ASTM D3645-15(2023)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D3645 − 15 (Reapproved 2023)
Standard Test Methods for
Beryllium in Water
This standard is issued under the fixed designation D3645; 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 D1068 Test Methods for Iron in Water
D1129 Terminology Relating to Water
1.1 These test methods cover the determination of dissolved
D1193 Specification for Reagent Water
and total recoverable beryllium in most waters and wastewa-
D1687 Test Methods for Chromium in Water
ters:
D1688 Test Methods for Copper in Water
Concentration
D1691 Test Methods for Zinc in Water
Range Sections
Test Method A–Atomic 10 μg ⁄L to 500 μg ⁄L 7 to 17 D1886 Test Methods for Nickel in Water
Absorption, Direct
D2777 Practice for Determination of Precision and Bias of
Test Method B–Atomic 10 μg ⁄L to 50 μg/L 18 to 26
Applicable Test Methods of Committee D19 on Water
Absorption, Graphite
Furnace D3370 Practices for Sampling Water from Flowing Process
Streams
1.2 The analyst should direct attention to the precision and
D3557 Test Methods for Cadmium in Water
bias statements for each test method. It is the user’s responsi-
D3558 Test Methods for Cobalt in Water
bility to ensure the validity of these test methods for waters of
D3559 Test Methods for Lead in Water
untested matrices.
D3919 Practice for Measuring Trace Elements in Water by
1.3 The values stated in SI units are to be regarded as
Graphite Furnace Atomic Absorption Spectrophotometry
standard. The values given in parentheses are mathematical
D4841 Practice for Estimation of Holding Time for Water
conversions to inch-pound units that are provided for informa-
Samples Containing Organic and Inorganic Constituents
tion only and are not considered standard.
D5673 Test Method for Elements in Water by Inductively
1.4 This standard does not purport to address all of the
Coupled Plasma—Mass Spectrometry
safety concerns, if any, associated with its use. It is the
D5810 Guide for Spiking into Aqueous Samples
responsibility of the user of this standard to establish appro-
D5847 Practice for Writing Quality Control Specifications
priate safety, health, and environmental practices and deter-
for Standard Test Methods for Water Analysis
mine the applicability of regulatory limitations prior to use.
For specific hazard statements, see Section 12 and 24.4.
3. Terminology
1.5 This international standard was developed in accor-
3.1 Definitions:
dance with internationally recognized principles on standard-
3.1.1 For definitions of terms used in these test methods,
ization established in the Decision on Principles for the
refer to Terminology D1129.
Development of International Standards, Guides and Recom-
3.2 Definitions of Terms Specific to This Standard:
mendations issued by the World Trade Organization Technical
3.2.1 total recoverable beryllium, n—a descriptive term
Barriers to Trade (TBT) Committee.
relating to the beryllium forms recovered in the acid-digestion
2. Referenced Documents procedure specified in these test methods.
2.1 ASTM Standards:
4. Significance and Use
D858 Test Methods for Manganese in Water
4.1 These test methods are significant because the concen-
tration of beryllium in water must be measured accurately in
These test methods are under the jurisdiction of ASTM Committee D19 on
order to evaluate potential health and environmental effects.
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic
Constituents in Water.
Current edition approved Dec. 1, 2023. Published January 2024. Originally
5. Purity of Reagents
approved in 1978. Last previous edition approved in 2015 as D3645 – 15. DOI:
10.1520/D3645-15R23.
5.1 Reagent grade chemicals shall be used in all tests.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Unless otherwise indicated, it is intended that all reagents shall
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
conform to the specifications of the Committee on Analytical
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. Reagents of the American Chemical Society, where such
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3645 − 15 (2023)
specifications are available. Other grades may be used, pro- 9. Interferences
vided it is first ascertained that the reagent is sufficiently high
9.1 Aluminum at concentrations greater than 500 μg/L has
in purity to permit its use without lessening the accuracy of the
been reported to depress the beryllium absorbance.
determination.
9.2 Sodium and silicon at concentrations in excess of
5.2 Unless otherwise indicated, reference to water shall be
1000 mg ⁄L have been reported to severely depress the beryl-
understood to mean reagent water conforming to Specification
lium absorbance.
D1193, Type I. Other reagent water types may be used
9.3 Beryllium is slightly ionized in the nitrous oxide-
provided it is first ascertained that the water is of sufficiently
acetylene flame. This ionization is suppressed by adding
high purity to permit its use without adversely affecting the
calcium chloride to give a final concentration of 900 mg/L
bias and precision of the test method. Type II water was
calcium in all standard and sample solutions.
specified at the time of round robin testing of this test method.
10. Apparatus
6. Sampling
10.1 Atomic Absorption Spectrophotometer, for use at
6.1 Collect the samples in accordance with Practices
234.9 nm.
D3370. The holding time for samples may be calculated in
accordance with Practice D4841. NOTE 2—The manufacturer’s instructions should be followed for all
instrument parameters.
6.2 Preserve samples with HNO (sp gr 1.42), adding about
10.2 Beryllium Hollow Cathode Lamp.
2 mL/L, to a pH of 2 or less immediately at the time of
collection. If only dissolved beryllium is to be determined,
10.3 Pressure Regulators—The supplies of oxidants and
filter the sample, before acidification, through a 0.45 μm
fuel shall be maintained at pressures somewhat higher than the
membrane filter.
controlled operating pressure of the instrument by suitable
regulators.
NOTE 1—Alternatively, the pH may be adjusted in the laboratory if the
sample is returned within 14 days. However, acid must be added at least
11. Reagents and Materials
24 hours before analysis to dissolve any metals that adsorb to the container
walls. This could reduce hazards of working with acids in the field when
11.1 Beryllium Solution, Stock (1.00 mL = 1000 μg Be)—
appropriate.
Dissolve 1.000 g of beryllium metal in a minimum volume of
HCl (1 + 1) and dilute to 1 L. (Beryllium is toxic and the
TEST METHOD A—ATOMIC ABSORPTION, DIRECT
solution should be prepared in a well-ventilated hood.) A
purchased metal stock solution of appropriate known purity is
7. Scope
also acceptable.
7.1 This test method is applicable in the range from 10 μg ⁄L
11.2 Beryllium Solution, Intermediate (1.00 mL = 100 μg
to 500 μg ⁄L of beryllium. The range may be extended upward
by dilution of the sample. Be)—Dilute 10.0 mL of the beryllium stock solution to
100.0 mL with nitric acid (HNO , 1 + 499).
7.2 The precision and bias data were obtained on reagent
water, tap water, salt water, river water, lake water, spring 11.3 Beryllium Solution, Standard (1.00 mL = 1.00 μg
Be)—Dilute 5.00 mL of the beryllium intermediate solution to
water, and untreated wastewater. The information on precision
and bias may not apply to other waters. It is the user’s 500.0 mL with nitric acid (HNO , 1 + 499).
responsibility to ensure the validity of this test method for
11.4 Calcium Solution (10 g/L)—Dissolve 25 g of calcium
waters of untested matrices.
carbonate in a minimum volume of HCl (1 + 1) and dilute to
1 L with water.
8. Summary of Test Method
11.5 Filter Paper—Purchase suitable filter paper. Typically
8.1 Beryllium is determined by atomic absorption spectro-
the filter papers have a pore size of 0.45 μm membrane.
photometry. Dissolved beryllium is determined by aspirating a
Material such as fine-textured, acid-washed, ashless paper, or
filtered sample directly with no pretreatment. Total recoverable
glass fiber paper are acceptable. The user must first ascertain
beryllium in the sample is determined in a portion of the filtrate
that the filter paper is of sufficient purity to use without
obtained after a hydrochloric-nitric acid digestion of the
adversely affecting the bias and precision of the test method.
sample. The same digestion procedure is used to determine
11.6 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
total recoverable cadmium (Test Methods D3557), chromium
(Test Methods D1687), cobalt (Test Methods D3558), copper chloric acid (HCl).
(Test Methods D1688), iron (Test Methods D1068), lead (Test
NOTE 3—If a high reagent blank is obtained, distill the HCl or use
Methods D3559), manganese (Test Methods D858), nickel
spectrograde acid. (When HCl is distilled, an azeotropic mixture is
(Test Methods D1886), and zinc (Test Methods D1691). obtained (approximately 6 N HCl). Therefore, whenever concentrated HCl
is specified in the preparation of a reagent or in the procedure, use double
the amount if distilled acid is used.)
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
11.7 Hydrochloric Acid (1 + 1)—Mix 1 volume of HCl (sp
Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by the American Chemical gr 1.19) with 1 volume of water. Always add acid to water.
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
11.8 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
copeial Convention, Inc. (USPC), Rockville, MD. (HNO ).
D3645 − 15 (2023)
NOTE 4—If a high reagent blank is obtained, distill the HNO or use
13.5 Prepare an analytical curve by plotting the absorbance
spectrograde acid.
versus the standard concentration for each standard on linear
11.9 Nitric Acid (1 + 499)—Add 1 volume of HNO (sp gr graph paper. Alternatively, use a direct concentration readout if
1.42) to 499 volumes of water. the instrument is so equipped.
11.10 Oxidant:
14. Procedure
11.10.1 Air, which has been passed through a suitable filter
to remove oil, water, and other foreign substances, is the
14.1 Measure 100.0 mL of a well-mixed acidified sample
oxidant used prior to switching to nitrous oxide.
into a 150 mL beaker.
11.10.2 Nitrous Oxide is the required oxidant.
NOTE 5—If only dissolved beryllium is to be determined, start with
11.11 Fuel:
14.5.
11.11.1 Acetylene—Standard commercially available acety-
14.2 Add 5 mL of HCl (sp gr 1.19) (11.6) to each sample.
lene is the required fuel. Acetone, always present in acetylene
cylinders, can affect analytical results. The cylinder should be
14.3 Heat the samples on a steam bath or hot plate until the
replaced at a gage pressure of 517 kPa (75 psi). (“Prepurified”
volume has been reduced to 15 mL or 20 mL, making certain
grade acetylene containing a special proprietary solvent other
that the samples do not boil. (Perform in a well-ventilated
than acetone should not be used with poly (vinyl chloride)
hood.)
tubing as weakening of the walls can cause a potentially
NOTE 6—For brines and samples with high levels of suspended matter
hazardous situation.)
or total dissolved solids, the amount of reduction is left to the discretion
of the analyst.
12. Hazards
NOTE 7—Many laboratories have found block digestion systems a
12.1 Due to the high toxicity of beryllium, all sample
useful way to digest samples for trace metals analysis. Systems typically
preparation and digestion steps should be carried out in a consist of either a metal or graphite block with wells to hold digestion
tubes. The block temperature controller must be able to maintain unifor-
well-ventilated hood. Also, the atomic absorption unit should
mity of temperature across all positions of the block. For trace metals
be vented as recommended by the manufacturer.
analysis, the digestion tubes should be constructed of polypropylene and
have a volume accuracy of at least 0.5 %. All lots of tubes should come
13. Standardization
with a certificate of analysis to demonstrate suitability for their intended
purpose.
13.1 Prepare a blank and at least four standard solutions to
bracket the expected beryllium concentration range of the
14.4 Cool and filter the samples through a suitable filter
samples to be analyzed by diluting the beryllium standard (11.5) (such as a fine-textured, acid-washed, ashless paper) into
solution (11.3) with HNO (1 + 499) (11.9). Analyze at least
100 mL volumetric flasks. Wash the filter paper two or three
three working standards containing concentrations of beryllium times with water and adjust to volume.
that bracket the expected sample concentration prior to analysis
14.5 Add 1.0 mL of calcium solution (11.4) to a 10.0 mL
of samples to calibrate the instrument. Prepare the standards
aliquot of each sample and mix thoroughly.
(100 mL) each time the test is to be performed or as determined
by Practice D4841.
14.6 Aspirate each sample and determine its absorbance or
concentration. Aspirate HNO (1 + 499) between each sample.
13.2 For total recoverable beryllium, add 0.5 mL of 3
HNO (sp gr 1.42) (11.8) and proceed as directed in 14.2 –
15. Calculation
14.6. For dissolved beryllium, proceed with 13.3.
13.3 Add 1.0 mL of calcium solution (11.4) to a 10.0 mL 15.1 Calculate the concentration of beryllium in each
aliquot of each standard and blank solution. Mix thoroughly. sample, in micrograms per litre, using the analytical curve
described in 13.5.
13.4 Aspirate the blank and standards and record the instru-
ment readings. Aspirate HNO (1 + 499) between each stan-
dard. (The atomic absorption unit should be vented properly.)
TABLE 2 Precision and Bias, Atomic Absorption, Direct
Amount Amount Statistically
TABLE 1 Overall (S ) and Single-Operator (S ) Interlaboratory
T O
Added, Found, % Bias Significant (95 %
Precision for Beryllium by Flame AAS, Test Method A
μg/L μg/L Confidence Level)
Reagent Water Reagent Water, Type II
Concentration (X), μg/L 15.4 211.0 444.8 16 15.4 −3.75 no
S 2.7 10.8 21.3 220 211.0 −4.09 yes
T
S 1.2 4.4 11.9 460 444.8 −3.30 yes
...