ASTM D4107-08(2013)
(Test Method)Standard Test Method for Tritium in Drinking Water
Standard Test Method for Tritium in Drinking Water
SIGNIFICANCE AND USE
5.1 This test method was developed for measuring tritium in water to determine if the concentration exceeds the regulatory statutes of drinking water. This test method also is applicable for the determination of tritium concentration in water as required by technical specifications governing the operations of nuclear power facilities. With suitable counting technique, sample size, and counting time a detection limit of less than 37 Bq/L (1000 pCi/L) is attainable by liquid scintillation.
SCOPE
1.1 This test method covers the determination of tritium in drinking water by liquid scintillation counting of the tritium beta particle activity.
1.2 This test method is used successfully with drinking water. It is the user's responsibility to ensure the validity of this test method for untested water matrices.
1.3 The tritium concentrations, which can be measured by this test method utilizing currently available liquid scintillation instruments, range from less than 0.037 Bq/mL (1 pCi/mL) to 555 Bq/mL (15 000 pCi/mL) for a 10-mL sample aliquot. Higher tritium concentrations can be measured by diluting or using smaller sample aliquots, or both.
1.4 The maximum contaminant level for tritium in drinking water as given by the United States Environmental Protection Agency (U.S. EPA) National Interim Primary Drinking Water Regulations (NIPDWR) is 0.740 Bq/mL (20 pCi/mL). The NIPDWR lists a required detection limit for tritium in drinking water of 0.037 Bq/mL (1 pCi/mL), meaning that drinking water supplies, where required, should be monitored for tritium at a sensitivity of 0.037 Bq/mL (1 pCi/mL). In Appendix X1, Eq X1.3 is given for determining the necessary counting time to meet the required sensitivity for drinking water monitoring.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D4107 − 08 (Reapproved 2013)
Standard Test Method for
Tritium in Drinking Water
This standard is issued under the fixed designation D4107; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the determination of tritium in
D1129Terminology Relating to Water
drinking water by liquid scintillation counting of the tritium
D1193Specification for Reagent Water
beta particle activity.
D2777Practice for Determination of Precision and Bias of
1.2 This test method is used successfully with drinking
Applicable Test Methods of Committee D19 on Water
water.Itistheuser’sresponsibilitytoensurethevalidityofthis
D3370Practices for Sampling Water from Closed Conduits
test method for untested water matrices.
D3648Practices for the Measurement of Radioactivity
1.3 The tritium concentrations, which can be measured by
3. Terminology
thistestmethodutilizingcurrentlyavailableliquidscintillation
3.1 Definitions—For definitions of terms used in this test
instruments, range from less than 0.037 Bq/mL (1 pCi/mL) to
method, refer to Terminology D1129. For terms not defined in
555 Bq/mL (15000 pCi/mL) for a 10-mL sample aliquot.
this test method or in Terminology D1129, reference may be
Higher tritium concentrations can be measured by diluting or
made to other published glossaries.
using smaller sample aliquots, or both.
4. Summary of Test Method
1.4 The maximum contaminant level for tritium in drinking
water as given by the United States Environmental Protection
4.1 In this test method, a 100-mL drinking water sample
Agency (U.S. EPA) National Interim Primary Drinking Water
aliquotistreatedwithasmallamountofsodiumhydroxideand
Regulations (NIPDWR) is 0.740 Bq/mL (20 pCi/mL). The
potassium permanganate, distilled, and a specified fraction of
NIPDWRlistsarequireddetectionlimitfortritiumindrinking
the distillate is collected for tritium analysis. The alkaline
waterof0.037Bq/mL(1pCi/mL),meaningthatdrinkingwater
treatmentistopreventotherradionuclides,suchasradioiodine
supplies, where required, should be monitored for tritium at a
and radiocarbon from distilling over with the tritium. Some
sensitivity of 0.037 Bq/mL (1 pCi/mL). In Appendix X1, Eq
drinking water supplies will contain trace quantities of organic
X1.3 is given for determining the necessary counting time to
compounds, especially surface water sources that contain fish
meet the required sensitivity for drinking water monitoring.
and other life. The permanganate treatment is to oxidize trace
organics in the sample aliquots which could distill over and
1.5 The values stated in SI units are to be regarded as
cause quenching interferences.Amiddle fraction of the distil-
standard. No other units of measurement are included in this
late is collected for tritium analysis because the early and late
standard.
fractions are more apt to contain interfering materials for the
1.6 This standard does not purport to address all of the
liquid scintillation counting process.
safety concerns, if any, associated with its use. It is the
4.2 As the sample distills, there is a gradient in the tritium
responsibility of the user of this standard to establish appro-
concentration in the accumulating distillate due to isotope
priate safety and health practices and determine the applica-
effects; therefore, it is important to collect the same fraction of
bility of regulatory limitations prior to use.
the distillate for all samples and standards for tritium analysis.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is under the jurisdiction ofASTM Committee D19 on Water contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
andisthedirectresponsibilityofSubcommitteeD19.04onMethodsofRadiochemi- Standards volume information, refer to the standard’s Document Summary page on
cal Analysis. the ASTM website.
Current edition approved June 15, 2013. Published July 2013. Originally American National Glossary of Terms in Nuclear Science and Technology,
approved in 1991. Last previous edition approved in 2008 as D4107–08. DOI: available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th
10.1520/D4107-08R13. Floor, New York, NY 10036, www.ansi.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4107 − 08 (2013)
4.3 Thecollecteddistillatefractionisthoroughlymixedand where such specifications are available. Other grades may be
a portion (up to 10 mL) is mixed with liquid scintillator used, provided it is first ascertained that the reagent is of
solution, and after dark adapting, is counted in the liquid sufficiently high purity to permit its use without lessening the
scintillation counting system for tritium beta particle activity. accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, references
5. Significance and Use
towatershallbeunderstoodtomeanreagentwaterconforming
5.1 Thistestmethodwasdevelopedformeasuringtritiumin
to Specification D1193, Type III.
water to determine if the concentration exceeds the regulatory
8.3 Reagents of Distillation Treatment:
statutes of drinking water. This test method also is applicable
8.3.1 Sodium Hydroxide Pellets.
for the determination of tritium concentration in water as
8.3.2 Potassium Permanganate.
requiredbytechnicalspecificationsgoverningtheoperationsof
nuclear power facilities. With suitable counting technique,
8.4 Background Water, with tritium activity below the
samplesize,andcountingtimeadetectionlimitoflessthan37
minimumdetectableactivity(mostdeepwellwatersarelowin
Bq/L (1000 pCi/L) is attainable by liquid scintillation.
tritium content).
8.5 Scintillator Solutions:
6. Interferences
8.5.1 Dioxane Liquid Scintillator Solution—Dissolve4gof
6.1 Areduced detection efficiency may result from quench-
scintillation-grade PPO (2,5-diphenyloxazole), 0.05 g of
ing in the sample scintillator mixture. Quenching is caused by
scintillation-grade POPOP [1,4-bis (5-phenyloxazolyl-2-yl)-
impurities in the sample, which can inhibit the transfer of
benzene], and 120 g of naphthalene in 1 L of spectroquality,
energy,orbycoloredmaterials,whichmayabsorbsomeofthe
1,4-dioxane. Store the solution in a dark (amber) bottle. This
emitted light. Corrections for quenching can be made by the
solution can be used with glass or polyethylene vials.
3 4
use of internal standards or by the ratio method. The
8.5.2 Solution G Scintillator Solution—Dissolve 18 g of
approach described in this test method, distillation after alka-
scintillation-grade PPO (2,5-diphenyloxazole) and 3.6 g of
linepermanganatetreatment,eliminatesquenchingsubstances,
scintillation-grade BIS-MSB [p-bis (o-methylstyryl) benzene]
as well as radionuclides which might be present in a volatile
in 2 L of spectroquality p-xylene. Add 1 L of Triton N-101
chemical form such as radioiodine and radiocarbon.Aboiling
detergent to the p-xylene scintillator solution. Dissolve 50 g of
chip must be used with each distillation to avoid bumping,
SXS (sodium xylene sulfonate) in 100 mL of water and add
which can amount to a carry over excursion.
this solution to the p-xylene scintillator-Triton solution. Mix
6.2 Scintillator stock solution or samples exposed to day-
thoroughly. Store the solution in a dark (amber) bottle. This
light must be dark-adapted. Also, toluene or xylene base
solution should be used with glass vials since the p-xylene
scintillators exposed to fluorescent lighting should be dark-
solventevaporatesslowlythroughthewallofthepolyethylene
adapted for a minimum of 6 h and dioxane base scintillators
vials.
exposed to fluorescent lighting for 24 h. All fluors should be
8.5.3 Other commercially available scintillators can be
checked for excitation under lighting conditions being used,
used, such as the environmentally safe di-isopropyl napthalene
and if possible, they should be exposed only to red light.
based scintillators. It is the responsibility of the user to verify
the acceptability of a substitute scintillator.
7. Apparatus
8.6 Tritium standard solution as tritiated water traceable to
7.1 Liquid Scintillation Spectrometer, coincidence-type.
a National Standards Laboratory such as NIST or NPL,
7.2 Liquid Scintillation Vials, of low-potassium glass are
approximately 17 kBq/mL.
recommended. Polyethylene vials may be used when other
than dioxane scintillator solution is used.
9. Sampling
7.3 Distillation Apparatus—For aqueous distillation,
9.1 Collect the sample in accordance with Practices D3370.
250-mL and 1000-mL round bottom borosilicate flasks, con-
9.2 Sincetritiumindrinkingwaterislikelytobeintheform
necting side arm adapter, condenser, graduated cylinder,
of T O or HTO, there is no need for special handling or
boiling chips, and heating mantle.
preservation.
8. Reagents and Materials
8.1 Purity of Reagents—Reagent grade chemicals shall be
Reagent Chemicals, American Chemical Society Specifications, American
used in all tests. Unless otherwise indicated, it is intended that
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
all reagents shall conform to the specifications of the Commit-
listed by the American Chemical Society, see Annual Standards for Laboratory
tee onAnalytical Reagents of theAmerican Chemical Society, Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
The sole source of supply of the apparatus known to the committee at this time
Bush, E. T., “General Applicability of the Channels Radio Method of is Rohm and Haas Company, Independence Mall West, Philadelphia, PA 19105. If
Measuring Liquid Scintillation Counting Efficiencies,” Analytical Chemistry,Vol you are aware of alternative suppliers, please provide this information to ASTM
35, No. 1024, 1963. International Headquarters. Your comments will receive careful consideration at a
5 1
Corning Part No. 9060 has been found satisfactory for this purpose. meeting of the responsible technical committee, which you may attend.
D4107 − 08 (2013)
10. Calibration scintillator as used in the preparation of samples. Use low
tritium background distilled water for these preparations (dis-
10.1 Determination of Recovery and Detection Effıciency
tillate of most deep well water sources is acceptable, but each
Factors:
source should be checked for tritium activity before using).
10.1.1 Prepare in a 1-L volumetric flask, a tritium standard
solution containing approximately 17 Bq/mL using low level
11.5 Dark-adapt all samples, backgrounds, and standards.
tritiumbackgroundrawwater,RWS(undistilled),andstandard Count the samples, backgrounds, and standards at least long
tritium activity. Label this solution as raw water tritium
enough to meet the required detection limit (0.037 Bq/mL) for
standard solution, RWTS. the sample (see Appendix X1 for calculating counting time for
10.1.1.1 Distill approximately 600 mL of water obtained
required detection limit). The DRWS distillate should be
from the same raw water source (RWS) as above (without counted for sufficient time to accumulate at least 50 000 net
tritium activity added). Use this distillate for background
counts.
tritiumdeterminations.Usingthedistillateandstandardtritium
activity, prepare a tritium standard solution in a 500-mL
12. Calculation
volumetricflasktocontainthesamespecificactivityastheraw
12.1 Detection Effıciency, ε:
water tritium standard solution. Label this solution as distilled
R 2 R
water tritium standard solution, DWTS.
DWTS b
ϵ 5 (1)
A
10.1.2 Aqueous Alkaline Permanganate Distillation—Place DWTS
a 100-mL aliquot of the RWTS solution in a 250-mL distilla-
R R
DWTS b
tion flask.Add 0.5 g of sodium hydroxide, 0.1 g of potassium 1
t t u~A !
DWTS b DWTS
permanganate, and a boiling chip. Proceed with the distillate u ϵ 5 1ϵ
~ ! ! S D
A A
DWTS DWTS
according to the procedure described in 11.1, discard 10 mL,
where:
and collect 50 mL of distillate for analysis. Mix the 50-mL
distillate fraction. Repeat the distillation with two more
A = activity of distilled water tritium standard, in
DWTS
100-mLaliquotsfortriplicateanalyses.Thisisthedistilledraw
becquerels (Bq),
water tritium standard (DRWTS). R = background aliquot count rate, in counts per
b
−1
10.1.3 Prepare for counting three aliquots of the DRWTS second (s ),
−1
R = distilled water tritium standard count rate (s ),
distillate tritium standard solution (from 10.1.2), three aliquots
DWTS
u(A ) = standard uncertainty of the activity ADWTS
of the DWTS, and three aliquots of the distilled raw water (for
DWTS
(Bq),
background). Mix 4 mL of water with 16 mL of the dioxane
t = count time for the distilled water tritium stan-
scintillatorsolution,or10mLofwaterwith12mLofSolution DWTS
dard (seconds), and
G scintillator solution in a liquid scintillator vial (glass vials
t = count time for the background sample
b
should be used for detergent-type scintillator solutions). Shake
(seconds).
well, dark-adapt the vials overnight, and count in a liquid
scintillation counter. Count each vial long enough to meet the
12.2 Recovery Correction Factor, F:
required detection (0.037 Bq/mL) or longer (see Appendix X1
R 2 R
DWTS b
for calculating required counting time).
F 5 (2)
ϵ 3A
RWTS
where:
11. Procedure
−1
R = count rate of distilled raw water standard (s ),
DRWTS
11.1 Add 0.5 g of sodium hydroxide and 0.1 g of potassium
and
permanganate to a 100-mL aliquot of the sample in a 250-mL
A = activityof(undistilled)rawwatertritiumstandard
RWTS
distillation flask. Add a boiling chip to the flask. Connect a
Bq.
side-arm adapter and a condenser to the outlet of the flask.
Place a graduated cylinder at the outlet of the condenser. Heat
12.3 Sample Tritium Activity, AC, for each aliquot:
the sample to boiling to distill, collect the first 10 mL of
R 2 R
a b
distillate as a separate fraction and discard it. AC 5 (3)
2λt
ϵ 3F 3V 3e
11.2 Collectthenext50mLofdistillatefortritiumanalysis.
where:
Thoroughly mix the 50-mL distillate fraction.
−1
R = sample aliquot gross count rate (s ),
a
−1
NOTE 1—It is important that only the first 10-mLfraction be discarded
R = background aliquot count rate (s ),
b
or the same fraction for samples and standards alike since there is a
ε = detection efficiency, as determined in Eq 1,
gradient in the tritium concentration of the distillate.
V = volume of the
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