Measuring Anionic Contaminants in High-Purity Water by On-Line Ion Chromatography
Measuring Anionic Contaminants in High-Purity Water by On-Line Ion Chromatography
Measuring Anionic Contaminants in High-Purity Water by On-Line Ion Chromatography
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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detector background and at the same time enhance detector 5.2 These anions and others cause low product yields in
response to the ions of interest. semiconductor manufacturing. They are also monitored and
3.2.4 breakthrough volume, n—the maximum sample vol- controlled at similarly low levels as in the electric power
ume that can be passed through a concentrator column before industry.
the least tightly bound ion of interest is eluted. 5.3 Low molecular weight organic acids (acetate, formate,
3.2.4.1 Discussion—All of the columns in series contribute propionate) have been detected in steam generator feed water.
to the overall capacity of the analytical column set. These low molecular weight organic materials are believed to
be high-temperature degradation products of chemicals used to
3.2.5 concentrator column, n—an ion exchange column
control cycle water pH and organic contaminants in cycle
used to concentrate the ions of interest and thereby increase
makeup water.
method sensitivity.
3.2.6 eluant, n—the ionic mobile phase used to transport the 5.4 In the semiconductor industry, anion contaminants may
sample through the analytical column. come from the breakdown of low molecular weight organic
materials by ultraviolet light radiation, which is frequently
3.2.7 guard column, n—a column used before the analytical used to produce bacteria-free water. These organic compounds
column to protect it from contaminants, such as particulate may also contribute to low product yield.
matter or ionic species that may chemically foul the resins and
degrade their performance. 5.5 The production of high-purity water for process makeup
and use frequently employs the use of demineralizers to
3.2.8 ion chromatography, n—a form of liquid chromatog- remove unwanted anion contaminants. Also in the electric
raphy in which ionic constituents are separated by ion ex- power industry, demineralizers are used in the process stream
change followed by a suitable detection means. to maintain low levels of these contaminants. As such, it is
3.2.9 resolution, n—the ability of an analytical column to important to monitor this process to ensure that water quality
separate constituents under specific test conditions. standards are being met. These processes can be monitored for
the above-mentioned anions.
4. Summary of Test Method 5.6 On-line measurements of these contaminants provide a
4.1 A continuously flowing sample is injected into the greater degree of protection of the processes by allowing for
instrument through a sample injection valve. The sample is frequent on-line measurement of these species. Early detection
pumped through a concentrator column where the anions of of contaminant ingress allows for quicker corrective action to
interest are collected on ion-exchange resin. After a suitable locate, reduce, or eliminate, or combination thereof, the source.
volume of sample has been passed through the concentrator Grab samples will not provide the same level of protection
column, sample flow is diverted and an eluant is pumped because of their intermittent nature and the longer time
through the concentrator column to remove the trapped anions. required to obtain and then analyze the sample.
This eluant then flows through an analytical column set where 5.7 Additionally, on-line monitoring significantly reduces
the anions are separated based on the retention characteristic of the potential for contamination of high-purity water samples, a
each anion relative to the eluant used. The eluant stream significant problem when sampling and testing high-purity
containing the anions of interest passes through a suppressor water.
device where the cations from the eluant are exchanged for
hydrogen ions, converting the anions to their acid form. After 6. Interferences
the suppressor device, the eluant solution passes through a
conductivity detector where the separated anions are detected. 6.1 When working with low concentration samples, blanks,
Detection limits for the anions are enhanced because the anions and standards, contamination can be a serious problem. Ex-
are in the acid form rather than the salt. treme care must be exercised in all phases of this test method.
4.2 The anions are identified based on the retention time as 6.2 Improper sample line material or sample lines that have
compared to known standards. By measuring peak height or not been properly conditioned can give results that may not be
area and comparing the detector response to known standards, truly representative of the process stream. Absorption/
the anions can be quantified. desorption of anions on sample line wall deposits can change
analytical results. Maintaining a minimum sample flow of 1.8
5. Significance and Use m/s (6 ft/s) will minimize deposit buildup on sample line walls,
reducing the potential for absorption/desorption of anions.
5.1 In the power-generation industry, high-purity water is
used to reduce corrosion from anions, such as sulfate, chloride, 6.3 A single anion present at a concentration significantly
and fluoride. These anions are known to be detrimental to higher than other anions could mask closely adjacent peaks on
materials of construction used in steam generators, reactor the chromatogram.
vessel internals and recirculation piping, heat exchangers, 6.4 Low breakthrough volumes may be experienced when
connective piping, and turbines. Most electric generating plants continuously monitoring for anions in water that has had its pH
try to control these anions to <1.0 µg/L in the steam generator raised by ammonia, morpholine, or other additives. This
feed water. Some nuclear power plants have been able to interference can be eliminated by taking the sample from the
control anion contaminants at less than 0.02 µg/L. effluent of a cation resin column.
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6.5 Identification of the anion is based on retention time of 8.3 Prepare eluant for the specific columns used and for the
the anion of interest. An interfering anion having the same anions of interest in accordance with manufacturer’s direc-
retention time as one of the anions of interest will result in tions.
erroneously high values for that anion. 8.4 Prepare regenerant for the specific suppressor used in
6.6 When loading a concentrator column, high concentra- accordance with the manufacturer’s directions if required.
tions of interfering anions may cause low breakthrough vol- NOTE 1—There are numerous combinations of analytical columns,
umes of other anions. These interfering anions may act as an suppressors, eluants, and regenerants that may be used with this test
method. It is not practicable to list all the combinations. Users should use
eluant and displace other anions from the concentrator column.
the appropriate combination of concentrator column, analytical column,
See Annex A1 to determine breakthrough volume. Do not load suppressor, eluant, and regenerant to achieve the desired resolution and
a sample volume greater than 80 % of the breakthrough detection.
volume. 8.5 Fluoride Solution, Stock (1.00 mL = 1.00 mg F)—Dry
sodium fluoride at 110°C for 2 6 0.5 h and cool in a desiccator.
7. Apparatus
Dissolve 2.210 g of dried salt in water and dilute to 1 L.
7.1 Ion chromatograph with the following components:
8.6 Acetate Solution, Stock (1.00 mL = 1.00 mg acetate)—
7.1.1 Eluant Introduction System—The wetted portion of
Dissolve 1.389 g of sodium acetate in water and dilute to 1 L
the eluant pump should be nonmetallic or of a corrosion-
with water. Store in a brown glass bottle with a TFE-
resistant metal to prevent contamination of the chromatography
fluorocarbon lined cap in a refrigerator.
columns.
7.1.2 Sample Injection System—The wetted portion of the 8.7 Formate Solution, Stock (1.00 mL = 1 mg formate)—
sample pump should be nonmetallic or of a corrosion-resistant Dissolve 1.511 g sodium formate in water and dilute to 1 L
metal to prevent metal contamination of the chromatography with water. Store in a brown glass bottle with a TFE-
columns. fluorocarbon lined cap in a refrigerator.
7.1.3 Anion Suppressor Device. 8.8 Chloride Solution, Stock (1.00 mL = 1.00 mg Cl)—Dry
7.1.4 Conductivity Cell, low dead volume (1 µL). Tempera- sodium chloride (NaCl) for 2 6 0.5 h at 110°C and cool in a
ture compensated or corrected flow through conductivity desiccator. Dissolve 1.648 g of the dry salt in water and dilute
detector should be capable of measuring conductivity from 0 to to 1 L.
1000 µS/cm. If temperature controlled conductivity detector is
used, temperature control should be at 60.5°C or better. 8.9 Phosphate Solution, Stock (1.00 mL = 1.00 mg PO4)—
7.1.5 Suppressor Device Regenerant System—Some manu- Dissolve 1.433 g of potassium dihydrogen phosphate
facturers provide integrated regenerant systems that reduce the (KH2PO4) in water and dilute to 1 L with water.
consumption of eluant. Electrochemical suppressor regenerant 8.10 Sulfate Solution, Stock (1.00 mL = 1.00 mg SO4)—Dry
systems can be used, eliminating the need to prepare regener- sodium sulfate for 2 6 0.5 h at 110°C and cool in a desiccator.
ant solutions. Dissolve 1.479 g of the dried salt in water and dilute to 1 L.
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volumetric pipettes can be reduced by preparing the standards gravimetri- forming this validation are given in Guide D3864. Use Test
cally. Methods D5542 to validate the on-line instrument.
9. Sampling 13. Quality Control
9.1 Collect the sample in accordance with Practice D1066, 13.1 In order to be certain that analytical values obtained
Guide D1192, and Practices D3370. using these test methods are valid and accurate within the
9.2 When volatile amines are used to control process pH, confidence limits of the test, the following QC procedures must
samples should be taken from the effluent of a rinsed strong be followed when analyzing anions in water.
acid resin exchange column. Typically on-line ion chromatog- 13.2 Calibration and Calibration Verification:
raphy samples are taken from the effluent of cation resin 13.2.1 Analyze at least three working standards containing
columns used to continuously monitor cation conductivity. concentrations of anions in water that bracket the expected
Samples taken from this source will have cation contaminants sample concentration, prior to analysis of samples, to calibrate
or additives such as ammonia removed by the cation resin. This the instrument. The calibration correlation coefficient shall be
will eliminate high pH conditions that can cause low break- equal to or greater than 0.990. In addition to the initial
through volumes. Process water such as boiling water reactor calibration blank, a calibration blank shall be analyzed at the
feedwater and water used in the semiconductor industry end of the batch run to ensure contamination was not a problem
generally do not have pH additives, and sampling from the during the batch analysis. In many situations for online
effluent of a cation resin column is not required. analysis of ultrapure water the calibration blank and the sample
9.3 Provide samples to the instrument that meet the manu- are one and the same.
facturer’s required sample conditions, such as pressure, 13.2.2 Verify instrument calibration after standardization by
temperature, and minimum sample flow. analyzing a standard at the concentration of one of the
calibration standards. The concentration of a mid-range stan-
10. Calibration dard should fall within 615 % of the known concentration.
13.2.3 If calibration cannot be verified, recalibrate the
10.1 Determine the retention time for the anions being instrument.
determined by running an intermediate concentration solution
containing only that anion and noting the retention time. The 13.3 Initial Demonstration of Laboratory Capability:
concentration of the anion in the solution used to determine the 13.3.1 If a laboratory has not performed the test before, or if
retention time should be in the mid range of the standards used there has been a major change in the measurement system, for
to calibrate the instrument. Inject the working solutions in example, new analyst, new instrument, etc., a precision and
accordance with the manufacturer’s recommendations. bias study must be performed to demonstrate laboratory
capability.
10.2 Analyze a blank and the working solutions prepared in 13.3.2 Analyze seven replicates of a standard solution
8.12. Prepare a calibration curve in accordance with the prepared from an Independent Reference Material containing a
manufacturer’s directions. mid-range concentration of anions in water. The matrix and
chemistry of the solution should be equivalent to the solution
11. Procedure used in the collaborative study. Each replicate must be taken
11.1 Set up the on-line ion chromatograph in accordance through the complete analytical test method including any
with the manufacturer’s instructions. sample preservation and pretreatment steps. The replicates may
11.2 Allow the system to equilibrate with eluant passing be interspersed with samples.
through all chromatography columns. Equilibrate with eluant 13.3.3 Calculate the mean and standard deviation of the
until a stable baseline is achieved. It is recommended that if the seven values and compare to the acceptable ranges of bias in
system is to be shut down for an extended time period that Guide D5810, Tables 4-11. This study should be repeated until
eluant flow be constantly maintained. This will reduce equili- the recoveries are within the limits given in Tables 4-11. If a
bration time when the system is returned to service. concentration other than the recommended concentration is
used, refer to Practice D5847 for information on applying the
11.3 Start sample flow in accordance with the manufactur- F test and t test in evaluating the acceptability of the mean and
er’s instructions. standard deviation.
12. Precision and Bias 13.4 Laboratory Control Sample (LCS):
13.4.1 To ensure that the test method is in control, analyze
12.1 Neither precision nor bias data can be obtained for this a LCS containing a known concentration of anions in water
test method from a collaborative study designed in accordance with each batch or 10 samples. If large numbers of samples are
with the requirements of Practice D2777 since this test method analyzed in the batch, analyze the LCS after every 10 samples.
is an on-line determination. This inability of Practice D2777 The laboratory control samples for a large batch should cover
procedures to obtain precision and bias data for on-line the analytical range when possible. The LCS must be taken
determination is recognized and stated in the scope of Practice through all of the steps of the analytical method including
D2777. sample preservation and pretreatment. The result obtained for
12.2 If it is desirable to validate the monitoring system a mid-range LCS shall fall within 615 % of the known
results relative to the laboratory method, directions for per- concentration.
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13.4.2 If the result is not within these limits, analysis of V = volume (mL) added with spike.
samples is halted until the problem is corrected, and either all
13.6.4 The percent recovery of the spike shall fall within the
the samples in the batch must be reanalyzed, or the results must
limits, based on the analyte concentration, listed in Guide
be qualified with an indication that they do not fall within the
D5810, Tables 4-11. If the percent recovery is not within these
performance criteria of the test method.
limits, a matrix interference may be present in the sample
13.5 Method Blank: selected for spiking. Under these circumstances, one of the
13.5.1 Analyze a reagent water test blank with each batch. following remedies must be employed: the matrix interference
The concentration of anions in water found in the blank should must be removed, all samples in the batch must be analyzed by
be less than 0.5 times the lowest calibration standard. If the a test method not affected by the matrix interference, or the
concentration of anions in water is found above this level, results must be qualified with an indication that they do not fall
analysis of samples is halted until the contamination is within the performance criteria of the test method.
eliminated, and a blank shows no contamination at or above
NOTE 3—Acceptable spike recoveries are dependent on the concentra-
this level, or the results must be qualified with an indication tion of the component of interest. See Guide D5810 for additional
that they do not fall within the performance criteria of the test information.
method.
13.7 Duplicate:
13.5.2 In many situations for online analysis of ultrapure 13.7.1 To check the precision of sample analyses, analyze a
water the calibration blank and the sample are one and the sample in duplicate with each batch. If the concentration of the
same. If this is the case, use of a method blank may not be analyte is less than five times the detection limit for the analyte,
feasible. a matrix spike duplicate (MSD) should be used.
13.6 Matrix Spike (MS): 13.7.2 Calculate the standard deviation of the duplicate
13.6.1 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 D5847 for informa-
batch by spiking an aliquot of the sample with a known tion on applying the F test.
concentration of anions in water and taking it through the 13.7.3 If the result exceeds the precision limit, the batch
analytical method. must be reanalyzed or the results must be qualified with an
13.6.2 The spike concentration plus the background concen- indication that they do not fall within the performance criteria
tration of anions in water must not exceed the high calibration of the test method.
standard. The spike must produce a concentration in the spiked 13.8 Independent Reference Material (IRM):
sample that is 2 to 5 times the analyte concentration in the 13.8.1 In order to verify the quantitative value produced by
unspiked sample, or 10 to 50 times the detection limit of the the test method, analyze an Independent Reference Material
test method, whichever is greater. (IRM) submitted as a regular sample (if practical) to the
13.6.3 Calculate the percent recovery of the spike (P) using laboratory at least once per quarter. The concentration of the
the following calculation: IRM should be in the concentration mid-range for the method
P 5 100 @ A ~ V s 1V ! 2 BVs # /CV (1) chosen. The value obtained must fall within the control limits
established by the laboratory. If an IRM is not commercially
where:
available (for example: Ultrapure water) a suitable substitute
A = analyte concentration (mg/L) in spiked sample, may be made up by the laboratory.
B = analyte concentration (mg/L) in unspiked sample,
C = concentration (mg/L) of analyte in spiking solution, 14. Keywords
Vs = volume (mL) of sample used, and
14.1 anions; high purity; ion chromatography; on-line
ANNEX
(Mandatory Information)
A1.1 The breakthrough volume is that volume of sample A1.1.3 The pH of the sample,
that causes one or more ions of interest to be eluted from,
A1.1.4 The ionic strength of the sample, and
rather than retained or concentrated on, the concentrator
column. The breakthrough volume is dependent upon the A1.1.5 The ion exchange capacity of the resin in the
following: column.
A1.1.1 The volume of sample loaded, A1.2 Ion exchange resins have a finite capacity in that they
A1.1.2 The rate at which the sample is loaded, can retain only a fixed number of ions at any given time. The
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number of ions that can be retained is dependent upon the eluant and flush the concentrator column with eluant to a stable
charge of the ion. An ion(s) may act as an eluant if its affinity baseline. See Fig. A1.1.
for the ion exchange resin is greater than the affinity of the ions A1.3.4 Switch to the simulated sample as an eluant and
associated with the resin. Early breakthrough is possible when inject a 50 µL portion of the 1 mg/L standard.
one or more ions act as an eluant phase.
A1.3.5 Record the resulting chromatogram and calculate the
A1.3 The breakthrough volume is determined as follows: breakthrough volume as shown in Fig. A1.2.
A1.3.1 Prepare 1 L of a solution that closely simulates the A1.3.6 Do not attempt to concentrate a volume of sample
type of sample to be analyzed. For example, if the sample greater than 80 % of the breakthrough volume.
contains ammonia, the simulated sample should also contain A1.3.7 Calculate the breakthrough volume (BTV) as fol-
ammonia. Ammonia in solution exists as ammonium hydroxide lows:
and ammonium anion. The resulting hydroxide (OH−) ion will
act as an eluant. BTV 5 EF 3 RT (A1.1)
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APPENDIX
(Nonmandatory Information)
X1.1 Benefits of On-Line Analysis without manual preparation of eluent reagents. Further, when
X1.1.1 The two major benefits of on-line analysis of trace the hydroxide eluent passes through the suppressor, it is
level contaminants in high purity water is (1) there is no need converted to water, which results in a very low and stable
for a chemistry lab analyst to be involved in everyday ion baseline, compared to carbonate-based eluents. This stable
analysis procedures and (2) the sample analyzed is never baseline delivers less baseline noise, thus increasing method
exposed to sources of accidental ionic contamination to which sensitivity.
samples collected and brought to the laboratory are subject. X1.3 Electrolytic Regeneration of Suppressor
X1.1.2 The balance of this Appendix is devoted to a brief X1.3.1 The traditional regenerant for the suppressor cited in
summary of advances in ion chromatography (IC) technology this document is dilute sulfuric acid. Now, electrolytically
that have taken place since this test method (guidance) was generated acid can be used to supply the hydrogen ion required
introduced in 1996. The innovations presented here are appli- for regenerating an anion suppressor.
cable to high purity water analysis, whether it is used in the
power or semiconductor fabrication industry, or in any other X1.4 Reagent-Free IC
industry that requires ionic-contamination-free water for X1.4.1 The invention of electrolytic generation of hydrogen
proper operation. ion and hydroxide ion has brought the reagent-free technology
to ion analysis.
X1.2 Electrolytic Generation of Eluent
X1.2.1 IC has become simpler and more automated with the X1.5 Example of Results with These Advances
invention of electrolytic generation of a hydroxide eluent and X1.5.1 The example chromatogram below shows the sepa-
a corresponding development of hydroxide selective anion ration and concentration of example anions with these ad-
exchange columns. Now, anion separations can be made vances in place.
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