You are on page 1of 4

7500-I RADIOACTIVE IODINE*

7500-I A. Introduction

1. Occurrence and Significance 2. Selection of Method

Radioiodine that results from testing nuclear devices or is Of the three methods, the precipitation method (B) is preferred
released during use and processing of reactor fuels is a major because it is simple and involves the least time. Method C, in which
concern in radioactivity monitoring. Fission products may con- iodide is concentrated by absorption on an anion resin, purified, and
tain iodine-129 through iodine-135. Iodine-129 has a half-life of counted in a beta-gamma coincidence system, is sensitive and
1.6 ⫻ 107 years but a relatively low specific activity (1.73 ⫻ accurate. Method D uses distillation. With each method it is possi-
10⫺4 Ci/g for 129I as compared to 1.24 ⫻ 105 Ci/g for 131I). The ble to reach the EPA recommended detection limit of 1 pCi 131I/L.
half-life of 131I is 8 d while for the other isotopes it is shorter
3. Bibliography
(35 min to 21 h). At present, only 131I is likely to be found in
water. When ingested or inhaled, it concentrates in the thyroid KLEINBERG, J. & G.A. COWAN. 1960. The Radiochemistry of Fluorine,
gland and may cause thyroid cancer. Chlorine, Bromine and Iodine. Rep. NAS-NS-3005, U.S. Atomic
Energy Comm.
BRAUER, F.P., J.H. KAYE & R.E. CONNALY. 1970. X-ray and ␤-␥.
Coincidence Spectrometry Applied to Radiochemical Analysis
of Environmental Samples. Advances in Chemistry Ser., No. 93,
Radionuclides in the Environment, pp. 231–253. American
* Approved by Standard Methods Committee, 2000. Editorial revisions, 2011. Chemical Soc.

7500-I B. Precipitation Method

1. General Discussion d. Iodate carrier: Dissolve 1.685 g KIO3 in distilled water and
dilute to 100 mL. Store in dark flask; 1 mL ⫽ 10 mg I.
a. Principle: Iodate carrier is added to an acidified sample and, e. Nitric acid, HNO3, conc.
after reduction with Na2SO3 to iodide, the 131I is precipitated f. Palladium chloride, PdCl2: Dissolve 3.3 g PdCl2 in 100 mL
with AgNO3. The precipitate is dissolved and purified with zinc 6N HCl; 1 mL ⫽ 20 mg Pd.
powder and H2SO4 and the solution is reprecipitated as PdI2 for g. Silver nitrate, AgNO3, 0.1M: Dissolve 17 g AgNO3 in
counting. distilled water and dilute to 1000 mL. Store in dark flask.
b. Quality control (QC): The QC practices considered to be an h. Sodium sulfite, Na2SO3, 1M (freshly prepared): Dissolve
integral part of each method can be found in Section 7020. 6.3 g Na2SO3 in distilled water and dilute to 50 mL.
i. Sulfuric acid, H2SO4, 2N.
2. Apparatus j. Zinc, powder, reagent grade.
4. Procedure
a. Counting instrument: Low-background beta counter (see
Section 7030B.1) or gamma spectrometer (Section 7030B.5).
b. Fine-fritted glass funnel. a. To a 2000-mL sample, add 15 mL conc HNO3 and 1.0 mL
c. Filter apparatus: Two-piece filter funnel with filtering iodate carrier. Mix well. Add 4 mL freshly prepared 1M Na2SO3
equipment.* and stir for 30 min. Add 20 mL 0.1M AgNO3, stir for 1 h, and
d. Filter materials: Filter paper;† glass-fiber filter, 2.4 cm let settle for 1 h. Decant and discard as much of the supernatant
diam; or 0.8-␮m pore-diam membrane filter, 4.7 cm diam. as possible. Filter remainder through a glass-fiber filter and
discard filtrate.
3. Reagents b. Transfer filter to a centrifuge tube and slurry with 10 mL
distilled water. Add 1 g zinc powder and 2 mL 2N H2SO4 and stir
a. Ammonium hydroxide, NH4OH, 6N. frequently for at least 30 min. Filter, with vacuum, through a
b. Ethanol, 95%. fine-fritted glass funnel and collect filtrate in an erlenmeyer flask.
c. Hydrochloric acid, HCl, 6N. Wash both residue and filter with a minimum quantity of dis-
tilled water and add wash water to filtrate. Discard residue.
c. Add 2 mL 6N HCl and heat in water bath at 80°C for
* Fisher Filtrator or equivalent. 10 min. Add 1 mL 0.2M PdCl2 and digest for at least 5 min.
† Whatman No. 42 or equivalent. Centrifuge and discard supernatant.

1
RADIOACTIVE IODINE (7500-I)/Ion-Exchange Method

d. Dissolve precipitate in 5 mL 6N NH4OH and heat in boiling C


water bath for 5 min. Filter through a glass-fiber filter and collect
131
I, pCi/L ⫽
2.22 ⫻ EVR ⫻ A
filtrate in a centrifuge tube. Discard filter and residue.
e. Neutralize filtrate with 6N HCl, add 2 mL in excess, and where:
heat in a water bath. Add 1 mL 0.2M PdCl2 to reprecipitate PdI2
C ⫽ net count rate, cpm,
and digest for 10 min. Cool slightly and transfer to a tared filter
E ⫽ counting efficiency of 131I as function of mass of PdI2
with distilled water. Wash successively with 5-mL portions of
precipitate,
distilled water and 95% ethanol. Dry in a vacuum oven at 60°C V ⫽ volume of sample, L,
for 1 h, weigh precipitate, mount, and beta-count. R ⫽ fractional chemical yield
f. If final PdI2 precipitate on a glass-fiber filter is counted in a recovered PdI2⫻0.0704
low-background beta counter, the background counting rate is ⫽ , and
added iodine carrier
relatively high (about 1.3 cpm). If precipitate is collected on a
0.8-␮m membrane filter and dried for 30 min at 70°C it may be A ⫽ 131I decay factor for the time interval between sample
counted in a beta-gamma coincidence scintillation system with a collection and measurement.
background rate of less than 0.1 cpm.
If a low-background counter is used, confirm identity of 131I by 6. Bibliography
recounting precipitate after about 1 week to check the half-life.
U.S. ENVIRONMENTAL PROTECTION AGENCY. 1980. Prescribed Procedures
5. Calculation for Measurement of Radioactivity in Drinking Water. EPA-600/4-
80-032, Environmental Monitoring and Support Lab., Cincinnati,
Calculate concentration of radioiodine as follows: Ohio.

7500-I C. Ion-Exchange Method

1. General Discussion mark with distilled water. Concentration of carrier I, mg/L ⫽ g


KI ⫻ 0.7644.
a. Principle: A known amount of inactive iodine in the form b. Ethanol, absolute.
of KI is added as a carrier and the sample is taken through an c. Hydroxylamine hydrochloride, 1M: Dissolve 6.95 g
oxidation-reduction step using hydroxylamine and sodium bisul- NH2OH 䡠 HCl in distilled water and dilute to 100 mL.
fite to convert all iodine to iodide. Iodine, as the iodide, is d. Nitric acid, HNO3, conc, 8N, 1.6N.
concentrated by absorption on an anion-exchange column. Fol- e. Sodium bisulfite, 1M: Dissolve 1.04 g NaHSO3 in distilled
lowing an NaCl wash, iodine is eluted with sodium hypochlorite. water and dilute to 10 mL.
Iodine in the iodate form is reduced to I2, extracted into CCl4, f. Sodium hydroxide, 12N: Dissolve 480 g NaOH in distilled
and back-extracted as iodide into water. The iodine finally is water and dilute to 1 L.
precipitated as PdI2. g. Sodium hypochlorite, NaOCl, 5%: Use available household
b. Quality control (QC): The QC practices considered to be an bleach.
integral part of each method can be found in Section 7020. h. Anion-exchange resin.†
i. Carbon tetrachloride, CCl4, reagent grade.
j. Hydrochloric acid, HCl, 3N, 1N.
2. Apparatus k. Palladium chloride: Dissolve 3.3 g PdCl2 in 100 mL 6N
HCl; 1 mL ⫽ 20 mg Pd.
a. Counting instrument: Low-background beta counter (Sec- l. Sodium chloride, NaCl, 2M: Dissolve 117 g NaCl in distilled
tion 7030B.1) or gamma spectrometer (Section 7030B.5). water and dilute to 1 L.
b. Chromatographic column, 2 cm ⫻ 15 cm. m. Hydroxylamine hydrochloride wash solution: Add 20 mL
c. Vacuum filter holder, 2.5 cm2 filter area. conc HNO3 and 20 mL 1M NH2OH 䡠 HCl to 100 mL distilled
d. Filter paper,* 2.4 cm diam. water.
e. Vacuum oven.
4. Procedure
3. Reagents
a. To 1 L sample in a beaker add, while stirring, 2.0 mL iodine
a. Iodine carrier: Weigh approximately 13 g dried KI to the carrier and 5 mL 5% NaOCl, and heat for 2 to 3 min to complete
nearest 0.1 mg. Dissolve in a 1-L volumetric flask containing oxidation. After the interchange reaction (2 to 3 min), slowly add
100 mL distilled water. Add 10 mL 1M NaHSO3 and dilute to 5 mL conc HNO3. Add 25 mL 1M NH2OH 䡠 HCl and stir. Let

* Whatman No. 42 or equivalent. † Dowex 1 ⫻ 8, 50-100 mesh, chloride form, or equivalent.

2
RADIOACTIVE IODINE (7500-I)/Distillation Method

reaction go on for a few seconds, add 10 mL 1M NaHSO3, and organic phase. Transfer aqueous phase to a beaker. Add 10 mL
adjust pH to 6.5 with 12N NaOH or 1.6N HNO3. Stir thoroughly 3N HCl. Using a stirrer-hot plate, boil and stir the sample until
for a few minutes. (Stir samples containing a large amount of it evaporates to 10 to 15 mL or begins to turn yellow.
organic material, such as muddy water, for 45 min.) Filter f. Add 1.0 mL PdCl2 solution dropwise. Rinse sides of beaker
through a glass-fiber filter to remove suspended matter. Discard with 1N HCl and add sufficient 1N HCl to make a volume of
residue. 30 mL. Continue stirring until cool. Place beaker in a stainless
b. Pour 20 mL anion-exchange resin into a column and wash steel tray and store at about 4°C overnight.
sides down with distilled water. Pass sample through ion- g. Filter through a tared filter mounted in a filter holder. Wash
exchange column at a flow rate of 20 mL/min. Discard effluent. residue with 1N HCl and then with absolute alcohol. Dry in a
Wash column with 200 mL distilled water and then with 100 mL vacuum oven at 60°C for 1 h. Cool in a desiccator, weigh
2M NaCl at a flow rate of 4 mL/min. Discard wash solutions. precipitate, then seal it between polyester tape and polyester
c. Add 50 mL 5% NaOCl in 10- to 20-mL increments, stirring plastic film,‡ with the film over the precipitate. Count with a
the resin as needed to eliminate gas bubbles, and maintain a flow beta-gamma coincidence system.
rate of 2 mL/min. To the eluted volume of 50 to 60 mL, collected
in a beaker, carefully add 10 mL conc HNO3 to make sample 2 5. Calculation
to 3N in HNO3 and transfer to a separatory funnel. (Add acid
slowly with stirring until vigorous reaction subsides.) Calculate 131
I, pCi/L, as in 7500-I.B.5.
d. Add 50 mL CCl4 and 10 mL 1M NH2OH 䡠 HCl. Extract
iodine into organic phase by shaking for about 2 min. Let phases 6. Bibliography
separate and transfer organic phase to another separatory funnel.
Add 25 mL CCl4 and 5 mL 1M NH2OH 䡠 HCl to the first AMERICAN SOCIETY FOR TESTING AND MATERIALS. 1972 Book of ASTM
separatory funnel and shake for 2 min. Combine organic phase Standards. Part 23. D 2334-68, American Soc. Testing & Materials,
with the one obtained from the first extraction. Discard aqueous Philadelphia, Pa.
phase. Add 20 mL NH2OH 䡠 HCl wash solution to the organic GABAY, J.J., C.J. PAPERIELLO, S. GOODYEAR, J.C. DALY & J.M. MATUSZEK.
phase and shake for 2 min. Let phases separate and transfer 1974. A method of determining 129I in milk and water. Health Phys.
organic phase to a clean separatory funnel. Discard wash solu- 26:89.
tion.
e. Add 25 mL distilled water and 10 drops 1M NaHSO3 to
organic phase. Shake for 2 min, let phases separate, and discard ‡ Mylar, or equivalent.

7500-I D. Distillation Method

1. General Discussion c. Ethanol, 95%.


d. Hydrochloric acid, HCl, 6N, 1N.
a. Principle: Iodine carrier is added to an acidified sample and e. Iodide carrier: Dissolve 2.616 g KI in distilled water, add
iodine is distilled into a caustic solution. The distillate is acidi- 2 drops NaHSO3, and dilute to 100 mL. Store in dark flask. 1 mL
fied and the iodine is extracted into CCl4. After back-extraction ⫽ 20 mg I.
as iodide, the iodine is purified as PdI2 for counting. f. Nitric acid, HNO3, conc.
b. Quality control (QC): The QC practices considered to be an g. Palladium chloride: Dissolve 3.3 g PdCl2 in 100 mL 6N
integral part of each method can be found in Section 7020. HCl; 1 mL ⫽ 20 mg Pd.
h. Sodium bisulfite, NaHSO3, 1M: Dissolve 5.2 g NaHSO3 in
2. Apparatus distilled water and dilute to 50 mL. Prepare only in small quantities.
i. Sodium hydroxide, NaOH, 0.5N.
a. Distillation apparatus and 3-L round-bottom flask. j. Sodium nitrite, NaNO2, 1M: Dissolve 69 g NaNO2 in
b. Separatory funnel, 60 mL. distilled water and dilute to 1 L.
c. Filter apparatus: Two-piece filter funnel with filtering k. Sulfuric acid, H2SO4, 12N.
equipment.* l. Tartaric acid, C4H6O6, 50%: Dissolve 50 g C4H6O6 in
d. Filter paper: See 7500-I.B.2d. distilled water and dilute to 100 mL.

3. Reagents
4. Procedure
a. Ammonium hydroxide, NH4OH, conc.
b. Carbon tetrachloride, CCl4. a. To a 2000-mL sample in a 3-L round-bottom flask, add
15 mL 50% C4H6O6 and 1.0 mL iodide carrier. Mix well,
cautiously add 25 mL cold conc HNO3, and close distillation
* Fisher Filtrator, or equivalent. apparatus (Figure 7500-I:1).

3
RADIOACTIVE IODINE (7500-I)/Distillation Method

d. Add 5 mL CCl4 and 1 mL 1M NaNO2 to original separatory


funnel containing the aqueous layer and shake for 2 min. Com-
bine organic fractions. Repeat and discard aqueous layer.
e. Shake separatory funnel thoroughly until CCl4 layer is
decolorized; let phases separate and transfer aqueous layer to a
centrifuge tube. Add 2 mL 1M NaHSO3 to the separatory funnel
containing CCl4 and shake for several minutes. When phases
separate, add aqueous layer to centrifuge tube. Add 1 mL dis-
tilled water to separatory funnel and shake for several minutes.
When the phases separate, add aqueous layer to centrifuge tube.
Discard organic layer.
f. To combined aqueous fractions, add 2 mL 6N HCl and heat
in water bath at 80°C for 10 min. Add 1.0 mL PdCl2 solution
dropwise, with stirring, and digest for 15 min.
g. Cool, stir precipitate, and transfer to a tared filter mounted
in a two-piece funnel. Let precipitate settle by gravity for uni-
form deposition, then apply suction. Wash residue with 10 mL
1N HCl, 10 mL distilled water, and then with 10 mL 95%
ethanol. Dry in a vacuum oven at 60°C for 1 h. Cool in desic-
Figure 7500-I:1. Distillation apparatus for iodine analysis (not to scale). cator, weigh, mount, and make beta count.
5. Calculation
b. Connect an air line to still inlet, adjust flow rate to about
Calculate the concentration of radioiodine as given in 7500-
2 bubbles/s, and distill for at least 15 min into 15 mL 0.5N
I.B.5.
NaOH. Cool and transfer NaOH solution to a 60-mL separatory
funnel. Discard still residue. 6. Bibliography
c. Adjust distillate to slightly acid with 1 mL 12N H2SO4 and
oxidize with 1 mL 1M NaNO2. Add 10 mL CCl4 and shake for AMERICAN SOCIETY FOR TESTING AND MATERIALS. 1972 Book of ASTM
1 to 2 min. Transfer organic layer to a clean 60-mL separatory Standards. Part 23. D 2334-68, American Soc. Testing & Materials,
funnel containing 2 mL 1M NaHSO3. Philadelphia, Pa.