Designation: D511 – 09

Standard Test Methods for

Calcium and Magnesium In Water1
This standard is issued under the fixed designation D511; 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.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope* D5847 Practice for Writing Quality Control Specifications

1.1 These test methods cover the determination of calcium for Standard Test Methods for Water Analysis
and magnesium in water by complexometric titration and 3. Terminology
atomic absorption spectrometric procedures. Two test methods
are included, as follows: 3.1 Definitions—For definitions of terms used in these test
Sections
methods, refer to Terminology D1129.
Test Method A—Complexometric Titration 7 to 14
Test Method B—Atomic Absorption Spectrometric 15 to 23 4. Significance and Use
1.2 The values stated in SI units are to be regarded as 4.1 Calcium and magnesium salts in water are the primary
standard. No other units of measurement are included in this components of water hardness which can cause pipe or tube
standard. scaling.
1.3 This standard does not purport to address all of the 5. Purity of Reagents
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 5.1 Reagent grade chemicals shall be used in all tests.
priate safety and health practices and determine the applica- Unless otherwise indicated, it is intended that all reagents shall
bility of regulatory limitations prior to use. Specific hazard conform to the specifications of the Committee on Analytical
statements are given in 12.2.6 and 20.6. Reagents of the American Chemical Society.3 Other grades
may be used, provided it is first ascertained that the reagent is
2. Referenced Documents of sufficiently high purity to permit its use without lessening
2.1 ASTM Standards:2 the accuracy of the determination.
D1129 Terminology Relating to Water 5.2 Purity of Water—Unless otherwise indicated, references
D1193 Specification for Reagent Water to water shall be understood to mean reagent water conforming
D2777 Practice for Determination of Precision and Bias of to Specification D1193, Type 1, II, or III water. Type I is
Applicable Test Methods of Committee D19 on Water preferred and more commonly used. Type II water was
D3370 Practices for Sampling Water from Closed Conduits specified at the time of round-robin testing of these test
D4691 Practice for Measuring Elements in Water by Flame methods.
Atomic Absorption Spectrophotometry NOTE 1—The user must ensure the type of reagent water is sufficiently
D4841 Practice for Estimation of Holding Time for Water free of interferences. The water should be analyzed using this test method.
Samples Containing Organic and Inorganic Constituents
D5810 Guide for Spiking into Aqueous Samples 6. Sampling
6.1 Collect the sample in accordance with Practices D3370.
6.2 If total recoverable calcium and magnesium concentra-
1
tions are being determined, acidify the water sample with
These test methods are under the jurisdiction of ASTM Committee D19 on
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic
HNO3 (sp gr 1.42) to a pH of 2 or less immediately at the time
Constituents in Water.
Current edition approved May 1, 2009. Published May 2009. Originally
3
approved in 1937. Last previous edition approved in 2003 as D511 – 03. DOI: Reagent Chemicals, American Chemical Society Specifications, American
10.1520/D0511-09. Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
2
For referenced ASTM standards, visit the ASTM website, [Link], or listed by the American Chemical Society, see Annual Standards for Laboratory
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.

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

Copyright. (C) ASTM International. 100 Barr Harbour Drive, P.O. Box C-700, West Conshohocken PA. United States

Copyright by ASTM Int'l (all rights reserved); 1

 D511 – 09
of collection; normally about 2 mL/L are required. The holding 9.2.1 Orthophosphate and sulfate ions interfere at concen-
time for the samples may be calculated in accordance with trations in excess of 500 and 10 000 mg/L, respectively.
Practice D4841. 9.2.2 In the presence of aluminum concentrations in excess
6.3 If dissolved calcium and magnesium concentrations are of 10 mg/L, the blue color that indicates that the end point has
being determined, filter the samples through a 0.45-µm mem- been reached will appear and then, on short standing, will
brane filter and acidify with HNO3 (sp gr 1.42) to a pH of 2 or revert to red. The reversion should not be confused with the
less immediately at time of collection; normally about 2 mL/L gradual change that normally takes place in the titrated sample
are required. several minutes after the titration has been completed.
6.4 A number of sources of calcium contamination have 9.3 In the titration of calcium, ammonium purpurate reacts
been encountered in laboratories. Among the most common are with strontium but not with magnesium or barium. However,
plastic ware, paper towels, and dust. Rinsing plastic ware with the end point in the presence of strontium is sluggish, and the
sample prior to use, avoiding contact of apparatus with paper titration is not strictly stoichiometric. Barium does not titrate as
towels, and keeping exposure to the air to a minimum will limit calcium, but affects the indicator in some unknown way so that
the possibility of contamination. no end point, or at best a poor end point, is obtained. Barium
can be removed by prior precipitation with sulfuric acid, but
TEST METHOD A—COMPLEXOMETRIC care must be exercised to prevent precipitation of calcium.
TITRATION Orthophosphate will precipitate calcium at the pH of the test.
9.4 A possible interference from the commonly used poly-
7. Scope phosphates, organic phosphonates, and EDTA/NTA com-
7.1 This test method is applicable to most waters in a range pounds in water treatment should be recognized.
from 1 to 1000 mg/L of calcium plus magnesium expressed as 10. Apparatus
calcium, but may fail in the analysis of highly colored waters,
brines, or waters that contain excessive amounts of metals. The 10.1 Titration Assembly—Some analysts prefer to use con-
upper and lower limits may be extended by either dilution or ventional lighting and hand stirring. Others report better results
use of micro apparatus. by using a visual-titration assembly consisting of a motor-
7.2 Data are not available to determine which matrices were driven stirrer, 25-mL burette, white-porcelain-base burette
used to obtain the precision and bias data, and it is the holder, and shaded incandescent lamp. The sample beaker is
responsibility of the analyst to determine the acceptability of placed near the front of the porcelain base and the reaction is
this test method for the matrix being analyzed. viewed diagonally downward through the side of the beaker
and against the white background. Illumination is from behind
the beaker. The capacity of the burette, type lighting, and
8. Summary of Test Method
background color may be varied depending on the ionic
8.1 EDTA (ethylenediamine tetraacetic acid or its salts) is concentrations normally encountered and the indicator chosen.
added to a sample containing calcium and magnesium ions 10.2 pH Meter, with expanded mV scale.
after the pH of the solution is adjusted to 10 for the determi-
nation of calcium and magnesium or from pH 12 to 13 for the 11. Reagents
determination of calcium alone. The EDTA initially complexes 11.1 Buffer Solution, Ammonium Chloride-Ammonium
the calcium and then the magnesium. The end point is observed Hydroxide—Dissolve 67.6 g of ammonium chloride (NH4Cl)
by the use of a suitable indicator. At a pH of 12 to 13 in 200 mL of water. Add 570 mL of concentrated ammonium
magnesium is precipitated. Magnesium is determined by the hydroxide (NH4OH, sp gr 0.900). Add 5.00 g of magnesium
difference between an aliquot titrated at pH 10 and one titrated salt of EDTA and dilute to 1000 mL. Store in a tightly
at pH 12 to 13. stoppered plastic bottle to prevent the loss of ammonia.
Discard the solution when 1 mL added to a neutralized sample
9. Interferences fails to produce a pH of 10.0 6 0.1 at the titration end point.
9.1 EDTA reacts with iron, manganese, copper, zinc, lead, To attain highest accuracy, adjust the magnesium level to exact
cobalt, nickel, barium, strontium, calcium, magnesium, and equivalence through the appropriate addition of a small amount
several other metals. The interference of heavy metals is of either disodium EDTA or magnesium sulfate (MgSO4).
minimized by the addition of hydroxylamine and cyanide, 11.2 Calcium Indicator Solution:
which reduce or complex the metals, or both. Metal concen- 11.2.1 Ammonium Purpurate—Mix thoroughly 1.0 g of
trations as high as 5 mg/L of iron, 10 mg/L of manganese, 10 ammonium purpurate with 200 g of sucrose. Place in a bottle
mg/L of copper, 10 mg/L of zinc, and 10 mg/L of lead can be provided with a dispensing spoon of 0.2-g capacity.
tolerated when hydroxylamine and cyanide are added. 11.2.2 Fluorescein Methylene Iminodiacetic Acid 4—Grind
9.2 In the titration of calcium plus magnesium, the higher 0.2 g of fluorescein methylene iminodiacetic acid and 0.12 g of
oxidation states of manganese above Mn+2 react rapidly with thymolphthalein with 20 g of potassium chloride to 40 to 50
the indicator to form discolored oxidation products. Hydroxy- mesh size. Place in a bottle provided with a dispensing spoon
lamine hydrochloride reagent is used to reduce manganese to of 0.2-g capacity.
the divalent state. The divalent manganese interference can be
eliminated by addition of one or two small crystals of potas- 4
Calcein, W., Fluoroscein Complexon, and Fluorexon, supplied by various
sium ferrocyanide. commercial firms, have been found satisfactory for this purpose.

Copyright by ASTM Int'l (all rights reserved); 2

 D511 – 09
11.3 Calcium Solution, Standard (1.00 mL = 0.400 mg 100-mL volumetric flasks. Wash the paper two or three times
calcium)—Suspend 1.000 g of calcium carbonate (CaCO3), with water and bring to the volume.
dried at 180°C for 1.0 h before weighing, in approximately 600 12.1.5 Measure 50 mL of the filtered sample (50.00-mL
mL of water and dissolve cautiously with a minimum of dilute maximum) into a 150-mL beaker and adjust the volume to
HCl. Dilute to 1000 mL with water in a volumetric flask. approximately 50 mL. Adjust the pH to 7 to 10 by the dropwise
11.3.1 Alternatively, certified calcium stock solutions are addition of ammonium hydroxide (NH4OH, sp gr 0.900).
commercially available through chemical supply vendors and
NOTE 5—For analysis of brines an appropriate aliquot size often can be
may be used. determined from knowledge of the specific gravity, for example:
11.4 Chrome Black T Solution (4.0 g/L)—Dissolve 0.4 g of 1.000 to 1.025, use 25 mL
Chrome Black T in 100 mL of water. This solution has a shelf 1.025 to 1.050, use 10 mL
life of approximately 1 week. Alternatively, a dry powder 1.050 to 1.090, use 5 mL
1.090 to 1.120, use 1 mL
mixture composed of 0.5 g of dye and 100 g of powdered 1.120 to 1.180, use 0.1 mL
sodium chloride may be used. Store this in a dark-colored
12.1.6 Insert the beaker in the titration assembly and start
bottle provided with a dispensing spoon of approximately 0.2-g
the stirrer.
capacity. The shelf life is at least 1 year.
12.1.7 Add 1 mL of NH2OH·HCl solution (11.6).
NOTE 2—Chrome Black T is also known as Eriochrome Black T. 12.1.8 Add 1 mL of buffer solution (11.1). Measure the pH
11.5 EDTA Solution, Standard (0.01 M, 1 mL = 0.401 mg and verify that it falls in the pH range from 10.0 + 0.1. Adjust
calcium or 0.243 mg manganese)—Dissolve 3.72 g of by the dropwise addition of ammonium hydroxide.
Na2EDTA dihydrate, which has been dried overnight over 12.1.9 Add 2 mL of NaCN solution (11.8) Warning:
H2SO4 in a desiccator, in water (or at 80°C. for 1 hour) and Sodium cyanide is a deadly poison. Do not add NaCN to any
dilute to 1000 mL in a volumetric flask. The reagent is stable acid solution or acidify any solution containing it. Use this
for several weeks. Check the titer of the reagent by titrating reagent in a fume hood.
25.00 mL of CaCO3 standard solution as described in the 12.1.10 If manganese is present, add one or two small
procedure for sample analysis. crystals K4Fe(CN)6·3H2O (11.7).
11.6 Hydroxylamine Hydrochloride Solution (30 g/L)— 12.1.11 Add 4 to 5 drops of Chrome Black T indicator
Dissolve 30 g of hydroxylamine hydrochloride (NH2OH·HCl) solution (11.4). If powdered indicator is used add approxi-
in water and dilute to 1000 mL. mately 0.2 g.
11.7 Potassium Ferrocyanide—(K4Fe(CN)6·3H2O). 12.1.12 Titrate with standard EDTA solution (11.5) until
11.8 Sodium Cyanide Solution (25 g/L)—Dissolve 25 g of blue or purple swirls begin to show. The end point is reached
sodium cyanide (NaCN) in water and dilute to 1000 mL. when all traces of red and purple have disappeared and the
Warning: Sodium cyanide is a deadly poison. Do not add solution is pure blue in color. The titration should be completed
NaCN to any acid solution or acidify any solution containing it. within 5 min of the buffer addition. If more than 15 mL of
Use this reagent in a fume hood. titrant is required, take a smaller sample aliquot and repeat the
11.9 Sodium Hydroxide Solution (80 g/L or 2 M)—Dissolve test.
80 g of sodium hydroxide (NaOH) in 800 mL of water. Cool 12.1.13 Record the volume of EDTA solution required to
and dilute to 1000 mL. titrate calcium plus magnesium.
11.9.1 Alternatively, a commercially prepared solution of 12.1.14 Determine a reagent blank correction by similarly
sodium hydroxide is available through chemical supply ven- titrating 50 mL of water including all added reagents.
dors and may be used. 12.2 Calcium:
12.2.1 Refill the burette with EDTA standard solution
12. Procedure (11.5).
12.2.2 Pipette another aliquot of the same sample (50.00 mL
12.1 Calcium Plus Magnesium: maximum) into a 150-mL beaker and adjust the volume to
12.1.1 Measure 100.0 mL of a well-mixed acidified sample approximately 50 mL (see Note 5).
(see 6.2) into a 125-mL beaker or flask. 12.2.3 Insert the beaker in the titration assembly and start
NOTE 3—If only dissolved calcium plus magnesium is to be deter- the stirrer.
mined, omit 12.1.1 through 12.1.4 and proceed to 12.1.5. 12.2.4 Add 1 mL of NH2OH·HCl (11.6).
12.1.2 Add 5 mL of hydrochloric acid (HCl, sp gr 1.19) to 12.2.5 Add 1 mL of NaOH solution (11.9). The pH should
each sample. range from 12 to 13.
12.1.3 Heat the samples on a steambath or hot plate until the 12.2.6 Add 1 mL of NaCN (11.8) Warning: Sodium cya-
volume has been reduced to 15 to 20 mL, making certain that nide is a deadly poison. Do not add NaCN to any acid solution
the samples do not boil. or acidify any solution containing it. Use this reagent in a fume
hood.
NOTE 4—For samples with high levels of dissolved or suspended 12.2.7 Add 0.2 g of calcium indicator solution (11.2) and
matter, the amount of reduction in volume is left to the discretion of the proceed immediately with the titration.
analyst.
12.2.8 Titrate with standard EDTA solution (11.5) to the
12.1.4 Cool and filter the samples through a suitable filter appropriate end point. If ammonium purpurate is used, the end
(such as fine-textured, acid-washed, ashless paper) into point will be indicated by color change from orange pink to

Copyright by ASTM Int'l (all rights reserved); 3

 D511 – 09
pale pinkish purple. If fluorescein methylene iminodiacetic Statistically Sig-
acid is used, the end point will be indicated by a color change Amount Amount nificant, 95 %
Added, Found, Bias, Confidence
from deep green to purple. The titration should be completed mg/L mg/L % Level
within 5 min of the addition of NaOH solution. If more than 15 13.3 13.5 +1.5 no
mL of titrant is required, take a smaller sample aliquot and 41.8 43.0 +2.9 yes
84.6 87.7 +3.7 yes
repeat the test.
12.2.9 Record the volume of EDTA solution required to 14.4 This information was derived from round-robin testing
titrate the calcium. in which four laboratories, including eight operators, partici-
12.2.10 Determine a reagent blank correction by similarly pated. No data were rejected. Four sample levels were run on
titrating 50 mL of water including all added reagents. each of three days, but one level was rejected as having grossly
deteriorated in shipment. The method of “least squares” was
13. Calculation used to determine the precision statements.
13.1 Calculate the concentration of calcium and magnesium 14.5 The precision of this test method for magnesium
in milligrams per litre using Eq 1 and Eq 2: ranging in magnesium concentration from between 2.5 and 36
Calcium, mg/L 5 ~A 3 B/D! 3 40 100 (1)
mg/L may be expressed using Eq 8 and Eq 9:
ST 5 0.017 X 1 0.85 (8)
Magnesium, mg/L 5 ~~C 3 B/E! 2 ~A 3 B/D!! 3 24 300 (2)
SO 5 0.002 X 1 0.70 (9)
where:
A = EDTA standard solution required to titrate calcium in where:
12.2.9 minus the blank correction determined in ST = overall precision,
12.2.10, mL, SO = single-operator precision, and
B = molarity of EDTA standard solution, X = determined concentration of magnesium, mg/L.
C = EDTA standard solution required to titrate calcium 14.6 Bias—Recoveries of known amounts of magnesium
plus magnesium in 12.1.13 minus the blank correction using this test method were as follows:
determined in 12.1.14, mL, Amount Amount Statistically Signifi-
D = sample taken in 12.2.2, mL, and Added, Found, Bias, cant, 95 % Confi-
mg/L mg/L % dence Level
E = sample taken in 12.1.5, mL. 2.38 2.54 +6.7 no
13.2 If the concentration of strontium is determined to be 14.7 15.0 +2.0 no
significant (see Sections 9.1 and 9.3), make a correction for 22.2 21.8 −1.8 no
35.9 36.1 +0.6 no
strontium concentration using Eq 3:
Corrected mg/L calcium 5 mg/L calcium
14.7 This information was derived from round-robin testing
2 ~mg/L strontium 3 0.46! (3) in which four laboratories, including eight operators, partici-
pated. No data were rejected. Four sample levels were run on
13.3 Results for calcium and magnesium may be repre-
each of three days. The method of “least squares” was used to
sented as CaCO3 using Eq 4 and Eq 5:
determine the precision statements.
Calcium ~as CaCO3!, mg/L 5 mg/L Ca 3 2.50 (4) 14.8 The single-operator precision for calcium determined
for synthetic sodium chloride brines having the composition
Magnesium ~as CaCO3!, mg/L 5 mg/L Mg 3 4.12 (5) listed in Table 1 is as follows:
14. Precision and Bias 5 SO 5 76

14.1 Data are not available to determine which matrices

For magnesium, it is:
were used to obtain precision and bias data.
14.2 The precision of this test method for calcium, ranging SO 5 51
in calcium concentration between 13 and 88 mg/L, may be
expressed using Eq 6 and Eq 7: 14.9 These data may not apply to waters of other matrices.
ST 5 0.006 X 1 0.62 (6) 14.10 Four independent laboratories participated in the
round-robin study.
14.11 This section of precision and bias conforms to Prac-
SO 5 0.006 X 1 0.51 (7)
tice D2777 – 77, which was in place at the time of collabora-
where: tive testing. Under the allowances made in 1.4 of D2777 – 06,
ST = overall precision,
TABLE 1 Composition of Synthetic Sodium Chloride
SO = single-operator precision, and
X = determined concentration of calcium, mg/L. Compo- Brine Test Solutions
nent (All Concentrations, mg/L)
14.3 Bias—Recoveries of known amounts of calcium using
this test method were as follows: NaCl 30 000 50 000 100 000 150 000
Ba 1 000 1 000 1 000 1 000
Sr 1 000 1 000 1 000 1 000
Mg 1 200 5 000 7 000 10 000
5
Supporting data have been filed at ASTM International Headquarters and may Ca 2 500 12 000 15 000 25 000
be obtained by requesting Research Report D19-1027.

Copyright by ASTM Int'l (all rights reserved); 4

 D511 – 09
these precision and bias data do meet existing requirements of contamination at or above this level, or the results must be
interlaboratory studies of Committee D19 test methods. qualified with an indication that they do not fall within the
performance criteria of the test method.
15. Quality Control
15.6 Matrix Spike (MS)
15.1 In order to be certain that analytical values obtained 15.6.1 To check for interferences in the specific matrix
using these test methods are valid and accurate within the being tested, perform an MS on at least one sample from each
confidence limits of the test, the following QC procedures must batch by spiking an aliquot of the sample with a known
be followed when analyzing calcium and magnesium in water. concentration of calcium and magnesium in water and taking it
15.2 Calibration and Calibration Verification through the analytical method.
15.2.1 Standardize the titrating solution against the standard 15.6.2 The spike concentration plus the background concen-
EDTA (11.5) solution. tration of calcium and magnesium in water must not exceed the
15.2.2 Verify titrating solution by analyzing a sample with a high calibration standard. The spike must produce a concen-
known amounts of calcium and magnesium. The amounts of tration in the spiked sample that is two to five times the analyte
the sample should fall within 615 % of the known concentra- concentration in the unspiked sample, or 10 to 50 times the
tions. detection limit of the test method, whichever is greater.
15.2.3 If standardization cannot be verified, restandardize 15.6.3 Calculate the percent recovery of the spike (P) using
the solution. the following formula:
15.3 Initial Demonstration of Laboratory Capability
15.3.1 If a laboratory has not performed the test before, or if 100 [A~Vs 1 V! – BVs#
P5 CV (10)
there has been a major change in the measurement system, for
example, a new analyst, new instrument, and so forth, a where:
precision and bias study must be performed to demonstrate A = analyte concentration (mg/L) in spiked sample
laboratory capability. B = analyte concentration (mg/L) in unspiked sample
15.3.2 Analyze seven replicates of a standard solution C = concentration (mg/L) of analyte in spiking solution
prepared from an Independent Reference Material containing a Vs = volume (mL) of sample used
mid-range concentration of calcium and magnesium in water. V = volume (mL) of spiking solution added.
The matrix and chemistry of the solution should be equivalent 15.6.4 The percent recovery of the spike should fall within
to the solution used in the collaborative study. Each replicate the limits, based on the analyte concentration, listed in Guide
must be taken through the complete analytical test method D5810, Table 1. If the percent recovery is not within these
including any sample preservation and pretreatment steps. limits, a matrix interference may be present in the sample
15.3.3 Calculate the mean and standard deviation of the selected for spiking. Under these circumstances, one of the
seven values and compare to the acceptable ranges of bias in following remedies must be employed: the matrix interference
Table 2. If a concentration other than the recommended must be removed, all samples in the batch must be analyzed by
concentration is used, refer to Practice D5847 for information a test method not affected by the matrix interference, or the
on applying the F test and t test in evaluating the acceptability results must be qualified with an indication that they do not fall
of the mean and standard deviation. within the performance criteria of the guide.
15.4 Laboratory Control Sample (LCS)
NOTE 6—Acceptable spike recoveries are dependent on the concentra-
15.4.1 To ensure that the test method is in control, analyze tion of the component of interest. See Guide D5810 for additional
an LCS containing a known concentration of calcium and information.
magnesium in water with each batch or ten samples. If large
numbers of samples are analyzed in the batch, analyze the LCS 15.7 Duplicate
after every ten samples. The laboratory control samples for a 15.7.1 To check the precision of sample analyses, analyze a
large batch should cover the analytical ranger when possible. sample in duplicate with each batch. If the concentration of the
The LCS must be taken through all of the steps of the analytical analyte is less than five times the detection limit for the analyte,
method including sample preservation and pretreatment. The a matrix spike duplicate (MSD) should be used.
result obtained for a mid-range LCS should fall within 615 % 15.7.2 Calculate the standard deviation of the duplicate
of the known concentration. values and compare to the precision in the collaborative study
15.4.2 If the result is not within these limits, analysis of using an F test. Refer to 6.4.4 of Practice D5847 for informa-
samples is halted until the problem is corrected, and either all tion on applying the F test.
the samples in the batch must be reanalyzed, or the results must 15.7.3 If the result exceeds the precision limit, the batch
be qualified with an indication that they do not fall within the must be reanalyzed or the results must be qualified with an
performance criteria of the test method. indication that they do not fall within the performance criteria
15.5 Method Blank of the test method.
15.5.1 Analyze a reagent water test blank with each batch. 15.8 Independent Reference Material (IRM)
The concentration of calcium and magnesium in water found in 15.8.1 In order to verify the quantitative value produced by
the blank should be less than 0.5 times the lowest calibration the test method, analyze an Independent Reference Material
standard. If the concentration of calcium and magnesium in (IRM) submitted as a regular sample (if practical) to the
water is found above this level, analysis of samples is halted laboratory at least once per quarter. The concentration of the
until the contamination is eliminated, and a blank shows no IRM should be in the concentration mid-range for the method

Copyright by ASTM Int'l (all rights reserved); 5

 D511 – 09
chosen. The value obtained should fall within the control limits 20.2 Lanthanum Solution (5 % La)—Wet 58.7 g of lantha-
established by the laboratory. num oxide (La2O3) with water. Add slowly 250 mL of HCl (sp
gr 1.19) to the mixture. When dissolved, dilute to 1 L with
TEST METHOD B—ATOMIC ABSORPTION water.
SPECTROPHOTOMETRIC 20.3 Magnesium Solution, Standard (1 mL = 1.0 mg Mg)—
16. Scope Obtain commercially, or dissolve 1.000 g of magnesium ribbon
in a minimum of HCl (1 + 1), and dilute to 1 L with HCl
16.1 This test method can be used to determine the concen- (1 + 99).
tration of calcium and magnesium in water. The determination 20.4 Potassium Solution (2 % K)—Dissolve 38.1 g of po-
of these ions in brackish water, sea water, and brines requires tassium chloride (KCl) in water and dilute to 1 L.
the use of the method of additions described in Section 22. 20.5 Oxidant:
16.2 This test method is applicable for calcium concentra- 20.5.1 Air, which has been cleaned and dried through a
tions in the range from 1.0 to 15 mg/L and magnesium suitable filter to remove oil, water, and other foreign sub-
concentrations from 0.25 to 3.5 mg/L. The upper limits can be stances, is the usual oxidant.
increased to 1500 mg/L calcium and 350 mg/L magnesium by 20.5.2 Nitrous Oxide, medical grade is satisfactory.
proper single dilution technique. Serial dilution technique 20.6 Fuel: Acetylene—Standard, commercially available
should be used to further extend the limit. acetylene is the usual fuel. Acetone, always present in acety-
16.3 The precision and bias were obtained on reagent water lene cylinders, can be prevented from entering and damaging
(1 % HCl). It is the responsibility of the analyst to determine the burner system by replacing a cylinder which has only 50
the acceptability of this test method when analyzing untested psig (345 kPa) of acetylene remaining. Warning: Purified
matrices. grade acetylene containing a special proprietary solvent rather
17. Summary of Test Method than acetone should not be used with poly(vinyl chloride)
tubing as weakening of the tubing walls can cause a hazardous
17.1 Calcium and magnesium are determined by atomic situation.
absorption spectrophotometry. The sample is aspirated follow-
ing dilution and addition of interference-suppressing solution. 21. Calibration
18. Interferences 21.1 Prepare at least four standard solutions containing 1 %
La if the air-acetylene-flame is used, or 0.2 % K if the nitrous
18.1 Calcium and magnesium are subject to phosphate and oxide flame is used, to bracket the expected calcium or
aluminum interference, respectively. The addition of lantha- magnesium concentration range. Make all dilutions with HCl
num in the procedure eliminates the interference effect of up to (1+99). Prepare the standards each time the test is to be
600 mg/L of phosphate and 100 mg/L of aluminum. The use of performed and select concentrations to give zero, middle, and
a nitrous oxide-acetylene flame has been reported to remove maximum points for the analytical curve.
chemical interferences completely when used with the addition 21.2 Set the wavelength of the instrument to 422.7 nm for
of potassium to control ionization interference. calcium or 285.2 nm for magnesium by atomizing a standard
19. Apparatus (see Note 7).
21.3 Atomize standards and record the instrument readings
19.1 Atomic Absorption Spectrophotometer for use at 422.7 in absorbance units. Atomize water between each standard.
nm and 285.2 nm for calcium and magnesium, respectively. A 21.4 Prepare an analytical curve by plotting on linear graph
general guide for the use of flame absorption applications is paper the absorbance versus concentration for each standard, or
given in Practice D4691. calculate a standard curve. Alternatively, read concentration
NOTE 7—The manufacturer’s instructions should be followed for all directly if provided on instrument.
instrumental parameters. Wavelengths other than 422.7 mm and 285.2 mm
may be used for calcium and magnesium, respectively, if they have been 22. Procedure
determined to be equally suitable. 22.1 If total calcium and magnesium are to be determined,
19.1.1 Calcium, Hollow-Cathode Lamp. prepare the sample as directed in 12.1.1 through 12.1.4.
19.1.2 Magnesium, Hollow-Cathode Lamp. 22.2 Prepare sample dilutions and add lanthanum solution
19.1.3 Multielement, Hollow-Cathode Lamps. (5 % La) so that the final concentration of lanthanum in the
19.2 For suggested oxidant and fuel used for atomic absorp- sample is 1 %. For example, using a 50-mL volumetric flask,
tion spectrophotometry, see 20.5 and 20.6. add 10 mL of lanthanum solution (5 % La), sample aliquot, and
19.3 Pressure-Reducing Valves—The supplies of fuel and make to volume with HCl (1 + 99). If the nitrous oxide flame
oxidant shall be maintained at pressures somewhat higher than is used, omit lanthanum and add potassium solution (2 % K) to
the controlled operating pressure of the instrument by suitable yield a final concentration of potassium of 0.2 %.
valves. 22.2.1 Method of Additions—For high solids solutions such
as sea water or brines, prepare three volumetric flasks, each
20. Reagents and Materials containing a sample aliquot that will yield approximately 1
20.1 Calcium Solution, Standard (1 mL = 0.1 mg Ca)— mg/L calcium after dilution. To each add lanthanum solution
Dilute 250 mL of calcium standard solution (see 11.3) to 1 L (5 % La) to yield a final concentration of 1 % La (if the nitrous
with HCl (1+99). oxide flame is used, omit lanthanum and add potassium

Copyright by ASTM Int'l (all rights reserved); 6

 D511 – 09
solution to yield a final concentration of 0.2 % K), add calcium Amount Amount Statistically Sig-
standard solution to yield 0, 1, and 2 mg/L in the final dilution. Added, Found, nificant, 95 %
mg/L mg/L Bias, % Confidence Level
22.2.2 For the magnesium determination prepare three volu- 1.20 1.21 +0.83 no
metric flasks with sample aliquots to give about 0.1 mg/L 3.00 3.02 +0.67 no
magnesium, lanthanum solution (5 % La) to give 1 % La (if the 5.00 5.02 +0.40 no
15.0 14.8 −1.33 no
nitrous oxide flame is used, omit lanthanum and add potassium
solution to yield a final concentration of 0.2 % K) and 24.4 Bias—Recoveries of known amounts of magnesium
magnesium standard solution to give final concentrations of 0, using this test method were as follows:
0.1, and 0.2 mg/L of magnesium. Amount Amount Statistically Signifi-
22.3 Atomize the samples and record absorbance readings Added, Found, cant, 95 % Confi-
mg/L mg/L Bias, % dence Level
for each. Atomize water between each sample. 0.26 0.23 −11.5 yes
0.52 0.52 0 no
23. Calculation 1.10 0.99 −10.0 yes
3.20 3.18 −0.63 no
23.1 Calculate the concentration of calcium or magnesium
in each sample in milligrams per litre obtained from 21.4 and 24.5 This information was derived from round-robin testing
multiply by the dilution factor. in which seven laboratories, including eight operators, partici-
23.2 For sea water and brine samples using the method of pated. Of eight data sets ranked as described in Practice D2777,
additions and assuming a straight line analytical curve for the one was rejected as an outlier. Four sample levels were run on
range of sample dilutions, calculate the concentration of each of three days. The method of “least squares” was used to
calcium or magnesium in the diluted sample in milligrams per determine the precision statements.
litre using Eq 11: 24.6 The single-operator precision for calcium determined
on synthetic sodium chloride brines having the composition
Calcium or magnesium, mg/L 5 A 3 Cstd/~Astd 2 A! (11)
given in Table 1 is:
where: SO 5 253 mg/L
A = absorbance of sample,
Astd = absorbance of one of the standard additions, and For magnesium it is:
Cstd = concentration of the same standard addition as Astd, SO 5 31 mg/L
mg/L. 24.7 These data may not apply to waters of other matrices.
Since there are two standard additions, the calculation is 24.8 This section on precision and bias conforms to Practice
made for each and the two results averaged. The concentration D2777 – 77, which was in place at the time of collaborative
of the original water or brine is obtained by multiplying the testing. Under the allowances made in 1.4 of D2777 – 06, these
concentration of the diluted sample by the dilution factor. precision and bias data do meet existing requirements of
interlaboratory studies of Committee D19 test methods.
24. Precision and Bias
24.1 The precision and bias were obtained on reagent water 25. Quality Control
(1 % HCl). It is the responsibility of the analyst to determine
25.1 In order to be certain that analytical values obtained
the acceptability of this method for other matrices.
using these test methods are valid and accurate within the
24.2 The overall and single-operator precision for calcium
confidence limits of the test, the following QC procedures must
are as in Eq 12 and Eq 13:
be followed when analyzing calcium and magnesium in water.
ST 5 0.036 X 1 0.03 (12) 25.2 Calibration and Calibration Verification
25.2.1 Analyze at least four working standards containing
SO 5 0.002 X 1 0.04 (13) concentrations of calcium and magnesium in water that bracket
For magnesium they are as in Eq 14 and Eq 15: the expected sample concentration, prior to analysis of
ST 5 0.078 X 1 0.03 (14) samples, to calibrate the instrument. The calibration correlation
coefficient should be equal to or greater than 0.990. In addition
SO 5 20.001 X 1 0.01 (15)
to the initial calibration blank, a calibration blank shall be
where: analyzed at the end of the batch run to ensure contamination
ST = overall precision, mg/L, was not a problem during the batch analysis.
SO = single-operator precision, mg/L, and 25.2.2 Verify instrument calibration after standardization by
X = concentration of calcium or magnesium determined, analyzing a standard at the concentration of one of the
mg/L. calibration standards. The concentration of a mid-range stan-
NOTE 8—The precision data were obtained using the air-acetylene dard should fall within 615 % of the known concentration.
flame with lanthanum solution addition. The nitrous oxide-acetylene flame 25.2.3 If calibration cannot be verified, recalibrate the
with potassium solution addition provides more positive interference instrument.
removal and is reported to provide equivalent sensitivity. 25.3 Initial Demonstration of Laboratory Capability
24.3 Bias—Recoveries of known amounts of calcium using 25.3.1 If a laboratory has not performed the test before, or if
this test method were as follows: there has been a major change in the measurement system, for

Copyright by ASTM Int'l (all rights reserved); 7

 D511 – 09
example, a new analyst, new instrument, and so forth, a concentration in the unspiked sample, or 10 to 50 times the
precision and bias study must be performed to demonstrate detection limit of the test method, whichever is greater.
laboratory capability. 25.6.3 Calculate the percent recovery of the spike (P) using
25.3.2 Analyze seven replicates of a standard solution the following formula:
prepared from an Independent Reference Material containing a 100 [A~Vs 1 V! – BVs#
mid-range concentration of calcium and magnesium in water. P5 CV (16)
The matrix and chemistry of the solution should be equivalent
where:
to the solution used in the collaborative study. Each replicate
must be taken through the complete analytical test method
including any sample preservation and pretreatment steps. A = Analyte Concentration (mg/L) in Spiked Sample
25.3.3 Calculate the mean and standard deviation of the B = Analyte Concentration (mg/L) in Unspiked Sample
seven values and compare to the acceptable ranges of bias in C = Concentration (mg/L) of Analyte in Spiking Solution
Table 2. If a concentration other than the recommended Vs = Volume (mL) of Sample Used
concentration is used, refer to Practice D5847 for information V = Volume (mL) of spiking solution added
on applying the F test and t test in evaluating the acceptability 25.6.4 The percent recovery of the spike should fall within
of the mean and standard deviation. the limits, based on the analyte concentration, listed in Guide
25.4 Laboratory Control Sample (LCS) D5810, Table 1. If the percent recovery is not within these
25.4.1 To ensure that the test method is in control, analyze limits, a matrix interference may be present in the sample
an LCS containing a known concentration of calcium and selected for spiking. Under these circumstances, one of the
magnesium in water with each batch or 10 samples. If large following remedies must be employed: the matrix interference
numbers of samples are analyzed in the batch, analyze the LCS must be removed, all samples in the batch must be analyzed by
after every 10 samples. The laboratory control samples for a a test method not affected by the matrix interference, or the
large batch should cover the analytical ranger when possible. results must be qualified with an indication that they do not fall
The LCS must be taken through all of the steps of the analytical within the performance criteria of the guide.
method including sample preservation and pretreatment. The NOTE 9—Acceptable spike recoveries are dependent on the concentra-
result obtained for a mid-range LCS should fall within 615 % tion of the component of interest. See Guide D5810 for additional
of the known concentration. information.
25.4.2 If the result is not within these limits, analysis of 25.7 Duplicate
samples is halted until the problem is corrected, and either all 25.7.1 To check the precision of sample analyses, analyze a
the samples in the batch must be reanalyzed, or the results must sample in duplicate with each batch. If the concentration of the
be qualified with an indication that they do not fall within the analyte is less than five times the detection limit for the analyte,
performance criteria of the test method. a matrix spike duplicate (MSD) should be used.
25.5 Method Blank 25.7.2 Calculate the standard deviation of the duplicate
25.5.1 Analyze a reagent water test blank with each batch. values and compare to the precision in the collaborative study
The concentration of calcium and magnesium in water found in using an F test. Refer to 6.4.4 of Practice D5847 for informa-
the blank should be less than 0.5 times the lowest calibration tion on applying the F test.
standard. If the concentration of calcium and magnesium in 25.7.3 If the result exceeds the precision limit, the batch
water is found above this level, analysis of samples is halted must be reanalyzed or the results must be qualified with an
until the contamination is eliminated, and a blank shows no indication that they do not fall within the performance criteria
contamination at or above this level, or the results must be of the test method.
qualified with an indication that they do not fall within the 25.8 Independent Reference Material (IRM)
performance criteria of the test method. 25.8.1 In order to verify the quantitative value produced by
25.6 Matrix Spike (MS) the test method, analyze an Independent Reference Material
25.6.1 To check for interferences in the specific matrix (IRM) submitted as a regular sample (if practical) to the
being tested, perform an MS on at least one sample from each laboratory at least once per quarter. The concentration of the
batch by spiking an aliquot of the sample with a known IRM should be in the concentration mid-range for the method
concentration of calcium and magnesium in water and taking it chosen. The value obtained should fall within the control limits
through the analytical method. established by the laboratory.
25.6.2 The spike concentration plus the background concen-
tration of calcium and magnesium in water must not exceed the 26. Keywords
high calibration standard. The spike must produce a concen- 26.1 atomic absorption; calcium; complexometric; magne-
tration in the spiked sample that is two to five times the analyte sium; spectrophotometry; titration; water

Copyright by ASTM Int'l (all rights reserved); 8

 D511 – 09
SUMMARY OF CHANGES

Committee D19 has identified the location of selected changes to this standard since the last issue (D511 – 03)
that may impact the use of this standard. (Approved May 1, 2009.)

(1) Section 15.2 was modified to state that the method is a (3) Section 10.2 was added to describe the pH meter used.
titration. (4) Section 11 was modified to allow for reagent clarification.
(2) Sections 15.3.2 and 15.6.3 were modified. (5) Reagent references were added to Section 12.

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@[Link] (e-mail); or through the ASTM website
([Link]).

Copyright by ASTM Int'l (all rights reserved); 9