EPA-600/4-75-008
September 1975
Environmental Monitoring Series
                    RADIOCHEMICAL METHODOLOGY
                                                      FOR
                                      DRINKING WATER
                         Environmental Monitoring and Support Laboratory
                                     Office of Research and Development
                                    U.S. Environmental Protection Agency
                                              Cincinnati, Ohio 45268

-------
                     RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agency, have been grouped into
five series.  These five broad categories were established to
facilitate further development and application of environmental
technology.  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields.  The five series are:

           1.  Environmental Health Effects Research
           2.  Environmental Protection Technology
           3.  Ecological Research
           4.  Environmental Monitoring
           5.  Socioeconomic Environmental Studies

This report has been assigned to the ENVIRONMENTAL MONITORING STUDIES
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 Information Service, Springfield, Virginia  22151.

-------
                                         EPA-600/4-75-008
                                         September 1975
  RADIOCHEMICAL METHODOLOGY FOR DRINKING WATER
                       by

               Herman L. Krieger
  Radiochemistry § Nuclear Engineering Branch
Environmental Monitoring and Support Laboratory
           Cincinnati, Ohio  45268
           Program Element No. 2FH120
                  Prepared for

          Office of Radiation Programs
      U.S. Environmental Protection Agency
            Washington, D.C.   20460
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
       OFFICE OF RESEARCH AND DEVELOPMENT
      U.S. ENVIRONMENTAL PROTECTION AGENCY
            CINCINNATI, OHIO  45268

-------
                                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.
                                    11

-------
                               FOREWORD
      Environmental measurements are required to determine the quality
of ambient waters and the character of waste effluents.  The Environ-
mental Monitoring and Support Laboratory - Cincinnati conducts research
to:
      •  Develop and evaluate techniques to measure the presence
         and concentration of physical, chemical, and radiological
         pollutants in water, wastewater, bottom sediments, and
         solid waste.
      •  Investigate methods for the concentration, recovery, and
         identification of viruses, bacteria and other microbio-
         logical organisms in water.  Conduct studies to determine
         the responses of aquatic organisms to water quality.
      •  Conduct an Agency-wide quality assurance program to assure
         standardization and quality control of systems for moni-
         toring water and wastewater.
      The Proposed Interim Drinking Water Regulations contain maximum
contaminant levels for the concentration of drinking water.  This manual
which was developed by the staff of Radiochemistry Branch, EMSL,  provides
the methodology for monitoring the quality of drinking water for these
radionuclides.  In detail, it describes the analytical procedures that
have been determined appropriate for measuring them with the necessary
sensitivity and precision.  This effort has been supported by the Office
of Radiation Programs, U. S. Environmental Protection Agency, Washington,
D. C.
                                  Dwight G. Ballinger
                                   Acting Director
                   Environmental Monitoring and Support Laboratory
                                     Cincinnati
                                   111

-------
                                 PREFACE

     The Environmental Protection Agency (EPA), has recently published
Proposed Interim Primary Drinking Water Regulations for radioactivity under
the Safe Drinking Water Act, PL 93-523.C1)  These regulations propose
maximum contaminant levels limiting the concentrations of natural and man-
made radioactivity in drinking water supplies and set out the proposed
monitoring requirements.  Subsequent revisions of the proposed regulations
may be made as pertinent information becomes available.  However, the
present Proposed Regulations set the following maximum contaminant levels
for drinking water:

     Radionuclides                    Maximum Contaminant Level, pCi/1

Natural alpha particle activity                       5
  226Ra  +  22§Ra

Gross alpha activity                                 15
  (including 226Ra)

Man-made radionuclides                a concentration not to produce an
                                      annual dose equivalent greater
                                      than 4 mrem per year.

The regulations specify the following detection limits for radionuclides
of primary interest:

Gross alpha activity      1 pCi/1       Strontium-90       1/2 pCi/1
Radium-226                1 pCi/1       Iodine-131        1    pCi/1
Radium-228                1 pCi/1       Cesium-134       10    pCi/1
Tritium                1000 pCi/1       Gross Beta       10    pCi/1
Strontium-89             10 pCi/1

where the detection limit is defined as that concentration that can be
measured with an accuracy of +_ 100% at the 95% confidence level, i,e.,
2 sigma.  Furthermore, the regulations require a radiochemical analysis if
the gross beta activity exceeds 50 pCi per liter.

     The Proposed Interim Regulations also recommend which methods may be
applicable for the analyses, selecting them from many sources.  Recognizing
the need for a collection of methods that can be used for measuring each of
these nuclides in drinking water, the Radiochemistry and Nuclear Engineering
Branch of the Environmental Monitoring and Support Laboratory, EPA, has
sought to bring various methods together in this one volume.  Such a
collection of sensitive procedures would be of significant value in making
a dose assessment, and would serve as a source for less-experienced labora-
tories to improve their technical capabilities.

     This compilation includes single-operator-tested procedures that have
the required sensitivity for drinking water guidelines.  They have been

                                     iv

-------
selected from a number of radiochemical methodology collections,^" ' and
have been prepared so they are readily adaptable for routine analysis.
Several of them have already been published as standard reference methods.
Although specific sample volumes are designated in each of these procedures,
most of the methods can easily be adapted for larger volumes with minor
changes in the initial treatment.  With such modifications, the minimum
detection level (MDL) can be lowered two- or three-fpld.  Factors considered
in selecting these procedures for this laboratory manual were procedure
time and method capabilities, and only when modifications were deemed
essential were the procedures lengthened to include scavenging or other
purification steps.  (See Appendix A.)

     Drinking water is normally collected at "grab" sampling points and
should not be acidified until the start of the analysis, if so indicated.
Radiochemical analysis should be performed immediately upon receipt of
sample, especially for 131j so that radioactive decay losses are minimized.
When quarterly composites are set aside for future analyses, the samples
should be acidified with 1 ml 16 N^ HNC>3 per liter to minimize losses caused
by adsorption on container wall.  Preparation of reagents is described in
Appendix B, and sources of supply in Appendix C.

     Other methods effective for the task and the specifications required
obviously are available or may become available in the future.   Revisions
or additions to these procedures are solicited and will be considered in a
subsequent edition of the manual.

References:

1.  Proposed Interim Primary Drinking Water Regulations - Radioactivity-
    U.  S. Environmental Protection Agency (40 CFR Part 141).  Notice of
    Proposed Maximum Contaminant Levels for Radioactivity.  Federal
    Register, August 1975.

2.  Krieger, H. L. and S. Gold.  Procedures for Radiochemical Analysis of
    Nuclear Reactor Aqueous Solutions.  EPA-R4-73-014, National Environ-
    mental Research Center, U. S.  Environmental  Protection Agency,
    Cincinnati, Ohio (May 1973).

3.  1972 Book of ASTM Standards, Part 23.   American Society for Testing
    and Materials, Philadelphia, Pa.  (1972).

4.  Harley, J. H.   Manual of Standard Procedures.   USAEC Rept.  HASL-300
    (1972).

5.  Nuclear Science Series, USAEC Rept.  NAS-NS-3001 to NAS-NS-3111 (1965).

6.  Standard Methods for the Examination of Water and Waste Water, 13th ed.
    American Public Health Association,  Washington, D. C.  (1971).

-------
                             CONTENTS
                                                               Page
Foreword	,  ,  , -,	iii
Preface	,	iv
Figures	viii
Acknowledgment  	   ix

Gross Alpha and Beta Radioactivity in Drinking Water  	    1
Radioactive Cesium in Drinking Water ...  	    4
Radioactive Iodine in Drinking Water
     Precipitation Method	    6
     Distillation Method 	    9
Radium-226 in Drinking Water
     Precipitation Method	13
     Radon Emanation Technique 	   16
Radium-228 in Drinking Water
     Sequential Method Radium-228/Radium-226  	   24
     Radium-226 by Precipitation 	   26
     Radium-226 by Radon Emanation 	   27
Radioactive Strontium in Drinking Water	29
Tritium in Drinking Water	34
Potassium-40 in Drinking Water 	   38
Appendices
     A.   Method Capabilities	41
     B.   Reagant Preparation	42
     C.   Sources of Supply	47
                                VII

-------
                                  FIGURES
                                                                        Page
1.   Generalized Gross Alpha and Gross Beta Self-Absorption Curves ...   2
2.   Distillation Apparatus for Iodine Analysis  	  11
3.   Radon Emanation Apparatus with Scintillation Cell 	  17
4.   A Typical Radon Bubbler	18
5.   The Growth of Radon-222 from Radium-226	20
6.   A Typical Scintillation Cell for Radon Counting 	  21
7.   Distillation Apparatus for Tritium Analysis 	  35
                                    viii

-------
                               ACKNOWLEDGMENT
     The Radiochemistry § Nuclear Engineering Branch (R&NEB) of the Environ-
mental Monitoring and Support Laboratory, EPA, was requested to prepare
this manual by the end of fiscal year 75.  It is one task milestone in the
Research Objective Achievement Plan of the Office of Research and Develop-
ment, and is intended for use by agencies responsible for monitoring drinking
water for radioactive contamination.  George W. Frishkom, Mrs. Betty Jacobs,
and Mrs. Eleanor Martin, R$NEB, were responsible for the thorough testing
of these procedures and for recommending modifications so that they satisfy
the limiting concentrations of the standard.  Editorial comments and
suggestions for improvement in the clarity of the manual were submitted by
Dr. Bernd Kahn, Environmental Resources Center, Georgia Institute of
Technology, Atlanta, Georgia and Mr. Robert Lieberman,  Eastern Environmental
Radiation Laboratory, Montgomery, Alabama.

     Their assistance is gratefully acknowledged.
                                      IX

-------
            GROSS ALPHA AND BETA RADIOACTIVITY IN DRINKING WATER
Principle of Method

     A specified volume of drinking water is evaporated to dryness, transferred
to a counting dish, and counted for gross alpha or gross beta activity.

Procedure Time

     Evaporation time, 1 to 2 hours for eight 250-ml samples.

Reagents and Supplies

     Planchets, stainless steel.

Procedure

1.  Transfer 100 to 500 ml drinking water sample (Note 1) to a beaker and evap-

    orate to dryness on a hot plate.  Do not bake.

2.  Slurry residue to a tared stainless-steel planchet using a rubber police-

    man and as little water as possible.

3.  Dry under infra-red lamps, cool, weigh, and store in desiccator.

4.  Alpha and beta count (Note 2).

Calculation

     Calculate the concentration, D, of the gross activity (alpha and/or beta)
in picocuries per liter as follows:
                               D =
                                   2.22 x EVW

where:

C = net count rate, counts/minute,
E = counter efficiency, alpha or beta (Note 3),
V = milliliters of sample used,
W = self-absorption factor (determined from solids concentration), and
2.22 = conversion factor from disintegrations/minute to picocuries.

Notes:

1.  The specified volume of drinking water to be evaporated will be a function
    of its hardness and solids concentration.  Self-absorption factors for
    the solids present in these volumes have to  be determined to correct for
    losses due to self-absorption.  In any event, the maximum sample thick-
    ness should be less than 3 mg/cm^.  (See Fig. 1.)

-------
                                Sample Thickness, mg/cm2
Figure 1.  Generalized Gross Alpha and Gross Beta Self-Absorption Curves
                                                                                   4.0

-------
2.  The same planchet can be counted for alpha and beta activities in desig-
    nated instruments provided their counting chambers are capable of handling
    the same size planchet.

3.  It is recommended that NBS-calibrated standards be used for ascertaining
    instrument efficiencies.  A weightless deposit of 210po for a and a
    point source from a standard solution of i^Cs for 3 are suggested.
    Source of supply is:  Standard Reference Materials Catalog, NBS Publica-
    tion 260, U. S.  Department of Commerce (1974).  'Standards should also be
    prepared in the  geometry and weight ranges to be encountered in these
    gross analyses.

Literature

    Standard Methods for the Examination of Water and Waste Water,  13th ed.
    American Public  Health Association, Washington,  D.  C.  (1971).

-------
                    RADIOACTIVE CESIUM IN DRINKING WATER
Principle of Method
     Cesium carrier is added to the aqueous sample.  The cesium is collected
as the phosphomolybdate and purified as Cs2PtClg for counting.
Procedure Time
     Four samples in 5 hours.
Reagents
     Ammonium phosphomolybdate, (NH4)3PMoi2040:  prepared reagent
     Calcium chloride, CaCl2:  3 M
     Cesium carrier:  10 mg/ml
     Chloroplatinic acid, H2PtCl6-6H20:  0.1 M
     Ethanol, C2H5OH:  95%
     Hydrochloric acid, HC1:  12 N  (cone.), 6 N, 1 N
     Sodium hydroxide, NaOH:  6 N^
Procedure
1.  To a 1000-ml drinking water sample, add 1.0 ml cesium carrier and enough
    12 N HC1 to make the solution -0.1 N^ HC1.
2.  Slowly add 1 gram (NH.) PMo,20   and stir for 30 minutes, using a magnetic
    stirrer.  Allow precipitate to  settle for at least 4 hours, and discard
    supernatant.
3.  Slurry precipitate into a centrifuge tube.  Centrifuge and discard
    supernatant.
4.  Wash precipitate with 20 ml 1 N[HC1, and discard wash solution.
5.  Dissolve precipitate by dropwise addition of 3 to 5 ml 6 N[ NaOH.  Heat
    over a flame for several minutes to remove ammonium ions.  (Moist pH
    paper turns green as long as NH_ vapors are evolved.)  Dilute to 20 ml
                                    o
    with water.
6.  Add 10 ml 3 M CaCl  and adjust  to pH 7 with 6 N_ HC1 to precipitate
    CaMoO .  Stir, centrifuge, and  filter supernatant through Whatman #41
    filter paper (or equivalent) into a 50-ml centrifuge tube.
7.  Wash the precipitate remaining  in the centrifuge tube with 10 ml water;
   ' filter through the same filter  paper, and combine the wash with filtrate.

-------
     Discard filter paper.
 8.   Add 2 ml 0.1 M H.PtCl, and 5 ml ethanol.  Cool and stir in ice bath for
                  —  i    o
     10 minutes.
 9.   Transfer with water to a tared glass-fiber filter.  Wash with successive

     portions of water, 1 N_ HC1, and ethanol.
10.   Dry, cool, weigh, mount, and beta count.

 Calculation

      Calculate the concentration, D,  of the cesium activity in picocuries
 per liter as follows:
                                D =
                                    2.22 x EVR

 where :

 C = net count rate,  counts /minute,
 E = counter efficiency,
 V = liters of sample used,
 R = fractional chemical  yield,  and
 2.22 =  conversion factor from disintegrations/minute to picocuries.

 Literature :

     Finston, H. L.,  and  M. T. Kinsley.   The Radiochemistry of Cesium.   AEC
     Rept.  NAS-NS-3035 (1961).

-------
                     RADIOACTIVE IODINE IN DRINKING WATER
                            Precipitation Method         »
Principle of Method

     lodate carrier is added to an acidified sample of drinking water and,
after reduction with Na2S03 to iodide, the 131j ^s precipitated with
AgN03.  The precipitate is dissolved and purified with zinc powder and sul-
furic acid, and the solution is reprecipitated as Pdl2 for counting.

Procedure Time

     Eight samples in 6 hours.

Reagents

     Ammonium hydroxide, NH^OH:   6 >[
     Ethanol, C2HsOH:  95%
     Hydrochloric acid, HC1:  6 N
     lodate carrier,  (10$):  10 mg/ml
     Nitric acid, HN03:  16 N  (cone.)
     Palladium chloride, PdCl2:   0.2 M
     Silver nitrate, AgNOs:  0.1  M
     Sodium sulfite, Na2SOs:  1 M (freshly prepared)
     Sulfuric acid, H2S04:  2 f*
     Zinc, powder:  reagent grade

Procedure

1.   To  a 2000-ml drinking water sample,  add  15 ml  16  N HN03  and  1.0 ml iodate

    (I0~) carrier.  Mix well.
      O
2.   Add 4 ml freshly prepared  1 M Na2S03 and stir  for 30 minutes.
3.   Add 20 ml  0.1 M AgNO  ,  stir for  1  hour and settle for another hour.
                        O
4.   Decant and discard as much as possible of the  supernatant.   Filter the

     remainder  through a glass-fiber  filter and discard  filtrate.

5.   Transfer the filter to  a centrifuge tube and slurry with 10  ml water.
     Add 1  gram zinc powder and  2  ml  2  N_ H2SO , and stir frequently for at

     least  30 minutes.
6.   Filter, with vacuum,  through  a  fine-fritted  glass funnel and collect

     filtrate  in an Erlenmeyer  flask.   Use a  few  ml water to  wash both
     residue and filter  and add the wash to  filtrate in  the flask.  Discard

     residue.
7.   Add 2  ml  6 N HC1  to  the filtrate and heat.   Add 1 ml 0.2 M PdCl2  and

-------
     digest for at least 5 minutes.  Centrifuge and discard supernatant.

 8.  Dissolve the precipitate in 5 ml 6 N_ NH OH and heat in boiling water bath.

     Filter through a glass-fiber filter and collect filtrate in a centrifuge

     tube.   Discard filter and residue.

 9.  Neutralize the filtrate with 6 N_ HC1, add 2 ml additional, and heat in a

     water bath.  Add 1 ml 0.2 M PdCl_ to reprecipitate Pdl. and digest for
                              *       £*                     &
     10 minutes.  Cool slightly.

10.  Transfer to a tared glass-fiber filter with water (Note 1).  Wash

     successively with 5 ml portions of water and ethanol.

11.  Dry to constant weight at <100 C, mount, and beta count (Note 2).

 Calculation

      Calculate the concentration, D, of the iodine activity in picocuries per
 liter as follows:
                              D =
                                  2.22 x EVR x A

 where :

 C = net count rate,  counts/minute (c/m) ,
 E = counter efficiency,
 V = liters of sample used,
 R = fractional chemical  yield,
 A = decay correction for 131j (t\/2 = 8.06 d), and
 2.22 =  conversion factor from disintegrations/minute to picocuries.

 Notes:

 1.  Ordinarily, the  final Pdl2  precipitate is collected on a glass -fiber
     filter and counted in a G-M system where the natural background is about
     0.8 c/ra.  Glass-fiber filters add about 0.5 c/m to the background so that
     the Pdl2 counted this way will have about a 1.3 c/m background and a
     counting efficiency  of 35%.   However,  if the precipitate is collected on
     a 0.8-y membrane filter, and dried for 30 minutes at 70°C,  it is possible
     to  count the Pdl2 in a beta-gamma coincidence scintillation system where
     the background coincidence  count is less than 0.1 c/m and the counting
     efficiency is greater than  40% (see Brauer et^ al. reference) .
 2.   Confirmation of half-life of  3j an
-------
Environment, pp. 231-253.  American Chemical Society  (1970).

Kleinberg, J., and G. A. Cowan.  The Radiochemistry of Fluorine, Chlorine,
Bromine and Iodine.  AEG Rept. NAS-NS-3005  (I960).

-------
                    RADIOACTIVE IODINE IN DRINKING WATER

                             Distillation Method
Principle of Method

     Iodide carrier is added to a drinking water sample, which is acidified
to effect distillation of iodine into caustic solution.  The distillate is
acidified and the iodine is extracted into €014.  After back extraction, the
iodine is purified as Agl or Pdl2 for counting.

Procedure Time

     Two samples in 6 hours.

Reagents

     Ammonium hydroxide, NtfyOH:  15 N_ (cone.)
     Carbon tetrachloride, CC^
     Diethyl ether, (C2%)20:  anhydrous
     Ethanol, C2H5OH:  95%
     Iodide carrier:  20 mg/ml
     Nitric acid, HN03:  16 N^ (cone.), 4 N, 0.2 N
     Silver nitrate, AgN03:  0.1 M
     Sodium bisulfite, NaHS03:  1 M
     Sodium hydroxide, NaOH:  0.5 N_
     Sodium nitrite, NaN02:  1 M
     Sulfuric acid, H2S04:  12 N
     Tartaric acid, C4H606:  50%

Procedure

1.  To a 2000-ml drinking water sample in a 3-liter round-bottom flask, add

    15 ml 50% C.H.O^ and 1.0 ml iodide carrier.  Mix well, cautiously add
               4 O D
    25 ml cold 16 N^ HNO_, and close the distillation apparatus (Fig. 2)

    (Note 1).
2.  Connect an air line to the inlet, adjust the flow rate to about 2

    bubbles/second, then distill for at least 15 minutes into 15 ml 0.5 N^

    NaOH.  Cool and transfer the NaOH solution to a 60-ml separatory funnel.

    Discard the solution in the round-bottom flask.

3.  Adjust the solution to slightly acid with 1 ml 12 N_ H_SO  and oxidize
    with 1 ml 1 M NaNO_.  Add 10 ml CC1. and shake for 1 to 2 minutes.  Draw
                —     2                4
    off organic layer into a clean 60-ml separatory funnel containing 2 ml 1 M

    NaHSO .
         o
4.  Add 5 ml CC14 and 1 ml 1 M NaN02 to the original separatory funnel

                                      9

-------
     containing the aqueous layer and shake for 2 minutes.   Combine the
     organic  fraction with that in the separator/ funnel in step 3.
 5.   Repeat step 4 and discard the aqueous layer.
 6.   Shake separator/ funnel thoroughly until CC1. layer is decolorized;
     allow phases to separate and transfer aqueous layer to a centrifuge  tube.
 7-   Add 2 ml 1 M NaHSO_ to separator" funnel which has the CC1, and shake for
                —      3                                       4
     several  minutes.  When the phases separate, combine this aqueous layer
     with that in centrifuge tube from step 6.
 8.   Add 1 ml water to separatory funnel and shake for several minutes.  When
     the phases separate, add aqueous layer to the same centrifuge tube.
     Discard  organic layer.  (Note 2).
 9.   To the combined aqueous fractions, add 2 ml 0.1 M AgNO  plus 4 ml HNO_.
     Stir for 1 minute then allow to stand 30 minutes at room temperature to
     coagulate silver iodide.  Centrifuge at high speed for 10 minutes.
     Carefully decant and discard supernatant.
10.   Pipet 5  ml 15 N NH OH into the centrifuge tube and stir thoroughly for
                   —   4
     several  minutes.  Heat carefully while stirring until boiling begins.
     Centrifuge at high speed for 10 minutes.  Carefully decant and discard
     supernatant .
11.   Slurry precipitate in 10 ml water, add 1 ml 4 N_ HNO_, stir and immedi-
     ately transfer precipitate to tared glass-fiber filter.  Filter slowly
     at first to prevent loss.
12.   Wash precipitate on filter successively with 20 ml 0.2 N_ HN03, 20 ml
     ethanol  and 20 ml diethyl ether.  Let dry with suction at least
     10 minutes.  Store in desiccator.
13.   Weigh, mount, and store in light-tight container until ready to beta
     count.
 Calculation

      Calculate the concentration, D, of the iodine activity in picocuries
 per liter as follows:
                              D =
                                  2.22 x EVR x A
where :
C = net count rate, counts/minute,

                                      10

-------
                    18/9  Socket
             20/40 J  Joint
                3000ml  Flask
 Still
Delivery
  Tube
Figure 2.  Distillation Apparatus for Iodine Analysis
                    11

-------
E = counter efficiency,
V = liters of sample used,
R = fractional chemical yield,
A = decay correction for ISlj  (t\/2 = 8.06 d), and
2.22 = conversion factor from  disintegralions/minute to picocuries.

Notes:

1.  A distillation apparatus such as shown in Figure 2 or equivalent can be
    used:  a round-bottom flask fitted with a ground-glass joint that allows
    for a source of air to be  bubbled into the sample and that has a delivery
    tube on the other  end extending into a caustic trap.
2.  An alternate method, whereby the iodide is precipitated as Pdl2> provides
    a means for measuring radioiodine with less interference from chlorides.

    The procedure, after step  8, would then be:
    a.  To the combined aqueous fractions, add 2 ml 6 N^ HC1 and heat.  Add
        2 ml 0.2 M PdCl2 and digest for at least 5 minutes.  Centrifuge and
        discard supernatant.
    b.  Transfer to a  tared glass-fiber filter with water.  Wash twice with
        5-ml portions  of water and ethanol.
    c.  Dry to constant weight at 70 to 90°C, mount, and beta count.

 Literature:

    1972  Book of ASTM  Standards, Part 23.  American Society for Testing and
    Materials, Philadelphia, Pa.  D 2334-68  (1972).
                                      12

-------
                        RADIUM-226  IN DRINKING WATER
                            Precipitation Method
Principle of Method
     The radium in the drinking water sample is coprecipitated with barium as
the sulfate and purified by reprecipitation from EDTA  solution.   The  BaS04
precipitate containing 226Ra is counted for alpha activity.
Procedure Time
     One sample in 6 hours; four samples in 8 hours.
Reagents
     Acetic acid, CH?COOH:  17.4 1J  (glacial)
     Ammonium hydroxide, NfyOH:  15 N_  (conc.)> 2 ff
     Barium carrier:  16 mg/ml
     Citric acid, CgHgOy.^O:  1 M
     EDTA reagent:  prepared reagent
     Indicator, methyl orange:  0.1%
     Lead carrier:  15 mg/ml
     Sulfuric acid, ^804:  18 N
     Sodium hydroxide, NaOH:  6 N
Procedure
1.  To a 1000-ml drinking water sample, add 5 ml 1 M C-H00_.H,,0, 2.5 ml 15 N
                                                   —  o o 7  2             —
    NHOH, 1 ml lead carrier, and 2.0 ml barium carrier.
2.  Heat the solution to boiling and add 10 drops of methyl orange indicator.
3.  Add, with stirring, 18 If H_SO  to a permanent pink color and then 0.5 ml
    in excess.
4.  Digest 5 to 10 minutes and let the mixed BaSO.-PbSO  precipitate settle
    overnight.  Decant and discard supernatant.
5.  Transfer the precipitate to a centrifuge tube with a minimum amount of
    water.  Centrifuge and discard supernatant.
6.  Dissolve the precipitate by adding 15 ml EDTA reagent; heat in a water
    bath until clear.  If not entirely clear, continue heating and add a
    few drops of 6 14 NaOH.
7.  Add 2 ml 17.4 JJ CH COOH dropwise and digest 5 to 10 minutes (Note 1).
                      O
    Centrifuge, discard'the supernatant, and record time (Note 2).
8.  Wash the BaS04 precipitate containing the 226Ra with 15 ml 2 N^ NH OH.
    Centrifuge and discard wash.
                                      13

-------
 9.   Wash the BaS04 precipitate with 10 ml water, centrifuge, and discard wash.
10.   Transfer the precipitate to a tared stainless-steel planchet with a
     minimum of water, and dry under infra-red lamps (Note 3).
11.   Cool, weigh, and store in desiccator.
12.   Determine the alpha activity in an internal proportional counter (Note 4).

 Calculation

      Calculate the concentration, D, of the 226Ra activity  (which would
 include any 22^Ra an^ 223Ra that is present) in picocuries per liter as
 follows:
                              D =
                                   2.22 x EVR x IW

 where:

 C = net count rate,  counts/minute,
 E = counter  efficiency  for  alpha  counting,
 V = liters of sample used,
 R = fractional  chemical yield,
 I = ingrowth factor  (Note 5),
 W = self-absorption  factor,  and
 2.22  = conversion  factor from disintegrations/minute to picocuries.

 Notes;

 1.  This volume of acetic acid gives a pH of about 4.5 and is sufficient to
     destroy  the Ba-EDTA, but not  the Pb-EDTA, complex.

 2.  At this  step of  the procedure,  radon  (and daughters) grows into the BaS04
     precipitate.
 3.  Drying should  be rapid  but not  too vigorous to minimize  loss of 222Rn
     that has already grown  into the precipitate.

 4.  Alpha self-absorption losses  for 226Ra in an  internal proportional
     counter  as  a function of sample thickness are:
              Sample thickness,          Relative efficiency losses,
              	mg/cm2	          	%	
                    0.0                             0.00
                    0.31                            0.04
                    0.95                            0.06
                    1.26                            0.12
                    1.55                            0.14
                    1.90                            0.19
                    1.97                            0.20
                    2.20                            0.22
                    2.65                            0.30
                    3.14                            0.37
                                       14

-------
5.  The ingrowth factor can be calculated from Kirby's data  (see Kirby, H. W.
    reference).  Some of these alpha activities from initially pure 226Ra
    during the first 240 hours are:

                    Hours                 Ingrowth factor

                       0                      1.0000
                       1                      1.0160
                       2                      1.0363  '
                       3                      1.0580
                       4                      1.0798
                       5                      1.1021
                       6                      1.1238
                      24                      1.4892
                      48                      1.9054
                      72                      2.2525
                      96                      2.5422
                     120                      2.7838
                     144                      2.9853
                     192                      3.2939
                     240                      3.5086

Literature:

    Goldin, A. S.  Determination of Dissolved Radium.  Anal. Chem. 33,
    406-409 (March 1961).

    Harley, J. H., ed.  Manual of Standard Procedures, USAEC Rept. HASL 300
    (1972).

    Kirby, H. W.  Decay and Growth Tables for the Naturally Occurring
    Radioactive Series.  Anal. Chem. 26, 1063-1071 (1954).
Although this procedure utilizes an internal proportional counter to determine
alpha activity, it can be modified so that the final precipitate (step 9) is
filtered on tared Whatman-#42 filter paper, dried, weighed, and covered with
an alpha phosphor and Mylar.  After storing for 30 days, the    Ra in the
sample can be determined with an alpha scintillation counter.
                                      15

-------
                        RADIUM-226 IN DRINKING WATER

                          Radon Emanation Technique
Principle of Method

     The radium in the drinking water sample is concentrated and separated by
coprecipitation with barium as the sulfate.  The precipitate is dissolved in
EDTA reagents, placed in a sealed bubbler and stored for ingrowth of 222Rn.

Procedure Time

     Four samples in 8 hours.

Equipment

     Radon Emanation Apparatus with Scintillation Cell  (Fig. 3).

Reagents

     Ammonium hydroxide, NfyOH:   15 14  (cone.)
     Ascarite:  drying reagent,  8-20 mesh
     Barium  carrier:  16 mg/ml
     EDTA reagent:  0.25 M
     Helium  gas
     Hydrochloric acid, HC1:   12  N  (cone.)
     Magnesium perchlorate, Mg(€104)2:   reagent grade
     Sulfuric acid, H2S04:   18 N, 0.1 N

Procedure

1.   To a  1000-ml  drinking water  sample, add 20 ml  12 N_ HC1  and  2.0 ml barium

     carrier  and heat  to boiling.
2.   Cautiously and  with vigorous stirring,  add  20 ml 18 N H2S04.  Digest 5 to
     10 minutes and  let precipitate  settle  overnight.   Decant and discard

     supernatant.
3.   Slurry  the precipitate  and transfer to a centrifuge tube with a minimum
     amount  of 0.1 N H SO  .   Centrifuge and discard supernatant.  Wash twice

     with  0.1 N^ H-SO.  and  discard washes.
4.   Add 20 ml EDTA  reagent,  2 drops 15 N NH4OH  and heat in  a water bath until

     the precipitate dissolves (Note 1).
5.   Transfer the  solution to a radon bubbler (Fig.  4). Open both the upper
     and lower stopcocks  and de-emanate the solution by slowly passing helium

     gas through  the bubbler for about 20 minutes.


                                       16

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

                                     Capillary  T-Tube

                                     Thermometer Capillary


                                     Anhydrous Magnesium Perchlorate

                                     Ascarite  (8-20 mesh)
                                    Aged Air From Compressed
                                      Air Regulator
                                    Radon  Bubbler
                                    Mercury Reservoir
Figure 3.  Radon Emanation Apparatus with Scintillation Cell
                               17

-------
                        7mm 0.0.
5 10/30
         Liquid
         Level
   135mm
          I7mrn
           0.0."
    33mm
                                     Corning No. 2
                                     or Equivalent
                                     Bubble Trap
                                     7 mm 1.0.
                           7mm Capillary Tubing
                           M/2  mm 1.0.

                           Fritted Gloss Disc
                           10-15  micron pores
                                     Volume to  be kept
                                     at minimum
Figure 4.  A Typical Radon Bubbler  (emanation  tube)
                            18

-------
 6.  Close the two stopcocks, and record time.  Store the solution for 4 to
                            OT^
     8 days for ingrowth of    Rn (Fig. 5).
 7.  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 2),
     Attach the tube to the radon bubbler and then attach the evacuated
     scintillation cell (Fig. 6) to the tube.
 8.  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  stop-
     cock.
 9.  Adjust the helium gas pressure so that the gas flows at slightly above
     atmospheric pressure.
10.  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.
11.  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 de-emanation.
12.  Toward the end of the de-emanation, 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
                                                                      222
     of the cell and bubbler, and record time.   This the beginning of    Rn
                           222
     decay and ingrowth of    Rn daughters.
13.  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 v/ith a light-tight enclosure that protects
     the photomultiplier tube.  Record the counting time to correct for the
              222
     decay of    Rn (Note 3).
 Calculation
                                             226
      Calculate the concentration, D, of the    Ra activity in picocuries per
 liter as follows:
            D =
                2.22 EV   l-e-xtl    e-

                                      19

-------
to
o
                  0
                                  Figure 5.  The Growth of Radon-222 from Radium-226

-------
         67mm
         90mm
                       Phosphor
                       'Coated
                     Clear Silica
                       V/indow
                         A
                                              Corning No. 2
                                              or Equivalent
                                              Brass Collar
                                              Kovar Metal
                iKiiimiiH      IIH    i mm
                       50 mm
Figure 6.  A Typical Scintillation Cell for Radon Counting
                            21

-------
where:

C  = net count rate, counts/minute  (Note  4),
E  = calibration constant  for the de-emanation system and the scintillation
     cell in counts per minute/disintegrations per minute of 222Rn  (Note 5),
V  = volume of sample in liters,
t-^ = the elapsed time in days between  the first  and  second de-emanations
      (steps 6 and  12) and  X  is  the  decay  constant of 222Rn  (0.181 d-1),
t2 = the time interval.between  the  second de-emanation  and counting and X
     is the decay  constant of 222Rn (0.00755  hr-1),  and
13 = the counting  time in  minutes and  X is the decay  constant of  222Rn
      (1.26 x 10-4  min'1).

Notes:

1.  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.
2.  For minimizing corrections  that would be  required in subsequent calcula-
    tions, 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.
3.  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  from  the cell and prevents  the build-up of radon
    daughter products.
4.  Before each analysis,  the scintillation cell should be evacuated, filled
    with helium and counted  to  ascertain  the  cell background.

5.  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. 3.
    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 22^Rn.  Set aside  for approximately 18 hours.
    d.  Evacuate the  scintillation  cell and attach to the column and
        bubbler.
    e.  Proceed with  steps 8-13,  Radon Emanation Technique, p. 19.
    f.  The calibration constant, E, is determined from the  226Ra activity
        in the bubbler and the  ingrowth time  of  222Rn by the equation:


                                      22

-------
                                      \1-    -\1-
                               A (l-e~Atl)(e   2)
where:
C  = net count rate, counts/minute,
A  = activity of 226Ra in the bubbler (d/m),
t, = ingrowth time of 222Rn in hours,
\-2 - decay time of 222Rn in hours occurring between de-emanation and
     counting, and
X  = decay constant of 222Rnt Q.00755 hour~l.

The calibration constant, E, includes the de-emanation efficiency of the
system, the counting efficiency of the cell, and the alpha activity contri-
buted by 218po and 214po> which will be in equilibrium with 222^ when the
sample is counted 4 hours after the de-emanation.  A 100-minute counting
time will be sufficient for the standard and will eliminate the need to
correct for decay of 222^f which occurs during counting.

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

Literature:

    Blanchard, R. L.  Uranium Decay Series Disequilibrium in Age Determina-
    tion of Marine Calcium Carbonates,  Doctoral Thesis, Washington
    University, St. Louis, Mo. (June 1963).

    Ferri, E., P. J. Magno, and L. R. Setter.  Radionuclide Analysis of
    Large Numbers of Food and Water Samples.  U. S. Department of Health,
    Education, and Welfare, Public Health Service Publication No.999-RH-17
    (1965).

    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 (August 1963).
                                    23

-------
                        RADIUM-228 IN DRINKING WATER

                   Sequential Method Radium-228/Radium-226
Principle of Method

     The 228Ra and 22^Ra ^n the drinking water sample are concentrated and
separated by coprecipitation with barium and lead as sulfates and purified
by EDTA-chelation.  After 36-hour ingrowth of actinium-228 from radium-228,
the 228Ac is carried on yttrium oxalate,   purified and beta counted.  The
radium-226 in the supernatant is either precipitated as the sulfate, purified
and alpha counted (see step 20), or is transferred to a radon bubbler and
determined by emanation (see step 27).

Procedure Time

     Two samples in 12 hours.

Reagents
     Acetic acid, IK^^C^:   17.4 fJ  (glacial)
     Acetone,  (CH3)2CO:  anhydrous
     Ammonium hydroxide, NfyOH:  15 N_ (cone.)
     Ammonium oxalate,  (NH/i^C 204.^0:   5%
     Ammonium sulfate,  (NH4)2S04:  200 mg/ml
     Ammonium sulfide,  (NH4)2S:  2%
     Barium carrier:  16 mg/ml
     Citric acid, C6H807.H20:  1 M
     EDTA reagent:  0.25 M
     Ethanol, C2H5OH:   95%
     Indicator, methyl  orange:  0.1%
     Lead carrier:  15  mg/ml, 1.5 mg/ml
     Nitric acid, HN03:  16  N (cone.), 6 N, 1 IJ
     Sodium hydroxide,  NaOH:  18 N, 10 N, 1 N
     Strontium-yttrium  mixed carrier:  0.9 mg/ml Sr*z-0.9 mg/ml Y+3
     Sulfuric acid, H2S04:   18 N
     Yttrium carrier:   18 mg/ml, 9 mg/ml

Procedure

1.  For each liter of drinking water, add 5 ml 1 M C..H O-.H-O and a few drops
                                                 —  Do'  £•
    methyl orange indicator.  The solution should be red  (Note 1).
2.  Add 10 ml lead carrier  (15 mg/ml), 2.0 ml barium carrier  (16 mg/ml), and

    1 ml yttrium carrier  (18 mg/ml);  stir well.  Heat to incipient boiling
    and maintain at this temperature  for 30 minutes.
3.  Add 15 N^ NH.OH until a definite yellow color is obtained, then add a
    few drops excess.   Precipitate lead  and barium sulfates by adding 18 N_
                                      24

-------
      H SO  until the red color reappears, then add 0,25 ml excess.  Add 5 ml
     (NH ) SO  (200 mg/ml) for each liter of sample.  Stir frequently and
     keep at a temperature of about 90 C for 30 minutes.
 4.  Cool slightly, then filter with suction through a 47-mm metricel
     membrane filter (GA-6,0.45 p-pore size).  Make a quantitative transfer
     of precipitate to the filter by rinsing last particles out of beaker
     with a strong jet of water.
 5.  Carefully place filter with precipitate in the bottom of a 250 ml beaker.
     Add about 10 ml 16 N^ HNO, and heat gently until the filter completely
     dissolves.  Transfer the precipitate with the aid of more 16 N^ HNO
                                                                       O
     into a polypropylene centrifuge tube.  Centrifuge and discard
     supernatant.
 6.  Wash the precipitate with 15 ml 16 N_ HNO , centrifuge, and discard
                                             O
     supernatant.
 7-  Repeat step 6.
 8.  Add 25 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.
 9.  Add 1 ml strontium-yttrium mixed carrier and stir thoroughly.  Add a
     few drops 10 N_ NaOH if any precipitate forms.
10.  Add 1 ml (NH ) SO  (200  mg/ml) and stir thoroughly.  Add 17.4 N
     HC-H 0  until barium sulfate precipitates, then add 2 ml excess.  Digest
       £ O L.
     in a hot water bath until precipitate settles.   Centrifuge and discard
     supernatant.
11.  Add 20 ml EDTA reagent,  heat in a hot water bath, and stir until precipi-
     tate dissolves.  Repeat  steps 9 and 10.  (Note time of last barium
                                                         22R
     sulfate precipitation;  this is the beginning of the    Ac ingrowth time.)
12.  Dissolve the precipitate in 20 ml EDTA reagent as before, then add 1.0 ml
     yttrium carrier  (9 mg/ml) and 1 ml lead carrier (1.5 mg/ml).  If any
     precipitate forms,  dissolve by adding a few drops 10 N^ NaOH.   Cap the
     polypropylene tube and age at least 36 hours.
13.  Add 0.3 ml (NH )  S and stir well.  Add 10 N^ NaOH dropwise with vigorous
     stirring until lead sulfide precipitates, then add 10 drops excess.  Stir
     intermittently for about 10 minutes.   Centrifuge and decant supernatant
     into a clean tube.
14.  Add 1 ml lead carrier (1.5 mg/ml), 0.1 ml (NH.) S,  and a few drops 10 N

                                     25

-------
     NaOH.  Repeat precipitation of lead sulfide as before.  Centrifuge and
     filter supernatant through Whatman #42 filter paper into a clean tube.
     Wash filter with a few ml water.  Discard residue.
15.   Add 5 ml 18 ^ NaOH (make at least 2 normal in OH~).  Stir well and
     digest in a hot water bath until yttrium hydroxide coagulates.  Centri-
     fuge and decant supernatant into a beaker.  Cover beaker and save
                     *)*) f\
     supernatant for    Ra analysis, step 20 or 27.  (Note time of yttrium
                                                     228
     hydroxide precipitation; this is the end of the    Ac ingrowth time and
                  228
     beginning of    Ac decay time.)
16.   Dissolve the precipitate in 2 ml 6 N_ HNO  .  Heat and stir in a hot water
                                             O
     bath about 5 minutes.  Add 5 ml water and reprecipitate yttrium hydroxide
     with 3 ml 10 N_ NaOH.  Heat and stir in a hot water bath until precipitate
     coagulates.  Centrifuge and discard supernatant.
17.   Dissolve precipitate with 1 ml 1 ^ HNO, and heat in hot water bath a
     few minutes.  Dilute to 5 ml and add 2 ml 5%  (NH ) C 0 .H 0.  Heat to
     coagulate, centrifuge and discard supernatant.
18.   Add 10 ml water, 6 drops 1 N HNO  and 6 drops 5% (NH ) C 0  H 0.  Heat
                                ~~~    O                   T" « £ T"  ^
     and stir in a hot water bath a few minutes.  Centrifuge and discard
     supernatant.
19.   Transfer quantitatively to a tared stainless-steel planchet with a
     minimum amount of water.  Dry under an infra-red lamp to a constant
     weight and count in a low-background beta counter (Note 2).
                         Radium-226 - By Precipitation

20.   To the supernatant from step 15, add 4 ml 16 N HN03 and 2 ml (NH4)2S04
     (200 mg/ml), stirring well after each addition.  Add 17.4 N HC2H 0
     until barium sulfate precipitates, then add 2 ml excess.  Digest on a
     hot plate until precipitate settles.  Centrifuge and discard supernatant.
21.   Add 20 ml EDTA reagent, heat in a hot water bath, and stir until
     precipitate dissolves.  Add a few drops 10 N^ NaOH if precipitate does
     not readily dissolve
22.   Add 1 ml strontium-yttrium mixed carrier, and 1 ml lead carrier
     (1.5 mg/ml); stir thoroughly.  Add a few drops 10 N NaOH if any precipi-
     tate forms.
23.   Add 1 ml (NH4)2S04 (200 mg/ml) and stir thoroughly.  Add 17.4 N_
                                      26

-------
     until barium sulfate precipitates, then add 2 ml excess.  Digest  in a

     hot water bath until precipitate settles.  Centrifuge and discard

     supernatant.
24.  Wash precipitate with 10 ml water.  Centrifuge and discard supernatant.

25.  Transfer precipitate to a tared stainless-steel planchet with a minimum

     amount of water.  Dry under an infra-red lamp and weigh (Note 3).

26.  Count immediately in an alpha proportional counter.

                        Radium-226 - By Radon Emanation

27.  To the supernatant from step 15,  proceed with steps 20 to  25.   Care-

     fully transfer barium sulfate from planchet with the aid of a  rubber

     policeman and 14 ml EDTA reagent  into a small beaker.   Add a few drops

     10 N NaOH and heat to dissolve.   Cool and transfer  to  a radon  bubbler

     (Figure 4), rinsing beaker with another ml EDTA reagent,  and proceed with
     Radium-226 in Drinking Water - Radon  Emanation Technique,  page 16,  step  5.

 Calculation  for 22&Ra


      Calculate the concentration, D,  of 228Ra ^n picocuries per liter as
 follows:


                              x
                   2.22 x EVR   (l-e~Xt2^*   (l-e~Xt3)    e~Xtl

 where:

 C  = average net count rate, counts/minute,
 E  = counter efficiency, for 228Ac,
 V  = liters of sample used,
 R  = fractional chemical yield of yttrium carrier (step 19)  multiplied by
      fractional chemical yield of barium carrier (step 25),
 2.22 =  conversion factor from disintegrations/minute to picocuries,
 A  = the decay constant for  228Ac (0.001884  min-1),
 tj  = the time interval (in minutes)  between  the first  yttrium hydroxide
      precipitation in step 15 and the start  of the  counting  time,
 t2  = the time interval of counting in minutes,  and
 t3  = the ingrowth time of 228Ac in minutes measured  from the last barium
      sulfate precipitation in step 11 to the first yttrium hydroxide
      precipitation in step 15.
     At2
  ,._  -Xt2-j  is  a factor to correct  the  average  count rate to  count  rate  at
  *•        •*  beginning  of counting time.
                                      27

-------
Calculation for 226Ra

a) by precipitation, refer to Radium-226 in Drinking Water - Precipitation
   Method, page 14, b) by radon emanation, refer to Radium-226 in Drinking
   Water - Radon Emanation Technique, page 19.

Notes:

1.  At the time of sample collection add 2 ml 16 N^ HN03 for each liter of
    water.

2.  If the 226Ra analysis is not desired, complete step 20 and then steps
    24 and 25 to obtain the fractional barium yield for calculating 22^Ra
    activity.

3.  If after sufficient beta decay of the actinium fraction, it is determined
    that there is no 228Ra in the sample, then the 226Ra fraction may be
    alpha counted directly.  If 228Ra is present, then the 226Ra must be
    determined by radon emanation.

Literature:

    Johnson, J. 0.  Determination of Radium-228 in Natural Waters.  Radio-
    chemical Analysis of Water, Geological Survey Water - Supply Paper
    1696-G., U. S. Govt. Printing Office, Washington, D. C. (1971).
                                     28

-------
                   RADIOACTIVE STRONTIUM IN DRINKING WATER
Principle of Method

     Strontium carrier is added to the drinking water sample, collected as
the soluble carbonate, and separated from most of the calcium as the nitrate.
Impurities are removed by an hydroxide scavenge.  After the barium is
removed as the chromate, the strontium is purified as SrC03 for counting.

Procedure Time

     Four samples in 6 hours.

Reagents

     Ammonium acetate -buffer, (CH3COOH-CH3COONH4):  pH 5.0
     Ammonium hydroxide, NfyOH:  15 N_ (cone.), 6 N^
     Barium carrier:  16 mg/ml
     Ethanol, C2H5OH:  95%
     Hydrochloric acid, HC1:  1 N_
     Indicator, methyl red:  0.1%
     Iron chloride, FeCl3:  0.1 M
     Nitric acid, HN03:  16 N_ (cone.), 6 N, 1 N_
     Oxalic acid, V.2^-2^^'  saturated
     Sodium carbonate, Na2C03:  1.5 M
     Sodium chromate, Na2Cr04:  0.5 M_
     Sodium hydroxide, NaOH:  6 N_
     Strontium carrier:  20 mg/ml
     Yttrium carrier:  10 mg/ml

Procedure

1.  To a 1000-ml drinking water sample, add 1.0 ml strontium carrier and 1 ml

    barium carrier.

2.  Make basic with 5 to 10 ml 6 N_ NaOH and heat to boiling.
3.  Add 5 ml 1.5 M Na CO , stir, and digest until SrCO  coagulates, cool,
                     £•  O                             O
    centrifuge, and discard supernatant.

4.  Wash precipitate with 15 ml water and discard wash solution.

5.  Dissolve precipitate with 1 ml 6 N_ HNO .
                                          O
6.  Add 25 ml 16 N^ HNO_, stir, and cool in an ice bath 5 minutes.
                 ^J    O
7.  Centrifuge, discard supernatant, and let drain a few minutes (Note 1).

8.  Dissolve precipitate with 10 ml water and add 0.5 ml 0.1 M_ FeCl .
                                                                   O
9.  Heat to near boiling in water bath and add 6 N^ NH.OH dropwise until
    Fe(OH)3 precipitates.

                                     29

-------
10.  Cool, centrifuge, and transfer supernatant to a clean centrifuge tube.
     Discard precipitate.  Note time of last precipitation; this is the
     beginning of yttrium ingrowth.  (Complete steps 11 through 18 without
                                   Qfi
     delay to minimize ingrowth of   Y.)
11.  Add 3 drops methyl red indicator, and adjust pH to near 5 with a few
     drops 1 N^HCl.   (Color change is from yellow to red.)
12.  Add 5 ml ammonium acetate buffer solution and heat in water bath.
13.  Slowly add 1 ml  0.5 M Na CrO  .  Stir, heat, and centrifuge.  Transfer
     supernatant to a clean centrifuge tube; discard residue.
14.  Add 2 ml 15 K[ NH OH to the supernatant, heat in water bath, and slowly
     add, with stirring, 5 ml 1.5 M Na CO  .  Digest until precipitation is
                                      £•  O
     complete, cool,  centrifuge, and discard supernatant.
15.  Dissolve precipitate with 5 ml 1 N_ HC1, add 10 ml water, and repeat
     step 14.
16.  Wash the strontium carbonate precipitate with 20 ml water, and discard
     wash solution.
17.  Slurry the precipitate with minimum of water and transfer to a tared
     stainless-steel  planchet.  Dry under  infra-red lamps.
18.  Cool, weigh, and beta count immediately  (Note 2).
 Calculation
      Calculate the concentration, D, of the strontium activity in picocuries
 per liter as follows:
                                 D  =
                                     2.22  x EVR
 where:
 C = net  count  rate,  counts/minute,
 E = counter  efficiency,
 V = liters of  sample used,
 R = fractional chemical  yield,  and
 2.22 = conversion  factor from disintegrations/minute to picocuries.
 Notes:
 1.  If the drinking  water samples contain much  CaCQ^  (hardness), it will be
     necessary  to repeat  steps 5, 6,  and  7 until it  is  all  eliminated from
     the  Sr(N03)7 precipitate.
 2.  The  counting  result,  immediately ascertained,  represents the total
     strontium  activity (90Sr +  89Sr) plus  an  insignificant  fraction of the
                                      30

-------
         that has grown in from the separated   Sr.  To determine the
     and 90sr with a greater precision, the planchet should be stored at
     least 2 weeks so that the 90gr_90y activity will be in equilibrium.
     At this point, steps 19-39 are performed on the precipitate to separate
     the yttrium from the strontium and determine the ^Sr activity.
                          90
19.  After the period for   Y ingrowth, slurry the precipitate on the
     planchet with 2 ml water and transfer to a centrifuge tube with the aid
     of a rubber policeman.   To make the transfer quantitative, wash the
     residue from the planchet with a small amount of 1 N^ HNOj.  Dissolve the
     precipitate in the tube with sufficient 1 N_ HNO , and dilute with water
     to 10 ml.
20.  Add 1.0 ml yttrium carrier and stir.
21.  Boil to expel dissolved carbon dioxide; cool to room temperature.
22.  Replace in water bath and make basic with 2 to 3 ml 15 N NH OH.  Stir
     and digest until the yttrium hydroxide precipitation is complete.
23.  Cool, centrifuge, and decant supernatant into a 100-ml beaker.   Note
     time of last precipitation; this is the end of ^Oy ingrowth and the
     beginning of   Y decay.
24.  Dissolve precipitate in 1 ml 1 IfHNO, and dilute with water to 10 ml.
                                    ~~"    «J
25.  Reprecipitate yttrium by dropwise addition of 15 N^ NH OH.
26.  Centrifuge and combine supernatant with solution in the 100-ml beaker
     (step 23).
27.  Repeat steps 24, 25, and 26.  Save the combined supernatant solutions in
     the beaker for strontium activity and gravimetric yield determination,
     step 35 (Note 3).
28.  Add 2 ml 1 N HNO  to the Y(OH)  precipitate from step 26 and dissolve.
                ~    3             3
     Dilute to 5 ml with water.  Filter through Whatman #42 filter paper and
     collect filtrate in a centrifuge tube.
29.  Slowly add 5 ml saturated H C 0 , with stirring, and digest in hot-water
     bath for 10 minutes.
30.  Cool in an ice bath to room temperature.
31.  Centrifuge and discard supernatant.
32.  Wash precipitate, twice with 10 ml hot water.  Centrifuge and discard
     wash solutions.
33.  Filter the yttrium oxalate on a tared glass-fiber filter.  Wash with
     hot water and ethanol.

                                      31

-------
34.  Dry, cool, weigh, mount, and beta count the 90Y immediately.

35.  Warm the combined supernatant solution from step 27, add 5 ml 1.5 M

     Na2C03J and diSest f°r 10 minutes.
36.  Cool, centrifuge, and discard supernatant.

37.  Wash the SrC03 with 15 ml water and discard wash solution.
38.  Slurry with a few ml water and transfer quantitatively to a tared
     stainless-steel planchet.  Dry under infra-red lamps.
39.  Cool, weigh, and beta count immediately.

 Calculation

      Calculate the concentration of 89Sr and 90Sr in picocuries per liter
 as follows:

      1 .  90Y c/m (corrected) =     *'
          90         90                    D
      2.    Sr c/m =   Y c/m  (corrected) x =-
      3   9°Y c/m =   Y C/m  Ccorrected) x G x B2
      4.  89Src/m=  (R - 90Sr c/m - 90Y c/m) ^
      5   9°Sr activity =     C/m  Corrected)
      i>.    br activity       2.22 x EIV

                           89
      6.  89sr activity .
 where :

 A  = decay factor for 9^y from step 23 to counting time,
 Bj = ingrowth factor of 90y from time of strontium purification to yttrium
      separation,
 B2 = ingrowth factor of 90y from time of yttrium separation to time of total
      strontium count,
 C  = fractional chemical yield for yttrium,
 D  = 90sr efficiency for counter in which radiostrontium is counted,
 E  = 90y efficiency for counter in which 90y is counted,
 F  = decay factor for 89sr from sample collection to counting time,
 G  = 90y efficiency for counter in which radiostrontium is counted,
 H  = 89sr efficiency for counter in which radiostrontium is counted,
 I  = fractional chemical .yield for strontium,
 R  = observed count rate of total radiostrontium fraction (steps 18 or 39),
 V  = liters of sample used, and
 2.22 = conversion factor from disintegrations/minute to picocuries.
                                     32

-------
Note:

3.  Steps 35-39 are a repeat of the strontium carbonate precipitation to
    determine chemical yield after the yttrium has been removed.  The beta
    activity should be comparable to that obtained previously for the
    precipitate from step 18.  It is a more accurate result, however, since
    the only correction that need be made is that for the ingrowth of 90y
    from the time of yttrium separation (step 27) to the time of the total
    strontium count.

Literature:

    Douglas, G. S., ed.  Radioassay Procedures for Environmental Samples,
    Environmental Health Series,  USDHEW Rept. 999-RH-27, National Center
    for Radiological Health, Rockville, Md.   10852 (Jan. 1967).

    Hahn, R. B. and C. P. Straub.  Determination of Radioactive  Strontium
    and Barium in Water.  J. Am.  Water Works Assoc.  47 (4)  335-340
    (April 1955).
                                   33

-------
                          TRITIUM IN DRINKING WATER
Principle of Method
     The aqueous sample is distilled to dryness to effect quantitative trans-
fer of tritium to the distillate and to remove interfering radionuclides and
quenching materials.  A portion of the distillate is mixed with scintillation
solution and counted in a liquid scintillation spectrometer.  Standard
tritium and background samples are prepared and counted alternately to nullify
errors produced by aging of the scintillation medium or instrument drift.
Procedure Time
     Four samples in 2 hours.
Reagents
     Scintillation solution:  prepared reagent
     Tritium, %:  standard tracer solution
Procedure
1.  Distill the drinking water sample  (50 ml or less) to dryness  (Fig. 7)
    and collect the distillate in a centrifuge tube (Note 1).
2.  Transfer 16 ml scintillation solution to a 25-ml scintillation vial.
3.  Add 4 ml sample distillate to the scintillation vial, cap tightly,
    and^ shake until thoroughly mixed.
4.  Prepare a background sample consisting of 4 ml water of minimal tritium
    concentration and 16 ml scintillation solution in same manner as sample.
5.  Prepare a standard consisting of 16 ml scintillation solution and 4 ml
    water, which contains a standard concentration of tritium activity in
    same manner as sample.
6.  Dark-adapt and cool sample, background, and standard solutions in
    instrument freezer to prepare for counting (Note 2).
7.  In normal counting operation, tritium is counted with a window setting
    where the figure of merit is at maximum (Note 3).  The high voltage is
    set to obtain the peak counting efficiency in the window.
    To confirm the purity and identify the tritium activity the following
    steps are necessary:
8.  Determine the count rate for each sample, background and standard.  Three
    successive results which are within 2 sigma of each other, ensure that

                                      34

-------
U)
Ul
                                                                             100 - ml
                                                                             DISTILLING
                                                                             FLASK
                       50-ml
                       CENTRIFUGE  TUBE
                       IN  HOLDER
                       j
                         Figure 7.  Distillation Apparatus for Tritium Analysis

-------
    the vials have been dark adapted.

9.  With a 2-channel spectrometer, one window is set to give the best figure

    of merit and the other is set as an impurity screen.  The ratios of the

    activity for the  H standard and for the distilled samples should be

    the same at the two window settings.  If not, the samples must be

    redistilled to remove interfering ionizing radiations and prepared

    again for counting.

Calculation

     Calculate the concentration, D, of the tritium activity in picocuries
per liter as follows:

                                D = C x 1000
                                    2.22 x EV

where:

C = net count rate, counts/minute,
E = efficiency for measuring 3ft in liquid scintillation spectrometer,
V = milliliters of sample used,
2.22 = conversion factor from disintegrations/minute to picocuries.

     Calculate the efficiency^ E, for measuring ^H in the liquid scintillation
spectrometer as follows:


                               "I

where:

Y = counts/minute determined by counting standard tritium sample (step 5)
    at the optimum instrument settings, and
S = standard tritium activity (disintegrations per minute/ml) as rated by
    NBS or equivalent, corrected for decay.

     Calculate the decay correction for the tritium activity as follows:


                              A = A0 e-°-693t/T

where:
A  = activity at time t,
AQ = activity at time of collection or from the date the standard was rated,
e  = base of natural logarithms,
t  = elapsed time  from collection or from the date the standard was rated,
     and
T  = half life of  tritium  (12.3 years).
                                      36

-------
Notes:

1.  As a general rule, all samples should be distilled to dryness for
    quantitative recovery of tritium and to remove interfering radionuclides,
    Iodine-131 in aqueous samples can be eliminated by adding stable iodine
    and AgN03 to the flask before the distillation.

2.  The freezer temperature must be maintained above 2°C or, in time, the
    solution will begin to solidify.  If an ambient temperature liquid
    scintillation spectrometer is employed, the vial must be dark-adapted,
    usually 24 to 48 hours, before counting begins.

3.  Figure of Merit = f gfficiencfl2
      6               B  (Background)

Literature:

    Butler,  F. E.  Determination of Tritium in Water and Urine.   Anal.  Chem.
    33, 409-414 (1961).
                                     37

-------
                   POTASSIUM-40 IN DRINKING WATER (Note 1)
Principle of Method
     Total potassium in drinking water is determined by one of several
methods—atomic absorption, flame photometry, or colorimetry.  From the
determination of mg/1 total potassium present, the concentration of 40K can
be calculated.
Preparation of Standards
     Stock Solution:  Dissolve 0.1907 g of KC1 (analytical reagent grade),
                      dried at 110°C, in deionized distilled water and
                      make up to 1  liter.
                      1 ml = 0.10 mg K  (100 mg/1).
     Prepare dilutions of the stock solution to be used as calibration
                      standards at  the time of analysis.
General  Instrumental Parameters for Atomic Absorption  (Note 2)
     Potassium hollow cathode lamp
     Wavelength:   766.6 nm
     Fuel:  Acetylene
     Oxidant:  Air
     Type of flame:  Slightly oxidizing
Procedure
1.  For  determining total potassium, the drinking water sample is acidified
    with 1:1 redistilled HNO- to a  pH of 2 at the time of collection.  The
    sample is not  filtered before processing.
2.  Transfer a representative aliquot of the drinking water sample (50 to
    100  ml) to a Griffin beaker and add 3 ml of concentrated redistilled
    HNO  .  Place the beaker on a hot plate and evaporate to dryness cautious-
       O
    ly,  making certain that the sample does not boil.  Cool the beaker and
    add  another 3  ml portion of concentrated redistilled HNO_.  Cover the
    beaker with a  watch glass and return to the hot plate.  Increase the
    temperature of the hot plate so that a gentle reflux action occurs.
    Continue heating, adding additional acid as necessary, until the
    digestion is complete  (generally indicated by a light colored residue).
    Add  sufficient distilled 1:1 HC1 and again warm the beaker to dissolve
    the  residue.
                                     38

-------
3.  Wash down the beaker walls and watch glass with distilled water and

    filter the sample to remove silicates and other insoluble material that

    could clog the atomizer.  Adjust the volume to some predetermined value

    based on the expected potassium concentration.  The sample is now ready

    for analysis (Notes 3 and 4).

Calculation

     Calculate the concentration, D, of 40^ in drinking water in picocuries
per liter as follows:

                                    K x 1.885
                                      2.22

where:
K = concentration of potassium in mg/1 of sample,
1.883 = disintegration/minute for each mg potassium,
2.22  = conversion factor from disintegrations/minute to picocuries

Notes:
1.  This technique(1) is presented for those interested in calculating the
    ^OK in drinking water.  All that is required is that total potassium
    be determined in any manner available, and from this value, the radio-
    active potassium value can be calculated.

2.  The Osram potassium vapor-discharge lamp may also be used in the Perkin-
    Elmer 303.  In this case, the current should be 350 ma or the optimum
    operating current.

     a.  Sodium may interfere if present at much higher levels than the
         potassium.   This effect can be compensated by approximately
         matching the sodium content of the potassium standards with that
         of the sample.

     b.  Potassium absorption is enhanced in the presence of Na, Li, and Cs,
         especially in a high-temperature flame.  This enhancement effect
         of sodium can be eliminated by changing the burner height and the
         type of flame used.  The burner assembly is set approximately
         0.05 cm below the optical light path so that the optical light
         path is sliced at the bottom by the burner head.  A fuel-rich
         flame is used.

     c.  The 404.4 nm line may also be used.  This line has a sensitivity
         of 5 mg/1 for 1% absorption.

     d.  To cover the range of potassium values normally observed in
         surface waters (0.1 to 20 mg/1), it is suggested that the burner
         be rotated 75°=^

3.  Flame photometric or colorimetric methods(2) may be used if atomic
    absorption instruments are not available.
                                     39

-------
4.  The precision and accuracy of the technique has been determined at the
    Methods Development and Quality Assurance Research Laboratory
    (MDQARL).  Using distilled water samples at concentrations of 1.6
    and 6.3 mg/1, the standard deviations were +_ 0.2 and +_ 0.5, respectively.
    Recoveries at these levels were 103% and 102%.  With an optimum
    concentration range between 0.1 and 2 mg/1 and with the use of a
    wavelength of 766.5 nm, the sensitivity was 0.04 mg/1 and the
    detection limit was 0.005 mg/1.

References:
1.  Methods for Chemical Analysis of Water and Wastes, p. 143.  Methods
    Development and Quality Assurance Research Laboratory, National
    Environmental Research Center-Cincinnati, EPA-625/6-74-003  (1974).
2.  Standard Methods for the Examination of Water and Waste Water. 13th ed.
    pp. 283-285.  American Public Health Association, Washington, D. C.
    (1971).
                                     40

-------
                                APPENDIX A

                            METHOD CAPABILITIES
                           METHOD CAPABILITIES*

Gross Beta
Gross Alpha
1S4Cs
137Cs
131j
226 . .
Ra-precipitation
Ra-Rn emanation
228R.
89Sr
90Sr
Tritium

Sample
Volume
100 ml
100 ml
1000 ml
1000 ml
2000 ml
2000 ml
1000 ml
2000 ml
1000 ml
1000 ml
4 ml
Parameter
Counting
Efficiency %
39
41
31
34
32
40
70
40
42
33
30
3a MDL pCi/1
Instrument
Background
1.0 c/m
0.2
1.2
1.2
1.0
0.5
0.03
1.5
1.2
1.2
9.0
1000 min
count
1.5
0.8
0.2
0.2
0.1
0.05
0.02
0.1
0.3
0.2
200
' 60 min
count
6
2.4
0.8
0.8
0.4
0.2
0.06
0.4
1.3
0.8
600
With these parameters, the procedures in this manual can obtain the
corresponding minimum detection levels (MDL), assuming good chemical yield
recovery.  The calculations were made with data from replicate testing of
these procedures.  Variability in instrument background is a significant
factor in the determination of these values.  The levels reported above
can be further reduced by the use of larger samples for analysis and
better instrument shielding.
                                    41

-------
                                 APPENDIX B
                             REAGENT PREPARATION
     Distilled or deionized water should be used to prepare all reagents
requiring water as the solvent.
I.  Carrier solutions - These solutions, prepared as the specific ion, are to
    be filtered and standardized before use in chemical yield determinations.
    Reagent blanks should be prepared  in the appropriate geometry with
    approximate final precipitate weight to ascertain instrument plus reagent
    background.
    Ba   - 16 mg/ml.  Dissolve 2.846 grams  BaCl-.ZH 0 in water, add 0.5 ml
                      16 N_ HNO,, and dilute to 100 ml with water.
      +                       ^
    Cs   - 10 mg/ml.  Dissolve 1.267 grams CsCl in water and dilute to 100 ml.
    I    - 20 mg/ml.  Dissolve 2.616 grams KI in water, add 2 drops Na SO ,
                                                                      £*  O
                      and dilute to 100 ml.  Store in dark flask.
    10   - 10 mg/ml.  Dissolve 1.685 grams KIO, in water and dilute to 100 ml.
      o                                       o
                      Store in dark flask.
    Pb   - 15 mg/ml.  Dissolve 2.397 grams Pb(NO )  in water, add 0.5 ml 16 N_
                                                O £
                      HNO , and dilute to  100 ml with water.
    Pb+* - 1.5 mg/ml. Dilute  10.0 ml Pb(NO )   (15 mg/ml) to 100 ml with
                                           O £.
                      water.
    Sr   - 20 mg/ml.  Dissolve 4.831 grams Sr(NO_)  in water and dilute to
                      100 ml.
    Y+   - 18 mg/ml.  Add 22.85 grams  Y 0  to an Erlenmeyer flask containing
                                       £ J
                      20 ml water.  Heat to boiling and continue stirring
                      with a magnetic  stirring hot plate while adding 16 fJ
                      HNO  in small amounts.  Usually about 30 ml 16 N
                         O
                      HNO_ is necessary to dissolve the Y 0 .  Small additions
                      of water may  be  required to replace that lost by
                      evaporation.  After  total dissolution add 70 ml 16 N_
                      HNO_ and dilute  to 1 liter with water.
    Y+3  - 10 mg/ml.  Dissolve 43.1 grams  Y(NO») .6H 0 in 800 ml water, add
                                              O O   £,
                      5 ml 6 N HNO  , and dilute to 1 liter.
    Sr++- Y+3  (mixed carrier) -  (0.9 mg/ml Sr+2 and  -0.9 mg/ml Y+3).
                                                      +3
         Solution A - Dilute  10.0 ml yttrium carrier Y   -(18 mg/ml) to 100 ml.
                                      42

-------
          Solution B - Dissolve 0.4348 grams Sr(NO )„ in water and dilute to

                       100 ml.   Combine Solutions A and B and label.

II.   Acids and Inorganic Reagents

     Ammonium acetate buffer, (CH COOH-CH COONH ) :   pH 5.0.  Mix 100 ml

     1.5 N CH,COOH and 100 ml 3 M CH_COONH, .
         —   o                  —   o     4
     Acetic acid,  CH COOH, 17.4 N_:  This is the concentrated (glacial) reagent;
     sp.  gr.  1.06,  99.5%.
     Acetic acid,  CH COOH,  1.5 N_:   Dilute 86 ml glacial (17.4 N) acetic acid
                    O
     to 800 ml with water and dilute to 1 liter.

     Ammonium acetate,  CH,COONH ,  3 M:   Dissolve 231 grams CH.COONH. in 600 ml
     _ 3 _ 4 _ —                        o     4
     water and dilute to 1 liter.

     Ammonium hydroxide, NH OH, 15 N^  This is the concentrated reagent;

     sp.  gr.  0.9,  50%.

     Ammonium hydroxide, 6 N_:  Add 400  ml 15 N_ NH OH to 400 ml water and

     dilute to 1 liter.

     Ammonium hydroxide, 2 N:  Dilute 100 ml 6 N NH OH to 300 ml with water.

     Ammonium oxalate,  (NH ) C 0 , 5%:   Dissolve 25 grams (NH4)2C204 in water

     and dilute to 500 ml.
     Ammonium phosphomolybdate (prepared reagent) :   Dissolve 100 grams of
     molybdic acid (85% MoOs) in a mixture of 240 ml of water and 140 ml
     15 N NH4OH.  When solution is complete, filter and add 60 ml of 16 N_
     HN03-   Mix 400 ml  of 16 N_ HNOs and 960 ml of water-   Allow both solutions
     to cool  to room temperature.   With constant stirring, add the ammonium
     molybdate solution to the nitric acid solution.  Allow to stand for
     24 hours.  Filter through Whatman  #42 filter paper.   Discard the
     insoluble material.
     Collect  the filtrates  in a 3-liter beaker and heat to 50° to 55°C.
     Remove from heating unit.  It is important that the solution not be
     heated above 55°C  to avoid contamination of the precipitate with molybdic
     anhydride.  Add 25 grams of NaH2P04 dissolved in 100 ml of water to the
     ammonium molybdate solution.   Stir occasionally for 15 minutes and allow
     the precipitate to settle (approximately 30 minutes) .  Filter through
     Whatman #42 filter paper.  Wash the precipitate with 1% potassium
     nitrate  and finally with water.  Dry the precipitate and paper at 100°C
     for 3 to 4 hours.   Transfer the (NH4)3(PMo^2^4o) solid to a weighing
     bottle,  and store  in a desiccator.

     Ammonium sulfate,  200  mg/ml:   Dissolve 20 grams (1^4)2804 in a minimum
     of water and dilute to 100 ml.

     Ammonium sulfide,  2%:   Dilute 10 ml  (NH4)2S,  (20-24%),  to 100 ml  with
     water.
                                      43

-------
Calcium chloride, 3 M:  Dissolve  330 grams CaCl2  in water and dilute to
1 liter"
Chloroplatinic acid, 0.1 M:  Dissolve  51.8 grams  H2PtCl6.6H20 in water
and dilute to 1  liter.
Citric acid, 1 M:  Dissolve  19.2  grams CfcHgOy  in  water and dilute to
100 ml.
Helium, gas
Hydrochloric acid, HC1,  12 N:  This  is  the  concentrated reagent;
sp. gr. 1.19,  37%.
Hydrochloric acid, 6 N:  Add 500 ml  12  N HC1  to  400 ml water and dilute
to 1 liter.
Hydrochloric acid,  4 N:  Add  333 ml  12  N HC1  to  500 ml water  and dilute
to 1 liter.
Hydrochloric  acid,  2  N:   Dilute  333  ml  6  N  HC1  to  1  liter with water.
Hydrochloric  acid,  1  N:   Dilute  250  ml  4  N  HC1  to  1  liter with water.
Hydrofluoric acid,  HF,  48%  (~  30  N):   This  is  the  concentrated reagent;
sp. gr.  1.15.
Iron chloride,  0.1  M:   Dissolve 27  grams  FeCl3-6H20  in water plus 2 ml
12 N_ HC1 and dilute to  1  liter.
Magnesium perchlorate,  Mg(C104)2:   reagent  grade.
Nitric acid, HNO_,  16 N_:  This is the  concentrated reagent; sp. gr. 1.42,
                 j       -
_____
Nitric acid, 6  N:   Cautiously  add 395  ml  16 N_ HN03 to 600 ml water and
dilute to 1 liter.
Nitric acid, 4  N^   Cautiously  add 250  ml  16 N_ WO^ to 700 ml water and
dilute to  1  liter.
Nitric acid,  1 N_:   Add 62  ml  16  N_ to  m05  to  900 ml water and dilute to
1 liter.
Nitric acid,  0.2 N_:  Add  12.5 ml  16 N_ HN03  to  900 ml water and dilute
to 1  liter.
Oxalic acid,  saturated:   Dissolve 150 grams H2C204  in  1  liter boiling
water.
Palladium chloride,  0.2 M:   Dilute 118 ml 5% PdCl2  to  167 ml with 2 N HC1.
Phosphoric acid, H  PO  ,  85%  (44 N):  This  is  the  concentrated reagent;
                  O *r
sp. gr. 1.69.
                                   44

-------
Silver nitrate, 0.1 M:  Dissolve 17 grams AgNOj in water and dilute to
1 liter.  Store in dark flask.
Sodium bisulfite, 1 M:  Dissolve 5.2 grams NaHS03 in water and dilute to
50 ml.  Prepare only in small quantities.
Sodium carbonate, 1.5 M:  Dissolve 160 grams Na2C03 in 600 ml water and
dilute to 1 liter.
Sodium chromate, 0.5 M:  Dissolve 171.1 grams Na2Cr04.10H20 in 400 ml
water and dilute to 1 liter.
Sodium hydroxide, 18 N:  Dissolve 720 grams NaOH in 500 ml water and
dilute to 1 liter.
Sodium hydroxide, 10 N:  Dissolve 400 grams NaOH in 500 ml water and
dilute to 1 liter.
Sodium hydroxide, 6 N:  Dissolve 240 grams NaOH in 800 ml water and dilute
to 1 liter.
Sodium hydroxide, 1 N:  Dilute 100 ml 10 N NaOH to 1 liter with water.
Sodium hydroxide, 0.5 N:  Dilute 50 ml 6 N NaOH to 600 ml with water.
Sodium nitrite, 1 M:  Dissolve 69 grams NaN02 in water and dilute to
1 liter.
Sodium sulfite, 1 M:  Dissolve 5 grams Na2S03 in 40 ml water.  Prepare
fresh reagent every week.
Sulfuric acid, H2S04, 36 N^  This is the concentrated reagent; sp. gr.
1.84, 95-98%.
Sulfuric acid, 18 J4:  Cautiously add, with stirring, 500 ml 36 N H2S04 to
400 ml water and dilute to 1 liter.
Sulfuric acid, 12 N;.  Cautiously add, with stirring, 333 ml 36 N H2S04
to 500 ml water and dilute to 1 liter.
Sulfuric acid, 9 N^:  Cautiously add, with stirring, 250 ml 36 N H2S04 to
600 ml water and dilute to 1 liter.
Sulfuric acid, 2 N^:  Dilute 100 ml 12 N_ H2S04 to 600 ml with water.
Sulfuric acid, 0.1 N:  Dilute 50 ml 2 N H2S04 to 1 liter with water.
Zinc, powder:  Reagent grade.
                                   45

-------
III.  Organic reagents

      Acetone, (CI^^CO, anhydrous
      Ascarite, granular, 8 to 20 mesh
      Carbon tetrachloride, CC1.

      Di ethyl ether,  ^Hg^O* anhydrous
      EDTA reagent:  Dissolve 20 grains NaOH in about 750 ml water, heat, and
      slowly add 93 grams ^2^(^1403^.21120  (disodium ethylenedinitriloacetate
      dihydrate) while stirring.  After the salt is in solution, filter through
      coarse filter paper and dilute to 1  liter.  This solution is  - 0.25 M.
      Ethanol, C2H5OH, 95%

      Scintillation solution*:   (If prepared  in the presence of daylight or
      fluorescent  light, store  in dark place  2 days before use.)
      Dissolve 120 grams naphthalene, 0.05 grams 1,4-di  (2-(5-phenyloxazolyl)
      benzene) (POPOP), and  4 grams 2, 5-diphenyloxazole  (PPO) , in 1 liter of
      p-dioxane.   Store in an amber-colored bottle.  Scintillation grade
      reagents are recommended  to ensure sample stability.
      Tartaric acid, 50%:  Dissolve 50 grams  C4H606 in water and dilute to
      100 ml.
  IV.  Indicators
      Methyl red,  0.1%:  Dissolve 0.1 grams methyl red indicator in 100 ml
      ethanol .
      Methyl orange, 0.1%:   Dissolve 0.1 grams methyl orange indicator in
      100 ml water.
  * Commercially prepared scintillation solutions  are  available from several
   supply houses,  and can be substituted for  this prepared stock solution.
                                       46

-------
                        '  ,  APPENDIX C
                        SOURCES OF SUPPLY
Glass-fiber filter paper:
  Reeve Angel
  9 Bridewell Place
  Clifton, N. J.
  Specification:  2.8 cm  Grade 934 AH
Liquid scintillation vials:
  Packard Instrument Co.
  2200 Warrenville Rd.
  Downers Grove, 111. 60515
  Catalog #6001075  Polyethylene vial 20 ml, w/22 mm screw cap
Membrane filters:
  Gelman Instrument Co.
  Ann Arbor, Mich. 48106
  Specification:  Metricel, A-6, 47 mm, 0.45 y
Mylar film:
  Cadillac Plastics
  3818 Red Bank Rd.
  Cincinnati, Ohio 45227
  Specification:  0.0005 inch thick
Plastic rings and discs:
  Control Molding Corporation
  84 Granite Ave.
  Staten Island, N. Y. 10303
  Catalog #J-356  1-inch dia (natural color) nylon type 6/6
Polypropylene centrifuge tube:
  Dynalab Corp.
  P. 0. Box 112
  Rochester, N. Y. 14601
  Catalog #3103-0050   134 x 28.7 mm O.D.   Closure #29C
Radon counter:
  Randam Electronics,'Inc.                Johnson Laboratories, Inc.
  3091 Shadycrest Drive                   3 Industry Lane
  Cincinnati, Ohio 45236                  Cockeysville, Md. 21030
  Specifications:  Bias network, detector circuits, 6 digit decade
                   counter.  External high voltage supply and 2-inch
                   photomultiplier tubes.

                                47

-------
Radon emanation bubblers and associated glassware:  These can be fabricated
  by local glass companies with the specifications from Figures 3 and 4.

Scintillation cell:

  Johnson Laboratories, Inc,
  3 Industry Lane
  Cockeysville, Md. 21030

  Specifications:  according to Figure 6,

Stainless-steel planchets:

  Hruden Laboratory Products
  P. 0. Box 1802
  Ann Arbor, Mich. 48106

  Catalog #75750   2 x 0.018 x 1/4 inches.

Teflon  filter holder:

  Atomic Products  Corp.
  Center Moriches, N. Y.  11934
                                    48

-------
                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-600/4-75-008
                                                            3. RECIPIENT'S ACCESSIOONO.
4. TITLE AND SUBTITLE
  RADIOCHEMICAL METHODOLOGY FOR  DRINKING WATER
                                                            5. REPORT DATE
                                                             September 1975  (Issuing Date)
                                                            6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

  Herman  L.  Krieger
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Radiochemistry and Nuclear Engineering Branch
  Environmental  Monitoring and Support Laboratory
  Cincinnati,  Ohio  45268
              10. PROGRAM ELEMENT NO. 2FH120
               (1HA527; ROAP  24-AAK;  Task 005)
              11. CONTRACT/GRANT NO.
 12. SPONSORING AGENCY NAME AND ADDRESS
  Office of Research and Development and
  Office of Radiation Programs
  U.S. Environmental Protection Agency
  Washington,  D.C.  20460
              13. TYPE OF REPORT AND PERIOD COVERED
              In-house
              14. SPONSORING AGENCY CODE
              EPA-ORD
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT
  A laboratory manual of radiochemical procedures has  been compiled and  edited for use
  in the analysis of specific radionuclides in drinking water; nuclides  for whom the
  Environmental Protection Agency  recommended maximum  contaminant levels  in its interim
  drinking water standards.  In  addition to gross activity analyses, the  procedures for
  134/137cs,  131I,  226/228Ra> 89/90Sr) 3H and 40j( were evaluated by replicate testing
  to determine the method capabilities and minimum  detection levels.  The results,
  which indicate that the sensitivity of these procedures is at least a  factor of ten
  greater than the present required limits, are given  in the Appendix.  Also appended
  is information on reagent preparation and suggested  sources for purchasing special
  equipment.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                           c. cos AT I Field/Group
  Chemical  analysis
  Potable water
  Quality control
  Radiactive  contaminants
  Radiochemistry
 Maximum contaminant  level
 Minimum detection  level
 Procedures
 Radiochemical analysis
13B
18. DISTRIBUTION STATEMENT
  RELEASE TO  PUBLIC
                                               19. SECURITY CLASS (This Report)
                                                   UNCLASSIFIED
                           21. NO. OF PAGES

                                  59
20. SECURITY CLASS (Thispage)
     UNCLASSIFIED
                                                                          22. PRICE
EPA Form 2220-1 (9-73)
                                             49
                                                  £• U. S. GOVERNMENT PRINTING OFFICE: 1975-657-695/5305 Reg i on No. 5-11

-------