United States
Environmental Protection
Agency
Environmental Vo~>'.    :-'•••'
Laboratory
Cincinnati OH 45268
Research and Development
Analysis
of Radioactive Contaminants
in By-Products
From Coal-Fired
Power Plant Operations

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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
      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 ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                                EPA-600/4-78-039
                                                July 1978
ANALYSIS OF RADIOACTIVE CONTAMINANTS IN BY-PRODUCTS

       FROM COAL-FIRED POWER PLANT OPERATIONS
                        by

          Herman Krieger and Betty Jacobs
  Environmental Monitoring and Support Laboratory
       U. S. Environmental Protection Agency
              Cincinnati, Ohio  45268
  ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
         -OFFICE OF RESEARCH AND DEVELOPMENT
       U. S. ENVIRONMENTAL PROTECTION AGENCY
              CINCINNATI, OHIO  45268

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                                  DISCLAIMER
       This report has been reviewed by the Environmental Monitoring and
Support Laboratory, U. S. Environmental Protection Agency, and approved for
publication.  Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
                                     ii

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                                   FOREWORD
       Man and his environment must be protected from the adverse effects of
pesticides, radiation, noise, and other forms of pollution, and the unwise
management of solid waste.  Efforts to protect the environment require a
focus that recognizes the interplay between the components of our physical
environment—air, water and land.  The Environmental Monitoring and Support
Laboratory contributes to the multidisciplinary focus through progress
engaged in:

       •Studies on the effects of environmental contaminants on the bio-
        sphere, and

       •A search for ways to prevent contaminaton and to recycle valuable
        resources.

       This report focuses on the radioactive contaminants released to the
environment in the course of fossil fuel power plant operations and
ascertains whether it has a deleterious effect on the population.
                                           Dwight G. Ballinger
                                           Director
                                           Environmental Monitoring and
                                             Support Laboratory
                                     iii

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                                   ABSTRACT

       Electrical power requirements for the next 200 years will necessitate
a doubling of our present generating capacity.  Even with the  imposition of
strong conservation measures, additional facilities and sources of fuel must
become available.  Because of restrictions on construction of  nuclear
installations, coal-fired power plants have to assume most of  this burden.
Since environmental discharges associated with the coal power  industry
contain not only the oxides of sulfur and nitrogen, but also significant
concentrations of natural radioactivity, a potential radiation hazard from
radium, thorium and uranium could result as more coal is burned.

       In this study, the major radionuclides detected in fossil fuel power
plant operations have been identified and quantified.  Samples of coal, fly
ash, bottom ash and scrubber sludge were collected from different regions in
the U.S. and analyzed for radium, thorium and uranium.  The standard
radiochemical procedures were modified in order to obtain reoroducible
results for the variety of samples analyzed, which then can be used to
calculate a radioactivity balance on the basis of normal operations.

       The report tabulates the spectrum of activity levels in a variety of
samples, and compares the results from non-destructive spectrometry and from
radiochemical separations.  The environmental impact of an expanding
fossil-fuel power plant operation is discussed, and it is concluded that for
the present, no radiation hazard exists.

       This report covers a period from January 1976 to December 1977 and
work was completed as of February 1978.
                                      iv

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                                   CONTENTS
Foreword	iii
Abstract	iv
Figures	vi
Tables   	vi
Acknowledgment 	 vii

     1.  Introduction  	   1
     2.  Experimental  	   5
     3.  Results	'	   7

References	16
Appendix   	18

     I.  Pretreatment of Samples	18
    II.  Radiochemical Analytical Procedures 	  18
          A.   Radium-226 Analysis  	  18
          B.   Uranium and Thorium Analysis	27

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                                   FIGURES


Number                                                               Page

  1     Growth of Population and Energy Consumption from 1900 to
          Present and Predictions to 2000	2

  2     Schematic of Coal Burning Plant Depicting Sampling Ports  .  .  4

  3     Ge(Li) Spectra Comparing Instrument Background, Kentucky
          Coal, and Electrostatic Precipitated Fly Ash	8

  4     Radon Emanation Apparatus with Scintillation Cell 	 20

  5     A Typical Radon Bubbler (Emanation tube)  	 21

  6     The Growth of Radon-222 from Radium-226	22

  7     A Typical Scintillation Cell for Radon Counting 	 24


                                    TABLES

Number                                                               Page

   1     Comparison of Non-Destructive and Radiochemical  '
           Analysis of 226Ra	10

   2     Radiochemical Analysis of Coal and Coal By-Products,
           pCi/g	11

   3     By-Product Production and 22^Ra Activity Data for
           a  1000 Megawatt Fossil Fuel Plant	13
                                      vi

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                                ACKNOWLEDGMENT
       The cooperation of the Cincinnati Gas and Electric Company and of the
Radiation Control Branch, Bureau of Health Services, Frankfort, Kentucky, is
gratefully acknowledged.  Their engineers and technicians were most helpful
in obtaining and delivering the representative samples required.

       The thorium and uranium analyses were performed by the analytical
section under Mrs. Ann Strong, EERL, Montgomery, Alabama, and the dose
determinations were computed and interpreted by Dr. R. L. Blanchard, EERL,
Montgomery, Alabama.  This assistance is deeply appreciated.
                                    vii

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                                  SECTION 1

                                 INTRODUCTION

       Today, the vulnerability and future needs of  the U.S.  in  the  area of
electrical power are uppermost in the minds of the consuming  public.   The
energy crisis has become a complex of economic, environmental, conservation
and cost-benefit issues that must be resolved to preserve the way-of-life as
we now know it.  The oil embargo showed how dependent we were on foreign
nations for the raw materials to keep oil-burning engines in  operation;  the
extremely cold winters of 1977 and 1978 cautioned us about  our depleted
natural gas reserves and the importance of energy conservation;  and  the
environmental battle against nuclear power stations, coupled  with the
presidential edict against fuel reprocessing operations, emphasized  our
energy predicament.  In addition, the latest energy  plan stressed both fuel
conservation and a penalty for those industrial consumers who would  not  or
could not convert to coal, the dwindling coal reserves resulting from  labor
disputes notwithstanding.
                                                              f
       The search for alternative sources of energy  plus the  need for  energy
conservation is a must.  But the fact that population growth  and electrical
power requirements have been increasing more rapidly than electricity
generating capacity has aggravated this problem.^'  This observation  is
graphically depicted in Figure 1, and predicts the situation  that will be in
existence at the turn of the century.  In spite of the most stringent
conservation efforts or the effectiveness of alternative sources of
electricity, power requirements should more than double over  the next  20
years.

       The alternative sources of electrical power do not give us cause  to
be optimistic.  Solar, hydroelectric and geothermal power are potential
sources, but in the opinion of the experts, their full-scale  operation is at
least 10 years away.  A similar prediction is made for coal degasification
operations, which will utilize all types and grades of coal without
pretreatment.  Since the present state of the art is pilot plant evaluation,
since gas and oil reserves are severely limited, and since there remain  many
environmental problems connected with the construction and operation of
nuclear power stations, the main thrust in the energy picture today  is that
additional coal burning power plants must be built.  Our electrical needs
may be satisfied if these are brought rapidly into operation, but to
accomplish this, the fossil fuel economy must undergo major changes, and
energy consumption must be controlled.

       The United States has an almost inexhaustible supply of fossil  fuel,
which today accounts for more than half of the thermal electrical energy
production.  A conservative estimate^2) puts the availability of our coal

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     10
              20
30
         40
1950
                                                60
                  70
                                                                  80
                                                    90
Figure 1.  Growth  of population and energy  consumption from 1900 to present

                           and predictions to  2000.
                                                                                          V?



                                                                                          O
                                                                                          Ul





                                                                                          VI


                                                                                          O
                                                                                         O
                                                                                         ?

                                                                                         -J


                                                                                         i
                                                                                     60
                                           2000

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reserves at 200 years or more, with deposits  in more  than  30  states that are
potentially developable for commercial purposes.  Fuel  production
operations, however, have not been able to keep up with the unusual increase
in coal consumption, especially during periods of labor disputes.

       The ineffectiveness of present mining  techniques usually  results in
the discarding of potential coal reserves in  the overall process.   Because
of the projected heavy demand for fuel, this  waste product needs to be
recovered.  And, as these demands increase, mining operations will  become
less selective, and a poorer grade of ore will be extracted.  This  projected
increase in coal consumption, coupled with the decreasing  quality of
available coal, will also result in substantially increased quantities of
coal ash.

       The geological and geographic factors  associated with  the fossil fuel
beds determine the nature of the ultimate residue; the  actual mining devices
determine the extent of environmental insult.  Even with low  sulfur coal,
mined primarily in Western U.S., several million tons of S02, N02 and
particulates find their way into the environment as emissions from  coal
burning plants.  Projecting this into the future, it  is evident  that double
this volume may be released in 1999.'3)  The  bulk of  this  solid  waste will
be recovered from scrubber operations and therefore its disposal needs to be
considered.

       The schematic diagram that shows the flow of air, fuel and ash in a
typical fossil fuel plant is depicted in Figure 2.  By  analyzing each
segment of the coal burning process, and with the information available
regarding plant operation, a material balance could be  made and  a dose
committment from releases could be calculated.

       There have been investigations into the health hazards resulting from
increased use of coal and other fossil fuels  - the effect  of N02, S02
and particulates that are found in plant exhaust.  These,  however,  are the
non-radioactive components from fossil fuel combustion.

       There have been studies that have measured the concentration of
radium, thorium, and uranium that have been released  to the environ-
ment as fly ash from the combustion of coal in fossil-fuel plant
operations.(^-5)  There have been investigations that have compared stack
discharges from coal-fired plants with that from nuclear power plants and
have determined that a greater hazard results from the  ^2opa emitted from
fossil fuel than from the noble gases and 131i released from a comparable
size nuclear plant.(6-8)

       Therefore, if the radiation hazard from coal burning plants  is to be
determined, the activity in coal and its operational by-products must be
obtained.  With this information available, dose commitment results for each
component can be estimated.

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                          ^r
                                     SCRUBBER
FLY ASH  -*•
    SUPER
   HEATER
                        ELECTROSTATIC
                        PRECIPITATOR
                                       •*• TO BOILERS
                          FURNACE
                                                           COAL
                                                           FROM
                                                           HOPPER
                                                   MIXER
                                               a
r
                                                             HOT AIR
                                      BOTTOM ASH
                 Figure 2.  Schematic of coal burning plant
                           depicting Sampling ports.

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                                  SECTION 2

                                 EXPERIMENTAL

       Through the assistance of the radiation representatives  of  several
regional offices, samples of coal and combustion by-products were  collected
during fossil-fuel plant operations.  Additional coal samples were obtained
from different mines in the United States.

       During this study, 75 samples of coal and products of combustion were
collected during actual operations, and shipped to the laboratory  for
analysis.  The quality control data relating to these aliquots, obtained
from the Federal Power Commission, indicated the annual operating  experience
of these plants.  The radionuclides present in these fossil fuels  were then
determined using radiochemical procedures applicable to liquid  samples.  The
methods had to be modified to assure quantitative recovery of all  activity.

       Each sample was air dried, pulverized if necessary, ard  homogenized
until uniform.  In a few instances the samples were sieved to a 60  mesh size
in order to separate any non-uniform aggregates.  Each sample was  placed in
a 400 ml polyethylene container and filled to the mark.  After  recording the
tare weight, the gamma radioactivity in the sample was determined.
Radionuclides that emit gamma rays were identified by their characteristic
gamma-ray energies.  A 2048-channel spectrometer and a Ge(Li) detector were
employed to obtain the spectra.  Because of the low activity and the low
abundance of these nuclides, overnight and long week-end counting  times were
required.  Once the gamma emitters were identified, the activities  of
several of them were determined and concentration factors were  calculated.

       The radium, thorium and uranium concentrations were ascertained by
radiochemistry using methodology applicable to aqueous samples  that had to
be modified to accommodate the variety of samples and sample sizes.  Testing
continued until reliable and reproducible results were obtained on  replicate
determinations.  The selected methods were effective for all kinds  of
fossil-fuel and by-product samples and assured that all the activity was
completely solubilized at the start of the analysis.

       Various methods were evaluated for solubilizing the sample matrices.
These included hydrogen fluoride digestion, Parr bomb ignition  and  fusion
with different flux combinations.  The modified procedures appear  in the
Appendix*, and are summarized as follows.
*We appreciate the cooperation and assistance of Mrs. Ann Strong, Chief,
Analysis Section, Eastern Environmental Research Laboratory, Montgomery,
Alabama, for the thorium and uranium analyses.

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       1.  226Ra:  The  fossil-fuel sample is dried at 110°C for a few
days, cooled, pulverized and  sieved for  homogeneity using a sixty mesh
sieve..  In order to avoid  activity loss  during ignition,  a weighed aliquot
(5-10 g) is carefully pre-ashed  with a Meker burner.

       The pre-ashed sample is placed in a muffle furnace and ashed
overnight or longer if  the ashing is incomplete.   During this operation the
temperature is  slowly increased  to 600°C.  The sample is cooled and
weighed to determine ash content.   For the initial solubilization, a 1-gm
aliquot is fused with an alkaline flux and dissolved with strong acid.  The
BaSOij, carrying the radium activity, is  precipitated, dissolved and
transferred to  a radon  bubbler.   The radon in the sample is deemanated, and
the bubbler is  set aside for  about a week for the ingrowth of 222Rn from
its 22°Ra parent.

       The radon that has  grown  in is deemanated into a calibrated
scintillation cell, and the radon and its alpha-emitting daughters are
allowed to come to equilibrium.   The 222Rn ^n the cell is determined with
an alpha scintillation  counter.

       This modification of the  radon emanation' technique'9) assures
complete dissolution of the sample and quantitative measurement of radium
activity.

       2.  Uranium and  Thorium:   The fossil-fuel sample is dried at 110°C
overnight, cooled, pulverized and sieved for homogeneity using a sixty-mesh
sieve.  Up to 5 g of  sample is ashed in  the muffle furnace at 550°C
overnight.

       The ashed sample is transferred to a teflon beaker and standardized
232{j and 23^Th  tracers  are added for yield calculations.  After an HF
digestion, the  residue  is  transferred to a platinum crucible for a
pyrophosphate  fusion.   Sulfuric  acid digestion, evaporation to fumes and
dissolution in  hydrochloric acid complete the solubilization.

       Uranium  is extracted into triisoctylamine and coprecipitated with
lanthanum  fluoride.   The thorium in the  acid phase of the extraction is
purified by anion exchange and coprecipitated with lanthanum fluoride.

       The planchets  are counted by alpha spectroscopy to determine the
uranium  and  thorium  isotopes, respectively.  This improvement of existing
methodology^10-11^ enables all the activity to be determined on the same
aliquot.

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                                  SECTION 3

                                   RESULTS
       Gamma Spectroscopy - The gamma-ray activities in  the coals, ashes  and
sludges were found to be a function of the source and type of fuel
combusted—a fact which was recently reported.'12)  Although most of  the
nuclides were evident in all samples, there were some differences.  As
evidenced by differences in photopeak height, none of the activities  were
lost during combustion, but were concentrated in the ash.  The Ge(Li)
spectra of these samples revealed the presence of the 23o\j and 232^
series and indicated qualitatively what could be expected in stack releases.

       An indication of what activities may be present can be obtained by
comparing the gamma photopeaks of the coal and fly ash samples with that  of
normal background.  The peaks that have been identified  verify the presence
of 214pb, 226Ra, 21^Bi, and ^°K.  These scans are shown  in Figure 3,
and refer to coal and by-products collected from operating plants in  Ohio
and Kentucky.  A similar compilation was made recently on Western
Pennsylvania coal plant operations.  The small differences that existed were
attributed to differences in equilibrium that had been attained in the
respective coal fields and to different coal mining operations.

       Radiochemical Analyses - Methodology for determining radium, thorium
and uranium in aqueous samples have been tested and found quite reliable  for
many years.  The scientific literature has described these procedures, and
reported on modifications that were required when samples of silt, biota  and
vegetation were analyzed.  Several procedures were evaluated by replicate
analyses of the coal and ash samples.  The non-agreement of results
suggested that the sample was not completely in solution, and initial
treatment had to be more rigorous to overcome this obstacle.

       Investigations involving replicate analysis of coal and ash samples
demonstrated that an acceptable treatment consisted of ashing and
hydrofluoric acid digestion in platinum, ashing overnight at high pressure
in a Parr bomb capable of handling one gram samples and  finally an
assortment of flux fusions.  For some samples one of these treatments was
sufficient, but it was generally agreed that a universal dissolution
technique for all coal and by-product samples would assure uniformity of
analytical results and provide reliable values for dose  calculations.  An
alkaline borax flux was determined as satisfactory for all samples.   Using 8
g of flux per gram of sample assured complete dissolution of the sample
which was subsequently purified as the sulfate and dissolved for radon
emanation analysis.

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            1,000,000
00
              100,000 .
                           200
                                                                                                   1800
                                Figure 3.   Ge(Li) spectra comparing  instrument background,
                                           Kentucky coal, and  electrostatic precipitated fly  ash.

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       The initial preparation of  samples  for  the  uranium and thorium
procedures included prior ashing,  a hydrofluoric acid  digestion,  plus a
pyrosulfate fusion.  This meant  that  for the uranium and  thorium  extractions
to be considered complete,- both  a  digestion and fusion technique  were
necessary.

       Although the same procedure was  employed on'all samples, obvious
differences were noted in the appearance of the ash  initially and in
subsequent steps.  Dependent on  the nature of  the  coal sample,  the ash took
on a reddish, whiteish or grayish  texture.  Despite  differences in
appearance, the ash was readily  solubilized during the fusion treatment,  and
the final separation was a purified precipitate.

       After obtaining the gamma spectra for these samples,  the areas under
the 187 keV 22^Ra and the 1462 keV ^°K  photopeaks  were summed and
quantified.  The 22°Ra was then  determined by  radiochemical  analysis using
the modified radon emanation technique.  Comparing the values listed in
Table I, it can be concluded that  the 2  error associated with gamma
spectral analyses, results in values that are  significantly  higher even with
a 1000-minute counting time.   This difference may be  attributed  to the
235y contribution to the 0.186 MeV peak.  As an indication of the presence
of 22°Ra and other nuclides in the uranium and thorium series,
non-destructive spectral analysis  is satisfactory  if long counting time is
available, but for the measurement of this activity  and the  calculation of a
radiation dose, radiochemical analysis  is required.

       The analytical results indicate  small differences  in  the 22°Ra in
coal, the average value being less than 1.0 pCi/g.   The activity  in the ash,
however, varies as a function of the plant operation and  possible prior
treatment of the fossil fuel following mining operation.   A  1-10  fold
concentration has been observed  and similar results  have  been described in
the literature.  Generally speaking, the levels in fly ash and bottom ash
indicate possible differences in mining and coal washing  operations,  and
differences in the source of the fossil fuels.

       The results from the radiochemical analyses of  samples from the
Louisville, Kentucky power plant one year apart are  listed in Table II.   No
stack samples  could be collected, so no activity  balance is  possible.  The
aliquots for the uranium, thorium  and 226pa analyses were taken at the
same time so that a close correlation of all activities could be  made.  From
this data it can be concluded that radioactive composition varies as coal
sources vary.  This will result when the natural acitivity is in  a different
state of equilibrium at the time of mine operations.

       It is generally accepted  that a 1000-megawatt power plant,  the
average capacity for a fuel plant, burns 2 x 10" tons  of  coal annually.
Even though the sources of coal  in the United States do vary  with respect to
chemical composition, ash content, burn-up and activity,  average  values have
been selected in order to calculate a radiation dose.   The Louisville Gas
and Electric Company has indicated that the ash content of coal last year
averaged 15$.  This value is a little higher than  the  norm,  and indicates

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                                   Table  1

      Comparison of Non-Destructive  and Radiochemical  Analyses  of
   Sample              4°K                      226Ra,  pCi/g
Identification        pCi/g          Spectral  Result    Radiochemical  Analysis


Coal:
 W. Ky 3/76          3.6 + 1.0          1.'7  + 1.2              0.49  + 0.01
 W. Pa 4/76          8.3 +0.5          1.0  + 0.2              0.49  + 0.01
 E. Pa 4/76          8.1 + 0.05         1.1  + 0.2              0.55  + 0.01
 E. Ky 11/76         4.2 + 0.4          1.3  + 0.5              0.49  + 0.02
 Ohio 6/76           4.4 + 0.3          0.4  + 0.3              0.29  + 0.01
 W. Montana 5/76     1.1 + 0.2          0.7  + 0.5              0.65  + 0.20
 E. Ky 4/77          6.2 + 0.4          1.6  + 0.4              0.56  + 0.01
 W. Ky 4/77          4.6 + 0.2          1.1  + 0.3              0.59  + 0.04

Fly Ash:
 W. Pa 4/76          23.0 + 0.9          4.6  + 0.3              1-36  + 0.02
 Ohio 6/76           18.0 + 1.0          8.8  + 0.6              4.04  + 0.07
 E. Ky 11/76         18.0 + 2.0          5.8  + 1.0              3.86  + 0.07
 W. Ky 4/77          19.0 + 1.0          7.2  + 0.5              3-92  + 0.07

Bottom Ash:
 E. Ky 6/76          15.0 + 1.0         10.6  + 1.0              4.89  + 0.11
 E. Ky 6/77          18.5 + 0.7          7-5  + 0.7              3.08  + 0.07
                                      10

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                          Table  2
Radiochemical Analysis of Coal and Coal  By-Products,  pCi/g
              234.
226
235
238.
228.
230,,
Date
6/76





6/77





Identification Ra
E.
W.
W.

W.

E.
W.
W.

W.

Ky.
Ky.
Ky.
Ash
Ky.
torn
Ky.
Ky.
Ky.
Ash
Ky.
torn
Coal
Coal
Fly

Bot-
Ash
Coal
Coal
Fly

Bot-
Ash
0.28±0.01
1.98+0.01

7.0 ±0.1

5.0 ±0.1
0.46±0.01
0.72+0.01

3.8 ±0.1

3.1 ±0.1
U
0.54+0.07
0.80±0.10

6.3 ±1.1

5.6 +0.8
0.56+0.16
0.92+0.10

4.2 +0.5

2.7 ±0.4

0.
0.

0.

0.
0.
0.

0.

0.
U
03+0.01
04+0.01

33±0.09

22+0.07
07±0.02
05±0.02

20±0.07

09±0.04
U
0.51+0.07
0.78+0.03

8.6 ±1.1

5.5 ±0.8
0.58+0.12
0.92±0.10

4.4 +0.5

2.7 ±0.3
Th
0.40+0.04
0.21+0.03

1.9 +0.1

1.9 ±0.4
0.60±0.08
0.34±0.04

1.8 ±0.2

1.7 ±0.2
Th
0.46±0.03
0.71±0.05

6.5 ±0.3

6.0 ±0.7
0.61+0.13
0.85±0.05

4.5 +0.3
i
2.7 +0.3
Th
0.30+0.03
0.19±0.02

1.8 ±0.1

1.6 ±0.3
0.39±0.09
0.27+0.03

1.57±0.18

1.3 ±0.2

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the possibility of poorer  grade  of coal being mined.   Continued
deterioration can be expected  in the  future.

       With this information and with our results,  the following
calculations evolve:

       The annual total  ash production would  be 3 x 10^ tons (2 x
tons x 0.15); divided  into bottom residue (15%) and fly ash (85?).   The
quantity of bottom ash,  4.5 x  101* tons (3 x 10^ tons x 0.15) is normally
buried and completely  covered  for disposal.   Airborne pollution will be
negligible from this operation,  and no hazard from the alpha activity will
result.

       The 3 x 105 tons  of fly ash that are generated annually are
collected by electrostatic precipitation followed by stack scrubbers.  This
fly ash is normally used in the  building trades or road improvement
operations.  If the coal ash is  incorporated  in concrete and concrete
products as a replacement for  cement, radon emanation may become a  problem,
and regular monitoring would then be  required.  Past experience has shown
that a radiation problem may result from possible radioactive emanations
from walls and floors  of buildings constructed from this material.   Other
uses of the fly ash have been  in reclaiming surface mine spoil and  as a soil
nutrient.

       The efficiency  of electrostatic precipitators has been rated at
90-95?.  Hence most of the fly ash will be trapped in this operation.
Effectively operating  scrubbers  which can clean up about 80-90? of  the stack
influent will collect  that fraction of the residue.  Hence, about 5000 tons
of fly ash could  find  its way  into the environment as stack gas effluent.

       Subsequent methods development and radiochemical analysis for 22°Ra
and the other important  nuclides entering the fossil fuel plant stack as
gaseous effluent may provide a more accurate determination of the activity
balance that  is experienced when coal is burned in 1000 megawatt fossil fuel
power plants  for one year- The  data  obtained in the radiochemical  analysis
of coal,  fly ash and the other by-products were used to calculate the
following assessment which is  shown in Table III.

       This assessment is based  only  on the grab samplings of the coal, fly
ash and scrubber  sludge  and the  22^Ra content as determined by our
procedures.  Levels  of 22^Ra  ±n  coai as indicated in the literature ranged
from 0.2  - U.O pCi/gm  of coal, from 3-0 - 10.0 pCi/gm of fly ash and from
0.2 - 1.0 pCi/gm  dried scrubber  sludge.  Depending on the source of mining
operations, the 20 mCi 22*>Ra  that is  calculated as an average discharge
from a 1000 megawatt plant may be a conservative estimate.  The activity
levels selected  for  this assessment can also be much higher.  In any event,
direct measurement of  the activity in the stack effluent will provide a more
reliable  estimate  of radiation dose.
                                       12

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                                   Table 3

                By-Product Production and 22^Ra Activity Data
                       for a 1000 Megawatt Fossil Plant
Component

Coal

Bottom Ash

Fly Ash

Scrubber
 Sludge

Stack
Effluent
  Annual
Production,
   tons

2    x 106

0.05 x 106

0.3  x 106


0.1  x 106


    5000
 Average
Activity,
  pCi/g

  0.9

  5.0

  5.0


  0.5


  5.0
 Total Acti-
vity Available
  Annually,
    Ci/yr

    1.65

    0.23

    1.35


    0.05
Potential
  Annual
Discharge,
   Ci/yr
                      0.02
                                     13

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       The foregoing  analytical  and calculated results plus general
operation data and assumptions are  to  be  utilized to calculate the annual
dose rate.  The  criteria  have been  compiled in a report soon to be
published.
       These then  are  the  assumptions:

       1.  Electrostatic precipitators  and stack scrubbers operate at
maximum efficiency.

       2.  Operating information:

             Stack height  - 500  ft.  (150  m.)
             Average stability -neutral condition
             Max.  downwind concentration  - at 5.5 km (3.4 mi.)
             Wind  direction - SSW to NNE  - 15% of the time
             Average wind  speed  - 8.4 mph
             Regular source of fuel

       3.  Relatively  flat terrain between stack and receptor.

       4.  No  plume rise  due to  buoyancy  of heated effluent.

       The critical organ  for 22^Ra, which is designated as a "W
compound*",  is the bone, where the dose limit has been set at 25 mrem/yr.
The  average  annual concentration of  22°Ra that is released from a 1000
megawatt  coal  burning  plant is 20 mCi or  2.4 x ID'11 Ci/m3.  The dose to
the  bone  for this  activity is 3.7 x  10~2  mrem/yr. or 2 x 10~3 of the
bone dose limit.   The  radiation dose to the lungs for the 22°Ra discharge
is about  a factor  of 10 lower.
        Similar calculations for the 232Th and 23^u being emitted from
 the  plants indicated only a small fraction of the allowable radiation dose
 occurring.  The chemical toxicity from these was more significant.

        In summary,  then,  a very minimal radiation hazard results from the
 discharges from present-day coal plants under the optimum conditions
 stated.   However,  if scrubbers are not employed, or if these collectors
 operate at less than maximum efficiency, the radiation hazard may become
 significant.   If present coal supplies are replaced with fuel of a higher
 radioactive and ash content, an increase in the radiation hazard could
 result.   For the present, the greater hazard results from mining and
 pre-combustion operations, and it is these activities that must be carefully
 monitored.  Therefore,  if plant operations are carefully monitored, an
 expanding fossil- fuel economy need not have a serious environmental
 radiation impact.
 *A  "W compound" is defined as one having a clearance time of a few
  days to a few weeks.
                                      14

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       The procedures which have been developed for measuring ""Ra,
      and 23°u ^n COal and coal by-products have been instrumental in
calculating an activity balance in a coal plant operation.  From these
radiochemical results, the minimal radiation hazard could be calculated.
                                      15

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                                  REFERENCES

1.     "Outlook for Coal" - ACS Symposium on Coal Dilemma, Feb. 1977.
       Report in Chem. and Eng. News, Feb. 14, 1977.

2.     Guerrieri, S.A.  "Achieving Energy Self-Sufficiency With Coal,"
       Combustion, 11-22  (April 1977).

3-     "Trends in Powerplant Capacity and Utilization - Inventory of
       Powerplants in the United States."   Report, Federal Energy
       Administration, Washington, D.C.  (1976).

4.     Eisenbud, M. and Petrow, H.,  "Radioactivity  in the Atmospheric
       Effluents of Power Plants that Use Fossil Fuels".  Science, 144,
       April 17, 1964.

5.     Marquardt, W., Hoehle,  R., and Schub, U., "Radioactive  Emissions by
       Coal-Fed Power Stations."  Z. Gesamte Hyg. Ihre Grenzgeb 16, 188-191
       (1970).

6.     Martin, J. E., Harward, E. D., Oakley, D. T., "Comparison of
       Radioactivity From Fossil Fuel and Nuclear Power Plants."  DHEW,
       Bureau of Radiological  Health, Public Health Service Report, Appendix
       14  (Nov. 1969).

7.     Hull, A. P., "Some Comparisons of the Environmental Risks from
       Nuclear and Fossil Fueled Power  Plants."  Nuclear Safety, 12 (3)
       185-196 (1971).

8.     Terrill, J. G., Harward, E. D.,  Leggett, I., "Environmental Aspects
       of  Nuclear and Conventional Power Plants."   Industrial Medicine and
       Surgery, 36, 412-418  (June 1967).

9.     Rushing, D. E., "The  Analysis of Effluents and Environmental Samples
       from Uranium Mills and  of Biological Samples for Uranium, Radium and
       Polonium."  SM/41-44,   Symposium on Radiological Health and Safety,
       Vienna, Austria  (1963).

10.    Hyde, E. K., "The  Radiochemistry of Thorium."  National Academy of
       Sciences, National Research Council, NAS-NS  3004 (I960).

11.    Grindler, J. E.,  "The Radiochemistry of Uranium."  National Academy
       of  Sciences, National Research Council, NAS-NS 3050 (1962).
                                      16

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12.    Barber, D. E., Giorgio, H. R., "Gamma-Ray Activity in Bituminous,
       Sub-bituminous and Lignite Coals."  Health Physics, 32, £, 83-88
       (Feb. 1977).

13.    Blanchard, R. L., Kolde, H. E., Montgomery, D. M., "Criteria for the
       Estimation of Radiation Dose."  Office of Radiation Programs, U. S.
       E.P.A. (to be published).
                                     17

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                                   APPENDIX
                             Methods of Analysis

I.  Pretreatment of Samples  (Note  1)

       A.  Coal - Take an aliquot  (20-30  g),  grind  in  a mortar  and  put
through a 60-mesh sieve.  Transfer to a tared porcelain dish, weigh and
pre-ash with a Meker burner.  The  pre-ashing  must proceed  carefully and
slowly-  Starting with a low flame, to keep losses  at  a minimum, gradually
increase the flame until all gases are released and the carbon  deposits  are
burned off the rim of the dish.  Continue ashing overnight in a muffle
furnace at 600°C.  After cooling and weighing, take a  1 gm aliquot  of the
ash for the initial alkaline fusion step.

       B.  Bottom Ash - Take an aliquot (5-10 gm),  grind in a mortar, put
through a 60-mesh sieve and  transfer to a porcelain dish.   Ash  overnight in
a muffle furnace at 600°C, cool, weigh and take a 1 gm aliquot  for  the
initial alkaline fusion step.

       C.  Fly Ash - Ash an  aliquot (1-2  g) overnight  in a muffle furnace at
600°C.  After cooling, take  a 1 gm aliquot for the  initial alkaline fusion
step.

       D.  Scrubber Sludge - Dry an aliquot  (5-10 g) in a  drying oven
overnight at 105°C.  Transfer to a mortar and grind till uniform.   Ash
overnight in a muffle furnace at 600°C.   After cooling, take a  1 gm
aliquot for the initial alkaline fusion step.

II.  Radiochemical Analytical Procedures

       A.  Radium-226 Analysis - Radon Emanation Technique (Fig. 4).

             1.  Principle of Method

                 The radium  in the coal and by-product sample is recovered
             by an alkaline  fusion of a pretreated  ash.  The melt is
             dissolved in sulfuric acid and  the activity is concentrated and
             separated by coprecipitation with barium  as the sulfate.  The
             precipitate is  dissolved in  EDTA, placed  in a bubbler,
             deemanated, sealed and stored for ingrowth of 222Rn.

             2.  Reagents

             Radioactive tracer standard: 22°Ra
             Alkaline flux reagent - prepared reagent
             Ammonium hydroxide, NHiiOH:   15  N (cone.)
             Ascarite:  drying reagent, 8-20  mesh

                                     18

-------
Barium carrier:  16 rag/ml
EDTA reagent:  0.25 M  (Note 2)
Helium gas
Hydrochloric acid, HC1:  12 JI  (cone.)
Hydrogen peroxide, H202:  3%
Magnesium perchlorate, Mg(C10i|)2
Potassium carbonate,
Sodium carbonate,
Sodium borate decahydrate, Na2Bi}07' 10H20
Sodium hydroxide, NaOH:  10 N
Sulfuric acid, H2SOij:  36 N (cone.), 18 N, 0.1 N

3.  Procedure

a.  Prepare an alkaline flux reagent (Note 3), and  store  in  an
air-tight bottle.

b.  For each gram of ashed sample, mix thoroughly with  8  g of
the alkaline flux reagent in a 100 ml platinum dish.  Fuse the
sample by heating with a blast burner, swirling until the melt
is a clear red, then continue heating for 20 minutes.   Cool.

c.  Place crucible with melt in a  covered beaker containing  120
ml water, 20 ml 36 N H2SOn and 5 ml 3% H202 for each 8
g of alkaline flux reagent.  When  solids are dissolved, remove
and rinse dish, adding rinse to beaker.  Heat solution  and
slowly add 2.0 ml barium carrier.  Continue stirring and
heating for 30 minutes.  Allow the precipitate to settle
overnight, decant and discard supernatant.

d.  Slurry the precipitate and transfer to a centrifuge tube
with a minimum amount of 0.1 N H2S04-  Centrifuge and
discard supernatant.  Wash twice with 0.1 N H2SOij and
discard washes.

e.  Add 20 ml EDTA reagent, heat in a hot water bath and  stir
well.  Add a few drops 10 N NaOH if the precipitate does  not
readily dissolve (Note 4).

f.  Transfer the solution to a radon bubbler (Fig.  5).  Open
both the upper and lower stopcocks and deemanate the solution
by slowly passing helium gas through the bubbler for about 20
minutes.

g.  Close the two stopcocks, and record time.  Store the
solution for U to 8 days for ingrowth of 222Rn (Fig. 6).

h.  At the end of the storage period, fill the upper half of an
absorption tube with magnesium perchlorate and the  lower  half
with ascarite (Note 5).  Attach the tube to the radon bubbler
and then attach the evacuated scintillation cell (Fig.  7) to
the tube.
                         19

-------
                                     -Scintillation  Cell
                                      Manometer,  I 1/2mm,  1.0.

                                      Capillary  T-Tube

                                      Thermometer Capillary


                                      Anhydrous Magnesium Perchlorcta

                                      Ascarite  (8-20 mesh)
                                      Aged Air. From Compressed
                                        Air Regulator
                                      Radon  Bubbler
                         —	Mercury Reservoir
Figure 4.  Radon Emanation Apparatus with Scintillation Cell
                              20

-------

<:
135
<
<
33

Liquid^
Level
mm
I7mrn^
•>
^±
mm
->

^ -
ii
* — 7mm O.D.
k
ff^

*— - -—
ViT^-lfi
X
1
^
&35mm^
"1 ^\ Corning No. 2
1 .s^ or Equivalent
~^^^
=^C
f
l^ Bubble Trap
^ 7 mm I.D.
rtigiuiiy Draco
7mm Capillary Tubing
* IV? mm I.D.
Fritted Glass Disc
/" 10-15 micron pores
Volume to be kept
at minimum
Figure 5.  A Typical Radon Bubbler (emanation tube)
                          21

-------
to
   1.0


   0.9


   0.8



I 0-7
k_
J3
| 0.6


^0.5


° 0.4


I 0.3
o
o
£0.2


   O.I


   0.0
                                                       10

                                                     Days
                                                                            15
20
                  Figure 6.  The Growth of Radon-222 from Radium-226.

-------
i.  Open the stopcock on the cell and  check  the  assembly  for
leaks.  Gradually open the outlet stopcock on  the  bubbler,  and
when the stopcock is fully open and no  further significant
bubbling takes place, close the stopcock.

j.  Adjust the aged air or helium gas  pressure so  that  the  gas
flows at slightly above atmospheric pressure.

k.   Connect the hose to the bubbler inlet and gradually  open
the inlet stopcock using the bubbling as a guide.  When the
stopcock can be fully opened without a  significant amount of
bubbling, the bubbler is essentially at atmospheric pressure
again.

1.  Open the outlet stopcock very slightly and allow bubbling
to proceed at a rate, determined by experience,  such that 15 to
20 minutes are required to complete deemanation.

m.  Toward the end of the deemanation, when  the  vacuum  is no
longer effective, gradually increase the helium  gas pressure.
When the system is at atmospheric pressure,  shut off the  helium
gas, disconnect the .tubing from the bubbler  inlet  and close the
inlet and outlet stopcocks of the cell and bubbler, and record
time.  This is the beginning of 222Rn  decay  and  ingrowth  of
222Rn daughters.

n.  Store the scintillation cell for at least  4  hours to  ensure
equilibrium between radon and radon daughters.   Count the alpha
scintillations from the cell in a radon counter  with a
light-tight enclosure that protects the photomultiplier tube.
Record the counting time to correct for the  decay  of 222Rn.

4.  Calculation

Calculate the concentration, D, of the 22°Ra activity in
picocuries per gram as follows:

     D-    C          1        _J_        ^3
     D   2.22 EV  A    ^   A   --1*
where:

C = net count rate, counts/minute  (Note 6),
E = calibration constant for the deemanation system  and  the
    scintillation cell in counts per minute/disintegrations  per
    minute of 222Rn (Note 7),
                         23

-------
       67mm
      90mm
                    Phosphor
                    ^Coated
                   Clear Silica
                     V/indow
                                            Corning No. 2
                                            or Equivalent
                                            Brass Collar
                                            Kovar Metal
              lit lit H   HUHilllII IIJ    U
                     50 mm
Figure  7.   A Typical Scintillation Cell  for Radon Counting
                              24

-------
 V = sample aliquot in grams,
t-1 = the elapsed time in days between the first and second
     deemanations (steps g and m) and A is the decay constant of
     222Rn (0.181 d-1),
^2 = the time interval between the second deemanation and
     counting and X is the decay constant of 222Rn (0.00755
     hr~l), and
^3 = the counting time in minutes and A is the decay constant
     of 222Rn (1.26 x 10-4 min"1).

 Notes:

 (1)  Sample weight prior to ashing should be obtained, as well
 as the weight of the ashed aliquot used in analysis.  This
 information is of value for relating pCi/g ash to pCi/g
 original sample.

 (2)  Preparation of 0.25 M EDTA reagent - Dissolve 20 grams
 NaOH in about 750 ml water,  heat and slowly add 93 grams
 Na2c10Hl4°8N2'2H2° (disodium ethylenedinitri-
 loacetate dihydrate) while stirring.  After the salt is in
 solution, filter through coarse filter paper and dilute to 1
 liter.
                                                  •
 (3)  An alkaline flux reagent is prepared by mixing thoroughly
 30 mg BaS04,  65.8 g K2C03, 50.5 g Na2CC>3 and 33-7 g
 ^26407• 101^0 in a 500 ml platinum dish.  Heat
 cautiously to expel water.  Using a blast burner, fuse the
 mixture by swirling constantly during the heating.   Cool the
 mixture, transfer to a large mortar and grind until the fines
 pass through a 10-mesh screen.  Store in an air-tight bottle.

 (U)  The volume of these bubblers is usually greater than 20 ml
 allowing for at least a 1 cm air space between the bubbler and
 the stopper.   In those instances where the solution volume
 exceeds the capacity of the bubbler, it will be necessary to
 continue the boiling in the water bath until the volume is
 reduced.

 (5)  For minimizing corrections that would be required in
 subsequent calculations, the voids above the bubbler must be
 kept very small.  Capillary tubing should be used whenever
 possible, and the drying tube volume with the Ascarite and
 magnesium perchlorate must be kept to a minimum.  A typical
 system consists of a drying tube 10 cm x 1.0 cm (I.D.), with
 each of the drying agents occupying 4 cm and being separated by
 small glass wool plugs.   The column can be reused several times
 before the chemicals need to be replaced.

 (6)  After each analysis, flush the cell three times by
 evacuation and filling with helium, and store filled with
 helium at atmospheric pressure.  This procedure removes radon

                          25

-------
from the cell and prevents  the build-up  of  radon  daughter
products.  Before each analysis, the scintillation  cell  should
be evacuated, filled with helium and counted  to ascertain  the
cell background.

(7)  The calibration constant, E,  is determined as  follows:

     (a) Place 50 pCi of the 226Ra standard solution  in  a
     bubbler (50 pCi of 226Ra will produce  about  6  pCi
     222Rn in 18 hours).  Attach the bubbler  to the assembly
     as shown in Fig. 4.

     (b) With the scintillation cell disconnected,  bubble
     helium gas through the solution for 20 minutes.

     (c) Close both stopcocks on the bubbler  to establish  zero
     time for ingrowth of 222Rn.   Set  aside for approximately
     18 hours..

     (d) Evacuate the scintillation cell and  attach to the
     column and bubbler.

     (e) Proceed with steps i-m, 22"Ra-Radon  Emanation
     Technique.

     (f) The calibration constant, E,  is determined from the
     22°Ra activity in the  bubbler and the  ingrowth time of
     222Rn by the equation:
             E =
                 A(l-e~Xtl)(e U2)
     where:

     C  = net  count  rate,  counts/minute,
     A  = activity of 22°Ra in the bubbler (d/m),
    tl  = ingrowth time of 222Rn in hours,
    t-2  - decay  time of 222Rn in hours occurring between
         deemanation and  counting,  and
      A  = decay  constant of 222Rn,  0.00755 hour -1.

     The calibration constant,  E,  includes the deemanation
     efficiency of  the system,  the counting efficiency of the
     cell, and  the  alpha  activity contributed bv 2l8Po and
     ^l^Po, which will be in equilibrium with 222Rn when
     the sample is  counted 4 hours after the deemanation.   A
     100-minute counting  time will be sufficient for the
     standard and will eliminate the need to correct for decay
     of 222Rn,  which occurs during counting.
                          26

-------
           The bubbler used for the   oRa standardization  should
           not be used for sample analysis.  It should be  set  aside
           to be retained for future calibrations.  Each
           scintillation cell should be calibrated periodically with
           the 226fla standard to ensure instrument quality control.

B.  Uranium and Thorium Analysis

      1.  Principle of Method
           an(j 23HTJ-J tracers are added to a pretreated ash of a
      coal or by-product sample.  Silicates are removed by repeated
      HF evaporations.  A pyrosulfate fusion solubilizes  the residue,
      and the final solution is made 8 N^ in HC1.  Uranium is
      separated by extraction with triisooctylamine, back extracted
      with water, coprecipitated with lanthanum fluoride for counting
      by alpha spectroscopy .  Thorium activity, which is not
      extracted, is concentrated on an anion column, eluted with HC1,
      and coprecipitated with lanthanum fluoride for counting by
      alpha spectroscopy.

      2.  Reagents

      Radioactive tracer standards:  232y an(j 234 Th
      Ascorbic acid, C6H805:  Crystals
      Ethanol, C2H5OH:  95?
      Hydrochloric acid, HC1:  12 N (cone.), 8 N, 6 N, 2 N, IN
      Hydrofluoric acid, HF:  28 N (cone.),  5% (3 N)
      Lanthanum carrier:  0.10 mg/ml
      Nitric acid, HNC^:  8 N, 6 N, 0.1 N
      Perchloric acid, HClOij:  70% (cone.)
      Potassium fluoride, KF:  solid
      Potassium pyrosulfate, ^8207:  solid
      Sulfuric acid, ^SCty:  6 N
      Titanium trichloride, TiC^:  0.4? (freshly prepared)
      Triisooctylamine/xylene solution,  TIOA/xylene:  10%

      3-  Procedure

      a.  Add 1-5 g (Note 1) of ashed sample to a 50 ml teflon
      beaker.  Add 1.0 ml each of 232U and 234Th tracer
      solutions.  Mix.

      b.  Add 28 N^ HF (5 ml HF per gm ash) and evaporate to dryness
      at a low heat.  Repeat 3 more times with 10 ml volumes of HF to
      volatilize the silica.  Additional treatment may be necessary
      if residue remains.

      c.  Add 25 ml 12 N HC1 and evaporate to dryness.

      d.  Transfer the powdery residue to a platinum crucible.  Add  2
      g KF for each gram of ash used and fuse with a Meker burner for

                               27

-------
30 minutes.  Continue swirling,  then  add 3  g K2S20j for
each gram of ash and continue  fusion  for another 30 minutes.

e.  Cool the crucible in an  ice  bath,  add 15 ml 12 {£ HC1 and
evaporate to dryness.  Slurry  residue with  water,  transfer to a
beaker, bring volume to 150  ml,  and evaporate to dryness.

f.  Take up residue with 100 ml  6  N f^SOij and evaporate
past white fumes.

g.  Add 10 ml 12 N[ HC1 and evaporate  to dryness.  Repeat.

h.  Add 115 ml 8 II HC1 to dissolve residue  and transfer to a  1
liter separatory funnel.

i.  To the solution in the separatory funnel, add 100 ml of a
IQ% TIOA/xylene solution.  Shake for  2 minutes and after the
phases separate, drain the aqueous acid solution into a beaker
and reserve for thorium analysis,  step s.

j.  To the organic phase add 50  ml 8  N HC1  and shake for 20
seconds.  Discard  the aqueous  wash solution.

k.  Add 100 ml 0.1 JJ HNOg to the separatory funnel and shake
for 2 minutes.  Drain the aqueous  layer into a 250 ml beaker.

1.  Repeat step k, adding the  aqueous fraction to that in the
250 ml beaker.  Evaporate to dryness.

m.  Add 10 ml 8 fl  HNO^, evaporate  to  dryness.  Repeat.

n.  Wet ash again  with 5 ml  8  JI  HC1 and 5 ml HC10j4 and
evaporate to dryness.

o.  Add 10 ml 12 N[ HC1, evaporate  to  dryness.  Repeat.

p.  Dissolve residue in 10 ml  1  II  HC1, plus a pinch of ascorbic
acid to reduce the iron.  Add  1.0  ml  lanthanum carrier, 1 ml  of
freshly prepared 0.4$ TiCl3  and  2  ml  5% HF.  Stir well, and
let stand 30 minutes.

q.  Filter through a 25-mm nucleopore filter (0.2 u pore
size).  Wash three times with  10 ml portions of alcohol.  Mount
on a s.s. planchet using double-stick tape to secure the sample.

r.  Count for 1000 minutes,  using  an  alpha  spectrometer to
determine ^U, 235u, and 23°U;  and for the chemical
recovery of 232U.  (Note 2).

s.  Evaporate to dryness the aqueous  acid solution from step  i
which contains the thorium activity.
                          28

-------
t.  Wet ash the residue with  10  ml  8  N_ HNC>3  and evaporate to
dry ness.  Repeat.

u.  Add 5 ml 8 N[ HC1 and 5 ml  HC104 and evaporate to dryness.

v.  Add 10 ml 8 1} HNO^ and evaporate  to dryness.

w.  Take up the residue in 100 ml 6 N HNC>3 and  heat until
dissolved.

x.  Cool and pass over prepared  anion resin  column (Note 3)  at
gravity flow.  Discard effluent.

y.  Wash the resin column with 100  ml 6 ^ HC1 and collect the
eluate in a 400-ml beaker; evaporate  to dryness.

z.  Add 10 ml 8 N HNO^ and evaporate  to dryness.   Repeat.

aa. Add 10 ml 2 IJ HC1 and evaporate to dryness.   Repeat.

bb. Dissolve residue in 10 ml  1  N^ HC1,  add 1.0  ml lanthanum
carrier, 2 ml 5% HF and stir well.  Let stand for 30 minutes.

cc. Filter through a 25-mm nucleopore filter (0.2 u pore
size).  Wash three times with  10 ml portions of alcohol.   Mount
on a s.s. planchet using double-stick tape to secure the sample.
                                                 •
dd. Beta count for 10 minutes  to obtain 23^Th recovery  (Note
4).  Count for 1000 minutes, using  an alpha  spectrometer to
determine 232Th, 230ih, 228Th, and  22?Th.

Notes:

(1)  If only 1 g samples are used,  the fusion step (d)  can be
eliminated, since the HF and HC1 treatments  will  completely
solubilize the sample.  The procedure can continue with step
(h).

(2)  A 232u standard used for  determining chemical recovery
of uranium is prepared by pipetting 1.0 ml 232u tracer  (f*3
dpm) into a beaker and coprecipitating as described in  steps p
and q.  Count 1000 minutes using an alpha spectrometer.

(3)  Preparation of anion resin  - Slurry  anion  resin (Dowex
1-X8 or equivalent) (50-100 mesh) with water and  transfer to a
column 1.0 cm (I.D.) x 20 cm until  a  layer 10 cm  deep is
formed.  Wash with 25 ml 6N HC1  followed  by  100 ml water before
use.
(4)  A    xh standard used for determining  chemical recovery
of thorium is prepared by pipetting  1.0 ml  23^Th tracer (^^
1000 dpm) into a beaker and coprecipitating as  described in

                         29

-------
steps cc and dd.  Beta count for 10 minutes on  the  same  day
samples are counted in the alpha spectrometer.

4.  Calculations

     (1)  Uranium

     Sum the counts in the 232u standard under  the  232U
     peak (5.32, 5.27 MeV), and compare with  the  counts  in the
     sample under the 232u peak.  For  calculating the
     specific isotopes of uranium, sum the counts under  the
     following peaks:
          234(j  (4.77,  4.72 MeV)

          235{j  (4.37,  4.40,  4.58 MeV)

          238.u  (4.20,  4.15 MeV)
                                      pop
pCi 23Vg - _ cpm ^
             cpin 232U in  sample    •  Eff . fEfi x sample x
               —   - - x      dPm   slze
             cpm   U in  standard
      (2)   Thorium

      Compare  the 23^Th beta counts in the sample to those in
      the  standard to  determine chemical recovery.   For
      calculating the  specific isotopes of thorium,  sum the
      counts under the following peaks:

           232Th (4.01, 3-95 MeV)

           230Th (4.68, 4.62 Mev)

           228Th (5.43, 5.34 MeV)
                                     232
 c- 232   ,  _ 	cpm  J Th
P X       g " cpm 23V in  sample   _ Eff. fES x sample
               r   23lti	e	X     dpm    size
              cpm   Th in  standard
                         30

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
 EPA-600/4-78-039
                                                            3. RECIPIENT'S ACCESSION-NO.
4. TITLE ANDSUBTITLE
 Analysis  of Radioactive  Contaminants in By-Products
 From  Coal-Fired Power Plant  Operations
             5. REPORT DATE
                July 1978
issuing date
             6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
 Herman Krieger and Betty Jacobs
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Rad.  Methods Section,  Phys.  § Chem. Methods  Branch
 EMSL-Cinti  U.S. EPA
 26  W.  St.  Clair St.
 Cincinnati, Ohio  45268
             10. PROGRAM ELEMENT NO.
                1BD612
             11. CONTRACT/GRANT NO.
 12. SPONSORING AGENCY NAME AND ADDRESS
  Env.  Monit. and  Support Lab
  Office of Research  and  Development
  U.S.  Environmental  Protection Agency
  Cincinnati, Ohio  45268
             13. TYPE OF REPORT AND PERIOD COVERED
                In-House	__
             14. SPONSORING AGENCY CODE
                 EPA/600/06
15. SUPPLEMENTARY NOTES
16. ABSTRACT
      The major radionuclides detected in fossil  fuel power plant  operations have been
identified and quantified.   Samples of coal,  fly ash, bottom ash  and scrubber sludge
were collected from  different regions in the  U.S.  and analyzed  for  radium, thorium,
and uranium.  The  standard radiochemical procedures were modified in order to obtain
reproducible results for the variety of samples  analyzed, which then can be used to
calculate a radioactivity balance on the basis of normal operations.

      The report tabulates the spectrum of  activity levels in a  variety of samples,
and compares the results from non-destructive spectrometry and  from radiochemical
separations.  The  environmental impact of  an  expanding fossil-fuel  power plant
operation is discussed,  and it is concluded that for the present, no radiation hazard
exists.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                           c. COSATI Field/Group
 Radioactive Contaminants*
 Environments
 Radium Isotopes*
 Coal
 Coal Mining
 Irradiation
 Gamma Ray Spectroscopy
 Radiochemical Analysis
 Procedures
 Radiation Exposure
 Environmental
    Monitoring
   97A
   99E
18. DISTRIBUTION STATEMENT

  Release  to  Public
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
 21. NO. OF PAGES
       39
                                              20. SECURITY CLASS (Thispage)
                                              UNCLASSIFIED
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
                                             31
                                                              •A U.S. GOVERNMENT PRINTING OFFICE: 1978-757.-14O/1376

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