An American National Standard

Designation: D 1068 – 05e1

Standard Test Methods for

Iron in Water1
This standard is issued under the fixed designation D 1068; 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 (e) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.

e1 NOTE—Warning notes were moved into the text editorially in July 2005.

1. Scope and Steam in Closed Conduits3

1.1 These test methods cover the determination of iron in D 1193 Specification for Reagent Water
water. Procedures are given for determining total iron, dis- D 1687 Test Methods for Chromium in Water
solved iron, and ferrous iron. Undissolved iron may be D 1688 Test Methods for Copper in Water
calculated from the total iron and dissolved iron determina- D 1691 Test Methods for Zinc in Water
tions. The test methods are given as follows: D 1886 Test Methods for Nickel in Water
Range Sections
D 2777 Practice for Determination of Precision and Bias of
Test Method A—Atomic Absorption, 0.1 to 5.0 mg/L 7 to 15 Applicable Methods of Committee D-19 on Water
Direct D 3370 Practices for Sampling Water from Closed Conduits
Test Method C—Atomic Absorption, 5 to 100 µg/L 16 to 24
Graphite Furnace
D 3558 Test Methods for Cobalt in Water
Test Method D—Photometric 40 to 1000 µg/L 25 to 36 D 3559 Test Methods for Lead in Water
Bathophenanthrolineµ g/L D 3919 Practice for Measuring Trace Elements in Water by
1.2 It is the user’s responsibility to ensure the validity of Graphite Furnace Atomic Absorption Spectrophotometry
these test methods to waters of untested matrices. D 4841 Practice for Estimation of Holding Time for Water
1.3 This standard does not purport to address all of the Samples Containing Organic and Inorganic Constituents
safety concerns, if any, associated with its use. It is the D 5810 Guide for Spiking into Aqueous Samples
responsibility of the user of this standard to establish appro- D 5847 Practice for the Writing Quality Control Specifica-
priate safety and health practices and determine the applica- tions for Standard Test Methods for Water Analysis
bility of regulatory limitations prior to use. Specific hazards E 60 Practice for Analysis of Metals, Ores, and Related
statements are given in Note 3, section 11.7.1, and section Materials by Molecular Absorption Spectrometry
X1.1.2. E 275 Practice for Describing and Measuring Performance
1.4 Two former photometric test methods were discontin- of Ultraviolet, Visible, and Near Infrared Spectrophotom-
ued. See Appendix X2 for historical information. eters

2. Referenced Documents 3. Terminology

2.1 ASTM Standards: 2 3.1 Definitions: For definitions of terms used in these test
D 858 Test Methods for Manganese in Water methods, refer to Terminology D 1129.
D 1066 Practice for Sampling Steam 3.2 Definitions of Terms Specific to This Standard:
D 1129 Terminology Relating to Water 3.2.1 total recoverable iron—an arbitrary analytical term
D 1192 Specification for Equipment for Sampling Water relating to the recoverable forms of iron that are determinable
by the digestion method which is included in these test
methods.

1
4. Significance and Use
These test methods are under the jurisdiction of ASTM Committee D19 on
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic 4.1 Iron is the second most abundant metallic element in the
Constituents in Water. earth’s crust and is essential in the metabolism of plants and
Current edition approved June 1, 2005. Published July 2005. Originally approved
in 1949. Last previous edition approved in 2003 as D 1068 – 03.
animals. If presented in excessive amounts, however, it forms
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
3
the ASTM website. Withdrawn.

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 D 1068 – 05e1
oxyhydroxide precipitates that stain laundry and porcelain. As user’s responsibility to ensure the validity of this test method
a result, the recommended limit for iron in domestic water for waters of untested matrices.
supplies is 0.3 mg/L. These test methods are useful for
determining iron in many natural waters. 8. Summary of Test Method
8.1 Iron is determined by atomic absorption spectrophotom-
5. Purity of Reagents etry. Dissolved iron is determined by atomizing the filtered
5.1 Reagent grade chemicals shall be used in all tests. sample directly with no pretreatment. Total recoverable iron is
Unless otherwise indicated, it is intended that all reagents shall determined by atomizing the sample following hydrochloric-
conform to the specifications of the Committee on Analytical nitric acid digestion and filtration. The same digestion proce-
Reagents of the American Chemical Society, where such dure may be used to determine total recoverable nickel (Test
specifications are available. 4 Other grades may be used, Methods D 1886), chromium (Test Methods D 1687), cobalt
provided it is first ascertained that the reagent is of sufficiently (Test Methods D 3558), copper (Test Methods D 1688), lead
high purity to permit its use without lessening the accuracy of (Test Methods D 3559), manganese (Test Methods D 858), and
the determination. zinc (Test Methods D 1691).
--`,,``,`-`-`,,`,,`,`,,`---

5.2 Purity of Water—Unless otherwise indicated, references

to water shall be understood to mean reagent water conforming 9. Interferences
to Specification D 1193, Type I. Other reagent water types may 9.1 Sodium, potassium, barium, chloride and sulfate (5000
be used, provided it is first ascertained that the water is of mg/L each), calcium, magnesium, chromium, manganese,
sufficiently high purity to permit its use without adversely cobalt, nickel, copper, zinc, palladium, silver, cadmium, tin,
affecting the bias and precision of the test method. Type II lead, lithium, mercury, selenium, aluminum, antimony, arsenic,
water was specified at the time of round-robin testing of these vanadium, boron, and molybdenum (100 mg/L) do not inter-
test methods. In addition, water used in preparing solutions for fere.
the determination of ferrous iron shall be freshly boiled and 9.2 Background correction (or chelation-extraction) may be
essentially oxygen free. necessary to determine low levels of iron in some waters.
6. Sampling NOTE 1—Instrument manufacturers’ instructions for use of the specific
correction technique should be followed.
6.1 Collect the sample in accordance with Practice D 1066,
Specification D 1192, or Practices D 3370, as applicable. 10. Apparatus
6.2 Samples should be preserved with HNO3 or HCl (sp gr
1.42) to a pH of 2 or less immediately at the time of collection. 10.1 Atomic Absorption Spectrophotometer, for use at 248.3
If only dissolved iron is to be determined, the sample shall be nm.
filtered through a 0.45-µm membrane filter before acidification. NOTE 2—The manufacturer’s instructions should be followed for all
The holding time for samples can be calculated in accordance instrumental parameters. A wavelength other than 248.3 nm may be used
with Practice D 4841. if it has been determined to be equally suitable.
6.3 If ferrous iron is to be determined, the sample should be 10.1.1 Iron Hollow-Cathode Lamp—Multielement hollow-
analyzed as soon as possible after collection and contact with cathode lamps are available and have also been found satis-
atmospheric oxygen should be minimized. factory.
6.4 Additional information on sampling requirements for 10.2 Pressure-Reducing Valves—The supplies of fuel and
Test Method D is provided in 34.1. oxidant shall be maintained at pressures somewhat higher than
the controlled operating pressure of the instrument by suitable
TEST METHOD A—ATOMIC ABSORPTION, DIRECT valves.
7. Scope 11. Reagents and Materials
7.1 This test method covers the determination of dissolved 11.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
and total recoverable iron in most waters and wastewaters. chloric acid (HCl).
7.2 This test method is applicable in the range from 0.1 to
5.0 mg/L of iron. The range may be extended to concentrations NOTE 3—If the reagent blank concentration is greater than the method
greater than 5.0 mg/L by dilution of the sample. detection limit, distill the HCl or use a spectrograde acid. Precaution—
When HCl is distilled an azeotropic mixture is obtained (approximately 6
7.3 This test method has been used successfully with N HCl). Therefore, when concentrated HCl is specified for the preparation
reagent water; tap, ground, and surface waters; unspecified of reagents or in the procedure, use double the volume specified if distilled
wastewaters; and a refinery primary treatment water. It is the acid is used.
11.2 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
(HNO3).
4
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not NOTE 4—If the reagent blank concentration is greater than the method
listed by the American Chemical Society, see Analar Standards for Laboratory detection limit, distill the HNO3 or use a spectrograde acid.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, 11.3 Nitric Acid (1 + 499)—Add 1 volume of HNO3(sp gr
MD. 1.42) to 499 volumes of water.

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11.4 Iron Solution, Stock (1 mL = 1.0 mg Iron)—Dissolve 14. Calculation
1.000 g of pure iron in 100 mL of HCL (1 + 1) with the aid of 14.1 Calculate the concentration of iron in the sample, in
heat. Cool and dilute to 1 L with water. milligrams per litre, referring to 12.4.
11.5 Iron Solution, Standard (1 mL = 0.1 mg Iron)—Dilute
100.0 mL of the iron stock solution to 1 L with water. 15. Precision and Bias 5
11.6 Oxidant: 15.1 The precision of this test method for 10 laboratories,
11.6.1 Air, which has been passed through a suitable filter to which include 16 operations within its designated range may be
remove oil, water, and other foreign substances is the usual expressed as follows:
oxidant. Reagent Water Type II:
11.7 Fuel: ST 5 0.047 X 1 0.053
11.7.1 Acetylene—Standard, commercially available acety-
lene is the usual fuel. Acetone, always present in acetylene S o 5 0.030 X 1 0.037
cylinders can affect analytical results. The cylinder should be
replaced at 50 psig (345 kPa). (Warning—“Purified” grade Water of Choice:
acetylene containing a special proprietary solvent rather than ST 5 0.050 X 1 0.114
acetone should not be used with poly vinyl chloride tubing as
weakening of the tubing walls can cause a potentially hazard- S o 5 0.024 X 1 0.078
ous situation.)

12. Standardization where:

ST = overall precision,
12.1 Prepare 100 mL each of a blank and at least four So = single-operator precision, and
--`,,``,`-`-`,,`,,`,`,,`---

standard solutions to bracket the expected iron concentration X = determined concentration of iron, mg/L.
range of the samples to be analyzed by diluting the standard 15.2 Recoveries of known amounts of iron in a series of
iron solution with HNO3 (1 + 499). Prepare the standards each prepared standards were as shown in Table 1.
time the test is to be performed. 15.3 The collaborative test data were obtained on reagent
12.2 When determining total recoverable iron add 0.5 mL of water; tap, lake, ground and surface water; unspecified waste-
HNO3 (sp gr 1.42) and proceed as directed in 13.1 through water; and a refinery primary treatment water. It is the user’s
13.5. When determining dissolved iron proceed as directed in responsibility to ensure the validity of this test method for
Note 5, 13.1. waters of untested matrices.
12.3 Aspirate the blank and standards and record the instru- 15.4 This section on precision and bias conforms to Practice
ment readings. Aspirate HNO3 (1 + 499) between each stan- D 2777 – 77 which was in place at the time of collaborative
dard. testing. Under the allowances made in 1.4 of D 2777 – 98,
12.4 Prepare an analytical curve by plotting the absorbance these precision and bias data do meet existing requirements of
versus concentration for each standard on linear graph paper. interlaboratory studies of Committee D19 test methods.
Alternatively read directly in concentration if this capability is
16. Quality Control
provided with the instrument.
16.1 In order to be certain that analytical values obtained
13. Procedure using these test methods are valid and accurate within the
13.1 Measure 100.0 mL of a well-mixed acidified sample
into a 125-mL beaker or flask.
5
Supporting data have been filed at ASTM International Headquarters and may
NOTE 5—If only dissolved iron is to be determined, start with 13.5. be obtained by requesting Research Report RR: D19–1035.

13.2 Add 5 mL of HCl (sp gr 1.19) to each sample.

TABLE 1 Determination of Bias, Atomic Absorption, Direct
13.3 Heat the samples on a steam bath or hotplate in a
well-ventilated hood until the volume has been reduced to 15 Reagent Water Type II: Statistically
Significant
to 20 mL, making certain that the samples do not boil. Bias, % (95 %
Amount Added, Amount Found,
Bias, mg/L Confidence
NOTE 6—When analyzing samples of brines or samples containing mg/L mg/L
Level)
appreciable amounts of suspended matter or dissolved solids, the amount 0.2 0.2 60.0 0.0 no
of reduction in volume is left to the discretion of the analyst. 2.4 2.4 60.0 0.0 no
4.4 4.3 −0.1 − 2.3 yes
13.4 Cool and filter the samples through a suitable filter Natural Water: Statistically
(such as fine-textured, acid-washed, ashless paper), into Significant
Bias, % (95 %
100-mL volumetric flasks. Wash the filter paper two or three Amount Added, Amount Found,
Bias, mg/L Confidence
times with water and adjust a volume. mg/L mg/L
Level)
13.5 Aspirate each filtered and acidified sample and deter- 0.2 0.2 60.0 0 no
2.4 2.3 − 0.1 − 4.17 yes
mine its absorbance or concentration at 248.3 nm. Aspirate 4.4 4.2 − 0.2 − 4.55 yes
HNO3 (1 + 499) between each sample.

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 D 1068 – 05e1
confidence limits of the test, the following QC procedures must less than 0.5 times the lowest calibration standard. If the known
be followed when analyzing iron. concentration of iron is found above this level, analysis of
16.2 Calibration and Calibration Verification: samples is halted until the contamination is eliminated, and a
16.2.1 Analyze at least three working standards containing blank shows no contamination at or above this level, or the
concentrations of iron that bracket the expected sample con- results must be qualified with an indication that they do not fall
centration, prior to analysis of samples, to calibrate the within the performance criteria of the test method.
instrument. The calibration correlation coefficient shall be 16.6 Matrix Spike (MS):
equal to or greater than 0.990. In addition to the initial 16.6.1 To check for interferences in the specific matrix
calibration blank, a calibration blank shall be analyzed at the being tested, perform a MS on at least one sample from each
end of the batch run to ensure contamination was not a problem batch by spiking an aliquot of the sample with a known known
during the batch analysis. concentration of iron and taking it through the analytical
16.2.2 Verify instrument calibration after standardization by method.
analyzing a standard at the concentration of one of the 16.6.2 The spike known concentration plus the background
calibration standards. The concentration of a mid-range stan- known concentration of iron must not exceed the high calibra-
dard should fall within 615 % of the known concentration. tion standard. The spike must produce a known concentration
16.2.3 If calibration cannot be verified, recalibrate the in the spiked sample that is 2 to 5 times the analyte known
--`,,``,`-`-`,,`,,`,`,,`---

instrument. concentration in the unspiked sample, or 10 to 50 times the

16.3 Initial Demonstration of Laboratory Capability: detection limit of the test method, whichever is greater.
16.3.1 If a laboratory has not performed the test before, or if 16.6.3 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~Vs 1 V! 2 B Vs# / C V (1)
bias study must be performed to demonstrate laboratory
capability. where:
16.3.2 Analyze seven replicates of a standard solution A = analyte known concentration (mg/L) in spiked
prepared from an Independent Reference Material containing a sample,
mid-range concentration of iron. The matrix and chemistry of B = analyte known concentration (mg/L) in unspiked
the solution should be equivalent to the solution used in the sample,
C = known concentration (mg/L) of analyte in spiking
collaborative study. Each replicate must be taken through the
solution,
complete analytical test method including any sample preser-
Vs = volume (mL) of sample used, and
vation and pretreatment steps. The replicates may be inter- V = volume (mL) added with spike.
spersed with samples.
16.6.4 The percent recovery of the spike shall fall within the
16.3.3 Calculate the mean and standard deviation of the limits, based on the analyte known concentration, listed in
seven values and compare to the acceptable ranges of bias in Guide D 5810, Table 1. If the percent recovery is not within
Table 1. This study should be repeated until the recoveries are these limits, a matrix interference may be present in the sample
within the limits given in Table 1. If a concentration other than selected for spiking. Under these circumstances, one of the
the recommended concentration is used, refer to Practice following remedies must be employed: the matrix interference
D 5847 for information on applying the F test and t test in must be removed, all samples in the batch must be analyzed by
evaluating the acceptability of the mean and standard devia- a test method not affected by the matrix interference, or the
tion. results must be qualified with an indication that they do not fall
16.4 Laboratory Control Sample (LCS): within the performance criteria of the test method.
16.4.1 To ensure that the test method is in control, analyze
a LCS containing a known concentration of iron with each NOTE 7—Acceptable spike recoveries are dependent on the known
concentration of the component of interest. See Guide D 5810 for
batch or 10 samples. If large numbers of samples are analyzed
additional information.
in the batch, analyze the LCS after every 10 samples. The
laboratory control samples for a large batch should cover the 16.7 Duplicate:
analytical range when possible. The LCS must be taken 16.7.1 To check the precision of sample analyses, analyze a
through all of the steps of the analytical method including sample in duplicate with each batch. If the known concentra-
sample preservation and pretreatment. The result obtained for tion of the analyte is less than five times the detection limit for
a mid-range LCS shall fall within 615 % of the known known the analyte, a matrix spike duplicate (MSD) should be used.
concentration. 16.7.2 Calculate the standard deviation of the duplicate
16.4.2 If the result is not within these limits, analysis of values and compare to the precision in the collaborative study
samples is halted until the problem is corrected, and either all using an F test. Refer to 6.4.4 of Practice D 5847 for informa-
the samples in the batch must be reanalyzed, or the results must tion on applying the F test.
be qualified with an indication that they do not fall within the 16.7.3 If the result exceeds the precision limit, the batch
performance criteria of the test method. must be reanalyzed or the results must be qualified with an
16.5 Method Blank: indication that they do not fall within the performance criteria
16.5.1 Analyze a reagent water test blank with each batch. of the test method.
The known concentration of iron found in the blank should be 16.8 Independent Reference Material (IRM):

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16.8.1 In order to verify the quantitative value produced by NOTE 9—The manufacturer’s instructions should be followed for all
the test method, analyze an Independent Reference Material instrumental parameters.
(IRM) submitted as a regular sample (if practical) to the 20.2 Iron Hollow-Cathode Lamp—A single-element lamp is
laboratory at least once per quarter. The known concentration preferred, but multielement lamps may be used.
of the IRM should be in the known concentration mid-range for 20.3 Graphite Furnace, capable of reaching temperatures
the method chosen. The value obtained must fall within the sufficient to atomize the element of interest.
control limits established by the laboratory. 20.4 Graphite Tubes, compatible with furnace device. Py-
rolytically coated graphite tubes are recommended to eliminate
TEST METHOD C—ATOMIC ABSORPTION, the possible formation of carbides.
GRAPHITE FURNACE 20.5 Pipets, microlitre with disposable tips. Sizes may range
17. Scope from 1 to 100 µL, as required.
20.6 Data Storage and Reduction Devices, Computer- and
17.1 This test method covers the determination of dissolved Microprocessor-Controlled Devices, or Strip Chart Recorders,
and total recoverable iron in most waters and wastewaters. shall be utilized for collection, storage, reduction, and problem
17.2 This test method is applicable in the range from 5 to recognition (such as drift, incomplete atomization, changes in
100 µg/L of iron using a 20-µL injection. The range can be sensitivity, etc.). Strip chart recorders shall have a full scale
increased or decreased by varying the volume of sample deflection time of 0.2 s or less to ensure accuracy.
injected or the instrumental settings. High concentrations may 20.7 Automatic sampling should be used if available.
be diluted but preferably should be analyzed by direct aspira-
tion atomic absorption spectrophotometry (Test Method A). NOTE 10—Manual injection has been reported to cause widely scattered
17.3 This test method has been used successfully with values even on purified waters due to contamination from pipetting
technique.
reagent grade water, filtered tap water, well water, demineral-
ized water, boiler blowdown water, and condensate from a 21. Reagents and Materials
medium Btu-coal gasification process. It is the user’s respon-
21.1 Iron Solution, Stock (1.0 mL = 1000 µg Fe)—See 11.4.
sibility to ensure validity of this test method to waters of
21.2 Iron Solution, Intermediate (1.0 mL = 10 µg Fe)—
untested matrices.
Dilute 10.0 mL of iron solution, stock (20.1) and 1 mL of
17.4 The analyst is encouraged to consult Practice D 3919
HNO3(sp gr 1.42) to 1 L with water.
for a general discussion of interferences and sample analysis
21.3 Iron Solution, Standard (1.0 mL = 0.2 µg Fe)—Dilute
procedures for graphite furnace atomic absorption spectropho-
20.0 mL of iron solution, intermediate (20.2) and 1 mL of
tometry.
HNO3(sp gr 1.42) to 1 L water. This standard is used to prepare
18. Summary of Test Method working standards at the time of the analysis.
21.4 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
18.1 Iron is determined by an atomic absorption spectro-
(HNO3) (see Note 4).
photometer used in conjunction with a graphite furnace. A
21.5 Argon, Standard, welders grade, commercially avail-
sample is placed in a graphite tube, evaporated to dryness,
able. Nitrogen may also be used if recommended by the
charred (pyrolyzed or ashed), and atomized. The absorption
instrument manufacturer.
signal generated during atomization is recorded and compared
to standards. A general guide for the application of the graphite 22. Standardization
--`,,``,`-`-`,,`,,`,`,,`---

furnace is given in Practice D 3919. 22.1 Initially, set the instrument according to the manufac-
18.2 Dissolved iron is determined on a filtered sample with turer’s specifications. Follow the general instructions as pro-
no pretreatment. vided in Practice D 3919.
18.3 Total recoverable iron is determined following acid
digestion and filtration. Because chlorides interfere with fur- 23. Procedure
nace procedures for some metals, the use of hydrochloric acid 23.1 Clean all glassware to be used for preparation of
in any digestion or solubilization step is to be avoided. If standard solutions or in the solubilization step, or both, by
suspended material is not present, this digestion and filtration rinsing first with HNO3(1 + 1) and then with water.
may be omitted. 23.2 Measure 100.0 mL of each standard and well-mixed
sample into 125-mL beakers or flasks. For total recoverable
19. Interferences
iron add HNO3(sp gr 1.42) to each standard and sample at a
19.1 For a complete discussion on general interferences rate of 5 mL/L and proceed as directed in 23.4 through 23.6.
with furnace procedures, the analyst is referred to Practice 23.3 If only dissolved iron is to be determined, filter the
D 3919. sample through a 0.45-µm membrane filter prior to acidifica-
tion and proceed to 23.6.
20. Apparatus
23.4 Heat the samples at 95°C on a steam bath or hotplate
20.1 Atomic Absorption Spectrophotometer, for use at 248.3 in a well-ventilated fume hood until the volume has been
nm with background correction. reduced to 15 to 20 mL, making certain that the samples do not
NOTE 8—A wavelength other than 248.3 nm may be used if it has been boil (see Note 6).
determined to be suitable. Greater linearity may be obtained at high 23.5 Cool and filter the sample through a suitable filter
concentrations by using a less sensitive wavelength. (such as fine-textured, acid-washed, ashless paper) into a

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D 1068 – 05e1
TABLE 2 Determination of Bias, Atomic Absorption, Graphite the instrument. The calibration correlation coefficient shall be
Furnace equal to or greater than 0.990. In addition to the initial
Reagent Water: calibration blank, a calibration blank shall be analyzed at the
Statistically
Amount Amount ST 6 Bias, µg/L 6 % Bias
Added, µg/L Found, µg/L
Significant end of the batch run to ensure contamination was not a problem
8.0 11.3 6.18 + 3.3 + 41.3 no during the batch analysis.
20 21.1 12.35 + 1.1 + 5.5 no
68 67.1 30.62 − 0.9 − 1.3 no
26.2.2 Verify instrument calibration after standardization by
Natural Water:
analyzing a standard at the known concentration of one of the
Statistically calibration standards. The known concentration of a mid-range
Amount Amount ST 6 Bias, µg/L 6 % Bias
Significant
Added, µg/L Found, µg/L standard should fall within 615 % of the known known
8.0 6.9 3.17 −1.1 −13.8 no
20 19.0 8.33 −1.0 −5.0 no
concentration.
68 70.1 21.63 + 2.1 + 3.1 no 26.2.3 If calibration cannot be verified, recalibrate the
instrument.
26.3 Initial Demonstration of Laboratory Capability:
100-mL volumetric flask. Wash the filter paper 2 or 3 times 26.3.1 If a laboratory has not performed the test before, or if
with water and bring to volume (Note 11). The acid concen- there has been a major change in the measurement system, for
tration at this point should be 0.5 % HNO3. example, new analyst, new instrument, etc., a precision and
NOTE 11—If suspended material is not present, this filtration may be bias study must be performed to demonstrate laboratory
omitted. The sample must be diluted to 100 mL. capability.
23.6 Inject a measured aliquot of sample into the furnace 26.3.2 Analyze seven replicates of a standard solution
device following the directions as provided by the particular prepared from an Independent Reference Material containing a
instrument manufacturer. Refer to Practice D 3919. mid-range known concentration of iron. The matrix and
chemistry of the solution should be equivalent to the solution
24. Calculation used in the collaborative study. Each replicate must be taken
24.1 Determine the concentration of iron in each sample by through the complete analytical test method including any
referring to Practice D 3919. sample preservation and pretreatment steps. The replicates may
be interspersed with samples.
25. Precision and Bias 6 26.3.3 Calculate the mean and standard deviation of the
25.1 The precision for this test method was developed by 13 seven values and compare to the acceptable ranges of bias in
laboratories using reagent water and 7 laboratories using tap Table 2. This study should be repeated until the recoveries are
water, filtered tap water, well water, demineralized water, within the limits given in Table 2. If a known concentration
boiler blowdown water, and condensate from a medium Btu other than the recommended known concentration is used,
coal gasification process. Although multiple injections may refer to Practice D 5847 for information on applying the F test
have been made, the report sheets provided allowed only for and t test in evaluating the acceptability of the mean and
reporting single values. Thus, no single-operator precision data standard deviation.
can be calculated. See Table 2 for bias data and overall 26.4 Laboratory Control Sample (LCS):
precision data. 26.4.1 To ensure that the test method is in control, analyze
25.2 These data may not apply to waters of other a LCS containing a known concentration of iron with each
matrices, therefore, it is the responsibility of the analyst to batch or 10 samples. If large numbers of samples are analyzed
ensure the validity of this test method in a particular matrix. in the batch, analyze the LCS after every 10 samples. The
25.3 This section on precision and bias conforms to Practice laboratory control samples for a large batch should cover the
D 2777 – 77 which was in place at the time of collaborative analytical range when possible. The LCS must be taken
testing. Under the allowances made in 1.4 of D 2777 – 98, through all of the steps of the analytical method including
these precision and bias data do meet existing requirements of sample preservation and pretreatment. The result obtained for
interlaboratory studies of Committee D19 test methods. a mid-range LCS shall fall within 615 % of the known known
concentration.
26. Quality Control
26.4.2 If the result is not within these limits, analysis of
26.1 In order to be certain that analytical values obtained samples is halted until the problem is corrected, and either all
using these test methods are valid and accurate within the the samples in the batch must be reanalyzed, or the results must
confidence limits of the test, the following QC procedures must be qualified with an indication that they do not fall within the
be followed when analyzing iron. performance criteria of the test method.
26.2 Calibration and Calibration Verification:
26.5 Method Blank:
26.2.1 Analyze at least three working standards containing
known concentrations of iron that bracket the expected sample 26.5.1 Analyze a reagent water test blank with each batch.
known concentration, prior to analysis of samples, to calibrate The known concentration of iron found in the blank should be
less than 0.5 times the lowest calibration standard. If the known
concentration of iron is found above this level, analysis of
6
Supporting data have been filed at ASTM International Headquarters and may samples is halted until the contamination is eliminated, and a
be obtained by requesting Research Report RR: D19–1102. blank shows no contamination at or above this level, or the

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results must be qualified with an indication that they do not fall of the IRM should be in the known concentration mid-range for
within the performance criteria of the test method. the method chosen. The value obtained must fall within the
26.6 Matrix Spike (MS): control limits established by the laboratory.
26.6.1 To check for interferences in the specific matrix
being tested, perform a MS on at least one sample from each TEST METHOD D—PHOTOMETRIC
batch by spiking an aliquot of the sample with a known known BATHOPHENANTHROLINE FOR BPA-REACTIVE
concentration of iron and taking it through the analytical AND
method. HCl-REACTIVE FERROUS FORMS
26.6.2 The spike known concentration plus the background 27. Scope
known concentration of iron must not exceed the high calibra-
tion standard. The spike must produce a known concentration 27.1 This test method is applicable to the determination of
in the spiked sample that is 2 to 5 times the analyte known two ferrous iron forms, bathophenanthroline (BPA)-reactive
concentration in the unspiked sample, or 10 to 50 times the and hydrochloric acid (HCl)-reactive, in water having ferrous
detection limit of the test method, whichever is greater. iron concentrations between 40 and 1000 µg/L. BPA-reactive
26.6.3 Calculate the percent recovery of the spike (P) using ferrous iron is essentially ionic Fe(II) and HCl-reactive ferrous
the following formula: iron most likely represents total Fe(II).
27.2 This test method has been used successfully with
P 5 100 [A~Vs 1 V! 2 B Vs# / C V (2) reagent water and fly ash pond effluent water. It is the user’s
where: responsibility to assure the validity of this test method for
A = analyte known concentration (mg/L) in spiked water of untested matrices.
--`,,``,`-`-`,,`,,`,`,,`---

sample,
28. Summary of Test Method
B = analyte known concentration (mg/L) in unspiked
sample, 28.1 The analysis for BPA-reactive ferrous iron consists of
C = known concentration (mg/L) of analyte in spiking the addition of BPA to a buffered sample which forms a
solution, red-colored complex with ferrous iron. The red ferrous com-
Vs = volume (mL) of sample used, and plex is extracted from the aqueous solution with n-hexyl or
V = volume (mL) added with spike. isoamyl alcohol and the intensity of its color is measured.
26.6.4 The percent recovery of the spike shall fall within the HCl-reactive ferrous iron is determined by the addition of
limits, based on the analyte known concentration, listed in buffer and BPA to a previously acidified sample followed by
Guide D 5810, Table 2. If the percent recovery is not within extraction and measurement of the red ferrous complex.
these limits, a matrix interference may be present in the sample Maximum absorption of the complex occurs at 533 nm, and
selected for spiking. Under these circumstances, one of the Beer’s law is valid.
following remedies must be employed: the matrix interference
must be removed, all samples in the batch must be analyzed by 29. Significance and Use
a test method not affected by the matrix interference, or the 29.1 The form of iron most directly toxic to aquatic life is
results must be qualified with an indication that they do not fall ferrous iron. This test method allows analysis for both ionic
within the performance criteria of the test method. and total ferrous iron in water with the sensitivity to detect the
trace concentrations normally found (40 µg/L to 300 µg/L).
NOTE 12—Acceptable spike recoveries are dependent on the known
concentration of the component of interest. See Guide D 5810 for 30. Interferences
additional information.
30.1 The metal ions other than ferrous iron which can form
26.7 Duplicate: a complex with bathophenanthroline are manganese, cadmium,
26.7.1 To check the precision of sample analyses, analyze a copper, zinc, cobalt, nickel, chromium, and ruthenium. The
sample in duplicate with each batch. If the known concentra- complexation/extraction is carried out at pH 4.0 to 4.5 in the
tion of the analyte is less than five times the detection limit for presence of excess bathophenanthroline to achieve maximum
the analyte, a matrix spike duplicate (MSD) should be used. color development with Fe(II) and also to eliminate interfer-
26.7.2 Calculate the standard deviation of the duplicate ences of competing ions. In acid solution, all competing ions
values and compare to the precision in the collaborative study form colorless complexes except ruthenium and cobalt which
using an F test. Refer to 6.4.4 of Practice D 5847 for informa- are yellow, and none except the colorless copper complex are
tion on applying the F test. extractable into an organic solvent. In a natural water sample
26.7.3 If the result exceeds the precision limit, the batch buffered at pH 4, cuprous copper is the only metal ion that
must be reanalyzed or the results must be qualified with an could potentially affect the measurement of ferrous iron; both
indication that they do not fall within the performance criteria species compete for the complexing agent. However, excess
of the test method. bathophenanthroline is present to complex both the ferrous iron
26.8 Independent Reference Material (IRM): and cuprous copper in the sample.
26.8.1 In order to verify the quantitative value produced by
the test method, analyze an Independent Reference Material 31. Apparatus
(IRM) submitted as a regular sample (if practical) to the 31.1 Photometer, a spectrophotometer or filter photometer
laboratory at least once per quarter. The known concentration suitable for use at 533 nm and equipped with absorption cell

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providing a light path length of 5 cm. Photometers, and 34.2 Proceed as directed in 35.1 to 35.14.
photometric practices prescribed in this test method, shall 34.3 Simultaneously carry out a blank determination to
conform to Practice E 60. Spectrophotometers shall conform to correct for iron in the reagents.
Practice E 275. 34.4 Prepare a calibration curve by plotting the absorbances
of the working standard solutions against the micrograms of
32. Reagents ferrous iron. Separate calibration curves must be prepared for
32.1 Acetate Buffer Solution (NaC2H3O2) (pH 4.0)— the BPA-reactive ferrous iron in HCI-reactive ferrous iron.
Dissolve 10 g NaC2H3O2 in 100 mL of water. If necessary, add
glacial acetic acid or ammonium hydroxide (1 + 1) to adjust 35. Procedure
pH to 4.0. Purify acetate buffer by adding BPA reagent and
extracting any complexed iron-BPA with hexanol. Allow 2 to 5 35.1 When testing for BPA-reactive ferrous iron, proceed
days for the organic and aqueous (acetate buffer) phases to with 35.2 and 35.3, followed immediately by 35.8. When
separate in a separatory funnel. Discard the alcohol layer. testing for HCl-reactive ferrous iron, proceed to 35.4.
32.2 Alcohol, n—-hexyl (preferred) or isoamyl (alternative). 35.2 Transfer 5 mL of acetate buffer into a clean 125-mL
32.3 Alcohol, methyl or ethyl (95 %). separatory funnel.
32.4 Ammonium Hydroxide Solution (1 + 1)—Dilute 500 35.3 Pipet 50 mL of sample from the sampling device
mL of ammonium hydroxide (NH4OH, sp gr 0.90) with 500 directly into the buffer solution. The pipet tip must be at or
mL of water and mix. slightly beneath the liquid-air interface while the sample is
32.5 Bathophenanthroline (BPA) Solution (0.668 g/L)— draining from the pipet. Swirl the separatory funnel to mix the
Dissolve 0.0668 g (4,7 diphenyl-1,10-phenanthroline) in 100 contents and then proceed to 35.8.
mL of ethyl alcohol (95 %). 35.4 When testing for HCl-reactive ferrous iron, place 4 mL
32.6 Hydrochloric Acid (HCl) (1 + 1)—Cautiously add 1 of HCl (1 + 1) into a clean 125-mL separatory funnel.
volume of HCl (sp gr 1.19) to 1 volume of water and mix. 35.5 Pipet 50 mL of sample from the sampling device
32.7 Iron Solution, Standard (1 mL = 10 µg Fe)—Dissolve directly into the acid. The pipet tip must be at or slightly
0.0702 g ferrous ammonium sulfate [Fe(NH4)2(SO4)2·6H2O] beneath the liquid-air interface while the sample is draining
into 700 mL of water that has had 20 mL of concentrated from the pipet. Swirl the separatory funnel to mix the contents
H2SO4(sp gr 1.84) added to it. Dilute to 1 L with water. Make and then wait exactly 10 min.
up fresh every 24 to 48 h. Keep standard solution out of direct
sunlight. 35.6 Add 5 mL of acetate buffer. Swirl to mix.
32.8 Sulfuric Acid (1 + 9)—Cautiously add 1 volume of 35.7 Add an adequate volume (approximately 5 mL) of
H2SO4(sp gr 1.84) to 9 volumes of water and mix. NH4OH (1 + 1) to bring the pH between 4.0 and 4.5. Swirl to
mix.
33. Sampling 35.8 Add 10 mL of bathophenanthroline solution to the
33.1 Sampling shall be done with any device that minimizes separatory funnel. Shake vigorously for 30 s.
the effect of atmospheric oxygen on the sample, for instance, a 35.9 Pipet either 10.0 mL of n-hexyl alcohol when testing
van-Dorn or hand-held and dipped bottle. Immediate analysis for BPA-reactive ferrous iron or 20.0 mL of n-hexyl alcohol
is preferred, but up to 1 h can elapse between sampling and when testing for HCl-reactive ferrous iron to the separatory
analysis without significant change to forms of iron if the funnel, and shake vigorously for 30 s.
sample is essentially free of air bubbles, is placed on ice, and 35.10 Allow 3 to 5 min for the organic and water phases to
held in the dark until analysis. For frequent monitoring of separate in the separatory funnel.
similar water matrices that are held up to 1 h, the analyst 35.11 Open the stopcock of the separatory funnel and drain
should confirm for those particular waters that the holding time off the aqueous (bottom) layer.
used is inconsequential for iron analyses. A holding period up

--`,,``,`-`-`,,`,,`,`,,`---
35.12 Pipet either 5.0 mL of methyl or ethyl alcohol when
to 24 h can probably occur without significant change to testing for BPA-reactive ferrous iron or 10.0 mL of methyl or
ferrous iron forms by mixing reagents and complexing ferrous ethyl alcohol when testing for HCl-reactive ferrous iron to the
iron forms in the field (35.2 to 35.11). Once the color is red-colored organic phase.
formed, the complex shall be stable, without contact with air,
35.13 Pour the organic phase through a suitable course filter
and out of direct sunlight. The analyst should verify for tested
into a beaker to remove particulates which could interfere with
waters that the holding time is inconsequential for iron
the absorbance measurement.
analyses.
35.14 Measure the absorbance of the organic phase by
34. Calibration means of any applicable apparatus listed in 31.1 at 533 nm.
34.1 Prepare a series of working standards to cover the
36. Calculation
expected range of ferrous iron concentration by diluting
appropriate volumes of standard iron solution (see 32.6). Add 36.1 Calculate the concentration of ferrous iron, in micro-
0.25 mL of 1 + 9 sulfuric acid (see 32.8) per 100 mL of grams per litre as follows:
solution as a preservative. Make up fresh every 24 h. Keep Ferrous Iron, µg/L 5 ~W 3 1000!/S
working standards out of direct sunlight.

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TABLE 3 Overall and Single Operator Precision Data- 37.2 The collaborative test was conducted by six laborato-
Photometric Bathophenanthroline ries with single operators analyzing reagent water and fly ash
Amount Overall Single Operator pond effluent water containing ferrous iron concentrations of
Added, Precision, St, Precision, So,
µg/L µg/L µg/L
50, 400, and 800 µg/L. In some instances, not all six labora-
tories analyzed each sample type at every concentration level.
Reagent water
Type 1 (BPA reactive) 37.3 Recoveries of known amounts of ferrous iron from the
50 16.9 4.9 same water were as shown in Table 4.
400 47.1 6.8
800 33.6 13.3
37.4 This data may not apply to waters of untested matrices.
Reagent water 37.5 This section on precision and bias conforms to Practice
Type 1 (HCl reactive) D 2777 – 77 which was in place at the time of collaborative
50 11.8 10.8
400 51.9 25.6 testing. Under the allowances made in 1.4 of D 2777 – 86,
800 291.6 28.9 these precision and bias data do meet existing requirements of
Water of choice interlaboratory studies of Committee D19 test methods.
(BPA reactive)
50 29.0 27.1
400 32.3 25.7 38. Quality Control
800 33.8 37.1
Water of choice 38.1 In order to be certain that analytical values obtained
(HCl reactive) using these test methods are valid and accurate within the
50 24.2 22.1
400 33.5 19.4
confidence limits of the test, the following QC procedures must
800 191.7 199.9 be followed when analyzing iron.
38.2 Calibration and Calibration Verification:
38.2.1 Analyze at least three working standards containing
TABLE 4 Determination of Bias, Ferrous Iron-Photometric known concentrations of iron that bracket the expected sample
Bathophenanthroline known concentration, prior to analysis of samples, to calibrate
Statistically the instrument. The calibration correlation coefficient shall be
Amount Amount Significant
Added, Found, 6 Bias 6 %Bias (95 % equal to or greater than 0.990. In addition to the initial
µg/L µg/L Confidence calibration blank, a calibration blank shall be analyzed at the
Level) end of the batch run to ensure contamination was not a problem
Reagent water during the batch analysis.
Type I (BPA reactive)
50 41.2 −8.8 −17.6 No
38.2.2 Verify instrument calibration after standardization by
400 427.8 +27.6 +6.9 No analyzing a standard at the known concentration of one of the
800 801.3 +1.3 +0.2 No calibration standards. The known concentration of a mid-range
Reagent water
Type 1 (HCl reactive) standard should fall within 615 % of the known known
50 48.3 −1.7 −3.4 No concentration.
400 413.3 + 13.3 +3.3 No 38.2.3 If calibration cannot be verified, recalibrate the
800 998.0 +198.0 +24.8 No
Water of choice instrument.
(BPA reactive) 38.3 Initial Demonstration of Laboratory Capability:
50 64.0 +14.0 +28.0 No
400 399.5 −0.5 −0.1 No
38.3.1 If a laboratory has not performed the test before, or if
800 806.6 +6.6 +0.8 No there has been a major change in the measurement system, for
Water of choice example, new analyst, new instrument, etc., a precision and
(HCl reactive)
50 64.1 +14.1 +28.0 No
bias study must be performed to demonstrate laboratory
400 422.3 +22.3 +5.6 No capability.
800 770.2 −29.8 −3.7 No 38.3.2 Analyze seven replicates of a standard solution
prepared from an Independent Reference Material containing a
mid-range known concentration of iron. The matrix and
chemistry of the solution should be equivalent to the solution
where: used in the collaborative study. Each replicate must be taken
W = ferrous iron read from the calibration curve, micro- through the complete analytical test method including any
grams, and sample preservation and pretreatment steps. The replicates may
S = original sample used, millilitres.
be interspersed with samples.
38.3.3 Calculate the mean and standard deviation of the
37. Precision and Bias 7
seven values and compare to the acceptable ranges of bias in
37.1 The single-operator and overall precision of this test Tables 3 and 4. This study should be repeated until the
method within its designated range varies with the quantity recoveries are within the limits given in Tables 3 and 4. If a
being tested in accordance with the data given in Table 3. known concentration other than the recommended known
concentration is used, refer to Practice D 5847 for information
on applying the F test and t test in evaluating the acceptability
7
Supporting data have been filed at ASTM International Headquarters and may of the mean and standard deviation.
be obtained by requesting Research Report RR: D19–1128. 38.4 Laboratory Control Sample (LCS):
--`,,``,`-`-`,,`,,`,`,,`---

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 D 1068 – 05e1
38.4.1 To ensure that the test method is in control, analyze B = analyte known concentration (mg/L) in unspiked
a LCS containing a known concentration of iron with each sample,
batch or 10 samples. If large numbers of samples are analyzed C = known concentration (mg/L) of analyte in spiking
in the batch, analyze the LCS after every 10 samples. The solution,
laboratory control samples for a large batch should cover the Vs = volume (mL) of sample used, and
analytical range when possible. The LCS must be taken V = volume (mL) added with spike.
through all of the steps of the analytical method including 38.6.4 The percent recovery of the spike shall fall within the
sample preservation and pretreatment. The result obtained for limits, based on the analyte known concentration, listed in
a mid-range LCS shall fall within 615 % of the known known Guide D 5810, Tables 3 and 4. If the percent recovery is not
concentration. within these limits, a matrix interference may be present in the
38.4.2 If the result is not within these limits, analysis of sample selected for spiking. Under these circumstances, one of
samples is halted until the problem is corrected, and either all the following remedies must be employed: the matrix interfer-
the samples in the batch must be reanalyzed, or the results must ence must be removed, all samples in the batch must be
be qualified with an indication that they do not fall within the analyzed by a test method not affected by the matrix interfer-
performance criteria of the test method. ence, or the results must be qualified with an indication that
they do not fall within the performance criteria of the test
38.5 Method Blank: method.
38.5.1 Analyze a reagent water test blank with each batch.
NOTE 13—Acceptable spike recoveries are dependent on the known
The known concentration of iron found in the blank should be concentration of the component of interest. See Guide D 5810 for
less than 0.5 times the lowest calibration standard. If the known additional information.
concentration of iron is found above this level, analysis of
38.7 Duplicate:
samples is halted until the contamination is eliminated, and a
38.7.1 To check the precision of sample analyses, analyze a
blank shows no contamination at or above this level, or the sample in duplicate with each batch. If the known concentra-
results must be qualified with an indication that they do not fall tion of the analyte is less than five times the detection limit for
within the performance criteria of the test method. the analyte, a matrix spike duplicate (MSD) should be used.
38.6 Matrix Spike (MS): 38.7.2 Calculate the standard deviation of the duplicate
38.6.1 To check for interferences in the specific matrix values and compare to the precision in the collaborative study
being tested, perform a MS on at least one sample from each using an F test. Refer to 6.4.4 of Practice D 5847 for informa-
batch by spiking an aliquot of the sample with a known known tion on applying the F test.
concentration of iron and taking it through the analytical 38.7.3 If the result exceeds the precision limit, the batch
method. must be reanalyzed or the results must be qualified with an
38.6.2 The spike known concentration plus the background indication that they do not fall within the performance criteria
known concentration of iron must not exceed the high calibra- of the test method.
tion standard. The spike must produce a known concentration 38.8 Independent Reference Material (IRM):
in the spiked sample that is 2 to 5 times the analyte known 38.8.1 In order to verify the quantitative value produced by
concentration in the unspiked sample, or 10 to 50 times the the test method, analyze an Independent Reference Material
detection limit of the test method, whichever is greater. (IRM) submitted as a regular sample (if practical) to the
38.6.3 Calculate the percent recovery of the spike (P) using laboratory at least once per quarter. The known concentration
--`,,``,`-`-`,,`,,`,`,,`---

the following formula: of the IRM should be in the known concentration mid-range for
the method chosen. The value obtained must fall within the
P 5 100 [A~Vs 1 V! 2 B Vs# / C V (3) control limits established by the laboratory.
where: 39. Keywords
A = analyte known concentration (mg/L) in spiked
39.1 analysis; atomic absorption; chelation-extraction; colo-
sample,
rimetric; flame; graphite furnace; iron; water

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 D 1068 – 05e1
APPENDIXES

(Nonmandatory Information)

X1. NOTES ON SOLUBILIZING REFRACTORY IRON COMPOUNDS

X1.1 Some forms of iron oxide are very resistant to the Evaporate to dense white fumes, cool the beaker, and wash the
dissolving action of hydrochloric acid. For example, a colloidal inside of the beaker carefully with water. Add a few drops of
form found in high pressure boiler condensate is very refrac- formic acid, and fume again to dense clouds of sulfur trioxide
tory. If it is suspected that a portion of the iron is insoluble with to remove the last traces of nitric acid. Cool, add water
the acid treatment given in the method, several techniques can carefully, and heat for a short time to dissolve easily soluble
be used to yield the iron in soluble form. Blank determinations salts. Cool, filter, if necessary, and continue with the steps for
should be made with all reagents used in any methods of color development. (Warning—Warm perchloric acid solu-
solubilizing the iron in order to correct for iron contamination. tions react explosively with organic matter. The use of nitric
After such treatments the procedure for determination of acid prevents this vigorous reaction.)
ferrous iron will no longer apply, since the relative quantities of X1.1.3 Thioglycolic Acid Method—Wilson 8 has shown that
ferrous and ferric iron in the samples will be altered. a sample made to 1 % (V/V) with thioglycolic acid and heated
for 30 min at 90°C (195°F) will completely dissolve“ unreac-
X1.1.1 Fusion Method—Evaporate the proper sized sample tive’’ iron. Pocock 9 confirms the finding and also eliminates
to dryness in a clean porcelain crucible. Fuse the residue with the use of hydroxylamine hydrochloride. Dilute the proper-
a minimum of potassium or sodium bisulfate (KHSO4 or sized portion of sample to 75 mL with water and acidify with
NaHSO4). Cool and leach in 50 mL of water containing 2 mL hydrochloric acid. Add 1 mL of thioglycolic acid and heat just
of hydrochloric acid (HCl, sp gr 1.19). Continue with filtration, under boiling for 30 min. Cool, filter, if necessary, and continue
if necessary, and with the steps for color development. with the steps for color development.
X1.1.2 Perchloric-Acid Treatment—After addition of HCl
and evaporation to a small volume, add 3 mL of nitric acid 8
Wilson, A. L., Analyst, Vol 89, June 1964, pp. 402, 410.
(HNO3, sp gr 1.42), 3 mL of perchloric acid (70 %) (see 9
Pocock, F. J., paper presented at the 152nd National Meeting of the American
X1.1.3), and 3 mL of sulfuric acid (H2SO4, sp gr 1.84). Chemical Society, New York City, Sept. 12, 1966.

--`,,``,`-`-`,,`,,`,`,,`---
X2. RATIONALE FOR DISCONTINUATION OF TEST METHODS

X2.1 Photometric Methods (Orthophenanthroline and Ba- complex with ferrous iron. The intensity of the color produced
thophenanthroline): is proportional to the amount of ferrous iron in the water.
X2.1.1 These test methods were discontinued in 1988. They Hydroxylamine hydrochloride is added to reduce ferric iron to
were last published in the 1988 Annual Book of ASTM the ferrous state when determining total and dissolved iron.
Standards, Vol 11.01. X2.1.3.2 Bathophenanthroline—Total iron is determined by
X2.1.2 These test methods cover the determination of iron this test method. Undissolved iron and iron oxides are put into
in water for samples containing 0.05 to 3.0 mg/L (orthophenan- solution by treatment with acid. The iron is reduced with
throline) and 0.02 to 0.2 mg/L (bathophenanthroline). Some hydroxylamine hydrochloride and then reacted with 4,7-
data relevant to these test methods are filed at ASTM Head- diphenyl-1,10-phenanthroline (bathophenanthroline). The red
quarters as research reports D19 - 52, D19 - 135, and D19 - ferrous complex is extracted from the aqueous solution with
148. n-hexyl or isoamyl alcohol and the intensity of its color is
X2.1.3 Summary of Test Methods: measured. Maximum absorption of the complex occurs at 533
X2.1.3.1 Orthophenanthroline—Undissolved iron and iron nm, and Beer’s law is valid.
oxides are put into solution by treatment with acids. If the iron X2.1.4 These test methods were discontinued because there
is not readily soluble in acids, fusion techniques are applied. were insufficient laboratories interested in participating in a
The iron is determined photometrically with 1,10- collaborative study to obtain the necessary precision and bias
phenanthroline (o-phenanthroline), which forms an orange-red data as required by Practice D 2777.

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