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

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                              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.

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                               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

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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

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         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

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                              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

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                            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

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     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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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     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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                                35

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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"
    in Pacific Northwest Laboratory Annual Report for 1978 to
    the DOE Assistant Secretary for Environment, Richland, Wash.,
    PNL-2850 PT3 UC-11,  p.  1.43 (1979).

21. S.  A.  Wise, S. N. Chesler, H. S.  Hertz, L. R.  Hilpert, and
    W.  E.  May, Anal.  Chem., 49_,  2306 (1977).
                               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

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                     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

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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

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                               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

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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

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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

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                 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

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                         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

-------
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

-------
     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

-------
                                 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

-------
 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

-------
                                  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

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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

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                                   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

-------
                                         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

-------
                  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

-------
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

-------
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

-------
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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Agency
Information
Cincinnati OH 45268
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Agency
EPA-335
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                                                                                                                                                              V_^^~®/
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