determined spectrographically.
Amer. Jour. Science, 251, pp. 814-830.
62
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12. Thompson/ G., and Bankston, D.C., (1970), Sample contamination
from grinding and sieving determined by emission spectrometry.
Appl. Spectroscopy, 24, pp. 210-219.
13. Flanagan, F.J., (1967), U.S. Geological Survey silicate rock
standards. Geochim. Cosmochim. Acta., 31, pp. 289-308.
14. Doering, W.P./ (1968), A rapid method for measuring the Rb/Sr
ratio in silicate rocks. U.S. Geol. Survey Prof. Paper 600C,
pp. C164-C168.
63
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TABLE I
Mineral and Chemical Composition of Oil-Shale from Core
C-230, Mahogany Zone (6)
Major
Elements
in Percent
Si0
MgO
CaO
K20
Na2O
P2°5
Total Sulfur
Ash
28
6.6
3.2
4 . 0
7.2
1.1
1.8
°'2
1.65
62.1
Trace Elements in ppm
Li
B
F
Sc
Ti
V
Cr
Mn
Co
Ni
Cu
70
100
1200
5
1200
200
30
224
12
30
70
Zn
Ga
As
Se
Sr
Y
Zr
Mo
Cd
Sb
Ba
La
Hg
Pb
80
10
30
1.
295
10
60
30
< .
3
300
45
2.
43
5
6
9
Oil Yield: 68.8 gal/ton
Minerals:
Raw Shale: Quartz, dolomite» albite, analcime, calcite »dawsonite
Shale Ashed: Quartz »dolomite, albite, (anhydrite)
@ 525°C
64
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Table II. Results of homogeneity tests for Rb and Sr on the
standard oil-shale and spent-shales.
OS-1
SS-1
SS-2
Number of Samples
Range for Sr (ppm)
Average for Sr (ppm)
Standard dev. for Sr (ppm)
Relative std. dev. for Sr (%)
Range for Rb (ppm)
Average for Rb (ppm)
Standard dev. for Rb (ppm)
Relative std. dev. for Rb (%)
Range for Rb/Sr
Average for Rb/Sr
Standard dev. for Rb/Sr
Relative std. dev. for Rb/Sr
Range for MA*
Average for MA
Standard dev. for MA
Relative std. dev. for MA
8
553-615
584
24
4.1
55.8-63.9
60.1
2.7
4.5
0.101-0.105
0.103
0.001
1.1
7.71-8.43
8.06
0.27
3.3
8
966-1051
1006
28
2.8
66.6-73.8
70.2
2.1
3.1
0.068-0.071
0.070
0.001
1.5
9.91-11.12
10.7
0.37
3.5
8
747-793
771
17
2.2
78.6-82.2
80.7
1.5
1.9
0.101-0.107
0.105
0.002
2.1
9.61-10.45
10.3
0.3
2.8
* MA is mass absorption coefficient in cm2/gm
65
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Discussion following Wildeman Presentation -
Question: What do you know about the composition of the flue gas?
Answer: Water, carbon dioxide, carbon monoxide, the ammonia and
H2S are stripped out. Very small amount of oxides of
nitrogen. Very little SCL due to absorption in the spent
shale. Some particulates from the grinding action of
the ball mill.
Question: Is there organic nitrogen in the shale oil?
Answer: The shale oil contains 1 to B% Nitrogen.
Question: What happens to the 1% sulfur in the shale and shale oil?
Answer: The sulfur in the oil comes out as HpS and would be re-
covered and sold as sulfur. The inorganic sulfur is found
mainly in the spent shale.
66
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MINOR ELEMENTS IN OIL SHALE AND OIL-SHALE PRODUCTS
by R. E. Poluson, J. W. Smith, N. B. Young, W. A. Robb, and T. J. Spedding
Laramie Energy Research Center, Energy Research and Development
Administration, Laramie, WY 82071
67
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MINOR ELEMENTS IN OIL SHALE AND OIL-SHALE PRODUCTS
by
R. E. Poulson, J. W. Smith, N. B. Young, W. A. Robb,
and T. J. Spedding
ABSTRACT
This paper presents order of magnitude analyses for minor elements in
several Green River Formation oil shales, shale oils and retort waters. The
oil shale analyses are found to be remarkably uniform throughout a wide region,
Crude shale oils and retort waters were found to have some large variations in
trace elements. The cause of the variations could not be determined from the
available data. The need for standard reference materials and methods, along
with cooperative testing for oil shale and its products was discussed.
68
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MINOR ELEMENTS IN OIL SHALE AND OIL-SHALE PRODUCTS
R. E. Poulson, J. W. Smith, N. B. Young
W. A. Robb, and T. J. Spedding1
INTRODUCTION
Accurate analyses of oil shale and its products are important in perfecting
control technology for a developing industry-and in anticipation of a need for
effluent regulation. Both organic and inorganic compounds are of concern, but
this paper is limited to only a part of that concern, ie. elemental analyses
without regard to particular chemical compounds.
Methods for accurate analysis are not available for all elements of pos-
sible concern in oil shale and oil-shale products. In the case of the total
oil-shale resource this does not seem a serious deficiency because an accurate
analysis of some particular oil shale would probably represent only that mate-
rial which was analyzed. It is possible that a few feet up or down in the
formation, different results would be obtained. Furthermore, it is the bio-
logical availability of the oil shale and the oil-shale product constituents
which seems more important environmentally than the exact elemental content.
Although accurate minor element analyses on any given oil shale or product
may be of small intrinsic importance, the ability to make accurate analyses has
an important role in revealing possible routes of biological availability of
oil-shale constituents. In a similar way, useful oil-shale processing informa-
tion may be obtained when routes for unwelcome intrusion of trace elements into
sensitive points in processing schemes (catalytic reactors, eg.) may be recog-
nized. One means toward this end is of course the material balance study which
l
All authors are with the Laramie Energy Research Center, ERDA, Laramie, WY.
69
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must begin with accurate oil-shale sampling and analysis and be completed with
comparably accurate product sampling and analysis.
The objective of this paper is to present a large body of data, primarily
for information, with emphasis on minor elemental contents of oil shale and oil-
shale products and to point out deficiencies in the data. We believe these
deficiences indicate the need for standard reference materials with certified
analyses for oil shale and oil-shale products, and the need for a cooperative-
laboratory analytical program based on those standard materials. The develop-
ment of techniques giving accurate results should then lead to means for eval-
uating transport of these minor elements in a processing plant or into an
ecosystem.
The data presented are termed survey analyses. By this is meant total
elemental analyses except for C, H, N, 0, In, and in some cases Re. The data by
and large are of order of magnitude precision only. Somewhat better precision
was expected with the techniques used, but the data nevertheless serve to show
comprehensively the range of elemental contents of oil shale in the Green River
Formation Mahogany zone, in a saline zone far below it, and of shale oils and
coproduced retort waters derived from Anvil Points, Colorado mine run shale.
Most previous work with Green River oil shale has been limited to selected
elements (J_, 2_, 3., k_, S)2- except for that of Cook (6) who presented a survey
analysis on a pyrolyzed oil shale. In the present work, survey analyses were
made using spark source mass spectrometry (_7_) for minor elements complemented by
various techniques which are more common for major elements and some minor
elements.
2
Underlined numbers in parentheses refer to references at the end of this
report.
70
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EXPERIMENTAL
Oil Shales
Two Green River Formation oil-shale zones were sampled for analysis, the
Mahogany zone in Colorado and Utah and a saline zone below the Mahogany zone in
Colorado. All shale samples were jaw-crushed to between 6" and I/A" then
reduced by core grinding to minus 8 mesh. Samples were reduced to minus 100
mesh in a hammermill and blended in a plastic V-mixer. The source of the 10
Mahogany zone cores is shown in table 1. A more detailed discussion is pre-
sented by Smith (2_). The saline zone samples were from an 821 foot section from
USBM-AEC" Colorado Corehole No. 3 in the Northern Piceance Creek Basin. Samples
were composited 10 foot intervals and were (in increasing order of depth) nos.
2, 16, 25, 32, 53, 63, 73, and 83 of reference (8). Sample no. 2 began at 1909
feet below Kelly bushing (elevation 6,397 feet).
Spark source mass spectrometry, neutron activation and X-ray fluorescence
analyses were done directly on raw oil-shale powder. The detectabi1ity limit
for elements in oil shales was taken as 0.1 ppm in the mass spectrometric meas-
urements. The X-ray fluorescence work used goniometric analysis (9_) • In ad-
dition, silicate concentrates were prepared from the Mahogany zone composites by
hydrochloric acid treatment, principally to remove carbonates, followed by 500°
C ashing prior to X-ray fluorescence analysis. Elemental detectabi1ities in X-
ray fluorescence as used are shown in table 2.
Shale Oils
Crude shale oils were obtained from retorts listed in table 3 using the
indicated oil shales. Oils with "F" suffix were filtered through Whatman k2
paper before analysis. Oils with "U" suffix were unfiltered crude shale oils
* Jointly funded by U.S. Bureau of Mines and U.S. Atomic Energy Commission.
71
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were pyrolyzed at ^50° C before analysis. Mass spectrometric detectabi1ity for
elements was 0.1 ppm in some runs and 0.01 ppm in others. Footnotes in the data
tables indicate which applies in various samples. For oils and waters auxilliary
analytical methods were used for major elements and certain minor elements.
These methods are listed in table k.
Retort Waters
Retort water was water formed with the oil and decanted from it. The
waters were all from the Laramie 10-ton simulated in situ retort. Shales and
particle sizes are listed in table 5- Each water was "deoiled" by filtering
through diatomaceous earth at 25° C. Subsequent separation of phases on standing
and cooling in storage presented an analytical problem. In such cases the
"deoiled" water was homogenized before sampling.
Water samples were evaporated to dryness and for mass spectrometry were
ashed at 450° C. The radioactivity measurements were made directly on the
residue from drying. A pure uranium standard was used. Uncertainties were
±50 percent because of the occurrence of uranium progeny to an undetermined
extent.
RESULTS AND DISCUSSION
As mentioned earlier, an accuracy of a factor of three was expected for
mass spectrometric analyses based on results with other materials. It will be
seen that order of magnitude is closer to the case for the work at hand. In the
discussion of the results for oil shale and oil-shale products, there are not
enough data to pinpoint sources of errors. It cannot be determined whether the
principal analytical problems are instrumental, sample handling or sample
preparation. The data will be discussed showing inconsistencies, consisten-
cies and such conclusions as seen warranted by order of magnitude analyses.
72
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ON Shales
Results for Mahogany zone oil-shale samples are shown in table 6. Samples
4A and 5A were prepared as samples identical to A and 5 submitted for analysis.
If the results for duplicates k and AA and 5 and 5A are considered, and a factor
of ten allowed for analytical precision on such a survey type analysis, many re-
sults are still outside that boundary. This illustrates the need to determine
whether the problem is in sampling or analysis and to develop appropriate methods
and materials for standardization.
Results from neutron activation analysis agree qualitatively with the mass
spectrometric data. However, the mercury analyses of oil shale by neutron ac-
tivation analysis, appear not very precise as seen for duplicate analyses on
samples 6 and 10.
Except for lead, x-ray fluorescence analysis for raw shale powder in table
7 and silicate concentrates in table 8 agree qualitatively with the spark source
mass spectrometry (table 6). Limits of detection by this technique were in many
cases well above those of mass spectrometry. Advances in x-ray fluorescence
techniques have resulted in improved sensitivities for most elements but no
results are currently available.
Alkali metal analyses by flame photometry for both HCl-soluble and insoluble
fractions of the Mahogany-zone samples are shown in table 9- These results
agree qualitatively with the survey results of table 6 for the major element
sodium and for potassium except for sample 5- Results for the minor element
lithium agree qualitatively with those of mass spectrometry and seem to be
closer to the values for the 4A and 5A samples than to values for 4 and 5-
These data confirm nevertheless the concept that the Mahogany-zone oil
shales of table 6 are remarkably uniform in their minor element content over a
wide region of the Green River Formation. Variations are no more between dif-
ferent cores than between duplicate samples.
73
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The oil shales in table 10 represent a vertical array in the saline-zone
below the Mahogany-zone, covering an interval of over 800 feet. Here also we
see little variation in trace elemental concentrations compared to probable
analytical uncertainties. Indeed, within those limits the results agree with
those for the Mahogany-zone samples.
The analyses of Desborough, Pitman, and Huffman (S) for 33 elements in
Mahogany zone and R-k zone oil shales agree in order of magnitude with results
here from the Mahogany and saline zones. The early work of Stanfield, et al (J_)
stated little variation was observed in 18 minor elements with oil-shale grade
(organic content) for six samples from various ledges near the Mahogany marker
in the vicinity of Rifle, Colorado. The results of Smith and Stanfield (k) for
12 minor elements in Uinta Basin Utah oil shales are also consistent with the
data on Colorado oil shale. The net observation from all this work is the
remarkable uniformity in minor elemental composition in Green River Formation
oil shales. This is consistent with the theory of Smith concerning the geochem-
ical genesis of Colorado's Green River Formation (10).
Crude Shale Oils
Table 11 shows survey analyses for crude shale oils from four different
retort systems shown in table 3. These oils were subjected to low temperature
pyrolysis before analysis in contrast to the oil shales which were run directly.
Ancillary standard methods were used for certain elements as shown in table 4.
The three oils reported in six columns to the right of table 11 were analyzed
with and without filtration. There appears to be no systematic variation of
results with filtrations so that it was assumed the differences observed were a
result of the sampling and analysis scheme. Here as with the oil shales a
factor of ten is required to reconcile most of the analyses for the low level
constituents in the filtered and unfiltered samples.
74
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In contrast to the monotonous similarity of oil shales mentioned by Smith
0_0), shale oils and retort waters have shown some real differences in trace
elemental composition. To the far left of table 11 results for two oils, 10T-
29U and 10T-31U, from the same retort are shown. Operating parameters were
different, but it has not been possible to correlate elemental analysis with
the parameters of various runs (11). There appear to be unequivocal differ-
ences in trace element contents of these oils, however. The analysis in table
11 shows a 12:0.01 ratio in uranium contents for 10T-31U oil relative to 10T-
29U oil. This difference has been confirmed qualitatively by alpha spec-
trometry. The corresponding retort waters also show elevated uranium contents
as will be discussed in the next section.
Another real difference in the oils is the arsenic content. The analysis
of the Rock Springs, Wyoming in situ oil shows 0.5 ppm and is the lowest of the
five oils analyzed. If we add to this comparison the results of Burger et al
(j_2_) showing AO ppm for a shale oil produced by a proprietary process we see the
possibility of nearly one-hundredfold range of arsenic levels in a variety of
oils. We will discuss some of the possible causes for trace elemental differ-
ences in oil-shale products after we have discussed the retort water data.
Retort Waiterj_
Table 12 shows survey analyses for retort waters produced in the Laramie
10-ton retort from retorting of shale particle size ranges shown in table 5- No
correlation of water properties with retorting parameters was detected (11).
Several standard water quality parameters were run by separate laboratories.
Parenthetical results in table 12 illustrate anything from fair agreement to
gross disagreement in values reported. Here again it is not known whether the
problem is sampling or analysis.
75
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The water 10T-31 shows a 4.6:0.023 ratio of uranium content relative to
10T-29 which tends to confirm the similar results with these two oils. The
uranium content of the waters was also confirmed with alpha spectrometry. Other
waters (produced from this system) have since been found showing radioactivity
up to 200 ppm uranium. A major elevation in tin level appears for the 10T-30
water. Most other differences in trace elements appear reconcilable by the
uncertainties of the survey analyses.
In summary for retort waters as with the crude shale oils differences are
definitely detectable among products even of nominally very similar sources.
Source of Variations of Trace Elements in
Crude Shale Oils and Retort Waters
The existing data for Green River Formation oil shales indicates a wide-
spread uniformity in minor elemental composition. It is surprising that there
would be thousandfold differences in trace elemental compositions of oils and
waters produced under apparently similar conditions. There are at least three
factors in oil-shale retorting which might lead products to differ. The data to
date cannot confirm or deny any of these however. First, the minor element
composition of the oil shale used may be different in spite of the evidence at
hand. Secondly, the retorting processes involved may be different in ways not
yet understood. Finally the products themselves may be subject to special
external influences after retorting, as for example the incursion of groundwater
into an in situ process after the pressure developed in retorting has subsided.
The applicability of these factors to the observed uranium and arsenic variations
in the products will be considered now.
The occurrence of enhanced uranium content in the 10T-31 products over
the 10T-29 products might have been ascribed to particle size either as an
effect on retorting or as a separative effect of crushing with uranium being
76
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enhanced in the 0-1" fraction. This does not appear to be so because a sub-
sequent run with 3"-6" shale from the same source also showed enhanced uranium
content in the products yielding over 200 ppm uranium in the water as deter-
mined by alpha spectrometry. More detailed measurements on a well defined
system are required to pin down the causes of the variations.
There is an interesting possibility as to the cause of variations in
arsenic levels in the various oils. The oil with the lowest value is the Rock
Springs, Wyoming Site k in situ produced oil which was liberally washed with
alkaline groundwater. The proprietary oil mentioned above had the highest
arsenic level and was produced in the driest way of any. Using the average of
the "U" and "F" values, the other oils in table 11 were intermediate in ar-
senic levels and in water contact with the 10-ton and 150-ton simulated in
situ processes being much wetter than the gas combustion process. Alkaline
washing is the basis for some processes for arsenic removal from shale oil
(12) and this may be the explanation for this observation. At present an
equally valid explanation would be shale source because the in situ oil was
from the Green River Basin (Wyoming) of the Green River Formation. Again
a more detailed study is necessary to pinpoint variables.
Suggestions for Further Work
The variability of the oil-shale product trace elemental composition is
intriguing with respect to environmental control technology, and raises sig-
nificant questions. To answer such questions, retorting experiments with mate-
rial balance assays of the elements of concern will be needed. To help such
studies, the analytical methodology for minor elements in oil shale and oil-
shale products needs to be improved based on the results we have presented here.
A program such as the National Bureau of Standards Standard Reference
Materials (SRM) work seems well suited in helping to develop methodology for
77
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attainment of accurate results for oil shale and oil-shale product minor elements.
If one looks to the SRM program, reference materials for trace elements in oils
and water do exist. These could be useful, with some alteration, in analyses
of shale oil and retort water and spent shale if the certification list were
extended to include more elements of environmental concern* None of the
existing water standards are alkaline, or have organic contents of up to 2%
that are characteristic of oil-shale retort waters, or up to 10% occuring in
some oil-shale formation waters (11). There is, however, no standard com-
parable to raw oil shale with respect to its intimate mix of organic and
refractory inorganic material. For these reasons it is suggested that work on
an SRM for oil-shale liquid products could be an extension of existing stand-
ards but for oil shale a new standard would need to be prepared and certified.
The certification of existing standards for oil, water, and ash along with
a new standard for raw oil shale should aim at certification of all elements of
potential environmental or product developmental concern. It would be useful,
for example, to have an oil certified for antimony, arsenic, beryllium, boron,
cadmium, chromium, cobalt, copper, fluorine, gallium, iron, lead, lithium,
manganese, mercury, molybdenum, n-ickel, selenium, tin, uranium, (with progeny),
vanadium, and zinc. Not all of these elements have been reported in shale oils,
but traces may occur in oil shales so methods should be available for screening
products until the fate of these elements is well understood.
As an adjunct to the preparation of standard reference materials, a coopera-
tive laboratory test program would probably do much to show up problems in
application of methodology. In addition to the analysis itself, guidelines in
sampling of oil shale and its products will need to be developed before any
analytical technology can be applied to a real process. This will require a
determination of the degree of heterogenity which might exist with respect to
78
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minor elements in oil shale, spent shale, shale oil and associated aqueous
phases.
Work in progress at the Laramie Energy Research Center will soon be published
on analyses of leach waters from raw and spent shales from the Laramie 10-ton
retort runs reported in this paper along with results from other runs. A pro-
gram on analysis of selected trace elements in runs from the Laramie Controlled-
State Retort (13) is being undertaken. The charge to this retort has been
riffled at 1/8 to 1/2 in particle size and might be more homogenous than the 10-
ton retorting charges.
SUMMARY
Order of magnitude minor elemental analyses for several Green River Formation
oil shales, shale oils, and retort waters were presented. The oil-shale analyses
showed a remarkable uniformity between Colorado Piceance Creek Basin Mahogany
zone and saline zone oil shales. Comparison with earlier data of other workers
extends this uniformity to rich and lean Mahogany zone oil shales, to the Mahogany
and R-A zones of the Piceance Creek (Colorado) and Uinta (Utah) Basins.
Crude shale oils and retort waters were shown to have variations in trace
elements of up to 10 even in products from very similar retorting runs. The
cause of such variations could not be determined from the data. Possible
important variables, postulated but not yet evaluated, are heterogeneity in the
oil shale, subtle differences in retorting processes, or special external in-
fluences, on the products after retorting.
Survey type analysis were shown to be larger than expected, but the survey
analysis with only order of magnitude precision was shown useful in delin-
eating potential problems. The expected gain from more precise analyses was
shown to be with respect to differentiating the causes of product variability
in oil-shale retorting.
79
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Suggestions for further work were for the generation of an oil-shale
standard reference material through the National Bureau of Standards or other
program with certification for a list of many elements of potential environmental
and processing concern. It was also recommended that existing SRM's for oil,
water and ash should be extended in certification for a larger list of elements.
A cooperative interlaboratory analysis program was suggested. The need for
development guidelines on sampling of oil shale and products was pointed out.
80
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REFERENCES
1. Stanfield, K. E., I. C. Frost, W. S. McAuley, and H. N. Smith. Properties
of Colorado Oil Shale. BuMines Rl 4825, 1951, 12 pp.
2. Smith, J. W., and L. W. Higby. Preparation of Organic Concentrate from
Green River Oil Shale. Anal. Chem., v. 32, I960, pp. 1718.
3. Smith, J. W. Ultimate Composition of Organic Material in Green River Oil
Shale. BuMines Rl 5725, 16 pp.
4. Smith, J. W. and K. E. Stanfield. Oil Yields and Properties of Green
River Oil Shales in Uinta Basin, Utah. Intermountain Assoc. Petrol.
Geol. Ann. Field Conference (Guidebook), v. 13, 1964, pp. 212-221.
5. Desborough, G. A., J. K. Pitman, and Claude Huffman, Jr. Concentration
and Mineralogical Residence of Elements in Rich Oil Shales of the Green
River Formation, Piceance Creek Basin, Colorado, and the Uinta Basin,
Utah.--A Preliminary Report. U.S. Dept. Interior, Geol. Survey, open-file
report 74-77, 1974, 14 pp.
6. Cook, E. W. Elemental Abundance in Green River Oil Shale. Chem. Geol.
v. 11, 1973, Pp. 321-324.
7. Brown, R., M. L. Jacobs, and H. E. Taylor. A Survey of the Most Recent
Applications of Spark Source Mass Spectrometry. American Lab., November
1972.
81
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8. Smith, J. W. , and N. B. Young. Determination of Dawsonite and Nahcolite
in Green River Formation Oil Shales. BuMines Rl 7286, 1969, 20 pp..
9. Campbell, J. C., and J. W. Thatcher. Fluorescent X-ray Spectrography:
Determination of Trace Elements. BuMines Rl 5966, 1962.
10. Smith, J. W. Geochemistry of Oil-Shale Genesis in Colorado's Piceance
Creek Basin. Rocky Mountain Assoc. of Geologists, D. K. Murray ed.,
197**, PP- 71-79.
11. Jackson, L. P., R. E. Poulson, T. J. Spedding, T. G. Phillips, and H. B.
Jensen. Characteristics and Possible Roles of Various Waters Significant
to In Situ Oil-Shale Processing. Environmental Oil-Shale Symposium Pro-
ceedings, Quart. Colo. School Mines, v. 70, No. k, 1975, PP- 105-134.
12. Burger, E. D., D. J. Curtin, G. A. Myers, and D. K. Wunderlich. Prerefining
of Shale Oil. Preprints, Div. Petrol. Chem., ACS, v. 20, No. k, 1975,
pp. 765-775-
13. Duvall, J. J., and H. B. Jensen. Simulated In Situ Retorting of Oil Shale
in a Controlled-State Retort. Proceedings of the Eighth Oil-Shale Sym-
posium, Quart. Colo. School Mines, v. 70, No. 3, 1975, pp. 187-205.
82
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TABLE
Description of cores and their selected sections
oo
00
Sample
!
2
3
4
5
6
7
8
9
10
Core
Selected section
Location
Source
Tell ErtI
Weber Oil Co.
Union Oi 1 Co.
U.S. Bureau of Mines
Pacific Oil Co.
U.S. Bureau of Mines
Pacific Oil Co.
Pacific Oi 1 Co.
Continental Oil Co.
Shell Oil Co.
Name of wel 1
Phil
Marcedus No. 2
Betty
Naval Hole E
Wheeler No. 1
D-5
Dragert No. 1
Hard! son No. 1
Corehole No. 2
Corehole No. 2
State
Colo.
Colo.
Colo.
Colo.
Colo.
Colo.
Colo.
Colo.
Colo.
Utah
County
Rio Blanco
Rio Blanco
Garf ield
Garf ield
Garf ield
Garf ield
Garf ield
Garf ield
Garf ield
Uintah
Sec.
25
30
21
2
12
12
5
2
3&4
17
T.
1 S.
3 S.
if S.
5 S.
5 S.
6 S.
6 S.
7 S.
7 S.
11 S.
R.
100 W.
98 w.
95 W.
95 W.
98 w.
95 W.
96 w.
98 w.
99 W.
2k E.
No. of
samples
84
56
169
9*t
105
84
136
68
41
56
Length1
ft.
85.5
170
201
155
111
84
Ut3
68
71.8
56
Reference to
marker, ft.2
27
85
76
54
35
22
53
17
35
24
.5 to -58
to -85
to -125
to -101
.4 to -75.1
to -62
to -90
to -51
to -36.8
to -32
1 Maximum continuous length of core averaging 25 gallons of oil per ton.
2 Positive values indicate top of section above the Mahogany marker, negative values
below the marker.
indicate bottom of section
-------
TABLE 2. - Limits of detectabi1ity for various elements in raw
oil-shale powder and in silicate concentrates using
x-ray fluorescence
Element
Uranium
Lead
Thai 1 ium
Gold
Lanthanum
Barium
Cesium
Iodine
Si Iver
Molybdenum
Method1
A
A
A
A
B
B
B
B
A
A
Detect
limit,
1-3
21
21
22
31
17
97
165
10
k
ion
ppm Element
Stront ium
Rub id ium
Arsenic
Gal 1 ium
Zinc
Nickel
Cobalt
Manganese
Chromium
Vanadium
Method1
A
A
A
A
A
A
A
B
B
B
Detect ion
1 imi t , ppm
k
k
5
6
3
3
8
k
3
k
Silicate Concentrate
Zi rconium
Ti tan ium
Calci urn
A
B
B
k
8
23
A - L5F crystal analyzer, air path, scintillation counter with
pulse height analyzer.
B - LiF crystal analyzer, helium path, gas-flow proportional counter
with pulse height analyzer. All elements determined with Ka line
except I, Cs, Ba, La, Tl, Pb, U with La line and Au with L0 line.
-------
TABLE 3. - Sources of crude shale oils
Symbol
10T-29
10T-31
150T-U1
150T-F2
IS-U1'3
,S_F2,3
GC-U1
GC-F2
Oil shale
LERC
LERC
LERC
LERC
Rock
Rock
Gas
Gas
simulated
s imulated
simulated
simulated
Springs S
Springs S
combust ion
combustion
i
i
4
4
in
in
i n
in
te
te
retort
si
si
si
si
k
k
tu
tu
tu
tu
in
in
1
1
1
1
s
s
0-ton
0-ton
50-ton
50- ton
itu
itu
Oi
Colo.
Colo.
Colo.
Colo.
Wyo. ,
Wyo. ,
Colo.
Colo.
1 shal
0-1"
1-3"
mine
mine
e
run
run
fractured
fractured
0.25"
0.25"
-3"
-3"
Unfiltered oil.
2 Oil filtered through Whatman k2 paper.
3 Oil contained 28% bound water not removable by decantation.
4 USBM gas combustion retort operated by Colorado School of Mines
Research Foundation.
85
-------
TABLE 4. - Analytical methods used in conjunction with spark source
mass spectrometry for oils and water
Element Method
Calcium, Magnesium Atomic absorption (AA)
Sodium, Potassium Flame photometry
Boron Colorimetric (Curcumin or Carmine)
Chloride Titration (Silver or Mercury)
Fluoride Specific ion electrode or SPADNS reagent
Sulfur Gravimetric
Mercury Flameless AA (Hatch-Ott) for waters,
Flameless atomic fluorescence from gold
amalgam for oi1s
Uranium Alpha spectrometry of natural activity,
using a silicon surface barrier detector
and 1024 channel pulse height analyzer.
Results were ±50% with a detectabi1ity of
1 ppm.
"*•Disti11 at ion to remove organics before this test.
86
-------
TABLE 5. - Sources of oil-shale retort waters1
Symbol
10T-28
10T-29
10T-30
10T-31
Oil-shale retort
LERC
LERC
LERC
LERC
simulated
s imulated
simulated
simulated
in
in
in
in
si
si
si
si
tu
tu
tu
tu
10- ton
10-ton
10- ton
10- ton
Oil shale
Colo.
Colo.
Colo.
Colo.
0-20"
0-1"
0-20"
1-3"
Each water was "deoiled" by filtering through diatomaceous
earth.
87
-------
TABLE 6. - ELEMENTAL ANALYSES OF MAHOGANY-ZONE OIL-SHALE COMPOSITE SAMPLES1 USING
SPARK SOURCE MASS SPCCTBOMCTR* OF RAW SHALE POWDER
PPH IN COMPOSITE2
SAMPLE
ELEMENT
Uranium
Thorium
Bismuth
Lead9
Thallium.
Mercury1*
Gold
Platinum
Irlditw
Osmium
Rhenium5
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thul 1 ium
Crblum
Holmlum
Oyspros 1 urn
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodynium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium5
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium ( ) »
Arsenic9 ( ) »
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus ( J1*
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen*
Nltrocen'
Carbon"
Boron
Beryllium
Lithium
1
3.7
1.2
]*>
190
780
84
•2600
3-4
>1X
91
•2600
1300(800)
MX
>l»
>0.5X
• 1200
42
2.4
9-2
2
2.4
1.3
O.IO
t.o
?:P
0.03
0.38
1.4
<0.08
0.32
0.11
0.54
0.20
2.6
0.24
18
0.69
3.3
42
19
81
40
73»
0.07
1.0
<0.38
0.20
1.5
0.05
0.04
IS
5.6
29
27
730
82
0.35
•« »
2.6
11
9.8
29
220
8.0
160
350
90
•1300
16
>U
>0.5X
98
-4900
650
>l*
-4300
• 1300
45
0.90
13
3
1.6
1.2
U
340
970
180
•2600
6.9
>1X
X).SX
250
•2600
610
>)%
>u
,'-,000
• 1200
42
2.4
10
1 Sar-i>tcs of about 25 93) Ion per ton oil shale were
2 Elements not reported were below dctcctabi 1 1 ty of
4 4A
3.3 S.2
1.9 12
<0.10 3.5
2.3 14
0.03 2.1
1.5 0.87
1.3 1.8
<0.06 0.38
0.30 1.6
<0.07 0.10
1.0 0.28
0.16 0.33
2.1 3-9
0.2 0.87
1.9 0.43
0.56 2.0
0.93 5.6
23 24
16 20
66 80
22 25
700 720
0.06 5.7
2.0 29
<0.3I
0.34 3.0
1.2 3-5
0.02 1.4
<0.02 1.7
12 37
4.6 14
12 60
22 18
400 '2700
67 • no
0.29 14
1.3 (2.5) 2.0
86 (22) 51
0.91 1-9
9.0 11
8.0 60
42 120
330 280
8.6 11
>1X >H
190 320
680 370
73 100
•2000 .1500
6.0 2.7
>U >1X
>IX >lt
140 76
• 1800 >U
530(800) 4200
>IX >1X
>ll >U
•3500 >U
.1000 «4400
73 230
2.1 0.60
3.8 160'
composited at -8 mesh,
0. 1 ppm. Al 1 elements
5
5.9
2.0
<0.10
4.4
r.4
<0.04
' 1.3
<0. 1 1
1-3
0.13
1.4
0.29
2.7
0.36
3.8
1.0
9.0
77
13-
210
17
610
0.10
0.13
<0.56
0.54
4.6
0.16
<0.04
10
3.9
22
40
720
120
1.2
5.2
28
2.9
16
14
77
600
>1X
390
770
130
•4100
16
>1X
2.7
220
• 1900
960
>'t
>«
•4400
•3700
110
3.8
1.9
5A
7-0
12
1.7
70
0.40
..6
1.1
1.9
1.8
0.21
1.6
0.10
0.28
0.33
3-4
0.87
0.43
1.2
3-3
24
9-3
80
25
750
8.5
1.3
5.2
2.0
1.4
0.80
37
14
60
18
•2700
110
28
3.5
23
1.4
11
120
44
150
11
>1X
180
190
100
•3100
2.7
>1X
>1X
60
2100
>1X
>lt
>0.5X
•2100
120
0.26
160
6
5.9
3.4
1X
300
=.1000
130
• 1900
II
>1X
>IX
260
•4100
540
>IX
>u
>0.5*
•3100
66
1.8
11
1.6
16
14
43
600
12
>U
380
770
280
•4100
5.4
>1X
>IX
260
960(530)
>l%
>u
-6400
• 1900
66
5.3
6.8
8
3.7
1.2
<0.10
1. 11
<0.67
..6
<0.03
1.4
1.4
0.07
0.80
0.10
0.51
0.27
1.9
0.23
2.1
0.64
S.I
26
8.3
75
25
680
0.15
0.22
<0.35
0.39
2.9
0.10
0.04
14
5.2
27
25
910
150
0.76
3.3
18
1.0
10
21
27
760
9.9
>!%
220
280
84
1200
69
>1X
>IX
160
1200
170
>IX
>it
'>0.5*
120
42
2.4
6.6
9
3-7
1.2
<0.10
6.2
<0.67
0.93
<0.03
0.84
1.4
0.10
0.80
0.12
0.89
0.18
2.4
0.23
2.1
0.64
3-0
26-
8.4
75
25
680
0.15
0.22
<0.35
0.27
1.4
0.10
0.04
14
5.2
14
11
460
ISO
0.57
3-3
52
1. 1
10
21
48
130
7.4
>IX
200
280
84
s2600
3-4
>IX
>!*
250
•2300
170
>l t
>1X
»o.5»
•2400
84
1.1
18
10
3.7
2.9
<0.10
2.7
<0.67
0.31. 0.70
0.09
3.4
1.1
<0.07
0.80
0.12
0.51
0.37
2.4
0.49
4.6
0.96
4.6
56
18
75
42
680
0.15
450
<0.35
0.18
2.9
0.10
0.18
14
5.2
27
38
910
450
3.3
2-9 (2.C
18 (21)
2.1
4.4
32
41
210
>1X
240
280
84
• 1200
6.9
>H
>U
340
• 1800
340 (460)
>lt
>u
>0.5i
• 1200
84
5.6
24
ground to -100 mesh and thoroughly blended. 4A and 5A duplicate 4 and 5.
standardized using National Bureau of Standards. Standard Reference Material
1632, a coat, where applicable.
J Standarlzed using N8S-SRM 1633. a coal fly ash.
* Neutron activation analysis.
5 Internal standard.
6 Not determined.
-------
TABLE 7. - Elemental analysis of Mahogany-zone oil-shale composite
samples using x-ray fluorescence of raw shale powder
ppm of compos i te
Sample
Element
Lead
Barium
Zi rconium1
Strontium
Rub id ium
Zinc
Nickel
Manganese
Chromium
Vanad ium
Ti tanium1
Calcium2
Boron
1
120
320
780
63
39
130
420
300
78
53
1 Not detectable
2 Major element,
2
130
300
850
59
38
86
430
200
73
58
i n
not
3
130
300
740
65
4o
90
430
200
78
66
raw oi 1
determ
4
130
310
740
67
41
120
440
310
84
76
5
120
330
790
64
39
98
420
230
84
68
6
110
300
730
66
38
130
420
330
78
67
shale under
ined.
7
110
300
790
65
38
97
410
230
78
66
cond i t
8
97
310
790
62
35
93
400
230
78
66
ions
9
130
300
790
64
^
68
390
140
78
110
used .
10
100
300
760
60
35
70
420
170
78
136
Average
118
307
776
64
38
98
418
234
79
77
89
-------
TABLE 8. - Elemental analysis of Mahogany-zone oil-shale composite samples
using x-ray fluorescence of oil-shale silicate concentrates
ppm of composite
Sampl e
Element
Lead
Bar ium
Zi rcon ium
Stront ium
Ru b i d i urn
Zinc
Nickel
Manganese
Chromium
Vanad ium
Ti tanium
Calcium
Boron
1
68
140
39
32
55
6
11
9
20
66
1300
480
38
2
83
120
37
30
59
6
10
7
15
62
1300
420
30
3
88
120
41
33
64
6
10
6
13
59
1400
440
37
4
91
130
37
30
64
6
11
6
14
59
1400
380
52
5
83
120
38
27
62
7
11
8
12
58
1400
410
54
6
82
90
41
20
58
6
10
8
16
60
1300
280
52
7
87
100
37
30
64
6
11
6
13
54
1300
380
47
8
72
110
39
19
48
6
10
8
17
68
1300
290
49
9
81
110
33
22
41
5
9
12
18
69
1200
340
77
10
86
100
33
18
41
5
9
14
18
76
1200
380
97
Average
82
114
38
26
56
6
10
8
15
63
1300
380
53
90
-------
TABLE 9. - HCl soluble and insoluble sodium, potassium, and lithium by flame photometry
in Mahogany-zone composite cores of Green River oil shale
Compos 5 te
1
2
3
4
5
6
7
8
9
10
Soluble
8270
7070
4800
5180
4800
5150
4510
5640
6140
2530
Sodium, ppm
Insoluble
3640
4320
7650
4630
3700
3480
3030
2020
2430
4930
Potassium, ppm
Total
11910
11390
12450
9810
8500
8630
7540
7660
8570
7460
Soluble
826
688
664
731
574
1060
635
1080
1770
2120
1 nsoluble
11960
11510
12230
12320
13810
10980
12030
9820
13730
13680
Total
12786
12198
12894
13051
14384
12040
12665
10900
15500
15800
Solubl
18
17
25
20
16
59
25
58
78
69
Lithium, ppm
e Insoluble
21
23
18
20
20
21
18
21
10
11
Total
39
40
43
40
36
80
43
79
88
80
-------
TABLE 10. - ELEMENTAL ANALYSES Of COLORADO COREHOLE NO. 3.SALINE-ZONE OIL-SHALE COMPOSITE
SAMPLES'US INC SPARK SOURCE MASS SPECTROMETRV OF RAW SHALE POUOER
ELEMENT
Uranium
Thorium
Bismuth
Lead!
Thallium
Mercury*
Gold
Platinum
Irldlum
Osmium
Rhenium'
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulllum
Erbium
Holmlum
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium*
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic'
Germanium
Gallium
Zinc
Copper
NlcSel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen"
Nitrogen*
Carbon"
Boron
Beryllium
Lithium
5.7
13
6.1
57
1.4
2.9
1.5
2.5
0.41
1.3
0.07
0.23
0.44
3.1
I.I
i!s
5.1
29
16
65
20
680
9.2
1.6
II
1.6
0.54
0.28
JO
20
49
14
610
92
23
1.6
25
1.5
18
49
63
80
17
>n
JIO
IJO
82
•1200
4.4
>1X
230
XJ.5X
*IX
MX
MX
840
51 -
0.98
47
2.3
6.9
0.40
I.I
0.87
1.8
0.21
1.2
0.09
0.21
0.16
1.8
0.43
0.4J
1.0
3.3
18
4.7
40
25
750
5.7
0.06
1.4
2.0
0.67
0.40
17
12
60
18
750
57
6.0
0.78
13
0.80
II
60
33
55
4.6
>1X
180
87
100
•1200
2-7
>0.5X
600
•4800
•4200
>IX
>tx
>IX
•1000
58
1.0
29
0.30
1.6
0.52
1.4
O.I 2
0.32
0.43
0.55
0.15
O.49
0.03
0.08
0.05
O.27
0.13
0.06
<0.18
0.50
2.4
0.60
4.0
I.I
61
0.43
<0.20
0.21
0.35
0.10
0:13
8.7
1.4
3.0
1.8
59
11
60
0.90
2.6
\.\
12
22
83
1.1
830
9.0
43
10
150
>0.5X
800
4*80
510
>IX
>0.5X
>0.5X
3*60
12
<0.18
5.7
2.6
3.2
1.5
7.0
0.30
0.46
0.87
0.55
<0.15
<0.49
0.03
0.10
0.07
0.90
0.19
0.21
0.26
1.7
12
4.7
20
' 9.2
130
13"
1.4
0.93
0.12
0.17
8.7
3.2
15
6.6
270
31
6.0
1.4
13
0.37
5.0
26
22
28
4.6
•3500
34
65
50
730
0.12
•1600
280
•4800
•2400
MX
MX
>)•
>IX
360
2J
0.26 -
29
7.8
7.6
16*
0.19
2.4
4.8
0.77
0.17
0.68
0.03
0.13
0.36
2.0
0.96
0.47
1.3 •
3.7
20
10
53
24
330
2.7
2.5
3.3
2.2
0.37
0.45
41
7.1
56
8.4
830
1.7
2.2
20
0.89
13
20
49
110
0.78
200
210
no
•1600
1-3
•3800
160
>0-5X
MX
>|V
MX
•1200
65
0.67
32
7.0
16
3.5
70
0.40
I.I
0.87
0.79
0.19
0.70
0.08
0.28
0.33
1.8
0.43
0.43
1.2
3.3
20
9-3
80
37
300
5.7
0.67
0.11
3.5
2.0
0.25
0.40
87
60
29
480
85
6.0
2.0
23
I.I
11
60
78
98
21
*IX
320
190
100
• 1500
4.0
>0.5X
28
•2400
MX
MX
MX
XJ.5X
•1000
120
• 1.2
100
2.1
3.2
0.65
12 .
0.5X
76
•4200
MX
MX
X> 5*
•1000
64
2.2
57
depth Increases I through 8. —
» Element! not reported were below detectabl11ty of O.I ppm. All elements standardized using National Bureau oF Standards, Standard
Reference Material (SRH) 1632, a coat, where applicable.
> Standardized using NBS-SRM 1633, a coal fly ash.
* Not determined.
» Internal standard.
92
-------
TAILE II. - ELEMENTAL ANALYSES OF CRUDE SHALC OILS' USING SPARK SOURCE MASS SPECTROMEW
sampi: —
ELEMENT
Uranium
Thorium
II Smut h
Lead
Thai Hun
Mercury3
Gold
Platinum
Irldlum
Osmium
Rhenium5
Tungsten
Tantalum
Hafnium
lutecium
Ytterbium
•Thulllum
Erbium
Holmlum
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymlum
Praseodynlum
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium5
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
lr?n
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium3
Potassium3
Chlorine3
Sulphur3
Phosphorus
Silicon
Aluminum
Magnesium3
Sodium3
Fluorine3
Oxygen"
Nl trogen"
Carbon"
Boron3
Beryllium
Lithium
1 OT-29-U
0.0*6
0.098
0.11
0.021
0.011
0.019
0.018
0.16
0.*7
0.023
0.037
0.092
*.}
0.56
0.087
2.5
0.75
19
0.013
0.021
I.I
0.052
3.*
0.85
0.057
66
0.15
21
1.3
0.38
<0.73
0.071
*
.4.26
lot-3'l-U
12
0.026
0.32
0.16
0.2*
0.028
0.021
0.016
0.27
0.68
0.15
0.093
0.013
0.095
6.9
0.037
1.2
0.15
2.1
0.86
33
0.0**
0.090
9.0
0.89
39
5.5
2.0
3.1
26
9.0
19
2.0
5.*
0.10
*
0.0*2
I50T-U
0.30
1.1
0.51
0.73
1.6
0.11
1*
0.35
5.8
3.5
0,*2
9.0
1.2
25
0.11
0.22
0.81
0.33
2.3
3.0
760*
1.3
1*
0.10
-------
TABLE 12. - ELEMENTAL ANALYSES OF OIL-SHALE RETORT WATERS" USING SPARK SOURCE MASS SPECTROMETRY
ELEMENT
Uranium 0.018
Thorium
Bismuth
Lead 0.14
Thallium
Mercury9 <0. 1
Cold
Platinum
Irldlum
Osmium
Rhenium5
Tungsten 0.003
Tantalum
Hafnium
Lutecium
Ytterbium
Thulllum
Erbium
Holmlum
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymlum 0.005
Praseodymium
Cerium 0.001
Lanthanum 0.003
Barium 0.002
Cesium 0.00$
Iodine 0.23
Tellurium
Antimony 0.005
Tin 16
Indium5
Cadmium
Silver 0.23
Palladium
Rhodium
Ruthenium
Molybdenum 0.13
Niobium
Zirconium 0.042
Yttrium
Strontium 0.003
Rubidium 0.08$
Bromine 0.18
Selenium 0.071
Arsenic 4.6
Germanium 0.001
Gallium
Zinc 0.47
Copper 0.007
Nickel 0.37
Cobalt 0.002
Iron 9.6
Manganese 0.098
Chromium 0.013
Vanadium 0.004
Titanium 0.7$
Scandium
Calcium9 36
Potassium9 16
Chlorine9 ' -
Sulphur9 34
Phosphorus 1.4
Silicon 4.0
Aluminum 0.13
Magnesium9 47
Sodium9 64
Fluorine* 54
Oxygen1*
Nitrogen11
Carbon"
Boron9 4.4
Beryl HWL
Lithium 0.004
1 Elements not reported «
and run directly.
1 Determined by alternate
* Not determined.
9 Internal standard.
PPH
55 Tot^
(
-------
Comments following Mr. Poulson's talk.
Comment: The mercury analysis is on raw oil by atomic absorption,
most other elements are done on ashed oil.
Comment: For water and oil separation you just decant. Oil in water
removed by filtering through wad of cellite to take out the
oil globules.
Comment; A standard oil shale would be useful in determining where
various materials go in the process. More standardized
methods are needed, for example how to define oil and water
phases.
95
-------
LOW-TEMPERATURE SPECTROSCOPIC ANALYSIS OF
POLYCYCLIC AROMATIC HYDROCARBONS
E. L. Wehry, G. Mamantov, R. R. Kemmerer, R. C. Stroupe, H. 0. Brotherton,
E. R. Hinton, Jr., P. T. Tokousbalides, and R. B. Dickinson, Jr.
Department of Chemistry
University of Tennessee
Knoxville, Tennessee 37916
96
-------
LOW-TEMPERATURE SPECTROSCOPIC ANALYSIS OF
POLYCYCLIC AROMATIC HYDROCARBONS
E. L. Wehry, G. Mamantov, R. R. Kemmerer, R. C. Stroupe, H. 0. Brotherton,
E. R. Hinton, Jr., P. T. Tokousbalides, and R. B. Dickinson, Jr.
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37916
A. INTRODUCTION
The possibility that oil shale processing may cause release of significant
quantities of polycyclic organic matter (POM) into the atmospheric and/or
aquatic environment has received consideration in the past and will receive
greatly increased attention as a shale oil industry begins to develop. In
"ex situ" retorting of oil shale, significant amounts of POM are found to be
present in both the gaseous and liquid products of the retorting operation.
In addition, the spent shale (which, it is envisioned, may be deposited as
fill into natural canyons in such areas as the Piceance Creek basin in Colorado)
contains significant quantities of POM, which may slowly volatilize into the air
2
or be leached by water. Some POM release may also be anticipated from "in
2
situ" retorting operations. Consequently, assessment of the environmental
impact of oil shale refining will require the availability of analytical
methodology for identifying, and quantitatively determining, individual polycyclic
hydrocarbons.
The analytical chemistry of POM resulting from fossil fuel refining and
use is an extraordinarily complex problem, and it seems obvious that no single
technique, or group of techniques, will be a panacea. Our efforts have been
directed to exploration of the feasibility of using low-temperature Fourier
transform infrared spectroscopy, low-temperature steady-state fluorescence
spectroscopy, and time-resolved fluorometry in the analysis of POM. In all
of this work, we are strongly emphasizing the mode of sample preparation
commonly known as matrix isolation.
97
-------
B. MATRIX ISOLATION
In matrix isolation (MI) spectroscopy, the sample (in the vapor phase)
is mixed with a large excess of an "inert" gaseous diluent, such as N_ or Ar.
The gaseous mixture is then deposited upon a cold (ca. 20 K) optical surface;
3
the quasicrystalline deposit is then examined spectroscopically. The objectives
of MI include:
(a) To minimize solute-solute interactions, in order that predictable
quantitative relationships (e.g., Beer's law in absorption spectrophotometry)
be satisfied.
(b) To minimize matrix-solute interactions, in order that the observed
spectral band widths be minimized and resolution enhanced - obviously a critical
requirement in the analysis of complex mixtures.
(c) To eliminate, whenever possible, contact of samples with liquid solv-
ents, which may introduce contaminants (a problem of particular concern with
very sensitive techniques, such as fluorometry).
Inasmuch as most polynuclear aromatic hydrocarbons are rather volatile,
4
converting then to the vapor phase is feasible by vacuum sublimation. A
sample cell for vacuum sublimation-Knudsen effusion is shown in Figure 1. The
sample is placed in the small glass tube shown at the left of the Figure; this
tube, which contains a small (% mm) orifice at the left-hand end, is heated
resistively. This cell is attached to an evacuable cryostat head (cf. Figure
2) via the 29/42 male glass joint at the right in Figure 1.
The cryostat head is in turn attached to a commercial closed-cycle
helium refrigerator, capable of operation in the 15-20 K range; the mount
for the optical surface upon which the sample is deposited is attached to the
body of the refrigerator. The entire assembly (Figure 3) can be inserted into
virtually any spectrometer having a cell compartment which opens at the top.
98
-------
C. FOURIER TRANSFORM INFRARED SPECTROSCOPY
Infrared (IR) spectroscopy has received virtually no use in POM analysis ,
owing to (inter alia) the following difficulties:
(a) Insufficient sensitivity, requiring use of large or concentrated
samples (in which case Beer's law is unlikely to obtain) and lengthy spectral
scan times;
(b) Optical problems (due to lack of IR transparency of most solvents or
solid matrices); and
(c) The complexity of the IR spectra of many polycyclic hydrocarbons,
signifying that analyzing the spectrum of a complex mixture may be difficult or
impossible.
The first two of the problems cited above can be greatly alleviated by
use of the Fourier transform (FT) procedure for obtaining IR spectra, and the
third can be at least partially overcome by MI. FT-IR is a "multiplex"
spectroscopic technique; i.e., all "resolution elements" of a spectrum are
viewed simultaneously by the detector , in contrast to the conventional
sequential scanning technique, wherein the resolution elements are viewed one at
a time. In IR spectroscopy, wherein detector dark noise is normally appreciable,
multiplexing results in a significant increase in signal-to-noise ratio, which
can be utilized either to examine samples too small to study by conventional
scanning spectrometry, or to obtain spectra in much shorter times than are
conventionally feasible. For example, we have obtained IR spectra of 50
nanomole quantities of polycyclic hydrocarbons with little difficulty by FTS-IR,
and a single FTS-IR spectral scan at a resolution of 8 cm requires only 20 sec.
Consequently, S/N enhancement by repetitive signal averaging is widely employed
in FT-IR measurements.
The process of converting the "raw data" (optical interferograms) of
an FT spectrometer to absorption spectra involves a Fourier transformation
99
-------
performed by computer. A digital computer is normally an integral component of
a FT spectrometer. This fact signifies that a number of data-handling operations,
such as storage of spectra of standard reference materials, background subtraction,
and scale expansion are readily executed. In addition, spectra of standards
can be compared with those of real sample mixtures; the techniques of pattern
recognition can in principle be employed to identify specific sample components.
Once individual components have been identified, they may be subtracted ("stripped")
from the spectrum of a mixture , an operation which, in essence, can be
regarded as a form of "chemical separation by computer". All of this assumes,
however, that standard reference samples of the various sample constituents
exist, a situation which does not obtain at present.
The combination of MI sampling and FT-IR measurement is currently being
explored intensively in our laboratory. An example FT-IR spectrum of a three-
component mixture is shown in Figure 4. It should be noted that the three
constituents (chrysene, benz(a)anthracene, and triphenylene) are isomeric;
they are difficult to separate by gas or liquid chromatography and virtually
12
impossible to resolve in a mixture by mass spectrometry. The three individual
compounds are readily detectable in the FT-IR spectrum, suggesting that FT-IR
will prove to be very useful for examining groups of closely related compounds
present in fractions obtained in the liquid chromatography of synthetic fuels.
D. LOW-TEMPERATURE FLUORESCENCE SPECTROMETRY
Fluorescence spectrometry has been widely employed in the analysis of POM ,
because of its high sensitivity, yet the technique, as conventionally performed,
is not well suited for the analysis of complex mixtures, for two principal
reasons:
(a) Electronic spectra tend to be relatively broad and featureless,
especially in liquid solution, causing severe spectral overlap; and
(b) Energy transfer and quenching phenomena, which
100
-------
can occur over distances whlch are lar§e b? comparison with molecular
diameters, can cause the "analytical response factor" for one solute to be
dependent upon the identities and concentrations of other solute species present
in the sample.
Each of these problems can be reduced in severity by use of low-temperature
matrices. Fluorescence spectroscopy in frozen solutions of organic fluorophores
has received considerable attention in the past; matrix isolation fluorescence
spectroscopy has received much less study. We are currently engaged in a
comparative study of frozen-solution and matrix-isolation fluorometry and phos-
phorometry of POM. Spectral resolution is significantly greater in either
frozen solutions or frozen rare-gas matrices than in fluid media; cf. Figures 5
and 6 for a comparison of the liquid-solution and MI fluorescence spectra of
anthracene.
Though it is premature to state definitive conclusions, it appears that
frozen solutions may tend to provide superior spectral resolution to MI, particularly
if "Shpol'skii matrices" or "monocrystalline frozen solutions" are employed.
However, frozen-solution spectroscopy is very susceptible to quantitative impre-
cision, owing to microcrystallite formation and aggregation of solute species
upon freezing. There is reason to believe that MI, which is not susceptible
to such effects, will be the preferred technique for low-temperature quantitative
fluorometry.
In order to "isolate" solute molecules from each other for fluorescence
spectroscopy in a low-temperature solid matrix, the sample-to-matrix ratio must
be very small (perhaps ca. 1:5000). It is particularly important to employ very
dilute samples in order to minimize the effects of long-range energy transfer,
which is often very efficient in mixtures of arenes. Thus, very sensitive
detection systems (high-gain photomultipliers; photon counting) may be required,
and freedom of the matrix from luminescent impurities is absolutely crucial.
101
-------
In this respect, MI is clearly superior to frozen-solution spectroscopy; it is
much easier to remove fluorescent organic impurities from argon or nitrogen
than from n-octane or tetrahydrofuran.
E. TIME-RESOLVED FLUOROMETRY
It is often asserted (correctly) that emission measurements are inherently
more selective than absorptiometry, because there are two wavelength parameters
in an emission measurement but only one in absorption. Less widely recognized
is an additional parameter - time - which can be employed in emission, but not
in absorption, to seek additional resolution of mixtures. The luminescence decay
times for organic molecules are finite (ca. 10 nsec for fluorescence and ca.
1 msec for phosphorescence). Consequently, if the luminescence spectra of two
solute species cannot be resolved spectrally, it is conceivable that they can
be resolved in the time domain, if their luminescence decay times differ appreciably.
18
Time-resolved phosphorometry is a well-established procedure ; time-
resolved fluorescence experiments are more difficult to perform because of the
nanosecond decay times. The recent development of laser systems (modelocked
cavity-dumped ion lasers and synchronously pumped dye lasers ) which can
produce subnanosecond pulses at repetition rates variable from 100 MHz to single
shot, together with development of detection and transmission-line systems which
21
can operate in the gigahertz frequency region , signify that time-resolved
fluorescence spectroscopy is now a feasible technique in analytical chemistry.
We are currently engaged in construction and evaluation of a time-
resolved fluorometer, shown in block-diagram form in Figure 7. The principal
component of the instrument is a modelocked, cavity-dumped argon ion laser, which,
when frequency-doubled, will produce 1 nsec pulses at 2573 A (where virtually all
polynuclear hydrocarbons absorb) at repetition rates as great as 100 MHz. The
basic electronic readout device is a sampling oscilloscope which, with relatively
102
-------
minor modifications, can be made to function in a manner analogous to a boxcar
21
integrator signal averager. Both fluorescence decay times (intensity vs. time
at a fixed wavelength) and time-resolved fluorescence spectra (intensity vs.
wavelength at a fixed "time window", 75 ps wide, following firing of the laser)
can be acquired with an instrument of this type.
The performance of time-resolved MI or frozen-solution fluorometry should,
by concomitant use of spectral and temporal resolution, extend the applicability
of fluorescence assay to complex samples of structurally similar molecules.
F. REQUIRED STANDARD MATERIALS
In recognition of the theme of this Workshop, it is appropriate to
conclude this paper with a brief statement of our views pertaining to SBM's.
In all of our studies, a "reference library" of spectral data (FT-IR spectra,
luminescence spectra, fluorescence decay times) must be acquired before any useful
studies of "real samples" can be carried out. At present, in the specific
field of POM analysis, many of the most important (carcinogenic) compounds
cannot be acquired from commercial sources; in fact, significantly fewer of these
materials are commercially available now than in 1970! Those materials which
are available are often of questionable purity. There do not appear to exist
well—defined channels for obtaining these materials from non-commercial sources.
We would contend that there is a very significant need for SRM samples
of the important polycyclic aromatic hydrocarbons, having definite, known
purity, available to a wide variety of workers by well-defined, well-publicized
channels. Until such a situation is achieved, research in the analytical
chemistry of POM will be significantly hindered. Eventually, SRM's of shale
oil (and other synthetic fuels) must be made available, but we find it difficult
to believe that such SRM's will be of widespread utility until SRM's of the
individual components of synthetic fuels exist.
103
-------
REFERENCES
1. Report on the Conference-Workshop of the Analytical Chemistry of Oil Shale
and Shale Oil, Washington, D. C., 24-25 June 1974, National Science Foundation,
p. 57.
2. F. Bonomo, in Ref. 1, p. 133-186.
3. B. Meyer, "Low Temperature Spectroscopy", American Elsevier, New York, 1971.
4. J. L. Monkman, L. Dubois, and C. J. Baker, Pure Appl.' Chem.,
14, 731 (1971).
5. National Research Council, "Particulate Polycyclic Organic Matter", National
Academy of Sciences, 1972, pp. 297-298.
6. P. R. Griffiths, "Chemical Infrared Fourier Transform Spectroscopy", Wiley,
New York, 1975.
7. A. G. Marshall and M. B. Comisarow, Anal. Chem., 47, 491A (1975).
8. P. R. Griffiths, C. T. Foskett, and R. Curbelo, Appl. Spectrosc. Rev.,
6., 31 (1972).
9. G. Horlick, Appl. Spectrosc.. .22,, 617 (1968).
10. P. C. Jurs and T. L. Isenhour, "Chemical Applications of Pattern Recognition",
Wiley, New York, 1975.
11. T. Hirschfeld, "Computer Unmixing of Unknown Sample Mixtures", Anal. Chem.,
submitted for publication.
12. R. A. Hites, paper presented at Symposium on Polynuclear Aromatic Hydrocarbons,
Battelle Memorial Institute, Columbus, Ohio, October 17, 1975.
13. E. Sawicki, Talanta, 16, 1231 (1969).
14. G. F. Kirkbright and C. G. de Lima, Analyst, 99_, 338 (1974).
15. M. Lamotte and J. Joussot-Dubien, J. Chem. Phys., 61, 1892 (1974).
16. E. L. Wehry, Fluorescence News, J3, 21 (1974).
17. A. A. Lamola and N. J. Turro, "Energy Transfer and Organic Photochemistry",
Interscience, New York, 1969, pp. 37-43.
18. R. P. Fisher and J. D. Winefordner, Anal. Chem., 44, 948 (1972).
19. R. Arrathoon and D. A. Sealer, Phys. Rev., A4, 815 (1971).
20. J. M. Harris, R. W. Chrisman, and F. E. Lytle, Appl. Phys. Lett.. 26, 16 (1975)
21. F. E. Lytle, Anal. Chem.. .46_, 817A (1974).
104
-------
FIGURE CAPTIONS
Figure 1. Cell for vacuum sublimation-Knudsen effusion of polycyclic hydrocarbons.
Figure 2. Knudsen cell assembly attached to cryostat head.
Figure 3. "Complete" refrigerator assembly, for operation at 15-20 K, with
head and Knudsen cell assembly attached. This is a closed-cycle refrigeration
system; no liquid refrigerants are used.
Figure 4. MI FT-IR spectrum of equimolar mixture of three isomeric polycyclic
hydrocarbons (chrysene, benz(a)anthracene, triphenylene).
Figure 5. Liquid solution fluorescence spectrum of anthracene.
Figure 6. MI fluorescence spectrum of anthracene.
Figure 7. Block diagram of time-resolved fluorometer. The laser can also
be operated in the CW mode. Thus, a high-resolution emission monochromator
is employed, so that the same optical arrangement can be employed for both
time-resolved and steady-state (conventional) fluorometry.
105
-------
901
^':5''-K.ry-I^E^^^fe- -raaieu^wA. ? dru
'
-------
73
m
ro
-------
FIGURE 3
108
-------
o
£18^12 Mixture
TRIPHENYLENE, CHRYSENE, BENZ[A]ANTHRACENE/N2 MATRIX
MATRIX : SAMPLE = 250
EQUIMOLAR MIXTURE - 1 mg of each
B-
T—
— C
c—
— T
B—
T = TRIPHENYLENE
C = CHRYSENE
B= BENZ [A] ANTHRACENE
— T
i i i
i
C—
I
-C
B
C"
|
^T
i i
h-B
1550 1450 1350 1250 1150
1050 950
v, cm"1
850 750 650 550 450
-------
-------
ANTHRACENE IN N2
300:1
370
450 440
-------
Fast
Detector
Laser
(Spectra-Physics
166/366)
Mode Locker
Cavity Dumper
Frequency
Doubler
(ADP)
Sample Chamber
(CTI "Spectrum")
hi/A
Monochromator
(Spexl702)
Fast PM
S-2
Sampling
Head
Trigger Signal
Tektronix
7704A
Scope
7S11
Sampler
7T11
Sweep Unit
Vertical Out
Horizontal Out
X-Y
REC
Romp
Generator
-------
Comment following Wehry's talk.
Comment; Your technique sounds very informative. The main problem I -
see is the need for pure compounds to define the individual
spectra. For shale oil just determining the compounds present
in several hundred peaks, determining each and preparing in
a pure form would appear to be a near impossible job.
113
-------
APPENDIX B
Information on Existing NBS-SRM's
Useful for Characterizing Oil Shale/Products
114
-------
U. S. Departn%gfof Commerce
Alexander BjyjTrowbridge,
National
A. V.
Standards
rector
Certificate of
Standard Reference Material 1621
Sulfur In Residual Fuel Oil
Sulfur Content 1.05±0.02 weight percent
This Standard Reference Material is intended as an analytical standard in the de-
termination of sulfur in residual fuel oil. It is a commercially available oil having the
following inspection properties which are supplied for identification only: gravity, 22.6°
API; flash point, 136 °F; furol viscosity at 122 °F, 21 seconds; pour point, 40 °F; Rams-
bottom carbon residue, 3.3 percent; ash, 0.02 percent; water, not detected; and sediment
0.01 percent.
Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr
Oxygen Bomb using 1-g samples. The method used is similar to ASTM Method D-129. It
differs only in that any iron present is removed with ammonium hydroxide before the pre-
cipitation of the sulfur as barium sulfate. The uncertainty shown represents the 95-per-
cent confidence limit of the mean based on 30 determinations and allowances for known
sources of possible error.
The oil sample was supplied by the Esso Research and Engineering Company of
Linden, New Jersey. Sulfur analyses were performed by B. S. Carpenter, R. A. Paulson,
and W. P. Schmidt of the Microanalysis Section.
WASHINGTON, D. C. 20234 W. Wayne Meinke, Chief
December 11, 1967 Office of Standard Reference Materials
115
-------
U. S. Departn^qj^of Commerce
Alexander EfefTrowbridge,
National
A. V.
,r\
sistilji, I>
Standards
rector
Certificate of
Standard Reference Material 1622
Sulfur In Residual Fuel Oil
Sulfur Content 2.14±0.01 weight percent
This Standard Reference Material is intended as an analytical standard in the de-
termination of sulfur in residual fuel oil. It is a commercially available fuel oil having
the following inspection properties which are supplied for identification only: gravity,
16.9° API; flash point, 152 °F; furol viscosity at 122 °F, 186 seconds; pour point, 30 °F;
Ramsbottom carbon residue, 11.9 percent; ash 0.05 percent; water, not detected; and
sediment 0.01 percent.
Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr
Oxygen Bomb using 1-g samples. The method used is similar to ASTM Method D-129. It
differs only in that any iron present is removed with ammonium hydroxide before the pre-
cipitation of the sulfur as barium sulfate. The uncertainty shown represents the 95-per-
cent confidence limit of the mean based on 17 determinations and allowances for known
sources of possible error.
The oil sample was supplied by the Esso Research and Engineering Company of
Linden, New Jersey. Sulfur analyses were performed by B. S. Carpenter, R. A. Paulson,
and W. P. Schmidt of the Microanalysis Section.
WASHINGTON, D. C. 20234 W. Wayne Meinke, Chief
December 11, 1967 Office of Standard Reference Materials
116
-------
U. S. Depardteafof Commerce
MauriceMl. Stans
(Heritfttate of
Standard Reference Material 1623
Sulfur in Residual Fuel Oil
W. P. Schmidt and R. A. Paulson
Sulfur Content 0.268 ± 0.004 weight percent
This Standard Reference Material is an analytical standard for determining sulfur in residual fuel
oil. It is a commercially available fuel oil having the following inspection properties that are
supplied for identification only: gravity, 27.0 °API; flash point (Pensky-Martens), 170 °F; viscosity
(kinematic), 5.8 centistokes; pour point, 47 °F; carbon residue (on 10 percent bottoms),
0.31 percent. The following analytical data are not certified, but are reported for information only:
carbon, 87.4 percent; hydrogen, 12.0 percent; water, not detected (<0.1 percent); sediment, not
detected (<0.01 percent); ash, not detected (<0.005 percent); and vanadium 3 ± 1 ng/g.
Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr Oxygen
Bomb using 1-g samples. The method is similar to ASTM Method D-129. It differs only in that any
iron present is removed with ammonium hydroxide before the precipitation of the sulfur as barium
sulfate. The uncertainty shown represents the 95-percent confidence limit of the mean based on
12 determinations and allowances for known sources of possible error.
The material was supplied by the Esso Research and Engineering Company of Linden,
New Jersey. Vanadium was determined by T. E. Gills, using non-destructive neutron activation
analysis.
The overall direction and coordination of the technical measurements leading to certification
were performed under the chairmanship of J. K. Taylor.
The technical and support aspects involved in the preparation, certification, and issuance of this
Standard Reference Material were coordinated through the Office of Standard Reference Materials
by T. W. Mears.
Washington, D. C. 20234 J. Paul Cali, Chief
April 7, 1971 Office of Standard Reference Materials
117
-------
U. S. Departrii$Q$' of Commerce
Maurice.:!!. Stans
,-,,
National Bireaf ef Standards
L. M. Brartsc^nt, Director
(Eerttfttat* of JVttalgst*
Standard Reference Material 1624
Sulfur in Distillate Fuel Oil
W. P. Schmidt and R. A. Paulson
Sulfur Content ....... 0.211 ± 0.004 weight percent
This Standard Reference Material is an analytical standard for determining sulfur in distillate fuel
oil. It is a commercially available oil having the following inspection properties that are supplied for
identification only: gravity, 33.8 °API; flash point (Pensky-Martens), 138 °F; viscosity (kinematic),
2.7 centistokes; pour point, — 16 °F; carbon residue (on 10 percent bottoms), 0.15 percent. The
following analytical data are not certified, but are reported for information only: carbon,
86.6 percent: hydrogen, 12.5 percent; water, not detected (<0.1 percent); sediment, not detected
(<0.01 percent); ash. not detected (<0.005 percent); vanadium, 14 ± 1 ng/g.
Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr Oxygen
Bomb using 1-g samples. The method is similar to ASTM Method D-129. It differs only in that any
iron present is removed with ammonium hydroxide before the precipitation of the sulfur as barium
sulfate. The uncertainty shown represents the 95-percent confidence limit of the mean based on
12 determinations and allowances for known sources of possible error.
The material was supplied by the Esso Research and Engineering Company of Linden,
New Jersey. Vanadium was determined by T. E. Gills, using non-destructive neutron activation
analysis.
The overall direction and coordination of the technical measurements leading to certification
were performed under the chairmanship of J. K. Taylor.
The technical and support aspects involved in the preparation, certification, and issuance of this
Standard Reference Material were coordinated through the Office of Standard Reference Materials
by T. W. Mears.
Washington, D. C. 20234 J. Paul Cali, Chief
April 7, 1971 Office of Standard Reference Materials
118
-------
U.S. Department of Commerce
Juanita M> Kreps
Secretary'
"""*' ' T
National Bureau of Standards
Ernest ^innljer, pirector
ttram of jltatutartte
(Eerttfitate of
Standard Reference Material 1630
Trace Mercury in Coal
This Standard Reference Material is intended as an analytical standard for the determination of trace mercury
in coal. The material is a commercially available coal that was crushed to a size of 210 to 500 micrometers with a
roll crusher. From a total of 500 packaged bottles, 30 were randomly selected for analysis. Duplicate
determinations were made on 0.5 g portions of 25 of these bottles, and single determinations were made on the
other five. The mercury content of this material was obtained by destructive neutron activation analysis.
The recommended value is the average of these 55 determinations on 30 bottles, which was found to be:
Mercury content = 0.13 /ig/g
The recommended value is not expected to change by more than ± 1 in the last significant figure.
A study of homogeneity showed no variability among bottles that could not be accounted for by analytical error.
Duplicate samples from the same bottle indicated a homogeneity for mercury of ± 5% (relative).
The mercury content was also determined by flameless atomic absorption spectrometry, yielding an average
value of 0.14 /ug/g.
Selenium was also determined using destructive neutron activation analysis. The value obtained, which is not
certified but included for information only, was found to be 2.1 jug/g.
The homogeneity testing and analyses for certification were performed in the NBS Analytical Chemistry
Division by T. E. Gills and H. Rook under the direction of P. D. LaFleur.
The technical and support aspects involved in the preparation, certification, and issuance of this Standard
Reference Material were coordinated through the Office of Standard Reference Materials by C. L. Stanley.
Washington, D.C. 20234
August 1, 1979
(Revision of Certificate dated 11-2-71
Editorial Revision only.)
George A. Uriano, Chief
Office of Standard Reference Materials
(over)
119
-------
ANALYTICAL PROCEDURE
The bottles containing the samples were allowed to remain open at room temperature (about 25 °C) for
twenty-four hours.
The coal samples, along with solution standards of mercury and NBS Standard Reference Material 1571
(Orchard Leaves) used as a control, were encapsulated in cleaned quartz vials. The geometry of both the samples
and the standards were optimized so that flux monitors were not needed. The samples were irradiated for four
hours at a thermal flux of 6 X 10 n-cm~ sec" . The samples were allowed to decay for three days to minimize
the personnel dose rate. The samples were postweighed into porcelain boats and burned in a combustion tube.
The volatile mercury compounds and other volatile products liberated during burning were trapped in a liquid
nitrogen cold trap. The cold trap was allowed to warm to room temperature. The mercury compounds were then
transferred to polyethylene bottles by washing the cold trap with concentrated nitric acid and water. For this
analysis, 197Hg produced by ' 6Hg(n,y) l97Hg was used as the measuring activity.
Bromine-82, an interfering isotope, was separated from the sample by using the classical silver bromide
precipitation.
The samples were counted on a 22 cm3 Ge(Li) detector connected to a 2048-multichannel analyzer. The
accumulated data was processed by computer for peak identification and integration. The concentrations were
determined by using a Standard Comparator Method.
NOTE TO USER
It is suggested that persons using SRM 1630 to check their analytical technique should adopt the following
criteria. If the average, X, of N replicate measurements on this SRM is found to lie in the interval—
0.013 .-._, 0.013
then the analytical technique used gives a result compatible with that found at NBS. However, if the value X lies
outside this interval, then the technique should be examined for possible bias or miscalibration.
NOTE: The above expression is not rigorously correct. It does not include a possible component for
between laboratory variability nor sources of systematic error.
SRM 1630
Page 2
120
-------
U. S. Departitejatfof Commerce
Frederiolli. Dent
** ~,™™^s. ~ —~
•^saf'
National Burean ;ol Standards
Richard WV-fr^, Director
ureau of j^tantfortb
Certificate of JVnalgsi*
Standard Reference Material 1631
Sulfur in Coal
Rolf A. Paulson
This Standard Reference Material is intended primarily for use as an analytical standard for the
determination of sulfur in coal. It is also certified for ash content. This standard consists of three
different low-volatile bituminus coals, ground to pass a 60-mesh sieve, packaged separately. Each
coal is certified for its sulfur and ash contents on an as-received basis.
Percent by Weight
Coal Sulfur Ash
A 0.546 ±0.003 5.00 ±0.02
B 2.016 ± .014 14.59+ .09
C 3.020 ± .008 6.17 ± .02
The certified values are the means of 20 determinations of sulfur and 10 determinations ot ash
on 10 samples selected randomly from the lot of 2500 samples. The uncertainty represents the half
widths of the 95% confidence intervals of the certified values. There was no evidence of heterogene-
ity of composition within the uncertainty limits reported.
The coals have been analyzed by four cooperating laboratories with results consistent with the
certified values. All of the analytical work is summarized under the supplementary information.
The overall coordination of the technical measurements leading to certification, was under the
chairmanship of J. K. Taylor.
The technical and support aspects involved in the preparation, certification, and issuance of this
Standard Reference Material were coordinated through the Office of Standard Reference Materials
by C. L. Stanley.
Washington, D. C. 20234 J. Paul Cali, Chief
August 15, 1973 Office of Standard Reference Materials
(over)
121
-------
Supplementary Information
Analysis of Material
The methods of analysis used for certifying this material were essentially those identified as
ASTM method D271. The following laboratories cooperated with NBS in the analysis of these
coals: Association Technique de 1'Importation Charbonniere, Hampton Roads Laboratory, Newport
News, Virginia; Combustion Engineering Inc., Windsor, Connecticut; Eastern Associated Coal
Corporation, Pittsburgh, Pennsylvania; and U. S. Bureau of Mines, Coal Analysis Laboratory, Pitts-
burgh, Pennsylvania.
Summary of Supporting Analytical Values
Coal Laboratory Sulfur, % Ash, %
A 1 0.540 ± 0.006 4.847 ± 0.044
2 .579 + .006 4.792+ .074
3 .551 ± .016 5.134 ± .085
4 .569± .017 4.865 ± .051
B 1 1.972 ± .016 14.50 ± .16
2 2.019 ± .014 14.58+ .06
3 1.969+ .031 14.61+ .19
4 1.988+ .028 14.58 ± .16
c 1 3.018+ .018 6.126 ± .031
2 3.035+ .031 6.013 ± .092
3 2.915 ± .017 6.092 ± .056
4 2.998+ .020 6.045 ± .072
For the work performed in the cooperating laboratories the values for sulfur are the averages of
twelve determinations. The values for ash are the averages of twelve determinations except labora-
tory No. 1, whose values are based upon 18 determinations for coals A and C and 17 determinations
for coal B. The uncertainties are the 95 percent confidence, limits.
Originally, the moisture content of these coals was to be certified; however, the lack of homog-
eneity in this respect prevented certification. Therefore, these values are reported for information
only. The ranges of NBS values for moisture were: Coal A, 0.72 to 1.06 percent; Coal B, 0.48 to
1.00 percent; and Coal C, 0.15 to 0.70 percent.
Source of Material
Coal A - Keystone Mine No. 2, West Virginia
Coal B - Colver Mine, Pennsylvania
Coal C - Stigler Bed, Arkansas
These coals were procured and ground through the assistance and courtesy of David E. Wolf son
and Forrest E. Walker, U. S. Bureau of Mines, Pittsburgh, Pennsylvania.
Use of Material
All analytical values are reported on an as-received basis so that no drying procedures should be
used. The coals are packaged in hermetically sealed envelopes each containing approximately 3.g of
the material. It is recommended that the envelopes be opened only at the time of analysis and that
any unused contents be discarded.
122
-------
U.S. Department of Commerce
Juanita M Ktrps
Secretary
National Kureftu of Standiircls
Krnest Ambti>r. Ailing Diwtur
ureau of jitattrfanb
Certificate of
Standard Reference Material 1632a
Trace Elements in Coal
(Bituminous)
This Standard Reference Material is intended for use in the calibration of apparatus and techniques employed in
the trace element analysis of coal and similar materials. The material should be dried without heat to constant
weight before use.
The recommended procedures for drying are either vacuum drying at ambient temperature for 24 hours,or freeze
drying in which the drying chamber is kept at room temperature. When not in use, the material should be kept in
a tightly sealed bottle and stored in a cool, dark place. Long-term (>1 year) stability of this SRM has not been
rigorously established. NBS will continue to monitor this material and any substantive change will be reported
to purchasers.
The certified values given below are based on at least a 250-mg sample of the dried material, the minimum
amount that should be used for analysis.
Element
A • a,b
Arsenic
Cadmium0'
Chromium0'6
Copper8'6
Iron°'d'f
Lead°'d
Manganese8 >e
Content,
9.3
0.17
34.4
16.5
11,100
12.4
28
wg/g2
± 1
± 0.02
± 1.5
± 1
± 200
± 0.6
± 2
Element
Mercury8 '*
Nickel0 ld
Selenium8'6
Thorium0 'e
Uranium0
Vanadium6'8
Zinc°'d
Content, jug/g
0.13 ± 0.03
19.4 ± 1
2.6 ± 0.7
4.5 ± 0.1
1.28 ± 0.02
44 ±3
28 ±2
e, Neutron Activation
f. Spectrophotometry
g. Flame Emission Spectrometry
1. Methods of Analysis:
a. Atomic Absorption Spectrometry
b. Photon Activation
c. Isotope Dilution Mass Spectrometry
d. Polarography
2. The estimated uncertainty is based on judgment and represents an evaluation of the combined effecus of method impreci-
sion, possible systematic errors among methods, and material variability for samples of 250-mg or more. (No attempt was
made to derive exact statistical measures of imprecision because several methods were involved in the determination of
most constituents.)
The overall direction and coordination of the analytical measurements leading to this certificate were performed
in the Analytical Chemistry Division under the chairmanship of L. J. Moore.
The technical and support aspects involved in the preparation, certification, and issuance of this Standard
Reference Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.
Washington, D.C. 20234
January 23, 1978
123
(over)
J. Paul Cali, Chief
Office of Standard Reference Materials
-------
PREPARATION, TESTING, and ANALYSIS
This material was prepared from one lot of coal designated as Pennsylvania Seam Coal. It was prepared under
the auspices of F. Walker and J. Douebruck of the U.S. Bureau of Mines, Pittsburgh, Pennsylvania. The
prepared and ground coal was then sieved through a 250 pm (No. 60) sieve and thoroughly blended in a V-type
blender.
Samples for homogeneity testing were taken from the top, middle, and bottom of three bulk containers of coal,
and analyzed by neutron activation analysis for scandium, chromium, iron, cobalt, cerium, and thorium.
Replicate analyses of 250-mg samples indicated a homogeneity for these elements of ±2% (relative). The
homogeneity measurements were performed in the NBS Analytical Chemistry Division by R. R. Greenberg.
Certification analyses for the various elements were made in the NBS Analytical Chemistry Division by T. J.
Brady, B. I. Diamondstone, L. P. Dunstan, M. S. Epstein, M. Gallorini, E. L. Garner, T. E. Gills, J. W.
Gramlich, R. R. Greenberg, S. H. Harrison, G. M. Hyde, G. J. Lutz, L. A. Machlan, E. J. Maienthal, J. D.
Messman, T. J. Murphy, and T. C. Rains.
The following values are not certified because they were based on a non-reference method, or were not deter-
mined by two or more independent methods. They are included for information only.
Content
Element
Antimony (0.58)
Cerium (30)
Cesium (2.4)
Cobalt (6.8)
Europium (0.54)
Gallium (8.49)
Hafnium (1.6)
Rubidium (31)
Scandium (6.3)
(wt. %)
Aluminum (3.07)
Sulfur (1.64)
Titanium (0.175)
124
-------
U.S. Department,of Commerce
Juanita M« Kreps
Secretary'
' "•*""-«
National Bureau of Standards
Ernest ^mblter, [Jirector
uratit of
(Esrttftcate af
Standard Reference Material 1633a
Trace Elements in Coal Fly Ash
This Standard Reference Material is intended for use in the calibration of apparatus and methods used in
analyses of coal fly ash and other materials with similar matrices for trace elements. This material should be
dried to a constant weight before using. Recommended procedures for drying are: (1) drying for 24 hours at
ambient temperature using a cold trap at or below -50 °C and a pressure not greater than 30 Pa (0.2 mm Hg);
(2) drying in a desiccator over PjOs or Mg(C104)2. When not in use, the material should be kept in a tightly
sealed bottle. Long term (>3 years) stability of this SRM has not been rigorously established. NBS will
continue to monitor this material and any substantive change will be reported to purchasers.
The certified values given below are based on at least a 250-mg sample of the dried material, the minimum
amount that should be used for analysis.
Element
/"> i • a,b,e
Calcium
r a,b,c
Iron
Potassium ' '
Magnesium" '
ci j- a,c
Sodium
Silicon '
. • a.c
Arsenic
Cadmium"'0'"'8
y-ii ' a,b,c
Chromium
/-i a,b,c
Copper
Content2
JL
1.11 ± 0.01
9.40 ± 0.10
1.88 ± 0.06
0.4551 0.010
0.17 1 0.01
22.8 i 0.8
jjg/g
145 i 15
1.0 1 0.15
196 1 6
118 i 3
Element
Mercury3 '°
Nickela'bld'e
LeadM'e
~ .... a,b,c,e
Rubidium
Selenium"'0'8
Strontium ' '
TI • b , c
Thorium
Thallium15'8
Uranium
zinca,b,d,e,f
Content
Mg/g
0.16+ 0.01
127 i 4
72.4 ± 0.4
131 1 2
10.3 1 0.6
830 1 30
24.7 i 0.3
5.7 ± 0.2
10.2 1 0.1
220 ± 10
I. Methods of Analysis:
a Atomic Absorption Spectrophotometry or Flame Emission
Spectrometry
Isotope Dilution Mass Spectrometry
Neutron Activation
Polarography
X-ray Fluorescence Spectrometry
Inductively Coupled Plasma Emission Spectrometry
8Isotope Dilution Spark Source Mass Spectrometry
Gravimetry
2. The estimated uncertainty is based on judgment and represents an evaluation of the combined effects
of method imprecision, possible systematic errors among methods, and material vanability for samples
of 250-mg or more. (No attempt was made to derive exact statistical measures of imprecision because
several methods were involved in the determination of most constituents.)
Washington, D.C. 20234
April 18, 1979
George A. Uriano, Chief
Office of Standard Reference Materials
(over)
125
-------
The overall direction and coordination of the analytical measurements leading to certification were performed
in the Center for Analytical Chemistry under the chairmanship of L. A. Machlan.
The technical and support aspects involved in the preparation, certification, and issuance of this Standard
Reference Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.
PREPARATION, TESTING, AND ANALYSIS
This fly ash material was supplied by a coal fired power plant and is a product of Pennsylvania and West Virginia
coals. It was selected as a typical fly ash and is not intended as a fly ash from a specific coal or combustion process.
The material was sieved through a # 170 sieve and blended for 2 hours in a Vee blender. The material was then
removed and placed in a series of bulk containers from which specific samples were taken.
Twelve bottles were selected for homogeneity tests. These samples were analyzed for cobalt, chromium,
europium, iron, scandium, and thorium by nondestructive neutron activation analysis. The observed standard
deviations for both 50 and 250 mg samples were consistent with counting statistics indicating that the fly ash is
homogeneous within ± 5% (relative) based on these elements. The homogeneity analyses were performed in the
NBS Center for Analytical Chemistry by R. R. Greenburg and J. S. Maples. Analyses for the various elements
were made in the NBS Center for Analytical Chemistry by the following analysts: J. R. Baldwin, T. J. Brady,
E. R. Deardorff, M. G. Dias, L. P. Dunstan, M. S. Epstein, E. L. Garner, T. E. Gills, C. A. Grabnegger, J. W.
Gramlich, R. R. Greenberg, S. Hanamura, S. H. Harrison, E. F. Heald, H. M. Kingston, E. C. Kuehner, L. A.
Machlan, E. J. Maienthal, J. S. Maples, J. D. Messman, L. J. Moore, P. J. Paulsen, P. A. Pella, T. C. Rains,
K. J. R. Rosman, T. A. Rush, P. A. Sleeth, and R. L. Waters, Jr.
The following values are not certified because they are based on a non-reference method, or were not determined
by two or more independent methods. They are included for information only.
Element
Aluminum
Barium
Titanium
Beryllium
Cerium
Cobalt
Cesium
Content
14
0.15
0.8
Mg/g
12
180
46
11
Element
Content
Mg/g
Europium
Gallium
Hafnium
Manganese
Molybdenum
Antimony
Scandium
Vanadium
4
58
7.6
190
29
7
40
300
126
-------
U.S. Department of Commerce
Juanita M. Kreps
Secretary
National Bureau ut Standards
Ernest Anbler, Acting Director
Rational ^uram of
(Eerttfttate of
tanttartb
Standard Reference Material 1634
Trace Elements in Fuel Oil
This Standard Reference Material is intended for use in the calibration of apparatus and evaluation of methods
used in analyses of fuel oil and other materials with similar matrices for trace elements. When not in use, the
material should be kept in a tightly sealed bottle. Long term stability of this SRM has not been rigorously
established. NBS will continue to monitor this material and any substantive change will be reported to
purchasers.
The certified values given below are based on at least a 250-mg sample of the material, the minimum amount
that should be used for analysis.
Constituent
Sulfur
Vanadium
Nickel
Iron
Zinc
Lead
Certified Value'
Estimated Uncertainty
Percent by Weight
2.14a b , 0.02
Mg/g
320ac
36cde
13.5a c e
0.23a e
.041de
15
4
1.0
0.05
.005
I. The certified values are based on the results of 4 to 15 determinations by each of at least two
analytical techniques.
a. Neutron Activation
b. Combustion with Titrimetry
c. Atomic Absorption Spectrometry
d. Isotope Dilution Mass Spectrometry
e. Polarography
2. The estimated uncertainties are not less than the 95% confidence limits computed for the
analyses and include sample variations, possible method differences, and errors of measure-
ment.
The overall direction and coordination of the analytical measurements leading to certification were performed
in the Analytical Chemistry Division under the chairmanship of P. D. LaFleur and D. A. Becker.
The technical and support aspects involved in the preparation, certification, and issuance of this Standard
Reference Material were coordinated through the Office of Standard Reference Materials by C. L. Stanley.
Washington, D.C. 20234
January, 1978
(Rev. of Cert, dated 5/14/75.
Editorial changes only.)
J. Paul Cali, Chief
Office of Standard Reference Materials
(over)
127
-------
PREPARATION, TESTING, and ANALYSIS
The material was obtained through a commercial supplier from a refinery on the island of Aruba in the West
Indies, and is essentially a "No. 6 Fuel Oil" as defined by the American Society for Testing and Materials.
A random scheme for sample selection was designed and a statistical analysis of the homogeneity data was per-
formed by J. Mandel of the NBS Institute for Materials Research. Fifteen of 500 bottles were selected for
homogeneity tests. These samples were analyzed for vanadium by nondestructive neutron activation analysis.
Replicate analyses on 250-mg samples indicated homogeneity within ±2% (relative) based on this element.
X-ray fluorescence analyses for sulfur on bulk samples before bottling support the conclusion of acceptable
material homogeneity. The homogeneity analyses were performed in the NBS Analytical Chemistry Division
by T. E. Gills, M. Darr, and R. Myklebust. Analyses for the various elements were made in the NBS Analytical
Chemistry Division by the following analysts: R. W. Burke, B. S. Carpenter, M.S. Epstein, E. L. Garner, T. E.
Gills, J. W. Gramlich, L. A. Machlan, E. J. Maienthal, T. J. Murphy, E. Orvini, T. C. Rains, H. L. Rook, T. A.
Rush, and S. A. Wicks.
The following values are not certified because they are based on a non-reference method, or were not determined
by two or more independent methods. They are included for information only.
Constituent
Arsenic
Beryllium
Cadmium
Chromium
Mercury
Manganese
Content'
Mg/g
(0.095)8
(<.01)b
(<.01)a c
(-09)a
(.0023)a
(.12)a
These values are not certified.
a. Neutron Activation
b. Spectrophotometry
c. Polarography
128
-------
L'.S. Department of Commerce
Juanita M. Kreps
Secretary
National Bureau of Standards
Ernest Ambler. Acting Director
ur*au of jlianrfanb
of
Standard Reference Material 1635
Trace Elements in Coal
(Subbituminous)
This Standard Reference Material is intended for use in the calibration of apparatus and techniques employed in
the trace element analysis of coal and similar materials. The material should be dried without heat to constant
weight before use.
The recommended procedures for drying are either vacuum drying at ambient temperature for 24 hours, or
freeze drying in which the drying chamber is kept at room temperature. The moisture content of this material is
approximately 20%. Because of this moisture level, it is recommended that small individual samples be dried
immediately before use.Drying of large samples may result in a violent discharge of water vapor and resultant
loss of sample. When not in use, the material should be kept in a tightly sealed bottle and stored in a cool, dark
place. Long-term (>1 year) stability of this SRM has not been rigorously established. NBS will continue to
monitor this material and any substantive change will be reported to purchasers.
The certified values given below are based on at least a 250-mg sample of the dried material, the minimum
amount that should be used for analysis.
Element1
Arsenic4'
Cadmium0' '*
Chromium0'
Copper"' °'e
¥ c,d,f
Iron
Lead°'d
Manganese" >c
Content, M8/B2
0.42 ± 0.15
0.03 ± 0.01
2.5 ± 0.3
3.6 ± 0.3
2390 ± 50
1.9 ± 0.2
21.4 ± 1.5
Element1
Nickel0 'd
Selenium" >e
Thorium0 >e
Uranium0
Vanadium8 'e
Zinc°'d
Content, Mg/g2
1.74 ± 0.1
0.9 ± 0.3
0.62 ± 0.04
0.24 ± 0.02
5.2 ± 0.5
4.7 ± 0.5
e. Neutron Activation
f. Spectrophotometry
g. Flame Emission Spectrometry
I. Methods of Analysis:
a. Atomic Absorption Spectrometry
b. Photon Activation
c. Isotope Dilution Mass Spectrometry
d. Polarography
2. The estimated uncertainty is based on judgment and represents an evaluation of the combined effects
of method imprecision, possible systematic errors among methods, and material variability for samples
of 250-mg or more. (No attempt was made to derive exact statistical measures of imprecision because
several methods were involved in the determination of most constituents.)
The overall direction and coordination of the analytical measurements leading to this certificate were performed
in the Analytical Chemistry Division under the chairmanship of L. J. Moore.
The technical and support aspects involved in the preparation, certification, and issuance of this Standard
Reference Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.
Washington, D.C. 20234
January 23, 1978
(over)
129
J. Paul Cali, Chief
Office of Standard Reference Materials
-------
PREPARATION. TESTING, and ANALYSIS
This material was prepared from one lot of subbituminous coal from the Eagle Mine of The Imperial Coal
Company, Erie, Colorado. The material was ground and sieved thru a No. 65 (230 /im) sieve by the Colorado
School of Mines Research Institute. The material was then blended in a V-type blender.
Samples for homogeneity testing were taken from the top, middle, and bottom of three bulk containers of coal,
and analyzed by neutron activation analysis for sodium, scandium, chromium, iron, cobalt, lanthanum,
cerium, and thorium. Replicate analyses of 250-mg samples indicated a homogeneity for these elements of
± 2.5% (relative) except for chromium, which was homogeneous within counting statistics of ± 6%. The homo-
geneity measurements were performed in the NBS Analytical Chemistry Division by R. R. Greenberg. Certifi-
cation analyses for the various elements were made in the NBS Analytical Chemistry Division by T. J. Brady,
B. I. Diamondstone, L. P. Dunstan, M. S. Epstein, M. Gallorini, E. L. Garner, T. E. Gills, J. W. Gramlich,
R. R. Greenberg, S. H. Harrison, G. M. Hyde, G. J. Lutz, L. A. Machlan, E. J. Maienthal, J. D. Messman,
T. J. Murphy, and T. C. Rains.
The following values are not certified because they were based on a non-reference method, or were not deter-
mined by two or more independent methods. They are included for information only.
Content
Element Qxg/g)
Antimony (0.14)
Cerium (3.6)
Cobalt (.65)
Europium (.064)
Gallium (1.05)
Hafnium (.29)
Scandium (.63)
(wt. %)
Aluminum (0.32)
Sulfur (.33)
Titanium (.02)
130
-------
uraw of
Standard Reference Materials
1636,1637,1638
Lead in Reference Fuel
This Standard Reference Material is intended for use in the calibration of instruments and
techniques used for the analysis of lead in gasoline. Samples of the leaded 91-octane-number
reference fuel (See page 2 for composition) are supplied at four concentrations, nominally 0.03,
0.05, 0.07, and 2.0 g/gal. The assigned Standard Reference Material numbers (1636, 1637, 1638)
refer to the composition of sets containing the above nominal concentrations in varying
combinations. The composition of each set is given in Table 1 on the reverse page.
The certified values for lead content are given in units of /ug/g. From these certified values the
lead concentrations in g/gal and g/1 at 20 °C and 25 °C were calculated. These values are given in
Table 2.
Nominal Certified
Lead Concentration Lead Concentration
g/gal Mg/g
0.03 12.31 ± 0.06
0.05 19.68 ± 0.05
0.07 27.70 ± 0.06
2.0 772.7 ±1.5
The uncertainties cited represent the pooled 95 percent confidence intervals for a single
determination with allowances for known sources of possible error. The certified values were
determined by isotope dilution mass spectrometry and supported by atomic absorption spectro-
metry.
The samples of leaded reference fuel should be protected from light. The ampoules should be
opened only at time of use. No attempt should be made to keep the material in opened ampoules
for future use.
Matrix effects may be observed with various gasolines. Certain adjustments in analytical data
may be necessary based on individual knowledge of the magnitude of these effects.
The lead in reference fuel samples were prepared by the Phillips Petroleum Co. of Bartlesville,
Oklahoma. Isotope dilution mass spectrometry measurements were performed by T. J. Murphy, N.
M. Caliman and E. F. Heald of the Isotopic Analysis Section, I. L. Barnes, Chief. Atomic
Absorption Spectroscopy Measurements were performed by R. Mavrodineanu, J. R. Baldwin, and J.
L. Weber of the Spectrochemical Analysis Section, 0. Menis, Chief.
The technical and support aspects involved in the preparation, certification and issuance of
these Standard Reference Materials were coordinated through the Office of Standard Reference
Materials by T. W. Mears.
Washington, D. C. 20234 131 J. Paul Cali, Chief
March 25, 1975 (over) Office of Standard Reference Materials
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Table 1
Number of ampoules of each concentration contained in
Standard Reference Material 1636, 1637, and 1638
SUM
1636
1637
1638
0.03
3
4
-
Nominal
0.05
3
4
-
Lead Concentration (g/gal)
0.07
3
4
-
2.0
3
.
12
Table 2
Composition of leaded reference fuels in g/gal and g/1
Nominal
g/gal
0.03
.05
.07
2.0
Lead Concentration3
g/
20°Cb
0.0322
.0515
.0725
2.024
gal
25 °C
0.0320
.0512
.0721
2.012
8/1
20 °C
0.00851
.01360
.01915
.535
25 °C
0.00845
.01352
.01903
.531
* The lead concentrations given in this table are considered accurate within a coefficient of variation of 0.005.
The concentration in g/gal at 20 "C is given in the sample labels.
The concentrations (C) in g/gal were calculated using the equation:
g/gal
_ 3785.4PCMgJg
- - =•
106
The concentrations (C) in g/1 were calculated using the equation:
PC,
The density (p) of each concentration was measured at 20 °C and 25 °C using a modification of
ASTM Method D1217. The stated interlaboratory reproducibility of this method is 0.00003 g/cm3.
Densities of the leaded fuels are given in the following table.
Nominal Concentration
g/gal
0.003
.05
.07
2.0
Density at 20 °C
g/cm3
0.69126
.69127
.69127
.69196
Density at 25 °C
g/cm3
0.68710
.68711
.68711
.68774
The 91-octane-number reference fuel is a mixture of 91 percent by volume (0.899 mol-fraction)
2,2,4-trimethylpentane and 9 percent by volume (0.101 mol-fraction) n-heptane. Lead was added in
the form of tetramethyllead-tetraethyllead motor mix.
132
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NBS
Standard
Reference
Materials
U.S. Department of Commerce
National Bureau of Standards
Standard Reference Material 1648
Urban Particulate Matter
Fall, 1978
The NBS Office of Standard Reference Materials announces the availability of SRM 1648, Urban Particulates.
This SRM is a fine particle dust consisting of 2 grams of material certified for a variety of trace and minor
constituents.
The material used for SRM 1648 is a portion of a large lot of material collected over a period of 1 l/2yearsinthe
vicinity of St. Louis, Missouri, and should be representative of dust found in many urban areas. SRM 1648 is
intended for use as a reference material by scientists making environmental measurements and developing
analytical techniques. Because this SRM represents a large homogeneous quantity of urban dust, it should
prove useful to scientists who wish to study the environmental impact of urban dust.
This SRM is certified for arsenic, cadmium, chromium, copper, nickel, zinc, uranium, iron and lead content.
Method dependent information is also provided for nitrate, ammonium, sulfate, silicate, and the freon-soluble
components.
SRM 1648 may be purchased from the Office of Standard Reference Materials, Room B311, Chemistry Build-
ing, National Bureau of Standards, Washington, D.C. 20234, for $88 per 2-gram unit.
1278
133
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U.S. Department of Commerce
Juanita J4> Kreps
Secretary
National Bureau of Standards
Ernest Ambler. Director
uraui af jtatufortte
Certtfttat* of
Standard Reference Material 1648
Urban P articulate Matter
This Standard Reference Material is intended for use in the calibration of methods used in the chemical analysis
of atmospheric paniculate matter and materials with similar matrices. The material is atmospheric paniculate
matter collected in an urban location.
The certified values are based on measurements of 6 to 30 samples by each of the analytical techniques indicated.
The estimated uncertainties include those due to sample variation, possible methodology differences, and errors
of measurement (see Preparation and Analysis). The certified values are based on a sample size of at least
100 mg of the dried material. The material should be dried at 105 °C for 8 hours before use.
Element
Arsenic* c
... . abed
Cadmium
Chromium
Copper8 be
Nickel" bd
„. abed
Zinc
Uranium
Mg/g
115 ± 10
75 ± 7
403 ± 12
609 ± 27
82 ± 3
4760 ± 140
5.5 ± 0.1
Element
, abce
Iron
Leadabd
Weight %
3.91 ±0.10
0.655 ± .008
Atomic Absorption Spectrophotometry
Isotope Dilution Mass Spectrometry
Neutron Activation Analysis
Polarography
Spectrophotometry
The overall direction and coordination of the technical measurements leading to certification were performed
under the chairmanship of J. K. Taylor.
The technical and support aspects involved in preparation, certification, and issuance of this Standard Refer-
ence Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.
Washington, D.C. 20234
November 16, 1978
J. Paul Cali, Chief
Office of Standard Reference Materials
(over)
134
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Preparation and Analysis
This SRM was prepared from urban paniculate matter collected in the St. Louis, Missouri, area in a baghouse
especially designed for this purpose. The material was collected! over a period in excess of 12 months and, there-
fore, is a time-integrated sample. While not represented to be typical of the area in which it was collected, it is
believed to typify the analytical problems of atmospheric samples obtained from industrialized urban areas.
The material was removed from the filter bags by a specially designed vacuum cleaner and combined into a
single lot. This product was screened through a fine-mesh sieve to remove most of the fibers and other
extraneous material from the bags. The sieved material was then thoroughly mixed in a V-blender, bottled, and
sequentially numbered.
Randomly selected bottles were used for the analytical measurements. Each analyst examined at least 6 bottles,
some of them measuring replicate samples from each bottle. No correlation was found between measured
values and the bottling sequence. Also, the results of measurements of samples from different bottles were not
significantly different than the measurements of replicate samples from single bottles. Accordingly, it is
believed that all bottles of this SRM have the same composition.
The analytical methods employed were those in regular use at NBS for certification of Standard Reference
Materials, except as noted in the following paragraphs. Measurements and calibrations were made to reduce
random and .systematic errors to no more than one percent, relative. The uncertainties of the certified values
listed in the table include those associated both with measurement and material variability. They represent the
95 percent tolerance limits for an individual sub-sample, i.e., 95 percent of the sub-samples from a single unit of
this SRM would be expected to have a composition within the indicated range of values 95 percent of the time.
The following values have not been certified because either they were not based on results of a reference
method, or were not determined by two or more independent methods.They are included for information only.
All values are in units of /ig/g of sample, unless otherwise indicated.
Aluminum
Antimony
Barium
Bromine
Cerium
Cesium
Chlorine
Cobalt
Europium
Hafnium
Indium
Iodine
Vanadium
(3.3 wt. %)
(45)
(737)
(500)
(55)
(3)
(0.45 WL %)
(18)
(0.8)
(4.4)
(1.05
(200
(130)
Lanthanum
Magnesium
Manganese
Potassium
Samarium
Scandium
Selenium
Silver
Sodium
Thorium
Titanium
Tungsten
(42)
(0.8 wt.%)
(860)
(1.0 wt.%)
(4.4)
(7)
(24)
(6)
(0.40 wt%)
(7.4)
(0.40 wt.%)
(4.8)
135
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The values listed below are based on measurements made in a single laboratory, and are given for information
only. While no reason exists to suspect systematic bias in these numbers, no attempt was made to evaluate such
bias attributable to either the method or the laboratory. The method used for each set of measurements is also
listed. The uncertainties indicated are two times the standard deviation of the mean.
Nitrogen (NO3) (1.07% ± 0.06)
Nitrogen (NH4) (2.01% ± .08)
Sulfate (15.42% ± .14)
SiO2 (26.8% ± .38)
Freon Soluble (1.19%± .47)
The above values were determined by the methods indicated below:
Nitrate - Extraction with water and measurement by ASTM Method D992.
Ammonia - NaOH addition followed by steam distillation and titration.
Sulfate - Extraction with water and measurement by ASTM D516.
SiO2 - Solution and measurement by ASTM Method E350.
Freon Soluble - Extraction with Freon 113, using the method described in "Standard
Methods in Examination of Water and Waste Water," 14th Edition, p. 518,
American Public Health Association, Washington, D.C.
J. W. Matwey supervised the collection of the material as well as sieving and bottling. The following members
of the staff of the NBS Center for Analytical Chemistry performed the certification measurements: R. W. Burke;
E. R. Deardorff; B. I. Diamondstone; L. P. Dunstan; M. S. Epstein; M. Gallorini; E. L. Garner; J. W. Gramlich;
R. R. Greenberg; L. A. Machlan; E. J. Maienthal; and T. J. Murphy.
136
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-80-125
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
A Summary of Oil Shale Activities at the National
Bureau of Standards 1975-1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Lottie T. McClendon
8. PERFORMING ORGANIZATION REPORT NO.
NBSIR80-1986
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Office of Environmental Measurements
National Bureau of Standards
Washington, DC 20234
10. PROGRAM ELEMENT NO.
684BE
11. CONTRACT/GRANT NO.
EPA IAG D5 E684
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Environmental Engineering & Technology
Office of Research & Development
Environmental Protection Agency
Washington, DC 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/ORD/17
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report provides a summary of NBS Oil Shale activities covering
the period 1975 to 1979. At the start of this period a Workshop on
Standard Reference Materials (SRM's) needed for Oil Shale Processing was
held at NBS and served to provide the priority guidance for the future
of this program. A summary of the recommendations of that Workshop, the
manuscripts presented during the Workshop, and the list of attendees is
included in this report. The status of the Oil Shale Research at NBS is
also presented consisting of developmental work on the feasibility of
producing an Oil Shale and a Shale Oil Standard Reference Materials
characterized for both trace inorganic and trace organic constituents.
Additionally, information is given dealing with the development of
measurement methods appropriate for Oil Shale and Shale Oil trace in-
organic and trace organic analysis. Several papers are also included
giving additional details on these matters. Other NBS Standard Reference
Materials, which may be appropriate for the use by the Oil Shale community,
are described briefly within this document. Finally, recommendations
for future Oil Shale projects dealing with the development of measurement
methods and Standard Reference Materials at NBS are presented.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Measurement Methods
Oil Shale
Standard Reference Materials
Water Pollution Control
7B
7C
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
142
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EDITION IS OBSOLETE
-------
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Environmental Protection
Agency
Information
Cincinnati OH 45268
Fees Paid
Environmental
Protection
Agency
EPA-335
I uSSuST I
V_^^~®/
Official Business
Penalty for Private Use, $300
Special Fourth-Class Rate
Book
$U.-W$&\
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