7500-Ra

Radium

Methods A and E approved by Standard Methods Committee, 2007. Methods B, C, D approved by Standard Methods Committee, 2001. Editorial revisions, 2011 and 2021.
Joint Task Group: 21st Edition—Bahman Parsa (chair), Edmond J. Baratta, Loren A. Berge, John G. Griggs, Nancy E. Kinner, David E. McCurdy, James W. Mullins, Stephen
H. Pia. 7500-Ra.A, E: Bahman Parsa (chair), Edmond J. Baratta, Loren A. Berge, James W. Mullins, Stephen H. Pia, Robert Rosson, Shiyamalie R. Ruberu, Carolyn T. Wong.

7500-Ra A. Introduction

1. Occurrence • alpha counting of barium–radium sulfate precipitate that has

been purified;
Radium is a radioactive member of the alkaline earth family • measurement of 222Rn produced from 226Ra in a sample or in
and is widely disseminated throughout the earth’s crust. It has 4 a soluble concentrate isolated from the sample;
naturally occurring isotopes: • measurement of 228Ac from 228Ra by beta-counting; and
• 11.43-d 223Ra (member of 235U series or actinium series), • measurement of 224Ra, 226Ra, and 228Ra by gamma-counting
• 3.66-d 224Ra (member of the 232U or thorium series), their respective 212Pb, 214Pb (and/or 214Bi), and 228Ac decay
• 1600-year 226Ra (member of 238U or uranium series), and products.
• 5.75-year 228Ra (member of the 232U or thorium series). The determination of radium by precipitation (7500-Ra B)
The contribution of 228Ra (a beta-emitter) to the total radium alpha includes all alpha-emitting radium isotopes. It is a screening tech-
activity is negligible because of the 1.9-year half-life of its first nique particularly applicable to drinking water. As long as the
alpha-emitting daughter product, 228Th. The other 3 radium iso- concentration of radium is less than the 226Ra plus 228Ra drinking
topes are alpha-emitters; each gives rise to a series of relatively water standard, examination by a more specific method is seldom
short-lived daughter products, including 3 more alpha-emitters. needed. This method also is applicable to sewage and industrial
Because of their longer half-lives and health significance, wastes, provided that steps are taken to destroy organic matter
226
Ra and 228Ra are the most important radium isotopes found in and eliminate other interfering ions (see Section 7110). However,
water. Even though it has a short half-life, 224Ra in groundwater avoid igniting sample ash.
is important in certain geographical areas because of their geo- The emanation technique (7500-Ra C), based on measurement
chemistry and the short delivery time of well water to consumers. of 222Rn, is nearly, but not absolutely, specific for 226Ra. Proce-
Radium is a bone-seeker, and high concentrations in bone can dures for soluble, suspended, and total 226Ra are given.
lead to malignancies. The sequential precipitation method (7500-Ra D) can be used
to measure either 228Ra alone or 228Ra and 226Ra.
2. Selection of Method The gamma-counting method (7500-Ra E) is used to measure
224
Ra, 226Ra, and 228Ra either concurrently or sequentially.
Four common methods for measuring radium are:

7500-Ra B. Precipitation Method

1. General Discussion 3.6-d half-life, also is decreasing, leading to a rather complicated

ingrowth and decay curve.
a. Application: This method is suitable for determination of the Lead and barium carriers are added to the sample containing
alpha-emitting isotopes of radium. alkaline citrate, then sulfuric acid (H2SO4) is added to precipitate
b. Principle: Because of the difference in half-lives of the radium, barium, and lead as sulfates. The precipitate is purified by
nuclides in the series, including the alpha-emitting Ra isotopes, washing with nitric acid (HNO3), dissolving in alkaline EDTA,
these isotopes can be identified by the rate of ingrowth and decay and reprecipitating as radium-barium sulfate after pH adjustment
of their daughters in a barium sulfate precipitate.1–3 The ingrowth to 4.5. This slightly acidic EDTA keeps other naturally occurring
of alpha activity from 226Ra increases at a rate governed primar- alpha-emitters and the lead carrier in solution.
ily by the 3.8-d half-life of 222Rn. The ingrowth of alpha activity c. Quality control (QC): The QC practices considered to be an
in 223Ra is complete by the time a radium-barium precipitate can integral part of each method can be found in Section 7020.
be prepared for counting. The ingrowth of the first two alpha-
emitting daughters of 224Ra is complete within a few minutes and 2. Apparatus
the third alpha daughter activity increases at a rate governed by
the 10.6-h half-life of 212Pb. The activity of the 224Ra itself, with a a. Counting instruments: One of the following is required:

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 7500-Ra RADIUM - B. Precipitation Method

1) Internal proportional counter, gas-flow, with scaler and register; this original precipitation as the separation of the isotopes from
2) Alpha scintillation counter, silver-activated zinc sulfide their parents; use a minimal settling time and complete procedure
phosphor deposited on thin polyester plastic, with photomulti- through 7500-Ra.B.4j without delay. Assuming the presence of
plier tube, scaler, timer, and register; or and separation of parents, decay of 223Ra and 224Ra begins at the
3) Proportional counter, thin end-window, gas-flow, with time of the first precipitation, but ingrowth of decay products is
scaler and register. timed from the second precipitation (7500-Ra B.4i). The time of
b. Membrane filter holder, or stainless steel or TFE filter fun- the first precipitation is not needed if the objective is to check the
nels, with vacuum source. final precipitate for its 226Ra content only.
c. Membrane filters (Millipore Type HAWP or equivalent) or f. Decant and discard the clear supernate. Transfer the precipi-
glass fiber filters (No. 934-AH, 2.4 cm diam, H. Reeve Angel and tate to a 40-mL or larger centrifuge tube, centrifuge, decant, and
Co., or equivalent). discard the supernate.
g. Rinse the wall of the centrifuge tube with a 10-mL portion of
3. Reagents conc HNO3, stir the precipitate with a glass rod, centrifuge, and
discard the supernate. Repeat rinsing and washing 2 more times.
a. Citric acid, 1 M: Dissolve 210 g H3C6H5O7 ⋅ H2O in reagent h. To precipitate, add 10 mL reagent water and 1 to 2 drops
water and dilute to 1 L. phenolphthalein indicator solution. Stir and loosen the precipitate
b. Ammonium hydroxide, conc and 5 N: Verify strength of old from the bottom of the tube (using a glass rod if necessary) and
5 N NH4OH solution before use. add 5 N NH4OH, dropwise, until the solution is definitely alkaline
c. Lead nitrate carrier: Dissolve 160 g Pb(NO3)2 in reagent (red). Add 10 mL EDTA reagent and 3 mL 5 N NH4OH. Stir occa-
water and dilute to 1 L; 1 mL = 100 mg Pb. sionally for 2 min. Most of the precipitate should dissolve, but a
d. Stock barium chloride solution: Dissolve 17.79 g BaCl2 ⋅ 2H2O slight turbidity may remain.
in reagent water and dilute to 1 L in a volumetric flask; 1 mL = 10 mg i. Warm in a steam bath to clear the solution (about 10 min), but
Ba. do not heat for an unnecessarily long period. (If solution does not
e. Barium chloride carrier: To a 100-mL volumetric flask, add clear in 10 min, cool, add 1 mL 5 N NH4OH, let stand 2 min, and
20.00 mL stock BaCl2 solution using a transfer pipet, dilute to heat for another 10-min period.) Add conc acetic acid dropwise
100 mL with reagent water, and mix; 1 mL = 2.00 mg Ba. until red color disappears; add 2 or 3 drops bromocresol green
f. Methyl orange indicator solution. indicator solution and continue to add conc acetic acid dropwise,
g. Phenolphthalein indicator solution. while stirring with a glass rod, until indicator turns green (aqua).
h. Bromocresol green indicator solution: Dissolve 0.1 g bro- (The endpoint is most easily determined by comparison with a
mocresol green sodium salt in 100 mL reagent water. solution of similar composition that has been adjusted to pH 4.5
i. Sulfuric acid (H2SO4), 18 N. using a pH meter.) BaSO4 will precipitate. Note the date and time
j. Nitric acid (HNO3), conc. of precipitation as zero time for ingrowth of alpha activity. Digest
k. EDTA reagent, 0.25 M: Add 93 g disodium ethylenedi- in a steam bath for 5 to 10 min, cool, and centrifuge. Discard the
minetetraacetate dihydrate to distilled water, dilute to 1 L, and mix. supernate. The final pH should be about 4.5, which is sufficiently
l. Acetic acid, conc. low to destroy the Ba-EDTA complex, but not Pb-EDTA. A pH
m. Ethyl alcohol, 95%. much below 4.5 will precipitate PbSO4.
n. Acetone. j. Wash Ba-Ra sulfate precipitate with reagent water and mount
o. Clear acrylic solution: Dissolve 50 mg clear acrylic in 100 mL in a manner suitable for counting as given in paragraphs k, l, or m
acetone. below.
p. Standard 226Ra solution: Prepare as directed in 7500- k. Transfer the Ba-Ra sulfate precipitate to a tared stainless
Ra C.3d-f, except that in 7500-Ra C.3f (standard 226Ra solution), steel planchet with a minimum of 95% ethyl alcohol and evapo-
add 0.50 mL BaCl2 stock solution (7500-Ra C.3a) before add- rate under an infrared lamp. Add 2 mL acetone and 2 drops clear
ing the 226Ra solution. A 1 mL final standard radium solution so acrylic solution, disperse precipitate evenly, and evaporate under
prepared contains 2.00 mg/mL Ba and approximately 3 pCi/mL an infrared lamp. Dry in an oven at 110 °C, weigh, and determine
226
Ra after the necessary correcting factors are applied. alpha activity, preferably with an internal proportional counter.
Calculate the net counts per minute and weight of the precipitate.
4. Procedure for Radium in Drinking Water and for Dissolved l. Weigh a membrane filter, a counting dish, and a weight (glass
Radium ring) as a unit. Transfer the precipitate to a tared membrane filter
in a holder and wash with 15 to 25 mL reagent water. Place the
a. To 1 L sample in a 1500-mL beaker, add 5 mL 1 M citric membrane filter in the dish, add the glass ring, and dry at 110 °C.
acid, 2.5 mL conc NH4OH, 2 mL Pb(NO3)2 carrier, and 3.00 mL Weigh and count in one of the counters mentioned under 7500-
BaCl2 carrier. In each batch of samples include a reagent water Ra B.2a. Calculate the net counts per minute and weight of the
blank. precipitate.
b. Heat to boiling and add 10 drops methyl orange indicator. m. Add 20 mL reagent water to the Ba-Ra sulfate precipitate, let
c. While stirring, slowly add 18 N H2SO4 to obtain a perma- settle in a steam bath, cool, and filter through a special funnel with
nent pink color. Then add 0.25 mL acid in excess. a tared glass fiber filter. Dry the precipitate at 110 °C to a constant
d. Boil gently 5 to 10 min. weight, cool, and weigh. Mount the precipitate on a nylon disk and
e. Set the beaker aside and let stand until precipitate has settled ring with an alpha phosphor on polyester plastic film,4 and count in
(3 to 5 h or more). (Note: If original concentrations of isotopes an alpha scintillation counter. Calculate net counts per minute and
of radium other than 226Ra are of interest, note date and time of weight of precipitate.

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 7500-Ra RADIUM - B. Precipitation Method

n. If the isotopic composition of the precipitate is to be esti- The optimum ingrowth periods can be selected only if the ratios
mated, perform additional counting as mentioned in the calcula- and identities of the radium isotopes are known. The number of
tion below. observed count rates at different ages must be equal to or greater
o. Determination of combined efficiency and self-absorption than the number of radium isotopes present in a mixture. In the
factor: Prepare standards from 1 L reagent water and the standard general case, suitable ages for counting are 3 to 18 h for the first
226
Ra solution (7500-Ra B.3p). Include at least one blank. The count. For isotopic analysis, additional counting at 7, 14, or 28 d
barium content imposes an upper limit of 3.0 mL on the volume is suggested, depending on the number of isotopes in mixture.
of the standard 226Ra solution that can be used. If x is the volume The amounts of the various radium isotopes can be determined by
of standard 226Ra solution added, then add (3.00 – x) mL BaCl2 solving a set of simultaneous equations.3 This approach is most
carrier (7500-Ra B.3e). Analyze standards as samples, beginning satisfactory when 226Ra is the predominant isotope; in other situa-
with 7500-Ra B.4a, but omit 3.00-mL BaCl2 carrier. tions, the approach suffers from statistical counting errors.
From the observed net count rate, calculate the combined fac-
tor, bc, from the formula: 6. Precision and Bias

net cpm In a collaborative study, 20 laboratories analyzed 4 water sam-

bc = ples for total (dissolved) radium. The radionuclide composition of
226
ad × 2.22 × pCi Ra
these reference samples is shown in Table 7500-Ra:1. Note that
Samples C and D had a 224Ra concentration equal to that of 226Ra.
where: The 4 results from each of 2 laboratories and 2 results from a
ad = ingrowth factor (see 7500-Ra B.5) multiplied by chemical yield. third laboratory were rejected as outliers. The average recoveries
of 226Ra from the remaining A, B, C, and D samples were 97.5%,
If all chemical yields on samples and standards are not essen- 98.7%, 94.9%, and 99.4%, respectively. At the 95% confidence
tially equal, the factor bc will not be a constant. In this event, level, the precision (random error) was 28% and 30% for the 2
construct a curve relating the factor bc to varying weights of sets of paired samples. The method is biased low for 226Ra, but
recovered BaSO4. (See calculation that follows.) not seriously. The method appears satisfactory for 226Ra alone or
in the presence of an equal activity of 224Ra when correction for
5. Calculation 224
Ra interference is made from a second count.
For the determination of 224Ra in Samples C and D, the results
net cpm of 2 laboratories were excluded. Hence the average recoveries
Radium, pCi/L =
a × b × c × d × e × 2.22 were 51% and 45% for Samples C and D, respectively. At the
95% confidence level, the precision was 46% for this pair of sam-
where: ples. The results indicated that the method for 224Ra is seriously
biased low. When the recoveries for 224Ra did not agree with those
a = ingrowth factor (as shown in the following tabulation): for 226Ra, this may have been due, in part, to incomplete instruc-
tions given in the method to account for the transitory nature of
Ingrowth h Alpha Activity from 226Ra 224
Ra activity. The method as given here contains footnotes calling
0 1.000 attention to the importance of the timing of the count. Still uncer-
1 1.016 tain is the degree of separation of 224Ra from its parent, 228Th, in
2 1.036 7500-Ra B.4a–g.
3 1.058 Analyzing 223Ra and 224Ra by this method may be satisfactory,
4 1.080 but special refinements and further investigations are required.
5 1.102
6 1.124
24 1.489 References
48 1.905
72 2.253 1. Kirby HW. Decay and growth tables for naturally occurring radioac-
tive series. Anal Chem. 1954;26(6):1063–1071.
b = efficiency factor for alpha counting, 2. Sill C. Determination of radium-226, thorium-230, and thorium-232;
c = self-absorption factor, Rep. No. TID 7616 (Oct.). Washington DC: U.S. Atomic Energy
d = chemical yield, and Commission; 1960.
e = sample volume (L). 3. Goldin AS. Determination of dissolved radium. Anal Chem.
1961;33(3):406–409.
The calculations are based on the assumption that the radium is 4. Hallden NA, Harley JH. An improved alpha-counting technique.
Ra. If the observed concentration approaches 3 pCi/L, it may be
226
Anal Chem. 1960;32(13):1861–1863.
desirable to follow the rate of ingrowth and estimate the isotopic
content2,3 or, preferably, to determine 226Ra by 222Rn.

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 7500-Ra RADIUM - C. Emanation Method

Table 7500-Ra:1. Chemical and Radiochemical Composition of Samples Used to Determine

Bias and Precision of Radium-226 Method
Samples
Pair 1 Pair 2
Radionuclide Composition A B C D
226
Ra (pCi/L)
a
12.12 8.96 25.53 18.84
228
Tha (pCi/L) none none 25.90 19.12
Uranium, natural (pCi/L) 105 77.9 27.7 20.5
210
Pba (pCi/L) 11.5 8.5 23.7 17.5
90
Sra (pCi/L) 49.1 36.3 13.9 10.2
137
Cs (pCi/L) 50.3 37.2 12.7 9.5
NaCl (mg/L) 60 60 300 300
CaSO4 (mg/L) 30 30 150 150
MgCl2 ⋅ 6H2O (mg/L) 30 30 150 150
KCl (mg/L) 5 5 10 10
a
Daughter products were in substantial secular equilibrium.

7500-Ra C. Emanation Method

1. General Discussion a single radon bubbler. However, because some 226Ra is present
in barium salts, reagent tests are necessary to account for 226Ra
a. Application: This method is suitable for the determination of introduced in this way.
soluble, suspended, and total 226Ra in water. In this method, total d. Interferences: Only the gaseous alpha-emitting radionuclides,
226
Ra means the sum of suspended and dissolved 226Ra. Radon 219
Rn (actinon) and 220Rn (thoron), can interfere. Interference from
means 222Rn unless otherwise specified. these radionuclides would be expected to be very rare in water not
b. Principle: Radium in water is concentrated and separated contaminated by such industrial wastes as uranium mill elements.2
from sample solids by coprecipitation with a relatively large The half-lives of these nuclides are only 3.92 and 54.5 s, respec-
amount of barium as the sulfate. The precipitate is treated to tively, so only their alpha-emitting decay products interfere.
remove silicates, if present, and to decompose insoluble radium Interference from stable chemicals is limited. Small amounts of
compounds, fumed with phosphoric acid to remove sulfite (SO32-), lead, calcium, and strontium, collected by the barium sulfate, do
and dissolved in hydrochloric acid (HCl). The completely dissolved not interfere. However, lead may cause deterioration of platinum
radium is placed in a bubbler, which is then closed and stored for ware. Calcium at a concentration of 300 mg/L and other dissolved
a period of several days to 4 weeks for ingrowth of radon. The solids (in brines) at 269 000 mg/L cause no difficulty.4
bubbler is connected to an evacuated system and the radon gas is The formation of precipitates in excess of a few milligrams
removed from the liquid by aeration, dried with a desiccant, and during the 222Rn ingrowth period is a warning that modifications2
collected in a counting chamber. The counting chamber consists of may be necessary because 222Rn recovery may be impaired.
a dome-topped scintillation cell coated inside with silver-activated e. Minimum detectable concentration: The minimum detect-
zinc sulfide phosphor; a transparent window forms the bottom able concentration depends on counter characteristics, back-
(Figure 7500-Ra:1). The chamber rests on a photomultiplier tube ground-counting rate of scintillation cell, length of counting
during counting. About 4 h after radon collection, the alpha-counting period, and contamination of apparatus and environment by 226Ra.
rate of radon and decay products is at equilibrium, and a count is Without reagent purification, the overall reagent blank (excluding
obtained and related to 226Ra standards similarly treated. background) should be between 0.03 and 0.05 pCi 226Ra, which
The counting gas used to purge radon from the liquid to the may be considered the minimum detectable amount under routine
counting chamber may be helium, nitrogen, or aged air. conditions.
Some radon (emanation) techniques employ a minimum f. Quality control (QC): The QC practices considered to be an
of chemistry but require high dilution of the sample and large integral part of each method can be found in Section 7020.
chambers for counting the 222Rn.1 Others involve more chemical
separation, concentration, and purification of 226Ra before de- 2. Apparatus
emanation into counting cells of either the ionization or alpha
scintillation types. The method2 given here requires a moderate The de-emanation assembly is shown in Figure 7500-Ra:1, and
amount of chemistry coupled with a sensitive alpha scintillation its major components are described in paragraphs b–e, below.
count of 222Rn plus daughter products in a small chamber.3 a. Scintillation counter assembly with a photomultiplier (PM)
c. Concentration techniques: The chemical properties of bar- tube 5 cm or more in diameter, normally mounted, face up, in
ium and radium are similar; therefore, because barium does not a light-tight housing. The photomultiplier tube, preamplifier,
interfere with de-emanation, as much as 100 mg may be used high-voltage supply, and scaler may be contained in one chassis;
to aid in coprecipitating radium from a sample to be placed in or the PM tube and preamplifier may be used as an accessory

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 7500-Ra RADIUM - C. Emanation Method

with a proportional counter or a separate scaler. A high-voltage added with the 133Ba and with the diluting solution, so the final
safety switch should open automatically when the light cover is barium concentration is near 2 mg/L. The use of 133Ba provides
removed, to avoid damage to the photomultiplier tube. a convenient means of checking on the recovery of 226Ra from
Use a preamplifier with a variable gain adjustment. Equip the the sample; see 7500-Ra C.7. Use the BaCl2 solution containing
counter with a flexible ground wire attached to the chassis and 133
Ba in steps described in 7500-Ra C.5a3, b8, and c3. Do not use
to the neck of the scintillation cell by an alligator clip or similar in d below; instead, use a separate dilution of stock BaCl2 solu-
device. Ascertain the operating voltage by determining a volt- tion for preparing 226Ra standard solutions.
age plateau using 222Rn in a scintillation cell as the alpha source. c. Acid barium chloride solution: To 20 mL conc HCl in a 1-L
Establish the operating voltage at a point nominally above the volumetric flask, add dilute BaCl2 solution to the mark and mix.
knee of the curve where values for slope meet or at least approach d. Stock radium-226 solution: Take every precaution to avoid
a relative change of 2% per 100 V. Calibrate and use the counter unnecessary contamination of working area, equipment, and
and the scintillation cell as a unit when more than one counter is glassware, preferably by preparing 226Ra standards in a separate
available. The background-counting rate for the counter assembly area or room reserved for this purpose. Obtain a National Insti-
without the scintillation cell in place should be 0.00 to 0.03 cpm. tute of Standards and Technology (NIST) gamma ray standard
b. Scintillation cells,2,3 Lucas-type, preferably having a volume containing 0.1 mg 226Ra as of date of standardization. Using a
of 95 to 140 mL, made in the laboratory, or commercially available. heavy glass rod, cautiously break neck of ampule, which is sub-
c. Radon bubblers, capacity 18 to 25 mL. Use gas-tight glass merged in 300 mL acid BaCl2 solution in a 600-mL beaker. Chip
stopcocks and a fritted glass disk of medium porosity. Use one the ampoule unit until it is thoroughly broken or until a hole is
bubbler for a standard 226Ra solution and one for each sample and large enough to give complete mixing. Transfer the solution to
blank in a batch.2 a 1-L volumetric flask, rinse the beaker with acid BaCl2 solu-
d. Manometer, open-end capillary tube or vacuum gauge hav- tion, dilute to the mark with the same solution, and mix; 1 mL =
ing volume that is small compared to volume of scintillation cell, approximately 100 pg 226Ra.
0 to 760 mm Hg. Determine the time in years, t, since the NIST standardization
e. Gas purification tube, 7 to 8 mm o.d. standard-wall glass of the original 226Ra solution. Calculate pCi 226Ra/mL as:
tubing, 100 to 120 mm long, constricted at lower end to hold glass
wool plug; thermometer capillary tubing.
pCi 226 Ra = [1 − (4.3×10−4 )(t )][100][0.990]
f. Sample bottles, polyethylene, 2- to 4-L capacity.
g. Membrane filters (Type HAWP, Millipore Filter Corp. or
equivalent.) e. Intermediate radium-226 solution: Dilute 100 mL stock
h. Gas supply: Helium, nitrogen, or air aged in high-pressure Ra solution to 1000 mL with acid BaCl2 solution; 1 mL =
226

cylinder with two-stage pressure regulator and needle valve. approximately 10 pCi 226Ra.
Helium is preferred. f. Standard radium-226 solution: Add 30.0 mL intermediate 226Ra
i. Silicone grease, high-vacuum. solution to a 100-mL volumetric flask and dilute to the mark with
j. Sealing wax, low-melting. acid BaCl2 solution; 1 mL = approximately 3 pCi 226Ra and contains
k. Laboratory glassware: Excepting bubblers, decontaminate about 2 mg Ba. See paragraph d above for correction factors.
all glassware before and between uses by heating for 1 h in EDTA g. Hydrochloric acid (HCl), conc, 6 N, 1 N, and 0.1 N.
decontaminating solution at 90 to 100 °C, then rinse in water, 1 N h. Sulfuric acid (H2SO4), conc and 0.1 N.
HCl, and again in reagent water to dissolve barium (radium) sul- i. Hydrofluoric acid (HF), 48%, in a plastic dropping bottle.
fate, Ba(Ra)SO4. (Caution.)
Removal of previous samples from bubblers and rinsing is j. Ammonium sulfate solution: Dissolve 10 g (NH4)2SO4 in
described in 7500-Ra C.5a17. More extensive cleaning of bub- reagent water and dilute to 100 mL in a graduated cylinder.
blers requires the removal of wax from joints, silicone grease k. Phosphoric acid (H3PO4), 85%.
from stopcocks, and the last traces of barium-radium compounds. l. Ascarite, 8 to 20 mesh.
l. Platinum ware: Crucibles (20–30 mL) or dishes (50–75 mL), m. Magnesium perchlorate, anhydrous desiccant.
large dish (for flux preparation), and platinum-tipped tongs (pref- n. EDTA decontaminating solution: Dissolve 10 g disodium
erably Blair type). Clean platinum ware by immersion and rota- ethylenediaminetetraacetate dihydrate and 10 g Na2CO3 in
tion in a molten bath of potassium pyrosulfate, remove, cool, rinse reagent water and dilute to 1 L in a graduated cylinder.
in hot tap water, digest in hot 6 N HCl, rinse in reagent water, and o. Special reagents for total and suspended radium:
finally flame over a burner. 1) Flux: Add 30 mg BaSO4, 65.8 g K2CO3, 50.5 g Na2CO3, and
33.7 g Na2B4O7 ⋅ 10H2O, to a 500-mL platinum dish. Mix thor-
3. Reagents oughly and heat cautiously to expel water, then fuse and mix thor-
oughly by swirling. Cool flux, grind in a porcelain mortar to pass
a. Stock barium chloride solution: Dissolve 17.79 g BaCl2 ⋅ 2H2O a 10- to 12-mesh (or finer) screen, and store in an airtight bottle.
in reagent water and dilute to 1 L; 1 mL = 10 mg Ba. 2) Dilute hydrogen peroxide solution: Dilute 10 mL 30% H2O2
b. Dilute barium chloride solution: Dilute 200.0 mL stock bar- to 100 mL in a graduated cylinder. Prepare daily.
ium chloride solution to 1000 mL as needed; 1 mL = 2.00 mg Ba.
Let stand 24 h and filter through a membrane filter. 4. Calibration of Scintillation Counter Assembly
Optionally, add approximately 40 000 dpm of 133Ba to this solu-
tion before dilution. Take account of the stable barium carrier a. Test bubblers by adding about 10 mL reagent water and
passing air through them at the rate of 3 to 5 mL (free volume)/min.

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 7500-Ra RADIUM - C. Emanation Method

Table 7500-Ra:2. Factors for Decay of Radon-222, Growth of Radon-222 from Radium-226, and Correction of Radon-222 Activity for
Decay During Counting
Factor for
Factor for Correction of
correction of Radon-222
Factor for Growth Radon-222 Factor for Growth Activity for
Factor for Decay of Radon-222 from Activity for Decay Factor for Decay of Radon-222 Decay during
of Radon-222 Radium-226 during Counting of Radon-222 from Radium-226 Counting
A = e–lt B = 1 – e–lt C = lt/(1 – e–lt) A = e–lt B = 1 – e–lt C = lt/(1 – e–lt)
Time Hours Days Hours Days Hours Time Hours Days Hours Days Hours
0.0 1.0000 0.000 00 1.000 29 0.8034 0.0052 0.1966 0.9948 1.113
0.2 0.9985 0.001 51 1.001 30 0.7973 0.0044 0.2027 0.9956 1.118
0.4 0.9970 0.003 01 1.001
0.6 0.9955 0.004 52 1.002 31 0.7913 0.0036 0.2087 0.9964 1.122
0.8 0.9940 0.006 02 1.003 32 0.7854 0.0030 0.2146 0.9970 1.126
33 0.7795 0.0025 0.2205 0.9975 1.130
1 0.9925 0.8343 0.007 52 0.1657 1.004 34 0.7736 0.0021 0.2264 0.9979 1.134
2 0.9850 0.6960 0.014 99 0.3040 1.008 35 0.7678 0.0018 0.2322 0.9982 1.138
3 0.9776 0.5807 0.022 40 0.4193 1.011
4 0.9703 0.4844 0.029 75 0.5156 1.015 36 0.7620 0.0015 0.2380 0.9985 1.142
5 0.9630 0.4041 0.037 05 0.5959 1.019 37 0.7563 0.0012 0.2437 0.9988 1.146
38 0.7506 0.0010 0.2494 0.9990 1.150
6 0.9557 0.3372 0.044 29 0.6628 1.023 39 0.7449 0.0009 0.2551 0.9991 1.154
7 0.9485 0.2813 0.051 48 0.7187 1.027 40 0.7393 0.0007 0.2607 0.9993 1.159
8 0.9414 0.2347 0.058 61 0.7653 1.031
9 0.9343 0.1958 0.065 69 0.8042 1.034 41 0.7338 0.0006 0.2662 0.9994 1.163
10 0.9273 0.1633 0.072 72 0.8367 1.038 42 0.7283 0.0005 0.2717 0.9995 1.167
43 0.7228 0.0004 0.2772 0.9996 1.171
11 0.9203 0.1363 0.079 69 0.8637 1.042 44 0.7173 0.0003 0.2827 0.9997 1.175
12 0.9134 0.1137 0.086 62 0.8863 1.046 45 0.7120 0.0003 0.2880 0.9997 1.179
13 0.9065 0.0948 0.093 49 0.9052 1.050
14 0.8997 0.0791 0.100 31 0.9209 1.054
15 0.8929 0.0660 0.107 07 0.9340 1.058 46 0.7066 0.0002 0.2934 0.9998 1.184
47 0.7013 0.0002 0.2987 0.9998 1.188
16 0.8862 0.0551 0.1138 0.9449 1.062 48 0.6960 0.0002 0.3040 0.9998 1.192
17 0.8795 0.0459 0.1205 0.9541 1.066 49 0.6908 0.0001 0.3092 0.9999 1.196
18 0.8729 0.0383 0.1271 0.9617 1.069 50 0.6856 0.0001 0.3144 0.9999 1.201
19 0.8664 0.0320 0.1336 0.9680 1.073
20 0.8598 0.0267 0.1402 0.9733 1.077 51 0.6804 0.0001 0.3196 0.9999 1.205
52 0.6753 0.0001 0.3247 0.9999 1.209
21 0.8534 0.0223 0.1466 0.9777 1.081 53 0.6702 0.0001 0.3298 0.9999 1.213
22 0.8470 0.0186 0.1530 0.9814 1.085 54 0.6652 0.0001 0.3348 0.9999 1.218
23 0.8406 0.0155 0.1594 0.9845 1.089 55 0.6602 0.0000 0.3398 1.0000 1.222
24 0.8343 0.0129 0.1657 0.9871 1.093
25 0.8280 0.0108 0.1720 0.9892 1.097 56 0.6552 0.0000 0.3448 1.0000 1.226
57 0.6503 0.0000 0.3497 1.0000 1.231
26 0.8218 0.0090 0.1782 0.9910 1.101 58 0.6454 0.0000 0.3546 1.0000 1.235
27 0.8156 0.0075 0.1844 0.9925 1.105 59 0.6405 0.0000 0.3595 1.0000 1.239
28 0.8095 0.0063 0.1905 0.9937 1.109 60 0.6357 0.0000 0.3643 1.0000 1.244

Air should form many fine bubbles rather than a few large ones; c. With the bubbler in a clamp or rack, dry the joint with lint-
the latter condition indicates nonuniform pores. Do not use bub- free paper or cloth, warm separate parts of the joint, apply sealing
blers requiring excessive pressure to initiate bubbling. Fritted wax sparingly to the male part, and make the connection with a
glass disks of medium porosity (7500-Ra C.2c) usually are sat- twisting motion to spread the wax uniformly in the ground joint.
isfactory. Let cool. Establish zero ingrowth time by purging liquid with
b. Apply silicone grease to stopcocks of a bubbler and, with gas counting gas for 15 to 20 min according to paragraph j below
inlet stopcock closed, add 1 mL stock BaCl2 solution and 10 mL and adjust the inlet pressure to produce a froth a few millime-
(30 pCi) standard 226Ra solution, and fill bubbler two-thirds to ters thick. Close stopcocks, record the date and time, and store
three-fourths full with additional acid BaCl2 solution. the bubbler, preferably for 3 weeks or more (with most samples)

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 7500-Ra RADIUM - C. Emanation Method

f. Center the scintillation cell on the photomultiplier tube, cover

with light-tight hood and, after 10 min, obtain a background
counting rate (preferably over a 100- to 1000-min period, depend-
ing on concentration of 226Ra in samples). Do not expose photo-
tube to external light with the high voltage applied.
g. Repeat paragraphs d–f above for each scintillation cell.
h. If the leakage test and background are satisfactory, continue
calibration.
i. With scintillation cell and standard bubbler (¶ c above) on the
vacuum train, open the stopcock on the scintillation cell and evacu-
ate the scintillation cell and purification system (Figure 7500-Ra:1)
by opening the stopcock to the vacuum source. Close the stopcock
to the vacuum source. Check the system for leaks as in paragraph
d above.
j. Adjust the gas regulator (diaphragm) valve so a very slow
stream of gas flows with the needle valve open. Attach the gas
supply to the inlet of the bubbler.
k. Note the time at the beginning of an approximately 20-min
de-emanation period. Very cautiously open the bubbler outlet
stopcock to equalize the pressure and transfer all or most of the
fluid in the inlet side arm to the bubbler chamber.
l. Close the outlet stopcock and very cautiously open the inlet
stopcock to flush the remaining fluid from the side arm and fritted
disk. Close the inlet stopcock.
m. Repeat paragaphs h and l above, 4 or 5 times, to obtain more
nearly equal pressures on the 2 sides of bubbler.
n. With the outlet stopcock fully open, cautiously open the inlet
stopcock so the gas flow produces a froth a few millimeters thick
at the surface of bubbler solution. Maintain the flow rate by grad-
ually increasing the pressure with the regulator valve and con-
tinue de-emanation until pressure in the cell reaches atmospheric
pressure. The total elapsed time for the de-emanation should be
15 to 25 min.
o. Close the stopcocks to the scintillation cell, close the bubbler
inlet and outlet, shut off and disconnect the gas supply, and record
the date and time as the ends of the 222Rn ingrowth and de-emana-
Figure 7500-Ra:1. De-emanation assembly. tion periods and as the beginnings of decay of 222Rn and ingrowth
of decay products.
p. Store bubbler for another 222Rn ingrowth in the event a sub-
before collecting and counting 222Rn. A much shorter ingrowth
sequent de-emanation is desired (Table 7500-Ra:2). The standard
period of 16 to 24 h is convenient for a standard bubbler. Obtain
bubbler may be kept indefinitely.
an estimate of 222Rn present at any time from the B columns in
q. Four hours after de-emanation, when daughter products are
Table 7500-Ra:2.
in virtual transient equilibrium with 222Rn, place the scintillation
d. Attach scintillation cell as shown in Figure 7500-Ra:1. The
cell on the photomultiplier tube, cover with a light-tight hood, let
system as described and shown in this figure is considered mini-
stand for at least 10 min, then begin counting. Record the date and
mal. In routine work, manifold systems and additional, more pre-
time counting was started and finished.
cise needle valves may be encountered. An occasional drop of
r. Correct the net counting rate for 222Rn decay (Table 7500-Ra:2)
solution will escape from the bubbler; provide enough free space
and relate it to picocuries 226Ra in standard bubbler (see 7500-
beyond the outlet stopcock to accommodate this liquid, prevent-
Ra C.6a). Unless the scintillation cell is physically damaged, the
ing its entrance into the gas-purifying train.
calibration will remain essentially unchanged for years. Occasional
Substitute a glass tube with a stopcock for bubbler so the com-
calibration is recommended.
pressed gas can be turned on or off conveniently. Open the stop-
s. Repeat paragraphs h–r above on each scintillation cell.
cock on the scintillation cell, close the stopcock to the gas, and
t. To remove 222Rn and prepare the scintillation cell for reuse,
gradually open the stopcock to the vacuum source to evacuate
evacuate and cautiously refill with counting gas. Routinely, repeat
the cell. Close the stopcock to the vacuum source and check the
the evacuation and refilling twice, and repeat the process more
manometer reading for 2 min to test the system, especially the
times if the cells have contained a high 222Rn activity. (Decay
scintillation cell, for leaks.
products with a half-life of approximately 30 min will remain in
e. Open the stopcock to the counting gas and cautiously admit
the cell. Do not check background on cells until activity of decay
gas to the scintillation cell until atmospheric pressure is reached.
products has had time to decay to insignificance.)

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 7500-Ra RADIUM - C. Emanation Method

5. Procedure to pass the acid rinse water sequentially through the fritted disk,
accumulate in the bubbler, and flush into the suction flask. Drain
a. Soluble radium-226: the bubbler with the aid of vacuum, heat the ground joint gently
1) Using a membrane filter, filter at least 1 L sample or a to melt the wax, and separate the joint. More extensive cleaning,
volume containing up to 30 pCi 226Ra and transfer to a poly- as indicated in 7500-Ra C.2k, may be necessary if the bubbler
ethylene bottle as soon after sampling as possible. Save the contained more than 10 pCi 226Ra.)
suspended matter for determination by the procedure described b. Radium-226 in suspended matter:
in 5b, below. Record the sample volume filtered if suspended 1) Suspended matter in water usually contains siliceous materi-
solids are to be analyzed as in the procedure for 226Ra in sus- als that require fusion with an alkaline flux to ensure the recovery
pended matter. of radium. Dry the suspended matter (up to 1000 mg inorganic
2) Add 20 mL conc HCl per liter of filtrate and continue anal- material) retained on the membrane filter specified in paragraph
ysis when convenient. a1 above in a tared platinum crucible and ignite as in paragraph
3) Add 50 mL dilute BaCl2 solution, with vigorous stirring, to a7 above.
1020 mL acidified filtrate (¶ a2 above) in a 1.5-L beaker. In each 2) Weigh the crucible to estimate the residue.
batch of samples include a reagent blank consisting of reagent 3) Add 8 g flux per gram of residue, but not less than 2 g flux,
water plus 20 mL conc HCl. and mix with a glass rod.
4) Cautiously, with vigorous stirring, add 20 mL conc H2SO4. 4) Heat over a Meker burner until melting begins, being careful
Cover the beaker and let precipitate overnight. to prevent spattering. Continue heating for 20 min after bubbling
5) Filter the supernate through a membrane filter, using 0.1 N stops, with an occasional swirl of the crucible to mix the contents
H2SO4 to transfer Ba-Ra precipitate to filter, and wash the precip- and achieve a uniform melt. A clear melt usually is obtained only
itate twice with 0.1 N H2SO4. when the suspended solids are present in small amount or have a
6) Place the filter in a platinum crucible or dish, add 0.5 mL high silica content.
HF and 3 drops (0.15 mL) (NH4)2SO4 solution, and evaporate 5) Remove the crucible from the burner and rotate as the melt
to dryness. cools to distribute it in a thin layer on the crucible wall.
7) Carefully ignite over a small flame until carbon is burned 6) When cool, place the crucible in a covered beaker containing
off; cool. (After filter is charred, a Meker burner may be used.) 120 mL reagent water, 20 mL conc H2SO4, and 5 mL dilute H2O2
8) Add 1 mL H3PO4 with a calibrated dropper and heat on a solution for each 8 g flux. (Reduce acid and H2O2 in proportion to
hot plate at about 200 °C. Gradually raise the temperature and flux used.) Rotate the crucible to dissolve melt if necessary.
maintain at about 300 to 400 °C for 30 min. 7) When the melt is dissolved, remove and rinse the crucible
9) Swirl the vessel over a low Bunsen flame, adjusted to avoid into a beaker. Save the crucible for paragraph b10 below.
spattering, while covering the walls with hot H3PO4. Continue 8) Heat the solution and slowly add 50 mL dilute BaCl2 solu-
to heat for a minute after precipitate fuses into a clear melt (just tion with vigorous stirring. Cover the beaker and let stand over-
below redness) to ensure complete removal of SO3. night for precipitation. (Precipitation with cool sample solution
10) Fill the cooled vessel one-half full with 6 N HCl, heat on a also is satisfactory.)
steam bath, then gradually add reagent water to within 2 mm of 9) Add about 1 mL dilute H2O2 and, if yellow color (from
the top of the vessel. titanium) deepens, add more H2O2 until there is no further color
11) Evaporate on a boiling steam bath until there are no more change.
vapors of HCl. 10) Continue the analysis according to paragraphs a5–16.
12) Add 6 mL 1 N HCl, swirl, and warm to dissolve BaCl2 11) Calculate the result as directed in 7500-Ra C.6a and b,
crystals. taking into account that the suspended solids possibly were con-
13) Close the gas inlet stopcock, add a drop of water to the frit- tained in a sample volume other than 1 L (see ¶ a1 above).
ted disk of the fully greased and tested radon bubbler, and transfer c. Total radium-226:
the sample from the platinum vessel to the bubbler with a medi- 1) Total 226Ra in water is the sum of soluble and suspended
cine dropper. Use the dropper to rinse the vessel with at least three 226
Ra as determined in 7500-Ra C.5a and b, or it may be deter-
2-mL portions of reagent water. Add reagent water until bubbler mined directly by examining the original water sample that has
is two-thirds to three-fourths full. been acidified with 20 mL conc HC1 per liter of sample and
14) Dry, wax if necessary, and seal the joint. Establish zero stored in a polyethylene bottle.
ingrowth time as instructed in 7500-Ra C.4c. 2) Thoroughly mix the acidified sample and take 1020 mL or
15) Close the stopcocks, record the date and time, and store a measured volume containing not more than 1000 mg inorganic
the bubbler for 222Rn ingrowth, preferably for 3 weeks for low suspended solids.
concentrations of 226Ra. 3) Add 50 mL dilute BaCl2 solution and slowly, with vigorous
16) De-emanate and count 222Rn as instructed for calibrations stirring, add 20 mL conc H2SO4 per liter of sample. Cover and let
in 7500-Ra C.4i–r, with sample replacing the standard bubbler. precipitate overnight.
17) The sample in the bubbler may be stored for a second 4) Filter the supernate through a membrane filter and transfer
ingrowth, or it may be discarded and the bubbler cleaned for the solids to the filter as in paragraph a5 above.
reuse. (A bubbler is readily cleaned while in an inverted position 5) Place the filter and precipitate in a tared platinum crucible
by attaching a tube from a beaker containing 100 mL 0.1 N HCl and proceed as in paragraphs b2–10 above but with the follow-
to the inlet and attaching another tube from outlet to a suction ing changes in the procedure given in paragraph b8: Omit adding
flask. Alternately open and close the outlet and inlet stopcocks dilute BaCl2 solution, digest for 1 h on a steam bath, and filter

[Link] 8
 7500-Ra RADIUM - C. Emanation Method

immediately after digestion without stirring up BaSO4. (If these where:

changes are not made, filtration will be very slow.)
D = pCi 226Ra found in sample, and
6) Calculate total 226Ra concentration as directed in 7500- E = pCi 226Ra found in reagent blank.
Ra C.6a and b.
7. Recovery of Barium (Radium-226) (Optional)
6. Calculations
If 133Ba was added in reagent b, check recovery of Ba by remov-
a. Calculate the 226Ra in a bubbler, including reagent blank, as ing the sample from the bubbler, adjusting its volume appropri-
follows: ately, gamma-counting it under standardized conditions, and
comparing the result with the count obtained from a 50-mL por-
226 R − Rb 1 1 λt3 tion (evaporated if necessary to reduce volume) of dilute barium
Ra, pCi = s × × ×
Rc 1 − e−λt1 e−λt2 1 − e−λt3 solution also counted under standardized conditions; add 1 mL
H3PO4 to the latter portion before counting. The assumption that
where:
the Ba and 226Ra are recovered to the same extent is valid in the
method described.
l = decay constant for 222Rn, 0.00755/h, Note: 226Ra and its decay products interfere slightly even if a
t1 = time interval allowed for ingrowth of 222Rn (h), gamma spectrometer is used. The technique works best when the
t2 = time interval between de-emanation and counting (h), ratio of 133Ba to 226Ra is high.
t3 = time interval of counting (h), Determinations of recovery are particularly helpful with irre-
Rs = observed counting rate of sample in scintillation cell (cph), placeable samples, both in gaining experience with the method
Rb = (previously) observed background counting rate of scintillation and in applying the general method to unfamiliar media.
cell with counting gas (cph),
Rc = calibration constant for scintillation cell [i.e., observed net
8. Precision and Bias
counts per hour, corrected by use of ingrowth and decay factors
(C/AB below) per picocurie of Ra in standard],
In a collaborative study, 7 laboratories analyzed 4 water sam-
or: ples for dissolved 226Ra by this method. No result was rejected as
an outlier. The average recoveries of added 226Ra from Samples
226 ( Rs − Rb ) C A, B, C, and D were 97.1%, 97.3%, 97.6%, and 98.0%, respec-
Ra, pCi = × tively. At the 95% confidence level, the precision (random error)
Rc AB
was 6% and 8% for the two sets of paired samples. Because of
the small number of participating laboratories and the low values
where:
for random and total errors, there was no evidence of laboratory
A = factor for decay of 222Rn (see Table 7500-Ra:2), systematic errors. Neither 224Ra at an activity equal to that of the
B = factor for growth of 222Rn from 226Ra (see Table 7500-Ra:2), and 226
Ra nor dissolved solids up to 610 mg/L produced a detectable
C = factor for correction of 222Rn activity for decay during counting error in the results.
(see Table 7500-Ra:2). Test samples consisted of 2 pairs of simulated moderately hard
and hard water samples containing known amounts of added the
For nontabulated times, obtain decay factors for 222Rn by multi- 226
Ra and other radionuclides. The composition of the samples
plying together the appropriate tabulated “day” and “hour” decay
with respect to nonradioactive substances was the same for a pair
factors, interpolating for less than 0.2 h if indicated by the preci-
of samples but varied for the two pairs. The radiochemical com-
sion desired. Obtain 222Rn growth factors for nontabulated times
position of the samples is given in Table 7500-Ra:1.
most accurately, especially for short periods (e.g., in calibra-
tions), by calculation from 222Rn decay factors given in Column
A and using the formula given in the heading for Column B (of References
Table 7500-Ra:2). Linear interpolations are satisfactory for rou-
tine samples. Obtain the decay-during-counting factors by linear 1. Hursh JB. Radium content in public water supplies. J Amer Water
Works Assoc. 1954:46(1):43–54.
interpolation for all nontabulated times.
2. Rushing DE, Garcia WJ, Clark DA. The analysis of effluents and
In calculating cell calibration constants, use the same equation, environmental samples from uranium mills and of biological sam-
but picocuries of 226Ra is known and Rc is unknown. ples for radium, polonium, and uranium. In: Radiological health and
b. Convert the activity into picocuries per liter of soluble, sus- safety in mining and milling of nuclear materials. Vienna, Austria:
pended, or total 226Ra by the following equation: International Atomic Energy Agency; 1964, Vol. 11, p. 187.
3. Lucas HF. Improved low-level alpha scintillation counter for radon.
Rev Sci Instrum. 1957;28:680–683.
226 ( D − E )×1000
Ra, pCi/L = 4. Rushing DE. Determination of dissolved radium-226 in water.
mL sample J Amer Water Works Assoc. 1967;59(5):593–600.

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 7500-Ra RADIUM - D. Sequential Precipitation Method

7500-Ra D. Sequential Precipitation Method

1. General Discussion h. Citric acid, 1 M: See 7500-Ra B.3a.

i. EDTA reagent, 0.25 M: See 7500-Ra B.3k.
a. Application: This method can be used to determine soluble j. Ethanol, 95%.
Ra alone or soluble 228Ra plus 226Ra.
228
k. Lead carrier:
b. Principle: Radium-228 and 226Ra in water are concentrated 1) Solution A—Dissolve 2.397 g Pb(NO3)2 in distilled water,
and separated by coprecipitation with barium and lead as sulfates add 0.5 mL conc HNO3, and dilute to 100 mL; 1 mL = 15 mg Pb.
and purified by EDTA chelation. After 36-h ingrowth of 228Ac 2) Solution B—Dilute 10 mL Solution A to 100 mL with
from 228Ra, 228Ac is carried on yttrium oxalate, purified, and beta- reagent water; 1 mL = 1.5 mg Pb.
counted. Radium-226 in the supernatant is precipitated as the sul- l. Methyl orange indicator solution: Dissolve 0.1 g methyl
fate, purified, and alpha-counted (7500-Ra B) or it is transferred orange powder in 100 mL distilled water.
to a radon bubbler and determined by the emanation procedure m. Nitric acid (HNO3), conc, 6 N, and 1 N.
(7500-Ra C), which is the preferred method. n. Sodium hydroxide, 18 N: Dissolve 720 g NaOH in 500 mL
If analysis of 226Ra is not required, the procedure for 228Ra may reagent water and dilute to 1 L.
be terminated by beta-counting the yttrium oxalate precipitate o. Sodium hydroxide, 10 N: Dissolve 400 g NaOH in 500 mL
with a follow-up precipitation of barium sulfate for yield deter- reagent water and dilute to 1 L.
mination. If it is determined that 228Ra is absent, the 226Ra fraction p. Sodium hydroxide (NaOH), 1 N.
may be alpha-counted directly. If 228Ra is present, 226Ra must be q. Strontium-yttrium mixed carrier:
determined by radon emanation. 1) Solution A—Dilute 10.0 mL yttrium carrier to 100 mL.
c. Sampling and storage: To drinking water or a filtered sample 2) Solution B—Dissolve 0.4348 g Sr(NO3)2 in reagent water
of turbid water, add 2 mL conc nitric acid (HNO3) per liter of and dilute to 100 mL. Combine equal volumes of Solutions A and
sample at the time of collection or immediately after filtration. B; 1 mL = 0.9 mg Sr and 0.9 mg Y.
d. Quality control (QC): The QC practices considered to be an r. Sulfuric acid (H2SO4), 18 N.
integral part of each method can be found in Section 7020. s. Yttrium carrier: Add 12.7 g Y2O3 (Section 7500-Sr B.3d)
to an Erlenmeyer flask containing 20 mL reagent water. Heat
2. Apparatus to boiling and, while stirring with a magnetic stirring hot plate,
add small portions of conc HNO3. (About 30 mL is necessary to
a. Counting instruments: One of the following is required: dissolve the Y2O3. Small additions of reagent water also may be
1) Internal proportional counter, gas flow, with scaler, timer, needed to replace water lost by evaporation.) After total dissolu-
and register; or a thin end-window (polyester plastic, Mylar or tion, add 70 mL conc HNO3 and dilute to 1 L with reagent water;
equivalent) proportional counting chamber with scaler, timer, 1 mL = 10 mg Y.
register amplifier, and preferably having an anticoincident system
(low background). 4. Procedure
2) Scintillation counter assembly: See 7500-Ra C.2a. This
equipment is necessary only if 226Ra is determined sequentially a. Radium-228:
with 228Ra and is analyzed by emanation of radon. 1) For 1 L sample add 5 mL 1 M citric acid and a few drops
b. Centrifuge, bench-size clinical, with polypropylene tubes. methyl orange indicator. The solution should be red. Add 10 mL
c. Filter funnels, for 2.4-cm filter paper. lead carrier (Solution A), 2.0 mL barium carrier, and 2 mL
d. Stainless steel pans, 5.1 cm. yttrium carrier; stir well. Heat to incipient boiling and maintain at
e. Infrared drying lamp assembly. this temperature for 30 min.
f. Magnetic stirrer hot plate. 2) Add conc NH4OH until a definite yellow color is obtained;
g. Membrane filters, 47-mm diam, 0.45-mm pore diam (Gel- add a few drops excess. Precipitate lead and barium sulfates by
man Ga-6, or equivalent). adding 18 N H2SO4 until the red color reappears; add 0.25 mL
excess. Add 5 mL (NH4)2SO4 solution per liter of sample. Stir
3. Reagents frequently and hold at about 90 °C for 30 min.
3) Cool and filter with suction through a membrane filter.
a. Acetic acid, conc. Quantitatively transfer precipitate to filter. Carefully place fil-
b. Acetone, anhydrous. ter in a 250-mL beaker. Add about 10 mL conc HNO3 and heat
c. Ammonium hydroxide (NH4OH), conc. gently until the filter dissolves completely. Using conc HNO3
d. Ammonium oxalate solution: Dissolve 25 g (NH4)2C2O4 in transfer precipitate to a centrifuge tube. Centrifuge and discard
reagent water and dilute to 500 mL. supernatant.
e. Ammonium sulfate solution: Dissolve 20 g (NH4)2SO4 in a 4) Wash precipitate with 15 mL conc HNO3, centrifuge, and
minimum of reagent water and dilute to 100 mL. discard the supernatant. Repeat the wash and centrifuge again.
f. Ammonium sulfide solution: Dilute 10 mL (NH4)2S (20% to Add 25 mL EDTA reagent, heat in a hot water bath, and stir well.
24%) to 100 mL with reagent water. Add a few drops 10 N NaOH if the precipitate does not dissolve
g. Barium carrier standardized: Dissolve 2.846 g BaCl2 ⋅ 2H2O readily.
in reagent water, add 0.5 mL conc HNO3, and dilute to 100 mL; 5) Add 1 mL strontium-yttrium mixed carrier and stir thor-
1 mL = 16 mg Ba. oughly. Add a few drops 10 N NaOH if any precipitate forms.

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 7500-Ra RADIUM - D. Sequential Precipitation Method

Add 1 mL (NH4)2SO4 solution and stir thoroughly. Add conc a hot water bath until precipitate settles. Centrifuge, discard the
acetic acid until BaSO4 precipitates; add 2 mL excess. The pH supernatant, and note the time.
should be about 4.5. Digest in a hot water bath (80 °C) until the 3) Wash the precipitate with 10 mL reagent water. Centrifuge
precipitate settles. Centrifuge and discard supernatant. and discard the supernatant. Transfer quantitatively to a tared
6) Add 20 mL EDTA reagent, heat in a hot water bath, and stir stainless-steel planchet using a minimum quantity reagent water.
until the precipitate dissolves. Repeat paragraph a5 above. Note Dry under an infrared lamp to a constant weight. If after sufficient
time of last BaSO4 precipitation as the zero time for ingrowth beta decay of the actinium fraction 228Ra is found to be absent,
of 228Ac. Dissolve the precipitate in 20 mL EDTA reagent, add make a direct alpha count for 226Ra. If 228Ra is present, determine
0.5 mL yttrium carrier and 1 mL lead carrier (Solution B). If any 226
Ra by radon emanation, paragraph c below.
precipitate forms, dissolve by adding a few drops 10 N NaOH. 4) Count immediately in an alpha proportional counter.
Mix well, cap tube, and age at least 36 h. c. Radium-226 by radon: Transfer the final precipitate obtained
7) Add 0.3 mL (NH4)2S solution and mix well. Add 10 N in b above to a small beaker using a rubber policeman and 14 mL
NaOH dropwise with vigorous stirring until PbS precipitates; add EDTA reagent. Add a few drops 10 N NaOH and heat on a hot
10 drops excess. Stir intermittently for about 10 min. Centrifuge plate to dissolve. Cool and transfer to a radon bubbler (Figure
and decant the supernatant into a clean tube. 7500-Ra:1) rinsing the beaker with 1 mL EDTA reagent. Proceed
8) Add 1 mL lead carrier (Solution B), 0.1 mL (NH4)2S solu- as in 7500-Ra C beginning with 7500-Ra C.5a14.
tion, and a few drops 10 N NaOH. Repeat precipitation of PbS.
Centrifuge and filter the supernatant through filter paper (What- 5. Calculation
man No. 42, or equivalent) into a clean tube. Wash the filter with
a few milliliters of reagent water. Discard the residue. a. Calculation of 228Ra concentration:
9) Add 5 mL 18 N NaOH (make at least 2 N in OH-). Because
of the short half-life of 228Ac (6.13 h) complete the following pro-
228 C λt2 1 1
cedure without delay. Mix well and digest in a hot water bath until Ra, pCi/L = × × ×
2.22 × EVR (1 − e−λt2 ) (1 − e−λt3 ) e−λt1
Y(OH)3 coagulates. Centrifuge and decant the supernatant into a
beaker. Cover the beaker and save the supernatant for 226Ra analysis
(¶s b or c below). Note the time of Y(OH)3 precipitation; this is the where:
end of 228Ac ingrowth and beginning of 228Ac decay. [t3 = time in
C = average net count rate (cpm),
minutes between last BaSO4 and first Y(OH)3 precipitations.] Dis-
E = counter efficiency for 228Ac,
solve the precipitate in 2 mL 6 N HNO3. Heat and stir in a hot water V = sample volume (L),
bath about 5 min. Add 5 mL reagent water and reprecipitate Y(OH)3 R = fractional chemical yield of yttrium carrier, 7500-Ra D.4a10,
with 3 mL 10 N NaOH. Heat and stir in a hot water bath until the multiplied by fractional chemical yield of barium carrier, 7500-
precipitate coagulates. Centrifuge and discard the supernatant. Ra D.4b3,
10) Dissolve the precipitate with 1 mL 1 N HNO3 and heat l = decay constant of 228Ac, 0.001884/min,
in a hot water bath for several minutes. Dilute to 5 mL with t1 = time between first Y(OH)3 precipitation and start of counting
reagent water and add 2 mL ammonium oxalate solution. Heat (min),
to coagulate, centrifuge, and discard the supernatant. Add 10 mL t2 = counting time (min), and
reagent water, 6 drops 1 N HNO3, and 6 drops ammonium oxa- t3 = ingrowth time of 228Ac between last BaSO4 precipitation and
late solution. Heat and stir in a hot water bath for several minutes. first Y(OH)3 precipitation (min).
Centrifuge and discard the supernatant. Transfer quantitatively
The factor lt2/(1-e-lt2) corrects the average count rate to the
to a tared stainless-steel planchet using a minimum quantity of
count rate at the beginning of the counting time.
reagent water. Dry under an infrared lamp to constant weight and
b. Calculation of 226Ra (plus any 224Ra and 223Ra) concentra-
count in a low-background beta counter. [t1 = time in minutes
tion: See 7500-Ra B.5.
between first Y(OH)3 precipitation and counting.]
c. Calculation of 226Ra (emanation) concentration: See 7500-
If analysis of 226Ra is not required, complete paragraphs b1 and
Ra C.6.
3 below to obtain the fractional barium yield to be used in calcu-
lating 228Ra activity.
b. Radium by precipitation: Bibliography
1) To the supernatant saved in paragraph a9 above add 4 mL
conc HNO3 and 2 mL (NH4)2SO4 solution, mixing well after Johnson JO. Determination of radium-228 in natural waters. Radiochem-
ical Analysis of Water; U.S. Geological Survey. Water Supply Paper
each addition. Add conc acetic acid until BaSO4 precipitates; add
1696-G. Washington DC: U.S. Government Printing Office; 1971.
2 mL excess. Digest on a hot plate until the precipitate settles. Krieger HL. Interim radiochemical methodology for drinking water;
Centrifuge and discard the supernatant. EPA-600/4-75-008 (revised). Cincinnati (OH): Environmental Mon-
2) Add 20 mL EDTA reagent, heat in a hot water bath, and stir itoring and Support Laboratory, U.S. Environmental Protection
until the precipitate dissolves. Add a few drops 10 N NaOH if Agency; 1976.
the precipitate does not dissolve readily. Add 1 mL strontium-yt- Krieger HL, Whittaker EL. Prescribed procedures for measurement of
trium mixed carrier and 1 mL lead carrier (Solution B), and stir radioactivity in drinking water; EPA-600/4-80-032. Cincinnati (OH):
thoroughly. Add a few drops 10 N NaOH if any precipitate forms. Environmental Monitoring and Support Laboratory, U.S. Environ-
Add 1 mL (NH4)2SO4 solution and stir thoroughly. Add conc mental Protection Agency; 1980.
acetic acid until BaSO4 precipitates; add 2 mL excess. Digest in

[Link] 11
 7500-Ra RADIUM - E. Gamma Spectroscopy Method

7500-Ra E. Gamma Spectroscopy Method

1. General Discussion d. Drying lamp.

e. Gamma-ray spectroscopy system with high-resolution intrin-
a. Application: The gamma spectroscopy method for measur- sic Ge detector (or lithium drifted Ge detector).
ing 224Ra, 226Ra, and 228Ra in ground and surface water may be f. Magnetic stirrers/hot plates and stirring bars.
used for drinking water. The radium isotopes can be assayed con- g. Membrane filters, 47-mm diam, 0.45-mm porosity.
currently or individually in one sample-preparation procedure. h. Petri dishes, approximately 3-in. diam.
Ensure that the analyst is experienced with gamma-ray mea- i. Planchets, stainless steel, 5-cm diam, either shallow or deep
surements and the mathematics and implications of transient type.
equilibrium, because commercial gamma software does not have j. Polyethylene squeeze-bottles, 250- or 500-mL capacity.
the capability to calculate sample concentration for transient k. Retaining rings, O-rings, or adhesives.
equilibrium. l. Snap-ring pliers to insert retaining rings.
Preferably, have the analyst prepare at least 3 samples with m. Stirring-bar retriever.
known additions by the method before it is used for samples. n. Suction filter apparatus.
This method also can be the basis for standard operating proce- o. Volumetric flasks, 100-, 500-, 1000-, and 2000-mL.
dures (SOPs) that may differ with respect to the intrinsic effi- p. Volumetric pipets, 1.0-, 5-, and 20-mL.
ciency of the detector, the method of precipitating radium, the
method of yield determination, and the sample volume used with 3. Reagents
the chemistry.
b. Principle: Radium in water is separated from a 1- to 3-L a. For procedure using lead as the carrier in the coprecipita-
sample by a fast lead sulfate (PbSO4) or barium sulfate (BaSO4) tion step:
coprecipitation technique. The radium isotopes 224Ra, 226Ra, and 1) Lead carrier, 100 mg Pb2+/mL—Dissolve 160 g reagent-
228
Ra are measured through their respective gamma-ray-emitting grade Pb(NO3)2 in 800 mL reagent water and dilute to 1 L.
decay products, 212Pb, 214Pb (and/or 214Bi), and 228Ac, by means of 2) Lead sulfate wash solution—Dissolve 25 g anhydrous
a high-resolution intrinsic Ge detector. If 224Ra is to be measured, sodium sulfate in 1 L 1% sulfuric acid.
prepare and count the water sample during the 2- to 4-d window 3) Mixed-nuclide gamma-ray standard solution, traceable to
after sample collection because of this isotope’s short half-life NIST—Prepare the source in a similar geometry as the precipi-
and radioactive growth/decay considerations (7500-Ra E.5). tated sample for detector efficiency calibration. Alternately, pur-
If the presence of unsupported 212Pb (212Pb not due to ingrowth chase a similar source from a commercial supplier.
from 224Ra parent) is suspected, at least 2 consecutive counts are 4) Radium-226 and 228Ra standards, for preparation of
required to assess this contribution. Repeat the counting after known-addition QC samples and calibration of instrumentation
about 21 d to ensure that 226Ra progeny are in equilibrium with (see Section 7020 A.3c, d, and e).
their parent. At this point, the 228Ac equilibration with its 228Ra 5) Reagent water, distilled or deionized.
parent is already established. Note: Secular equilibrium of 228Ac 6) Sodium sulfate (Na2SO4), anhydrous.
with 228Ra is achieved about 36 to 60 h after precipitation (about 7) Sulfuric acid (H2SO4), 18 M.
6 to 10 half-lives of 228Ac). b. For procedure using barium as the carrier in the coprecipi-
c. Interferences: Ensure, by running laboratory blanks, that all tation step:
materials used in the analysis are free from interferences under 1) Barium carrier, 9 mg Ba2+/mL—Dissolve 16.01 g reagent-
the conditions of the analysis. grade BaCl2 ⋅ 2H2O in reagent water, add 5 mL 16 N HNO3, and
Lead-214, a 226Ra progeny, has a 241.9-keV gamma ray (7.5% dilute to 1 L with reagent water.
abundance). Similarly, 224Ra has a 240.8-keV gamma ray (3.9% 2) Diethyl ether.
abundance). Resolve the photopeaks due to these 2 gamma rays 3) Ethanol.
correctly in the gamma-ray spectrum to minimize interference 4) Hydrochloric acid (HCl), 12 N.
with the 212Pb 238.6-keV peak, thus avoiding high bias for 224Ra 5) Mixed-nuclide gamma-ray standard solution—See para-
determination. graph a3 above.
The carryover of 228Th into the Pb(Ra)SO4 precipitate has been 6) Nitric acid (HNO3), 16 N.
measured to be about 5%. This is insignificant for drinking water 7) Radium-226 and 228Ra, for preparation of known-addition
samples because the typical range of activities for thorium radio- QC samples and calibration of instrumentation (see Section
nuclides is below 0.1 pCi/L. Consequently, the 224Ra activity due 7020 A.3c, d, and e).
to ingrowth, during the time span between sample preparation 8) Reagent water, distilled or deionized.
and counting, from the carried-over 228Th also is negligible and 9) Sulfuric acid (H2SO4), 18 N.
can be disregarded.
4. Procedure
2. Apparatus
a. Sample collection and preservation: Collect water samples
a. Analytical balance, 0.1 mg sensitivity. in plastic bottles and acidify in the field, immediately after collec-
b. Beakers, 4-L. tion, with HNO3 or HCl to a pH of 2.0 or lower. Record the time
c. Watch glasses.

[Link] 12
 7500-Ra RADIUM - E. Gamma Spectroscopy Method

and date of sample collection. If the sample is not preserved in the b) Radium-226 and 228Ra assay—This assay consists of one
field, acidify it in the laboratory and let it stand for at least 16 h 1000-min overnight counting (or an appropriate count time to
before chemical separation. reach the desired MDC) of the sample about 21 d after prepara-
b. Chemical separation: Use procedure 1 or 2 below. tion. The gamma rays of 226Ra progeny 214Pb/214Bi and of 228Ra
1) Separation with lead as the carrier in coprecipitation—Measure progeny 228Ac are used for determinations. Allow adequate time
3 L sample by weight and transfer to a 4-L beaker. Note: For other between Ra separation and counting to establish equilibrium
sample portions, vary the concentrations of chemicals used in the (ingrowth periods of 2 d and 21 d for 228Ra and 226Ra, respectively).
subsequent steps proportionally, except for the lead carrier solution. 2) Chemical yield determinations—After gamma-ray spec-
To the 3-L portion, add 24 g anhydrous sodium sulfate and troscopy measurements are completed, weigh the filter paper
18 mL conc H2SO4. Place a magnetic stirring bar in the beaker, (to nearest 0.1 mg) containing PbSO4 or BaSO4 precipitate for
cover with a watch glass, and bring sample to a rolling boil on chemical yield determination.
magnetic stirrer/hot plate. While stirring and boiling, add 1.0 mL 3) Detector efficiency calibration—Distribute a portion of the
lead carrier solution (100 mg/mL) dropwise to each beaker and mixed-gamma standard solution [7500-Ra E.3a3)] uniformly as
continue boiling for 2 min. Then, add another 1.0 mL lead carrier very fine droplets over a membrane filter (7500-Ra E.2g), or use
solution similarly, and boil an additional 15 min. Note: In most a similar source from a commercial supplier. Count the prepared
cases, the rolling boiling water is sufficient to facilitate rapid and calibration standard on the Ge detector. Select a count time to
nearly homogeneous PbSO4 precipitation. For samples with high achieve a relative counting uncertainty of 1% (about 10 000 net
total dissolved solids (TDS), constant stirring of the water sample counts in each photopeak used for the calibration. Alternately, the
is recommended to avoid bumping. detector can be calibrated specifically for the gamma rays asso-
Remove the stirring bar and place the beaker in an ice bath to ciated with Ra progeny detection using a calibration source pre-
cool. (Cooling without ice bath takes several hours.) pared by using deionized water fortified with 224Ra, 226Ra, and
Preweigh a membrane filter. Isolate the lead sulfate precipitate 228
Ra standards, and carried through the entire sample preparation
by carefully pouring contents of beaker through filtration system process. This calibration accounts for any summing effects as
fitted with preweighed filter. Use lead sulfate wash solution to with the 214Bi 609-keV gamma rays.
complete the transfer. 4) Background determination—Prepare a background sample,
Transfer the filter to a planchet. Insert a retaining ring using consisting of a membrane filter on a planchet without application
snap-ring pliers, and place planchet in a petri dish. Alternate of standard solution, and count for 1000 min or longer. The spec-
means of securing the filter paper in a flat position, such as an trum obtained from the analysis of background sample detector is
O-ring may be used. Retain the filter after gamma-ray measure- used to create distinct background files. For each sample analysis,
ment for chemical yield determination. subtract the contributions of background peaks (as determined
2) Separation with barium as the carrier in coprecipitation— from the background file) from the sample peaks.
Measure 3 L sample by weight and transfer to a 4-L beaker. Note:
For other sample portions, vary the concentrations of chemicals 5. Calculation
used in the subsequent steps proportionally except for the barium
carrier solution. Add 30 mL of 12 N HCl and stir. Using a volu- a. Radium-224 measurement:
metric pipet, add 15.0 mL barium carrier. Stir and heat to boiling. 1) Lead-212 activity—Calculate 212
Pb activity with the equa-
Precipitate the barium sulfate by adding 30 mL of 18 N H2SO4, tion:
stirring frequently. Boil for 30 min. Store overnight to let precipi-
tate settle, or for fast settling, cool for 30 min in ice bath.
C s − Cb  λ t 
Preweigh a membrane filter. Isolate the barium sulfate precipi-  224 s 
A212 =  
tate by carefully pouring contents of beaker through the filtration E × A × V × 2.22 × Y 1 − e−λ 224 ts 
system fitted with preweighed filter. Quantitatively transfer the
precipitate to the filter by rinsing the remaining particles from the where:
beaker with a jet of water.
Dry the precipitate on the filter with 10 mL ethanol, followed A212 = 212Pb activity at start of count time (pCi/L),
by 10 mL diethyl ether. Transfer the filter to a planchet and secure Cs = sample net count rate under 238.6-keV photopeak region (cpm),
the filter paper in a flat position via double-sided transparent tape Cb = background net count rate for 238.6-keV photopeak region
or a ring. Place the planchet in a petri dish. Retain the filter for (cpm),
E = detection efficiency for 238.6-keV gamma ray, (counts/gamma),
chemical yield determination.
A= fractional gamma-ray abundance for 238.6-keV 212Pb,
c. Instrumental analysis:
0.436 gamma/disintegration,
1) Sample counting procedure—Reproducibly position the
V = volume of sample (L),
petri dish containing the coprecipitated sample source planchet 2.22 = conversion factor from dpm to pCi,
on an intrinsic Ge detector. When performing gamma-ray mea- Y = chemical recovery,
surements, observe the following scheme in accordance with the -4
l224 = 224Ra decay constant = 1.31 × 10 /min, and
particular radium isotope of interest: ts = sample count time (min).
a) Radium-224 assay—This assay consists of one 1000-min
overnight counting [or an appropriate count time to reach the The multiplicative factor inside the parentheses in this equa-
desired minimum detectable concentration (MDC)] of the prepared tion represents the correction of 212Pb activity for decay during
sample 2 to 4 d after sample collection date. Use the 238.6-keV the counting period.
212
Pb photopeak to determine the 212Pb activity. Apply the standard 2) Radium-224 activity—The correlation between 224Ra parent
decay and ingrowth equations to calculate the parent 224Ra activity. and 212Pb decay products is expressed as:

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 7500-Ra RADIUM - E. Gamma Spectroscopy Method

λ 212 [(Cg + Cc ) /ts ] + [Cb /tb ]

A212 = A0224 (e−λ 224 t − e−λ 212 t )
λ 212 − λ 224
= 1.14 A0224 (e−λ 224 t − e−λ 212 t )
and the relative count uncertainty (in percent) at the 95% confi-
dence level is:
where:
l212 = 212Pb decay constant (1.086 × 10 /min),
-3
1.96 [(Cg + Cc ) /ts ] + [Cb /tb ] ×100
% 1.96 SD =
A0224 = 224Ra activity at sample-collection time, and C s − Cb
t = time from sample collection to the start of counting.

When the two equations above are combined, b. Radium-226 and 228Ra determinations: If commercial
gamma software is available, 226Ra and 228Ra activities are
C s − Cb  1  λ 224 ts  measured through their respective progeny, 214Pb (or 214Bi) and
A0224 =    228
Ac, and are reported in the appropriate result documenta-
1.14 × E × A×V × 2.22 ×Y  e−λ 224 t − e−λ 212 t 1 − e−λ 224 ts 
tion. Otherwise, the activity equation for both isotopes can be
written as:
3) Minimum detectable count rate (MDR)—The MDR is the
mean expected count rate of samples having a 5% probability of n
not being detected where activity is present. The MDR may be 1 Ci
As = ∑
2.22 × n ×V ×Y × D i =1 Ei Ai
calculated from the formula:

  where:
2.71  (Cc + Cb )  tb  
MDR = + 3.29× ×1 +  
tb  tb  ts   As = sample activity concentration (pCi/L),
 
n = the number of photopeaks used (ordinarily n = 2),
V = volume of sample (L),
where: Y = chemical yield,
tb = background count time, and D = correction factor for decay/ingrowth,
Cc = Compton continuum background count rate under 238.6-keV Ci = net count rate in counts per minute for the ith peak, corrected for
photopeak region. baseline, background, and interferences,
i = peak number (i = 1, 2, …, n)
In the more specific case where sample count time is equal to Ei = detection efficiency for peak i, and
background count time, tb = ts, this is simplified to Ai = branching fraction for peak i.

Other unit conversions can be handled by including a constant

2.71 factor in the denominator of the expression for As.
MDR = + 4.65 (Cc + Cb )/ts
ts The equation for the combined standard uncertainty (u) of As
is shown below.
4) Minimum detectable concentration (MDC)—The MDC for
Pb is calculated from the MDR as follows:
212
1 n
u2 (Ci )
uc ( As ) = ∑
n ×V ×Y × D i = 1 Ei2 Ai2
MDR  λ 224 ts 
MDC212 =  
E × A×V × 2.22 ×Y 1 − e−λ 224 ts 
The MDC for each photopeak i used in the analysis is calculated
as:
The MDC for 224Ra at sample collection time, MDC0224, can be
calculated using the first equation in 12 above and expressed as:
MDRi
MDCi =
2.22 × Ei × Ai ×Y × Ds
MDC212
MDC 0224 =
−λ 224 t
1.14(e − e−λ 212 t )
where:
5) Uncertainties—If Cg represents the gross count rate in the MDRi is defined as in 7500-Ra E.5a3).
238.6-keV region, then: When n photopeaks are used for each determination, the total
MDC is:
C s = C g − Cc
n
The standard deviation associated with Cs is equal to (Cg + Cc ) /ts Total MDC = ∑ ( MDCi2 )1/ 2 /n
i =1
and the standard deviation associated with the background sub-
tracted sample count rate under the 238.6-keV photopeak region
(i.e., Cs – Cb) is given by

[Link] 14
 7500-Ra RADIUM - E. Gamma Spectroscopy Method

Table 7500-Ra:3. Results of 224Ra Collaborative Study

Sample Repeatability Reproducibility Total
Portion Concentration No. of SD (Within-Laboratory SD) (Between-Laboratory Error) Uncertainty
Size (L) (pCi/L)a Results (pCi/L) (pCi/L) (pCi/L) (pCi/L)
1 3.6 2 1.6 1.4 0.7 1.6
5.8 4 1.3 1.7 0.6 1.8
12.2 5 1.6 1.2 1.4 1.9
3 2.7 4 0.3 0.1 0.3 0.3
5.8 8 1.0 1.2 0.9 1.5
12.0 10 0.6 0.4 0.6 0.7
6 3.4 2 0.1 – – –
6.0 4 0.2 – – –
14.3 5 0.3 – – –
SD = standard deviation.
a
Mean of individual laboratory means.

6. Quality Control The radiochemical bias of the method was determined by sin-
gle-laboratory analysis of water samples fortified at 2 levels with
The quality control practices considered to be an integral part 228
Ra standard solution, in equilibrium with its progeny, includ-
of each method can be found in Section 7020. ing 224Ra. For 224Ra sample concentration of 1350 pCi/L, recov-
ery was 98.5% and bias –1.5%; for concentration of 53.4 pCi/L,
7. Precision and Bias recovery was 108.9% and bias 8.9%.
Two approaches to gamma spectroscopic determination of
a. Radium-224 determination: A collaborative study, con-
224
Ra, comparing the use of Pb versus Ba carriers were evalu-
sisting of 3 laboratories analyzing 3 New Jersey groundwater ated by comparing results of analyses of 20 randomly selected
samples at 3 concentration levels, was conducted to determine groundwater split samples between the New Jersey Department
precision. The results are summarized in Table 7500-Ra:3. The of Health and Senior Services (NJDHSS) Radiation Laboratory
true activity concentrations were not known, but it was known and U.S. Geological Survey Laboratory in Reston, Va. Aside from
that the samples were at 3 distinct concentration levels. The sam- subtle differences, the 2 methods use similar approaches to the
ples were analyzed by gamma spectroscopy of the original water isolation of radium and its quantitation via gamma ray spectros-
and radiochemical analysis of 1-L, 3-L, and 6-L portions of the copy. Concentrations in the samples analyzed ranged from less
water. Two laboratories analyzed the 1-L and 3-L portions, while than 0.5 to 12.6 pCi/L, with a median of 2.7 pCi/L. Results of
the third analyzed the 6-L portions. The results of an analysis of the two-tailed paired t test indicated that the differences between
variance (calculated via standard statistical methods) of the 3-L concentrations in sample pairs were not different from zero at the
and 1-L portion data are given in the table. The precipitates from 95% confidence level.
these portions were gamma-counted for various count times, but b. Radium-226 and radium-228 determinations: A data vali-
the vast majority were counted for 1000 min. The data for the dation study was performed with the participation of the Georgia
6-L portions are presented with the standard deviations for the 3 Institute of Technology Environmental Resource Center and the
samples. New Jersey Department of Health and Senior Services (NJDHSS)
The chemical recoveries of lead carrier were determined by Radiation Laboratory. The study was based on an Alternate Test
single-laboratory testing and multilaboratory testing as described Procedure protocol developed by the U.S. Environmental Protec-
above. The chemical yields are 90% or greater and can be deter- tion Agency. The process included background characterization,
mined gravimetrically. method detection limit, and method ruggedness studies. As a part

Table 7500-Ra:4. 226Ra and 228Ra Collaborative Study: Interlaboratory Results for
Accuracy and Precision
226
Ra 228
Ra
% Recovery RPD % Recovery RPD
Average 100 7 101 6
Standard deviation 7 6 8 6
RPD Limit – 17 – 18
Recovery lower limit 87 – 84 –
Recovery upper limit 115 – 117 –
RPD = relative percent difference.
Note: N = 20.
Based on data from DeHart JM. Radiochemistry. Alternate test procedure (ATP) validation study
report. Alexandria (VA): EPA Sample Control Center (operated by CSC); 2003 (corrected 2007).

[Link] 15
 7500-Ra RADIUM - E. Gamma Spectroscopy Method

Table 7500-Ra:5. 226Ra and 228Ra Collaborative Study: Lead Carrier Equivalency Study, LFM, LFMD Sample Resultsa
226
Ra 226
Ra Measured 226
Ra Measured 228
Ra 228
Ra Measured
Addition Value Ra Percent Value Percent
226
Addition Ra Measured
228
Ra Percent Value Percent
228

Sample ID pCi/L pCi/L Recovery Difference pCi/L Value pCi/L Recovery Difference
304328 0 2.2 – – 0 5.2 – –
304328 spk-1 21.3 23.2 98.6 5.0 24.6 28.1 93.1 4.9
304328 spk-2 21.3 24.4 104 24.6 29.5 98.8
304329 0 3.3 – – 0 0.1 – –
304329 spk-1 21.4 24.3 98.1 0.82 24.7 23.1 93.1 8.3
304329 spk-2 21.5 24.5 98.6 24.7 25.1 101
304327 0 3.3 – – 0 0.5 – –
304327 spk-1 21.3 23.9 96.7 1.2 24.7 23.5 93.1 4.6
304327 spk-2 21.3 24.2 98.1 24.7 24.6 97.6
a
Percent recovery for each LFM and LFMD calculated following subtraction of result for the associated unfortified sample. Relative percent difference cal-
culated based on percent recovery for laboratory-fortified matrix (LFM) and laboratory-fortified matrix duplicate (LFMD) pairs. Adapted (percent recovery
and RPD values recalculated/rerounded) from data in DeHart JM. Radiochemistry. Alternate test procedure (ATP) validation study report. Alexandria
(VA): EPA Sample Control Center (operated by CSC); 2003 (corrected 2007).

of the study, samples from 3 public water supplies in different Restoration and Waste Management, Pacific Northwest National Lab-
physiographic regions of Georgia were analyzed. The participat- oratory, U.S. Department of Energy; 1997.
ing laboratories followed the sample preparation using Ba as the New Jersey Department of Health and Senior Services. Determination of
carrier for the coprecipitation step. In addition, to demonstrate radium-224 in drinking water, Revision 3; November. Trenton: N.J.
Department of Health and Senior Services; 1998.
the equivalency between the two carriers, the NJDHSS Radiation
Parsa B. Contribution of short-lived radionuclides to alpha-particle radio-
Laboratory performed the same analyses, using Pb as the carrier activity in drinking water and their impact on the Safe Drinking Water
in the coprecipitation step. Results are presented in Table 7500- Act Regulations. Radioact Radiochem. 1998;9:41.
Ra:4 and Table 7500-Ra:5. Szabo Z, DePaul VT, Kraemer TF, Parsa B. Comparison of two gam-
ma-spectroscopic approaches for determining radium-224 concentra-
Bibliography tion in ground water. 40th Rocky Mountain Conference on Analytical
Chemistry. 1998 July 25-Aug 1; Denver (CO).
Currie LA. Limits for qualitative detection and quantitative determina- Georgia Institute of Technology. Method for determination of radium-228
tion. Application to radiochemistry. Anal Chem. 1968;40(3):586–593. and radium-226 in drinking water by gamma-ray spectrometry using
Colle R, Abee HH, Cohen LK, Eisenhower EH, Jarvis AN, Fisenne IM, HPGE or Ge(Li) detectors. Atlanta (GA): Environmental Resource
Jackson M, Johnson RH Jr, Olson D, Peel J. Reporting of environmen- Center; 2003.
tal radiation measurements data. In: Upgrading environmental radia- DeHart JM. The results of a validation study for a method to eeter-
tion data; EPA 520/1-80-012. Washington DC: U.S. Environmental mine the radium-226 and radium-228 content of drinking water with
Protection Agency; 1980. gamma spectrometry. Prepared in support of work assignment 2-04,
Kahn G, Rosson B, Cantrell J. Analysis of 228Ra and 226Ra in public water EPA contract No. 68-C-98-139, Alexandria (VA): 2003.
supplies by a gamma-ray spectrometer. Health Phys. 1990;59(1):125– Parsa B, Obed RN, Nemeth WK, Suozzo G. Concurrent determination of
131.
224
Ra, 226Ra, 228Ra, and unsupported 212Pb in a single analysis for drink-
Goheen SC. DOE Methods for evaluating environmental and waste ing water and wastewater: dissolved and suspended fractions. Health
management samples. Richland (WA): Office of Environmental Phys. 2004;86(2):145–149.

Published Online: August 27, 2018

Revised: February 25, 2021
[Link] 16