Designation: C1416 − 04 (Reapproved 2009)

Standard Test Method for

Uranium Analysis Waste Water by X-ray Fluorescence1
This standard is issued under the fixed designation C1416; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope solubility at low pH are also collected and will interfere only at
1.1 This test method applies for the determination of trace large concentration (the maximum capacity of the paper is 8.5
uranium content in waste water. It covers concentrations of U µeq/cm2). As an example, for a solution containing 1 mg/L of
between 0.05 mg/L and 2 mg/L. each Pb, Bi, Sn, Zr, and As, and 0.3 mg/L of uranium, a bias of
5 % was detected on the uranium content. See also 9.2.
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 4.2 Other elements such as Fe, Cu, Ni, Al, Cr ..., which have
standard. a higher phosphate solubility at low pH were found to have no
effect even at concentration of 10 mg/L.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 4.3 The excess of anions forming strong complexes with the
responsibility of the user of this standard to establish appro- uranyl cation can also bias the uranium determination. As an
priate safety and health practices and determine the applica- example, for a solution containing 100 mg/L of F (added as
bility of regulatory limitations prior to use. NaF) and 0.3 mg/L of uranium, a bias of 30 % was found on
the uranium determination. On the contrary, anions forming
2. Summary of Test Method weak uranyl complexes (such as SO42-, Cl– ...) were seen to
2.1 Uranyl cations are collected on ion exchange cellulose have no effect even at concentration of several g/L.
phosphate papers by circulating the water to be analysed 5. Apparatus
through the paper with a peristaltic pump. After drying, the
uranium is determined using X-ray fluorescence. 5.1 Wavelength dispersive X-ray fluorescence spectrometer
equipped with a LiF (200) crystal, a molybdenum, tungsten or
3. Significance and Use rhodium target tube and a scintillation detector.
3.1 Uranium production facilities must control trace ura- NOTE 1—Energy dispersive instruments may be applicable.
nium content in their waste waters. 5.2 Peristaltic pump capable of achieving a flow rate of 50
3.2 Colorimetric and fluorimetric methods have been devel- mL/min.
oped but require a tedious separation of interfering elements. 5.3 A filtration apparatus which comprises a filter holder, a
Trace uranium can also be determined by ICP-MS but not all 250 mL flask located on top of the filter, and a pipe on bottom
water matrices are adapted (for example, waters with high salt of the filter connected to the peristaltic pump. The sample to be
content). Direct X-ray fluorescence can be done on the liquid analyzed is poured in the flask, flows through the phosphate
but with a detection limit of ;5 mg/L filter and the liquid collected on bottom is brought back to the
3.3 X-ray fluorescence after collection of uranium offers the flask through the peristaltic pump.
advantages to reach low detection limits (0.05 mg/L) and to 5.4 Pipet—0.2 mL, 1 mL, 5 mL, 10 mL, 20 mL.2
avoid handling a liquid in the spectrometer.
5.5 pH - meter.
4. Interferences 5.6 100 mL volumetric flasks.
4.1 Uranium is collected on the paper by the precipitation of
a uranyl phosphate complex at pH = 2.5. Other cations (for 6. Reagents and Materials
example, Pb, Bi, Sn, Zr, As,...) having a low phosphate 6.1 Purity of Materials—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
1
This test method is under the jurisdiction of ASTM Committee C26 on Nuclear
all reagents conform to the specification of the Committee on
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Analytical Reagents of the American Chemical Society where
Test.
Current edition approved June 1, 2009. Published July 2009. Originally approved
2
in 1999. Last previous edition approved in 2004 as C1416 – 04. DOI: 10.1520/ Dilution detailed in 6.5 and 6.7 may also be done by weight. In that case, pipets
C1416-04R09. are not necessary.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
Copyright by ASTM Int'l (all rights reserved); Sun Aug 26 18:14:28 EDT 2012
1
Downloaded/printed by
MIT Libraries pursuant to License Agreement. No further reproductions authorized.
 C1416 − 04 (Reapproved 2009)
such specifications are available.3 Other grades may be used add 100 mL of the ammonium chloride solution (6.6). The filter
provided it is first ascertained that the reagent is of sufficiently is then ready for collecting uranyl ions and should not dry in
high purity to permit its use without lessening the accuracy of between.
the determination. 7.2.3 Position the drain line so that sample solution is
6.2 Purity of Water—Conventional distilled water is found returned to the 250 mL flask. Pour the 100 mL solution (7.2.1)
acceptable for this analysis. in the 250 mL flask. Let it flow for 1.5 h.
7.2.4 Recover the filter and let it dry at 50° C for 1 h.
6.3 Phosphate paper filters.4
7.3 Place the seven filters in the spectrometer holder, and
6.4 Concentrated hydrochloric acid, 12.1 M (sp gr 1.187). analyze each by X rays at the uranium La peak, according to
6.5 Diluted hydrochloric acid, 5 M. Add 41 mL of concen- manufacturer’s recommendations to achieve the user’s perfor-
trated hydrochloric acid (sp gr 1.187) to 50 mL H2O in a 100 mance and quality assurance criteria.
mL flask. Dilute to 100 mL with water. 7.4 Calibrate the spectrometer with the seven standards.
6.6 Ammonium chloride solution, 2 M. Add 10.7 g of When plotting the X rays fluorescence intensity versus the
ammonium chloride salt to a 100 mL flask. Dilute to 100 mL concentration, a linear curve should be obtained.
with water.
8. Procedure
6.7 Diluted nitric acid, 6 M. Add 37 mL of concentrated
nitric acid (sp gr 1.42) to 50 mL H2O in a 100 mL flask. Dilute 8.1 Measure out 100 mL of sample and proceed with the
to 100 mL with water. analysis as in 7.2 and 7.3.
6.8 Uranium standard solution, 10 g/L. This solution can be NOTE 2—If the solution contains solids (precipitate, organic materials)
a preliminary filtration should be done after step 7.2.1 but before step
prepared by weighing 11.344 g of certified UO2 (for example, 7.2.3. A verification that all uranium has been dissolved after adjusting the
OU 1 from CETAMA5 with certified uranium content 88.12 6 pH at 2.5 is recommended.
0.09 %), or equivalent, and adding 10 mL diluted nitric acid NOTE 3—If the solution contains a lot of salts, or if 100 mL are not
(6.7). After dissolution, dilute to 1 L with distilled water. available, a dilution might be necessary prior to step 7.2.1. A correction
6.8.1 Uranium standard solution, 10 mg/L, obtained by factor is then taken in account.
dilution of solution 6.8. 8.2 Obtain directly the uranium concentration from the
calibration curve obtained in 7.4.
7. Calibration and Standardization
7.1 Calibration an be done either in pure water as described 9. Precision and Bias
here or, if an interference is suspected, in the matrix to be 9.1 Precision—For a sample containing 0.30 mg/L of ura-
analysed using spikes. In seven 100 mL volumetric flasks, add nium, 15 analyses have been performed to assess the short-
respectively 0, 1, 2, 5, 10, 15, and 20 mL of solution 6.8.1. term variability. The estimated relative standard deviation was
Dilute to 100 mL with distilled water. The uranium contration found 2 % relative. The long term variability has been calcu-
is respectively 0, 0.1, 0.2, 0.5, 1.0, 1.5 and 2.0 mg/L. lated over a four–month period (40 analyses), without recali-
7.2 For each of the seven solutions (7.1), proceed as bration, for a solution containing 0.1 mg/L uranium. The
follows: analyses were performed by two operators in one facility. The
7.2.1 Adjust the pH of the solution to 2.5 6 0.2 with estimated relative standard deviation was found 15 % relative.
concentrated HCl (6.4). The solution volume will then be 9.2 Bias:
slightly above 100 mL but will be refered as such for 9.2.1 Uranium Recovery Rate on the Phosphate Paper—
simplification purposes. The recovery rate was calculated by comparing a direct
7.2.2 Just before the analysis, the phosphate paper must be calibration of the X ray spectrometer and the analysis as
converted to the ammonium form: insert a P 81 filter in the described in Section 7. Direct calibration of the spectrometer
filter holder and start the peristaltic pump with a flow rate of 50 was performed by depositing uranium on thin films and
mL/min. Position the drain line so that the conditioning analyzing as in 7.3 and 7.4. On the other hand, a waste water
solution is not returned to the 250 mL flask. Add 50 mL of DI sample was spiked with various uranium concentrations and
water to the 250 mL flask. When this has been pulled through analyzed according to 7.1-7.4. Table 1 shows the obtained
the filter, add 100 mL of the dilute HCl (6.5). When complete results using the direct calibration. The recovery rate calculated
from the four last spikes was found to be above 90 %.
3
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not TABLE 1
listed by the American Chemical Society, see Analar Standards for Laboratory Uranium added in Measured fluorescence Concentration measured
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia waste water intensity (kCp/s) using direct calibration
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, Baseline is subtracted
MD. 0 mg/L 0.359 0.27 mg/L
4
The sole source of supply of the apparatus known to the committee at this time 0.1 mg/L 0.444 0.35 mg/L
is P81 Whatman filter. If you are aware of alternative suppliers, please provide this 0.2 mg/L 0.567 0.46 mg/L
information to ASTM International Headquarters. Your comments will receive 0.5 mg/L 0.805 0.69 mg/L
careful consideration at a meeting of the responsible technical committee,1 which 0.8 mg/L 1.144 0.98 mg/L
you may attend. 1.0 mg/L 1.379 1.19 mg/L
5
CEA/CETAMA, BP 171 30 207 Bagnols sur Ceze. France.

Copyright by ASTM Int'l (all rights reserved); Sun Aug 26 18:14:28 EDT 2012
2
Downloaded/printed by
MIT Libraries pursuant to License Agreement. No further reproductions authorized.
 C1416 − 04 (Reapproved 2009)
9.2.2 Interferences—Bias can be checked when comparing 10. Keywords
calibration in pure water and calibration directly in the matrix. 10.1 uranium; waste water; x-ray fluorescence
See Section 4 for examples of potential interferences.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/
COPYRIGHT/).

Copyright by ASTM Int'l (all rights reserved); Sun Aug 26 18:14:28 EDT 2012
3
Downloaded/printed by
MIT Libraries pursuant to License Agreement. No further reproductions authorized.