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: D6919 − 17

Standard Test Method for

Determination of Dissolved Alkali and Alkaline Earth
Cations and Ammonium in Water and Wastewater by Ion
Chromatography1
This standard is issued under the fixed designation D6919; 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* ization established in the Decision on Principles for the

1.1 This test method is valid for the simultaneous determi- Development of International Standards, Guides and Recom-
nation of the inorganic alkali and alkaline earth cations, mendations issued by the World Trade Organization Technical
lithium, sodium, potassium, magnesium, and calcium, as well Barriers to Trade (TBT) Committee.
as the ammonium cation in reagent water, drinking water, and
2. Referenced Documents
wastewaters by suppressed and nonsuppressed ion chromatog-
raphy. 2.1 ASTM Standards:2
D1129 Terminology Relating to Water
1.2 The anticipated range of the test method is 0.05–200
D1193 Specification for Reagent Water
mg/L. The specific concentration ranges tested for this test
D2777 Practice for Determination of Precision and Bias of
method for each cation were as follows (measured in mg/L):
Applicable Test Methods of Committee D19 on Water
Lithium 0.4–10.0 D3370 Practices for Sampling Water from Closed Conduits
Sodium 4.0–40.0
Ammonium 0.4–10.0 D3856 Guide for Management Systems in Laboratories
Potassium 1.2–20.0 Engaged in Analysis of Water
Magnesium 2.4–20.0 D4210 Practice for Intralaboratory Quality Control Proce-
Calcium 4.0–40.0
dures and a Discussion on Reporting Low-Level Data
1.2.1 The upper limits may be extended by appropriate (Withdrawn 2002)3
dilution or by the use of a smaller injection volume. In some D5810 Guide for Spiking into Aqueous Samples
cases, using a larger injection loop may extend the lower limits. D5847 Practice for Writing Quality Control Specifications
It is the responsibility of the user to ensure the validity of this for Standard Test Methods for Water Analysis
test method for concentrations if the range is extended. D5905 Practice for the Preparation of Substitute Wastewater
1.3 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 3. Terminology
standard. 3.1 Definitions:
1.4 It is the user’s responsibility to ensure the validity of 3.1.1 For definitions of terms used in this standard, refer to
these test methods for waters of untested matrices. Terminology D1129.
1.5 This standard does not purport to address all of the 3.2 Definitions of Terms Specific to This Standard:
safety concerns, if any, associated with its use. It is the 3.2.1 continuing calibration blank, n—a solution containing
responsibility of the user of this standard to establish appro- no analytes (of interest) which is used to verify blank response
priate safety and health practices and determine the applica- and freedom from carryover.
bility of regulatory limitations prior to use. For hazards 3.2.2 continuing calibration verification, n—a solution (or
statements specific to this test method, see 8.3. set of solutions) of known concentration used to verify freedom
1.6 This international standard was developed in accor- from excessive instrumental drift; the concentration is to cover
dance with internationally recognized principles on standard- the range of calibration curve.

1 2
This test method is under the jurisdiction of ASTM Committee D19 on Water For referenced ASTM standards, visit the ASTM website, www.astm.org, or
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
in Water. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved June 1, 2017. Published June 2017. Originally the ASTM website.
3
approved in 2003. Last previous edition approved in 2009 as D6919 – 09. DOI: The last approved version of this historical standard is referenced on
10.1520/D6919-17. www.astm.org.

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

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 1

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
4. Summary of Test Method 6.1.1 High concentrations of analyte cations can interfere
4.1 Inorganic cations and the ammonium cation, hereafter with the determination of low concentrations of other analyte
referred to as ammonium, are determined by ion chromatog- cations with similar retention times. For instance, high levels of
raphy in water and wastewater samples from a fixed sample sodium can interfere with the determination of low levels of
volume, typically 10–50 µL. The cationic analytes are sepa- ammonium (that is, at ratios >1000:1).
rated using a cation-exchange material, which is packed into 6.1.2 High levels of sample acidity, that is, low pH, can also
guard and analytical columns. A dilute acid solution is typically interfere with this analysis by overloading the column, leading
used as the eluent. to poor peak shape and loss of resolution. The pH at which the
4.1.1 The separated cations are detected by using conduc- chromatographic separation begins to exhibit poor peak shape
tivity detection. To achieve sensitive conductivity detection, it depends upon the ion-exchange capacity of the column. It is
is essential that the background signal arising from the eluent recommended that columns used for analysis of acidic samples
have low baseline noise. One means to achieve low back- in conjunction with the suppressed conductivity version of this
ground noise is to combine the conductivity detector with a test method be able to tolerate acid concentrations up to 50 mM
suppressor device that will reduce the conductance of the H+ (pH 1.3), such as the IonPac5 CS16 column. The columns
eluent, hence background noise, and also transform the sepa- used with nonsuppressed conductivity detection typically have
rated cations into their more conductive corresponding bases.4 lower capacity and can tolerate acid concentrations up to 10
4.1.2 Detection can also be achieved without chemical mM H+ (pH 2.0), such as the IC-Pak C/MD column.
suppression, whereby the difference between the equivalent 6.2 A slight decrease or increase in eluent strength often
ionic conductance of the eluent and analyte cation is measured allows interferences to elute after or before the peak of
directly after the analytical column. This test method will concern.
consider both suppressed and nonsuppressed detection tech- 6.3 Sodium is a common contaminant from many sources
nologies. The conductivity data is plotted to produce a chro- such as fingers, water, detergents, glassware, and other inci-
matogram that is used to determine peak areas. A chromato- dental sources. As a precaution, the user of this test method is
graphic integrator or appropriate computer-based data system advised to wear plastic gloves and use plasticware for all
is typically used for data presentation. solutions, standards, and prepared samples. In addition, method
4.2 The cations are identified based on their retention times blanks should be monitored for background sodium contami-
compared to known standards. Quantification is accomplished nation.
by measuring cation peak areas and comparing them to the
areas generated from known standards. The results are calcu- 7. Apparatus
lated using a standard curve based on peak areas of known 7.1 Ion Chromatography Apparatus, analytical system com-
concentrations of standards in reagent water. plete with all required accessories, including eluent pump,
injector, syringes, columns, suppressor (if used), conductivity
5. Significance and Use detector, data system, and compressed gasses (if required).
5.1 This test method is applicable to the simultaneous 7.1.1 Eluent Pump, capable of delivering 0.25–5 mL/min of
determination of dissolved alkali and alkaline earth cations and eluent at a pressure of up to 4000 psi.
ammonium in water and wastewaters. Alkali and alkaline earth 7.1.2 Injection Valve, a low dead-volume switching valve
cations are traditionally determined by using spectroscopic that allows the loading of a sample into a sample loop and
techniques, such as AAS or ICP; whereas ammonium can be subsequent injection of the loop contents into the eluent
measured by using a variety of wet chemical methods, includ- stream.
ing colorimetry, ammonia-selective electrode, and titrimetry. 7.1.3 Guard Column, cation-exchange column typically
However, ion chromatography provides a relatively straight- packed with the same material used in the analytical column.
forward method for the simultaneous determination of cations, The purpose of this column is to protect the analytical column
such as lithium, sodium, potassium, calcium, magnesium, and from particulate matter and irreversibly retained material.
ammonium, in fewer than 20–30 min. 7.1.4 Analytical Column, separator column, packed with a
weak acid functionalized cation-exchange material, capable of
6. Interferences separating the ions of interest from each other, and from other
ions that commonly occur in the sample matrix. The chosen
6.1 No individual interferences have been established, but it column must give separations equivalent to those shown in
is possible that some low-molecular-weight organic bases Figs. 1 and 2.
(amines) may have similar retention times to analytes of 7.1.5 Suppressor Device—If using the suppressed conduc-
interest, particularly later-eluting solutes, such as potassium, tivity detection mode, the suppressor must provide peak-to-
magnesium, and calcium. Potential interferences include peak noise of <2 nS per minute of monitored baseline.
amines such as mono-, di-, and trimethylamines; mono-, di-, 7.1.6 Conductivity Detector, a low-volume, flow-through,
and triethylamines; and alkanolamines. temperature-controlled (typically at 35°C) conductivity cell
equipped with a meter capable of reading 0–1000 µS/cm on a
4
linear scale.
International Standard ISO 14911, Water quality — Determination of dissolved
Li+, Na+, NH4+, K+, Mn2+, Ca2+, Mg2+, Sr2+ and Ba2+ using ion chromatog-
5
raphy — Method for water and waste water. IonPac is a trademark of Dionex Corporation, Sunnyvale, CA, 94088.

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 2

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17

FIG. 1 Example Chromatogram of Dissolved Alkali and Alkaline Earth Cations, and Ammonium by Ion Chromatography Using Sup-
pressed Conductivity Detection

FIG. 2 Example QC Standard Chromatogram of Dissolved Alkali and Alkaline Earth Cations, and Ammonium by Ion Chromatography
Using Nonchemically Suppressed Conductivity Detection (Single-Column Indirect Conductivity Detection)

7.1.7 Data System, a chromatographic integrator or the detector output signal versus time, as well as presenting the
computer-based data system capable of graphically presenting integrated peak areas.

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 3

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
8. Reagents and Materials NOTE 3—Neutral pH cation standards are preferred. Alternatively,
prepare stock standard solutions from the following salts, as described
8.1 Purity of Reagents—Reagent-grade chemicals shall be below:
used in all tests. Unless otherwise indicated, all reagents shall
8.6.1 Ammonium Solution, Stock (1000 mg/L)—Dissolve
conform to the specifications of the Committee on Analytical
2.965 g of anhydrous ammonium chloride in water and dilute
Reagents of the American Chemical Society,6 where such
to 1 L volumetrically; 1.00 mL = 1.00 mg NH4+.
specifications are available. Other grades may be used, pro-
8.6.2 Lithium Solution, Stock (1000 mg/L)—Dissolve 6.108
vided it is first ascertained that the reagent is of sufficiently
g of anhydrous lithium chloride in water and dilute to 1 L
high purity to permit its use without reducing the accuracy of
volumetrically; 1.00 mL = 1.00 mg Li+.
the determination.
NOTE 1—Prepare all reagents, standards, and samples in plasticware.
8.6.3 Sodium Solution, Stock (1000 mg/L)—Dissolve 2.541
Sodium will leach from glassware and bias the quantification of sodium. g of anhydrous sodium chloride in water and dilute to 1 L
volumetrically; 1.00 mL = 1.00 mg Na+.
8.2 Purity of Water—Unless otherwise indicated, references
8.6.4 Potassium Solution, Stock (1000 mg/L)—Dissolve
to water shall be understood to mean reagent water conforming
3.481 g of anhydrous potassium phosphate monobasic in water
to Specification D1193, Type IA. Other reagent water types
and dilute to 1 L volumetrically; 1.00 mL = 1.00 mg K+.
may be used, provided it is first ascertained that the water is of
8.6.5 Magnesium Solution, Stock (1000 mg/L)—Dissolve
sufficiently high purity to permit its use without adversely
10.144 g of magnesium sulfate hetpahydrate in water and
affecting the bias and precision of the determination. For
dilute to 1 L volumetrically; 1.00 mL = 1.00 mg Mg2+.
example, neutral organic compounds in the reagent water,
8.6.6 Calcium Solution, Stock e(1000 mg/L)—Dissolve
measured as total organic carbon (TOC), may significantly
3.668 g of calcium chloride dihydrate in water and dilute to 1
erode the performance of this test method over time. It is
L volumetrically; 1.00 mL = 1.00 mg Ca2+.
recommended that reagent water with less than 10 ppb TOC be
used for all prepared solutions in this test method. 8.7 Cation Working Standards—All calibration standards
and standards used for analysis should be prepared in 100–mL
8.3 Eluent Concentrate; Suppressed Conductivity Detection
volumetric flasks, as described below.
(1.0 M methanesulfonic acid)—Carefully add 48.040 g of
concentrated methanesulfonic acid to approximately 400 mL of Standard concentration ~ mg/L ! 5
water in a 500–mL volumetric flask. Dilute to the mark and ~ stock volume added ~ mL! ·1000 mg/L !
mix thoroughly. 100 ~ mL!
NOTE 2—Methanesulfonic acid is a corrosive, strong acid that should be Example:
handled with care. Always handle this reagent in a fume hood while
wearing gloves and eye protection. ~ 1 mL Na stock·1000 mg/L Na!
10 mg/L Na 5
8.4 Eluent Analysis Solution; Suppressed Conductivity De- 100 ~ mL!
tection (26 mM methanesulfonic acid)— Add 26.0 mL of eluent 8.8 Blank—The blank standard is a portion of the water used
stock (8.3) to a 1–L plastic volumetric flask containing to prepare the cation working solutions.
approximately 500 mL of water. Dilute to the mark and mix 8.9 Filter Paper—Purchase suitable filter paper. Typically
thoroughly. The eluent analysis solution must be filtered the filter papers have a pore size of 0.22-µm or 0.45-µm
through an appropriate 0.22– or 0.45–µm filter and degassed by membrane. Material such as fine-textured, ashless paper, or
vacuum sonication or helium sparging prior to use. glass fiber paper are acceptable. The user must first ascertain
8.5 Eluent Analysis Solution; Nonsuppressed Conductivity that the filter paper is of sufficient purity to use without
Detection (3 mM nitric acid)—Add 29 mg of EDTA (as the free adversely affecting the bias and precision of the test method.
acid) to a 1–L plastic volumetric flask containing approxi-
mately 500 mL of water. Using a magnetic stir bar, mix for 10 9. Precautions
min. Add 30 mL of 100 mM nitric acid, or 189 µL of 9.1 These methods address the determination of low con-
concentrated nitric acid. Dilute to the mark and mix thor- centrations of cations. Accordingly, every precaution should be
oughly. The eluent analysis solution must be filtered through an taken to ensure the cleanliness of sample containers, as well as
appropriate 0.22– to 0.45–µm filter and degassed by vacuum other materials and apparatus that come in contact with the
sonication or helium sparging prior to use. sample.
8.6 Standard Solutions, Stock (1000 mg/L)—Prepare all
standard solutions in plasticware. It is recommended that the 10. Sampling and Sample Preservation
user purchase certified stock standard solutions. Stock stan- 10.1 Collect the sample in accordance with Practices
dards typically used for AAS are also suitable for the prepa- D3370, as applicable.
ration of cation working standards. 10.2 Samples must be collected in plastic containers that are
clean and free of artifacts and interferences. The suitability of
6
the containers must be demonstrated for each new lot by
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not performing a container blank and laboratory fortified container
listed by the American Chemical Society, see Annual Standards for Laboratory blank.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 10.3 Samples that will not be analyzed immediately must be
MD. preserved with sulfuric acid to a pH of 2. Whereas samples to

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 4

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
TABLE 1 Instrument Conditions for the Analysis of Dissolved curve, prepare calibration standards, at a minimum of three
Alkali and Alkaline Earth Cations and Ammonium by Ion concentration levels, by accurately adding measured volumes
Chromatography Using Suppressed Conductivity Detection
of the stock standards (8.6) to a volumetric flask(s) and diluting
Eluent: 26 mM methanesulfonic acid
Flow rate: 1.5 mL/min
to volume with water. A minimum of five concentration levels
Column: Dionex IonPac CG16/CS16 is recommended if the curve covers two orders of magnitude.
Sample Loop: 10 µL
Detection: Suppressed conductivity 12.2 The order of peak elution and typical retention times
Suppressor: CSRS ULTRA are shown in Figs. 1 and 2 for suppressed and nonsuppressed
Background: ~2 µS conductivity detection, respectively. The retention time of each
Solutes: 1 = lithium (1.0 mg/L), 2 = sodium (1.0 mg/L),
3 = ammonium (1.0 mg/L), 4 = potassium (1.0 mg/L), analyte can vary with the type and state of the guard and
5 = magnesium (1.0 mg/L), 6 = calcium (1.0 mg/L) analytical columns and the eluent concentration, but should
remain consistent within a given analysis batch.
12.3 To establish the calibration curve, analyze a reagent
TABLE 2 Instrument Conditions for the Analysis of Dissolved
Alkali and Alkaline Earth Cations and Ammonium by Ion blank (8.8) and the calibration standards (8.7) in accordance
Chromatography Using Nonsuppressed Conductivity Detection with the procedure in Section 13. Tabulate peak area responses
(Single-Column Indirect Conductivity Detection) against concentration. These results are used to prepare a
Eluent: 3 mM nitric acid / 0.05 mM EDTA calibration curve using a linear least-squares fit for each
Flow rate: 1.0 mL/min analyte (with the exception of ammonium). The squared
Column: Waters IC-Pak™C/MD,
Injection 20 µL correlation coefficient of determination (r2) should be ≥0.995
Volume: for accurate results. Ammonia is a weak base; hence the
Detection: Nonsuppressed conductivity, indirect conductivity ammonium cation does not give linear response with sup-
Background: ~1300 µS
Analytes: 1 = lithium (1.0 mg/L), 2 = sodium (4.0 mg/L), pressed conductivity detection and should be calibrated using a
3 = ammonium (5.0 mg/L), 4 = potassium (10.0 mg/L), quadratic fit when using this detection method. However, a
5 = magnesium (5.0 mg/L), 6 = calcium (10.0 mg/L) linear least-squares curve fit can be suitably used for calibra-
tion of ammonium using the nonsuppressed version of this
method. Once the calibration curves have been established,
be analyzed for cations are typically preserved with nitric acid, verification must be performed on each analysis day, whenever
sulfuric acid is recommended for ammonium.7 Add 0.8 mL fresh eluent is prepared, and once for each batch of samples.
concentrated H2SO4/L of sample and store at 4°C. The pH of
samples preserved in this manner should be between 1.5 and 2, 13. Procedure
although some wastewaters may require more concentrated
13.1 Inject the reagent blank, calibration standard, or
H2SO4 to achieve this pH. This pH increases the holding time
sample into the eluent stream and record the chromatogram.
to 28 days.
With a fixed-loop manual injector, flush an excess of the
11. Preparation of Apparatus sample (approximately 5× loop volume) through the sample
injection port using a syringe prior to injection. Examples of
11.1 Set up the ion chromatograph according to the manu-
method chromatograms are shown in Figs. 1 and 2 for the
facturer’s instructions.
suppressed and nonsuppressed conductivity detection, ion
11.2 Typical operating conditions for the ion chromatographic separation of the target cation analytes.
chromatograph, in both suppressed and nonsuppressed conduc-
tivity modes, are summarized in Tables 1 and 2. A 10–µL 14. Calculations
sample injection is recommended for calibration and sample 14.1 Compare the peak areas for the cations in the sample to
analysis when using chemically suppressed conductivity detec- the calibration curves prepared in 12.3. Calculate and report the
tion. A larger injection volume, that is, up to 50 µL, may be concentration of each cation in mg/L by comparing the analyte
required when using nonsuppressed conductivity detection. response to that of the standard curve according to the
11.3 The detector ranges are variable. Choose a range following equation:
consistent with the concentration range in the expected samples Cation Concentration, mg/L 5 A 3 F (1)
and within the operating requirements of the chromatographic
system used. where:
11.4 Equilibrate the chromatographic system prior to use by A = reading from the appropriate calibration plot, in mg/L,
pumping the eluent (8.4 or 8.5) through the system until a and
stable baseline is obtained (approximately 30 min). F = dilution factor if the sample was diluted prior to analysis
14.1.1 Computing integrators and computer-based chro-
12. Calibration and Standardization matographic data systems can be programmed to perform these
12.1 Determine the range of concentrations that will be calculations automatically.
quantified for each analyte. For each individual calibration
15. Report
7
Standard Methods for the Examination of Water and Wastewater, APHA, 15.1 Report results as the constituent cation in mg/L.
Washington, DC, 1992. Ammonium results are frequently reported as mg of NH3-N/L.

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 5

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
To convert to mg of NH3-N/L, multiply the ammonium result 16.5 Precision and bias for this test method conforms to
by a factor of 0.778 (14/18). Practice D2777 – 98, which was in place at the time of
15.2 Report only those values that are bracketed within the collaborative testing. Under the allowances made in 1.4 of
range of the calibration curve. Any values that fall above that Practice D2777 – 13, these precision and bias data do meet
range shall be repeated with appropriate dilution(s). existing requirements for interlaboratory studies of Committee
D19 test methods.
16. Precision and Bias
17. Quality Control (QC)
16.1 The precision and bias data presented in this test
method meet the requirements of Practice D2777, and are 17.1 Before this test is applied to analyzing unknown
given in Tables 3-8. The full research report can be obtained samples, the analyst shall establish quality control procedures
from ASTM Headquarters. as recommended in Practices D4210 and D5847, and Guide
D3856. To be certain that analytical values obtained by this test
16.2 A total of fourteen laboratories, employing one opera- method are valid and accurate within the confidence limits of
tor each, contributed data to the test method interlaboratory the tests, the QC procedures described in this section must be
collaborative study. Three matrices were studied; reagent followed.
water, drinking water, and industrial wastewater. Each partici-
pant prepared and analyzed four Youden pairs for each of the 17.2 Initial Demonstration of Laboratory Capability:
six analytes in each of the three matrices. The Youden pair 17.2.1 The laboratory using this test shall perform an initial
samples were prepared in matrices provided by the participants demonstration of laboratory capability. Analyze seven repli-
from spiking concentrates provided by the study organizer. cates of an Initial Demonstration of Performance (IDP) solu-
Participants who requested it were provided with a substitute tion. The IDP solution contains method analytes of known
industrial wastewater matrix prepared by the study organizer concentration, prepared from a different source than the cali-
according to Practice D5905. bration standards, used to fortify reagent water. Ideally, the IPD
solution should be prepared by an independent source from
16.3 The participants prepared seven separate Method De- reference materials. The level 3 (mid-level) standard used for
tection Limit (MDL) standards by pipetting aliquots of the the test method precision and bias study is recommended as an
supplied MDL concentrate into seven separate, clean, plastic IDP solution.
volumetric flasks and diluting each to a total of 100 mL with 17.2.2 The mean and standard deviation of seven values for
reagent water. The participants were instructed to determine an each test method analyte shall then be calculated and
appropriate dilution that yielded a response of the analyte compared, according to Practice D5847, to the single operator
peaks in the MDL sample of approximately 3 to 5 times the precision and recovery established for this test method. The
signal-to-noise of the instrument. Because the MDL sample upper limit for acceptable precision and the range of acceptable
concentrations were outside the calibration range for the recoveries are detailed in Table 10.
purposes of this study, the calibrations were required to include 17.2.3 If the values obtained for the IDP precision and
the origin in the calibration curve. MDLs are given in Table 9. recovery do not meet the criteria described in Table 10, initial
16.4 The results of this collaborative study may not be demonstration of performance must be repeated until the
typical of results for matrices other than those studied. results fall within these criteria.

TABLE 3 Precision and Bias for Lithium

Amount
Amount Added, Bias, Number Retained So, So, St, St,
Matrix Found,
mg/L % Pairs mg/L % mg/L %
mg/L
Reagent water 0.4 0.36 –10.0 11 0.01 2.7 0.01 3.5
0.5 0.45 –9.6 0.02 5.0
1.6 1.47 –8.1 11 0.01 0.8 0.04 2.8
2.0 1.85 –7.6 0.05 2.7
5.0 4.59 –8.2 11 0.07 1.4 0.14 3.0
6.0 5.04 –16.0 0.15 3.1

Drinking water 0.4 0.36 –9.3 12 0.01 1.5 0.02 4.1

0.5 0.46 –8.5 0.02 4.2
1.6 1.48 –7.8 12 0.05 2.9 0.05 3.4
2.0 1.82 –9.1 0.10 5.5
5.0 4.54 –9.2 12 0.13 2.7 0.17 3.7
6.0 5.09 –15.2 0.20 3.8

Wastewater 1.6 1.49 –6.8 12 0.01 0.8 0.06 4.2

2.0 1.86 –6.9 0.07 3.5
5.0 4.58 –8.4 12 0.18 3.7 0.14 3.0
6.0 5.21 –13.2 0.32 6.2
8.0 8.07 0.9 12 0.30 3.5 0.40 5.0
10.0 9.00 –10.0 0.31 3.5

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 6

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
TABLE 4 Precision and Bias for Sodium
Amount Added, Amount Found, Bias, Number Retained So, So, S t, S t,
Matrix
mg/L mg/L % Pairs mg/L % mg/L %
Reagent water 4.0 3.99 –0.3 10 0.13 2.9 0.13 3.3
5.0 4.98 –0.4 0.22 4.3
10.0 9.97 –0.3 11 0.10 0.9 0.33 3.3
12.0 12.13 1.1 0.34 2.8
20.0 20.26 1.3 11 0.51 2.2 0.94 4.6
25.0 25.03 0.1 0.74 2.9

Drinking water 4.0 3.48 –13.1 11 0.20 5.0 0.46 13.2

5.0 4.48 –10.5 0.65 14.5
10.0 9.33 –6.7 12 0.15 1.5 0.86 9.2
12.0 11.32 –5.7 0.87 7.7
20.0 19.01 –5.0 12 0.80 3.7 1.40 7.4
25.0 24.37 –2.5 1.20 4.9

Wastewater 10.0 9.41 –5.9 12 0.66 6.3 0.87 9.3

12.0 11.26 –6.2 1.03 9.2
20.0 18.70 –6.5 12 0.97 4.5 1.12 6.0
25.0 24.61 –1.6 1.39 5.7
32.0 31.00 –3.1 12 1.01 2.9 2.15 6.9
40.0 38.70 –3.2 1.92 5.0

TABLE 5 Precision and Bias for Ammonium

Amount Added, Amount Found, Bias, Number Retained So, So, St, St,
Matrix
mg/L mg/L % Pairs mg/L % mg/L %
Reagent water 0.4 0.42 4.5 11 0.04 9.2 0.05 11.3
0.5 0.53 6.4 0.05 9.8
1.6 1.62 1.1 12 0.02 1.1 0.12 7.6
2.0 2.05 2.3 0.12 6.0
5.0 4.98 –0.4 12 0.08 1.4 0.24 4.9
6.0 5.94 –1.0 0.19 3.2

Drinking water 0.4 0.40 –1.2 13 0.03 7.0 0.07 18.2

0.5 0.52 4.5 0.08 14.8
1.6 1.65 3.2 13 0.04 2.3 0.17 10.4
2.0 2.05 2.6 0.22 10.5
5.0 4.96 –0.9 13 0.08 1.4 0.40 8.0
6.0 5.97 –0.5 0.44 7.3

Wastewater 1.6 1.66 3.7 11 0.11 6.0 0.27 16.5

2.0 2.09 4.7 0.26 12.3
5.0 4.95 –0.9 11 0.17 3.1 0.25 5.1
6.0 5.96 –0.6 0.31 5.2
8.0 7.95 –0.6 12 0.22 2.4 0.48 6.0
10.0 9.83 –1.7 0.51 5.2

17.3 Calibration and Calibration Verification: ously established calibration curves. If the determined analyte
17.3.1 When beginning use of this test method, a continuing concentrations fall outside acceptable limits (615 %), that
calibration verification (CCV) containing each test method analyte is judged out of control, and the source of the problem
analyte shall be analyzed to verify the calibration standards and must be identified before continuing with on-going analyses.
acceptable instrument performance. This verification should be All samples following the last acceptable CCV should be
performed on each analysis day or whenever fresh eluent has reanalyzed.
been prepared. The CCV is a solution of test method analytes
with known concentration (mid-calibration range) used to 17.4 Laboratory Control Sample (LCS):
fortify reagent water. The CCV must be prepared from a 17.4.1 One Laboratory Control Sample (LCS) shall be
different source than the calibration standards. If the deter- prepared and analyzed with each sample batch (maximum of
mined CCV concentrations are not within 615 % of the known 20 samples) to ensure the test method is in control. The LCS is
values, the analyst shall reanalyze the CCV. Analyze a calibra- a solution of the test method analytes spiked at concentration
tion blank to verify system cleanliness. The blank result should levels of the IDP solution (see 17.2) added to a matrix that
be less than the method reporting limit. sufficiently challenges the test method. The LCS must be taken
17.3.2 If the values still fall outside acceptable limits, a new through all of the steps of this analytical method including
calibration curve is required that must be confirmed by a sample preservation and pretreatment. The analyte recoveries
successful CCV before continuing with on-going analyses. for the LCS must fall within the control limits listed below:
17.3.3 One continuing CCV shall be analyzed with each Upper Control Limit 5 x13S
sample batch (maximum of 20 samples) to verify the previ- Lower Control Limit 5 x 2 3S

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 7

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
TABLE 6 Precision and Bias for Potassium
Amount Added, Amount Found, Bias, Number Retained So, So, S t, S t,
Matrix
mg/L mg/L % Pairs mg/L % mg/L %
Reagent water 1.2 1.15 –4.0 11 0.05 3.7 0.11 9.5
1.5 1.45 –3.5 0.08 5.8
5.0 5.00 0.0 10 0.03 0.5 0.08 1.5
6.0 6.05 0.8 0.06 0.9
10.0 10.06 0.6 11 0.18 1.6 0.35 3.4
12.0 11.99 –0.1 0.18 1.5

Drinking water 1.2 1.18 –1.6 11 0.06 4.2 0.07 6.1

1.5 1.49 –0.5 0.07 4.4
5.0 5.02 0.3 12 0.12 2.1 0.21 4.2
6.0 6.03 0.5 0.18 3.0
10.0 10.00 0.0 11 0.37 3.3 0.27 2.7
12.0 12.24 2.0 0.54 4.4

Wastewater 5.0 5.20 4.0 11 0.10 1.8 0.31 6.0

6.0 6.22 3.7 0.29 4.6
10.0 10.08 0.8 11 0.23 2.1 0.36 3.6
12.0 12.15 1.2 0.52 4.3
16.0 15.96 –0.2 12 0.43 2.4 0.88 5.5
20.0 19.91 –0.4 0.78 3.9

TABLE 7 Precision and Bias for Magnesium

Amount Added, Amount Found, Bias, Number Retained So, So, S t, S t,
Matrix
mg/L mg/L % Pairs mg/L % mg/L %
Reagent water 2.4 2.48 3.2 11 0.06 2.3 0.09 3.7
3.0 3.07 2.4 0.12 3.8
5.0 5.22 4.5 11 0.03 0.5 0.14 2.6
6.0 6.33 5.5 0.15 2.4
10.0 10.15 1.5 10 0.18 1.6 0.22 2.2
12.0 12.32 2.7 0.37 3.0

Drinking water 2.4 2.44 1.6 11 0.11 3.9 0.13 5.3

3.0 3.06 1.9 0.15 4.8
5.0 5.15 3.1 11 0.15 2.6 0.26 5.1
6.0 6.17 2.8 0.22 3.5
10.0 9.92 –0.8 12 0.27 2.5 0.47 4.7
12.0 12.22 1.9 0.36 2.9

Wastewater 5.0 5.29 5.9 11 0.09 1.6 0.23 4.3

6.0 6.43 7.2 0.21 3.3
10.0 10.27 2.7 12 0.15 1.3 0.38 3.7
12.0 12.41 3.4 0.40 3.2
16.0 16.31 1.9 12 0.42 2.3 0.53 3.3
20.0 20.12 0.6 0.57 2.8

where: 17.6 Matrix Spike:

x = percent mean recovery, and 17.6.1 One Matrix Spike (MS) shall be analyzed with each
S = standard deviation of the mean recovery, as determined sample batch (maximum of 20 samples) to test method
from historical values for the equivalent concentration recovery. Spike a portion of one sample from each batch with
and matrix. a known concentration of the test method analytes. The MS
17.4.2 If the results do not fall within these limits, analysis shall be prepared in accordance with that outlined in Guide
of samples is halted until the problem is corrected. Either all D5810 and section 11.11 of Guide D3856. The percent
samples in the batch must be reanalyzed to pass these perfor- recovery of the spike must fall within % recovery 6 analyst %
mance criteria, or the results must be qualified with an RSD for an equivalent spike concentration and matrix given in
indication that they do not fall within the performance criteria Tables 3-8.
of the test method. 17.7 Matrix Duplicate:
17.5 Reagent Blank: 17.7.1 One Matrix Duplicate (MD) shall be analyzed with
17.5.1 A reagent blank (8.8) shall be analyzed as part of the each sample batch (maximum of 20 samples) to test method
initial generation of calibration curves. A reagent blank shall precision. If nondetects are expected in all the samples to be
also be analyzed with each sample batch (maximum of 20 analyzed, a Matrix Spike Duplicate (MSD) shall be analyzed
samples) to check for contamination introduced by the labora- instead of a MD with a higher concentration within the
tory or use of the test method. calibration range. Prepare the MSD as outlined in Guides
D5810 and D3856. The percent recovery of the spike must fall

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 8

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
TABLE 8 Precision and Bias for Calcium
Amount Added, Amount Found, Bias, Number Retained So, So, S t, S t,
Matrix
mg/L mg/L % Pairs mg/L % mg/L %
Reagent water 4 3.86 –3.4 10 0.11 2.5 0.14 3.5
5 4.80 –4.0 0.21 4.3
10 9.52 –4.8 11 0.08 0.7 0.30 3.1
12 11.75 –2.1 0.37 3.1
20 16.64 –16.8 9 1.81 9.7 2.20 13.2
25 20.73 –17.1 4.03 19.4

Drinking water 4 3.92 –2.0 12 0.22 5.1 0.27 6.8

5 4.90 –2.0 0.44 8.9
10 9.57 –4.3 12 0.17 1.6 0.45 4.7
12 11.65 –2.9 0.39 3.3
20 16.75 –16.2 10 1.14 6.2 3.09 18.4
25 19.78 –20.9 4.16 21.0

Wastewater 10 9.64 –3.6 12 0.15 1.4 0.38 4.0

12 11.83 –1.4 0.39 3.3
20 17.53 –12.3 10 1.28 6.7 2.78 15.9
25 20.49 –18.1 3.88 18.9
32 25.54 –20.2 10 2.35 8.3 6.15 24.1
40 31.22 –22.0 8.16 26.1

TABLE 9 Method Detection Limits

Injected Concentration Number Pooled mean, Pooled SD, Pooled MDL,
Analyte
Range, µg/LA of Labs µg/L µg/L µg/LB
Lithium 3 to 18 10 8.3 0.9 2.9
Sodium 12 to 120 10 52.7 8.5 26.6
Ammonium 15 to 125 11 56.9 5.0 15.6
Potassium 30 to 90 10 73.9 11.4 35.9
Magnesium 15 to 60 10 38.9 6.1 19.1
Calcium 30 to 300 10 134.6 12.2 38.4
A
Labs could choose the dilution of the MDL stock solution as appropriate for their instrumentation.
B
On average, MDLs obtained using suppressed detection were approximately 2.1 times lower than those obtained using non-suppressed conductivity. This difference was
not considered significant for the purposes of this study, as the analytes for the P&B study were spiked at a concentration level approximately two orders of magnitude
greater than the calculated MDL values.

TABLE 10 Upper Limits for Acceptable Precision and the Range of Acceptable Recoveries
IDP Solution Acceptable IDP Acceptable IDP Method Mean Lower Acceptable Upper Acceptable
Analyte Method So
Amount Precision, n = 7 Range, n = 7 Recovery IDP Recovery IPD Recovery
Lithium 1.6 mg/L 0.01 mg/L 0.0314 mg/L 0.1266 mg/L 1.47 mg/L 1.344 mg/L 1.597 mg/L
Sodium 10.0 mg/L 0.10 mg/L 0.2349 mg/L 1.0035 mg/L 9.97 mg/L 8.965 mg/L 10.972 mg/L
Ammonium 1.6 mg/L 0.02 mg/L 0.0457 mg/L 0.3774 mg/L 1.62 mg/L 1.241 mg/L 1.996 mg/L
Potassium 5.0 mg/L 0.03 mg/L 0.0637 mg/L 0.2338 mg/L 5.00 mg/L 4.764 mg/L 5.231 mg/L
Calcium 10.0 mg/L 0.08 mg/L 0.1771 mg/L 0.9235 mg/L 9.52 mg/L 8.601 mg/L 10.448 mg/L
Magnesium 5.0 mg/L 0.03 mg/L 0.0639 mg/L 0.4290 mg/L 5.22 mg/L 4.794 mg/L 5.652 mg/L

within % recovery 6 analyst % RSD for an equivalent spike concentrations of the reference material should be in appropri-
concentration and matrix given in Tables 3-8. Calculate the ate range as cited in 1.2 of this test method. The recovery
standard deviation and use the F-test (see Practice D5847, values obtained for each test method analyte must fall within
section 6.3.1.1) to compare with the single operator precision the control limits specified by the supplier of the IRM.
given in Tables 3-8 for the equivalent analyte concentration
and matrix type. Evaluate performance according to Practice 17.9 The laboratory may perform additional quality control
D5847. as desired or as required for regulatory compliance.
17.8 Independent Reference Material (IRM):
18. Keywords
17.8.1 An Independent Reference Material (IRM) shall be
analyzed at least once per quarter in order to verify the 18.1 alkali and alkaline earth cations; ammonium cation;
quantitative values produced by the test method. The analyte conductivity detection; ion chromatography; wastewater; water

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 9

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG
 D6919 − 17
SUMMARY OF CHANGES

Committee D19 has identified the location of selected changes to this standard since the last issue
(D6919 – 09) that may impact the use of this standard. (Approved June 1, 2017.)

(1) Revised 1.2.1. (3) Revised Section 17 to current format.

(2) Revised Section 3 to update and add terms.

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 Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/

&RS\ULJKWE\$670,QW O DOOULJKWVUHVHUYHG :HG)HE87& 10

'RZQORDGHGSULQWHGE\
%HONDFHP5DEHKL 6*6 SXUVXDQWWR/LFHQVH$JUHHPHQW1RIXUWKHUUHSURGXFWLRQVDXWKRUL]HG