Designation: D4192 − 15

Standard Test Method for

Potassium in Water by Atomic Absorption
Spectrophotometry1
This standard is issued under the fixed designation D4192; 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* 2. Referenced Documents

1.1 This test method covers the determination of low 2.1 ASTM Standards:3
amounts of potassium in waters2 having low solids content. D1066 Practice for Sampling Steam
The applicable range of this test method is 0.20 to 4.0 mg/L D1129 Terminology Relating to Water
when using the 766.5-nm resonance line. The range may be D1193 Specification for Reagent Water
extended upward by dilution of an appropriate aliquot of D2777 Practice for Determination of Precision and Bias of
sample or by using the less-sensitive 404.4-nm resonance line. Applicable Test Methods of Committee D19 on Water
Many workers have found that this test method is reliable for D3370 Practices for Sampling Water from Closed Conduits
potassium levels to 0.02 mg/L, but use of this test method at D4841 Practice for Estimation of Holding Time for Water
this low level is dependent on the configuration of the aspirator Samples Containing Organic and Inorganic Constituents
and nebulizer systems available in the atomic absorption D5810 Guide for Spiking into Aqueous Samples
spectrophotometer as well as the skill of the analyst. The D5847 Practice for Writing Quality Control Specifications
precision and bias data presented are insufficient to justify use for Standard Test Methods for Water Analysis
of this test method in the 0.02-mg/L range.
3. Terminology
1.2 This test method has been used successfully with spiked
reagent water. It is the analyst’s responsibility to ensure the 3.1 Definitions:
validity of this test method to other low dissolved solids 3.1.1 For definitions of terms used in this test method, refer
matrices. to Terminology D1129.
1.3 The values stated in SI units are to be regarded as 4. Summary of Test Method
standard. The values given in parentheses are mathematical 4.1 Potassium is determined by flame atomic absorption
conversions to inch-pound units that are provided for informa- spectrophotometry. The potassium content is determined by
tion only and are not considered standard. aspirating the low solids sample directly with no sample
1.4 This standard does not purport to address all of the pretreatment.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 5. Significance and Use
priate safety and health practices and determine the applica- 5.1 Potassium occurs in rocks in a form that is not easily
bility of regulatory limitations prior to use. For a specific solubilized; therefore, the potassium content of natural waters
precautionary statement, see 8.6. is usually low. Most natural waters contain less than 20 mg/L
of potassium, but waters containing several hundred milli-
grams per litre are occasionally found. Potassium is essential to
1
This test method is under the jurisdiction of ASTM Committee D19 on Water animal nutrition, but a concentration of 1000 to 2000 mg/L in
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents stock water is regarded as the extreme limit permissible.
in Water.
Current edition approved Feb. 1, 2015. Published March 2015. Originally
3
approved in 1982. Last previous edition approved in 2008 as D4192 – 08. DOI: For referenced ASTM standards, visit the ASTM website, www.astm.org, or
10.1520/D4192-15. contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
2
Platte, J. A., and Marcy, V. M., “A New Tool for the Water Chemist,” Industrial Standards volume information, refer to the standard’s Document Summary page on
Water Engineering, May 1965 . the ASTM website.

*A Summary of Changes section appears at the end of this standard

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 D4192 − 15
6. Interferences (Warning—“Purified” grade acetylene containing a special
6.1 In the analysis of low-solids water, interferences are proprietary solvent rather than acetone should not be used with
usually negligible. poly(vinyl chloride) tubing as weakening of the tubing walls
can cause a potentially hazardous situation.)
7. Apparatus
9. Sampling
7.1 Atomic Absorption Spectrophotometer for use at 766.5
nm. 9.1 Collect the samples in accordance with the applicable
ASTM standard as follows: Practices D3370 and Practice
NOTE 1—The manufacturer’s instructions should be followed for all D1066.
instrumental parameters. Wavelengths other than 766.5 nm may be used
only if they have been determined to be equally suitable. 10. Standardization
7.2 Potassium Hollow-Cathode Lamps—Multielement hol- 10.1 Prepare 100 mL each of a blank and at least four
low cathode lamps are available and also have been found standard solutions to bracket the expected potassium concen-
satisfactory. tration range of the samples to be analyzed by diluting the
7.3 Pressure-Reducing Valves—The supplies of fuel and standard potassium solution 8.4 with water. Prepare the stan-
oxidant shall be maintained at pressures somewhat higher than dards each time the test is to be performed or as determined by
the operating pressure of the instrument by using suitable Practice D4841. Select the standards to give zero, median, and
valves. maximum points for an analytical curve.
8. Reagents and Materials 10.2 Analyze at least four working standards containing
concentrations of potassium that bracket the expected sample
8.1 Purity of Reagents—Reagent grade chemicals shall be concentration, prior to analysis of samples, to calibrate the
used in all tests. Unless otherwise indicated, it is intended that instrument. Aspirate the blank and the standards and record the
all reagents shall conform to the specifications of the Commit- instrument readings. Aspirate water between standards.
tee on Analytical Reagents of the American Chemical Society
where such specifications are available.4 Other grades may be 10.3 Read directly in concentration if this capability is
used, provided it is first ascertained that the reagent is of provided with the instrument or prepare a linear analytical
sufficiently high purity to permit its use without lessening the curve by plotting the absorbance versus concentration for each
accuracy of the determination. standard on linear graph paper.
8.2 Purity of Water—Unless otherwise indicated, reference 11. Procedure
to water shall be understood to mean reagent water conforming 11.1 Aspirate each sample and determine its absorbance or
to Specification D1193, Type I. Other reagent water types may concentration. Aspirate water between samples.
be used provided it is first ascertained that the water is of
sufficiently high purity to permit its use without adversely 12. Calculation
affecting the bias and precision of the test method. Type II 12.1 Calculate the concentrations of potassium in the
water was specified at the time of round robin testing of this samples, in milligrams per litre, by either reading directly in
test method. concentration if the capability is provided with the instrument
8.3 Potassium Solution, Stock (1.0 mL = 1.0 mg K)—Dry or referring the absorbance obtained for each sample to a
potassium chloride to constant weight at 105°C. Dissolve prepared analytical curve (see 10.3).
1.907 g of the dry potassium chloride (KCl) in water and dilute 12.2 If an aliquot of diluted sample was analyzed, multiply
to 1 L with water. the concentration of potassium, in milligrams per litre, by the
NOTE 2—Certified potassium stock solutions of appropriate known
purity are commercially available through chemical supply vendors. appropriate dilution factor.
8.4 Potassium Solution, Standard (1.00 mL = 0.1 mg K)— 13. Precision and Bias5
Dilute 100.0 mL of potassium stock solution to 1 L with water. 13.1 The overall and single-operator precision of this test
8.5 Oxidant: Air, which has been passed through a suitable method for eight laboratories, which included a total of twelve
filter to remove oil, water, and other foreign substances is the
usual oxidant. 5
Supporting data have been filed at ASTM International Headquarters and may
8.6 Fuel: Acetylene—Standard, commercially available be obtained by requesting Research Report RR:D19-1081. Contact ASTM Customer
Service at [email protected].
acetylene is the usual fuel. Acetone, always present in acety-
lene cylinders can affect analytical results. The cylinder should
TABLE 1 Determination of Bias for Potassium in Reagent Water
be replaced at 345 kPa (50 psig) to avoid acetone carry over.
by Atomic Absorption
Amount Amount
4
Reagent Chemicals, American Chemical Society Specifications, American Added, Found, St So Bias %
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not mg/L mg/L
listed by the American Chemical Society, see Annual Standards for Laboratory 0.15 0.164 0.037 0.014 + 9.33
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 1.50 1.62 0.085 0.044 + 8.00
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 3.00 3.03 0.179 0.062 + 1.13
MD.

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 D4192 − 15
operators analyzing each sample on three consecutive days, 14.3.3 Calculate the mean and standard deviation of the
within its range for reagent water varies with the quantity being seven values and compare to the acceptable ranges of bias in
measured according to Table 1. Table 1. This study should be repeated until the recoveries are
NOTE 3—Only reagent water was used to obtain the precision statement
within the limits given in Table 1. If a concentration other than
since this test method is designated for the determination of trace amounts the recommended concentration is used, refer to Practice
of potassium in low-solids water. D5847 for information on applying the F test and t test in
13.2 It is the user’s responsibility to ensure the validity of evaluating the acceptability of the mean and standard devia-
this test method for waters of untested matrices. tion.
13.3 Recoveries of known amounts of potassium (from 14.4 Laboratory Control Sample (LCS):
potassium chloride) in the series of prepared standards for the 14.4.1 To ensure that the test method is in control, analyze
same laboratories and operators were as given in Table 1. a LCS containing a known concentration of potassium with
each batch (laboratory-defined or twenty samples). The labo-
13.4 Precision and bias for this test method conforms to
ratory control samples for a large batch should cover the
Practice D2777 – 77, which was in place at the time of
analytical range when possible. The LCS must be taken
collaborative testing. Under the allowances made in 1.4 of
through all of the steps of the analytical method including
Practice D2777 – 13, these precision and bias data do meet
sample preservation and pretreatment. The result obtained for
existing requirements for interlaboratory studies of Committee
a mid-range LCS shall fall within 615 % of the known
D19 test methods.
concentration.
14. Quality Control 14.4.2 If the result is not within these limits, analysis of
samples is halted until the problem is corrected, and either all
14.1 In order to be certain that analytical values obtained the samples in the batch must be reanalyzed, or the results must
using these test methods are valid and accurate within the be qualified with an indication that they do not fall within the
confidence limits of the test, the following QC procedures must performance criteria of the test method.
be followed when analyzing potassium .
14.5 Method Blank:
14.2 Calibration and Calibration Verification:
14.5.1 Analyze a reagent water test blank with each
14.2.1 Analyze at least four working standards containing
laboratory-defined batch. The concentration of potassium
concentrations of potassium that bracket the expected sample
found in the blank should be less than 0.5 times the lowest
concentration, prior to analysis of samples, to calibrate the
calibration standard. If the concentration of potassium is found
instrument (see 10.2). The calibration correlation coefficient
above this level, analysis of samples is halted until the
shall be equal to or greater than 0.990. In addition to the initial
contamination is eliminated, and a blank shows no contamina-
calibration blank, a calibration blank shall be analyzed at the
tion at or above this level, or the results must be qualified with
end of the batch run to ensure contamination was not a problem
an indication that they do not fall within the performance
during the batch analysis.
criteria of the test method.
14.2.2 Verify instrument calibration after standardization by
analyzing a standard at the concentration of one of the 14.6 Matrix Spike (MS):
calibration standards. The concentration of a mid-range stan- 14.6.1 To check for interferences in the specific matrix
dard should fall within 615 % of the known concentration. being tested, perform a MS on at least one sample from each
Analyze a calibration blank to verify system cleanliness. laboratory-defined batch by spiking an aliquot of the sample
14.2.3 If calibration cannot be verified, recalibrate the with a known concentration of potassium and taking it through
instrument. the analytical method.
14.2.4 It is recommended to analyze a continuing calibra- 14.6.2 The spike concentration plus the background concen-
tion blank (CCB) and continuing calibration verification tration of potassium must not exceed the high calibration
(CCV) at a 10 % frequency. The results should fall within the standard. The spike must produce a concentration in the spiked
expected precision of the method or 615 % of the known sample that is 2 to 5 times the analyte concentration in the
concentration. unspiked sample, or 10 to 50 times the detection limit of the
14.3 Initial Demonstration of Laboratory Capability: test method, whichever is greater.
14.3.1 If a laboratory has not performed the test before, or if 14.6.3 Calculate the percent recovery of the spike (P) using
there has been a major change in the measurement system, for the following formula:
example, new analyst, new instrument, etc., a precision and P 5 100 @ A ~ V s 1V ! 2 B V s # /C V (1)
bias study must be performed to demonstrate laboratory
capability. where:
14.3.2 Analyze seven replicates of a standard solution A = analyte known concentration (mg/L) in spiked sample,
prepared from an Independent Reference Material containing a B = analyte known concentration (mg/L) in unspiked
mid-range concentration of potassium. The matrix and chem- sample,
istry of the solution should be equivalent to the solution used C = known concentration (mg/L) of analyte in spiking
in the collaborative study. Each replicate must be taken through solution,
the complete analytical test method including any sample V s = volume (mL) of sample used, and
preservation and pretreatment steps. V = volume (mL) of spiking solution added.

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 D4192 − 15
14.6.4 The percent recovery of the spike shall fall within the 14.7.2 Calculate the standard deviation of the duplicate
limits, based on the analyte concentration, listed in Guide values and compare to the precision in the collaborative study
D5810, Table 1. If the percent recovery is not within these using an F test. Refer to 6.4.4 of Practice D5847 for informa-
limits, a matrix interference may be present in the sample tion on applying the F test.
selected for spiking. Under these circumstances, one of the 14.7.3 If the result exceeds the precision limit, the batch
following remedies must be employed: the matrix interference must be reanalyzed or the results must be qualified with an
must be removed, all samples in the batch must be analyzed by indication that they do not fall within the performance criteria
a test method not affected by the matrix interference, or the of the test method.
results must be qualified with an indication that they do not fall 14.8 Independent Reference Material (IRM):
within the performance criteria of the test method. 14.8.1 In order to verify the quantitative value produced by
NOTE 4—Acceptable spike recoveries are dependent on the concentra- the test method, analyze an Independent Reference Material
tion of the component of interest. See Guide D5810 for additional (IRM) submitted as a regular sample (if practical) to the
information. laboratory at least once per quarter. The concentration of the
14.7 Duplicate: IRM should be in the concentration mid-range for the method
14.7.1 To check the precision of sample analyses, analyze a chosen. The value obtained must fall within the control limits
sample in duplicate with each laboratory-defined batch. If the established by the laboratory.
concentration of the analyte is less than five times the detection
limit for the analyte, a matrix spike duplicate (MSD) should be 15. Keywords
used. 15.1 analysis; atomic absorption; potassium; water

SUMMARY OF CHANGES

Committee D19 has identified the location of selected changes to this standard since the last issue
(D4192 – 08) that may impact the use of this standard. (Approved Feb. 1, 2015.)

(1) 8.3 was modified to clarify the purity of the commercial (3) Section 13 was modified to allow for direct reading
standards. instruments.
(2) Section 10 was modified with standard and calibration (4) 14.2.4 and 14.6.3 were modified.
information and to use a computer.

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