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Qualitative and Quantitative Anion Analysis of Drinking Water by Ion

Chromatography

Article  in  The Chemical Educator · May 2005

DOI: 10.1333/s00897050902a

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 Chem. Educator 2005, 10, 1–3 (web)1

Qualitative and Quantitative Anion Analysis of Drinking Water by Ion

Chromatography

Neal Phillip,* Thomas Brennan, and Panayiotis Meleties

Department of Chemistry, Bronx Community College of the City University of New York, Bronx NY, 10453,
Neal.Phillip@bcc.cuny.edu
Received January 24, 2005. Accepted March 9, 2005.

Abstract: Ion chromatography is employed in the analysis of commercial samples of drinking water. In this
laboratory experiment, third-semester chemistry and science students expand their understanding of the
qualitative- and quantitative-analysis concepts introduced during the first-year general chemistry course
sequence. The experiment is of interest to students because of its direct relevance to their lives and to the
environment. Furthermore, it provides students with the opportunity to gain experience in current analytical
methods and on state-of-the-art-instruments.

Introduction Safety. The instructor and students should follow routine

With its direct applications to monitoring water quality,
environmental research, wastewater management, and many
other applications, ion chromatography has become the method
of choice for ion analysis of water samples [1]. Specific
educational applications have been reported for commercial
product analysis, for instance, juices and hair dyes [2] and for
natural water analysis, for example, pond and lake water [3].
The quality of water is of paramount importance to our health
and our environment [4, 5]. For example, the presence of ions
such as nitrates or nitrites in drinking water may lead to a fatal
condition in infants called methemoglobinemia or “blue-baby
syndrome” [6], high concentrations of fluoride ion contribute
to fluorosis (7, 8), the presence of phosphates and nitrates in
drinking water samples can lead to bacterial regrowth in
drinking water distribution systems [9], and the presence of
sulfate and chloride ions in high concentrations imparts a salty
taste to drinking water [10].
This state-of-the-art analytical method is a direct extension
of the first-year general chemistry anion and cation analysis.
Students can easily apply the qualitative and quantitative
concepts from general chemistry courses to the instrumental
analysis in this experiment. Water analysis has consistently
been included in chemistry and environmental courses to
demonstrate applications of qualitative and quantitative
analytical techniques [11–14]. Ion chromatography presents an
ideal approach to introducing students trained in the traditional
wet-chemistry procedures to modern instrument-based
methods. The proliferation of bottled drinking water provides
easy access to samples for this experiment.
Experimental Section
Preliminary Remarks. This experimental protocol has been
developed for students who have at least one year of general
chemistry laboratory experience including qualitative and quantitative
analysis of ions. It can easily be modified for students in
environmental science courses. Chromatography concepts are
introduced in a prelaboratory lecture.
laboratory procedures for handling water samples, such as wearing
safety goggles and gloves to avoid eye or skin contact.
Ion-Chromatography System. The ion chromatograph employed
was a Model DX500 based on the LC-25 chromatography enclosure
from Dionex Corporation (Sunnyvale, CA) with a GP50 gradient
pump, a 25 µL injection loop, an anion self regenerating suppressor
(ASRS-Ultra) system, and a CD20 conductivity detector. The ASRS-
Ultra system employs auto suppression of the eluent through
electrolytic regeneration to supply the necessary ions [15]. The
DX500 is equipped with a Dionex AS9-HC/AG9-HC
separation/guard column system. Other available columns such as the
Dionex AS4A/AG4A and AS9-SC/AG9 can also be used. The eluent
is a 1.7 mM NaHCO3/1.8 mM Na2CO3 solution prepared with distilled
and deionized water. Approximately 1 mL of sample is injected in the
instrument’s injection loop of which 25 µL is automatically
transferred onto the analytical column after a six-second time delay. A
Dell Pentium III computer with Dionex PeakNet 5.11 software is used
to control the system as well as to acquire and process the data.
Experimental Protocol. Standard single-anion solutions of
bromide, chloride, fluoride, nitrate, nitrite, phosphate, and sulfate ions
were prepared for retention-time analysis. All single-anion solutions
were prepared from stock reference standards of each anion purchased
from ACCU Standards Inc. Distilled and deionized water with a
specific conductance of 17.8 µOhm/cm was used to prepare all
standard solutions. Standard solutions of each anion were injected into
the ion chromatograph to determine the retention times, which were
incorporated in the experiment analytical method. Stock solutions
were used to prepare four mixed-calibration standards, each of which
contained the seven anions at levels corresponding to the range of
their expected concentration in water samples. Samples from each
mixed-calibration standard solution were analyzed by the ion
chromatograph, and corresponding calibration curves for each
concentration level were obtained and incorporated into the
experiment analytical method. Samples of tap water and various
brands of bottled drinking water were then analyzed. The identity and
concentration of each anion in the unknown samples were determined
using experimental analytical method data (i.e., retention times and
calibration curves).
Results and Discussion
Ion chromatograms for each of the single-anion solutions,
the mixed-calibration standard solutions, and the drinking-

© 2005 The Chemical Educator, S1430-4171(05)0xxxx-x, Published on Web 05/23/2005, 10.1333/s00897050902a, xxxxxxaa.pdf
2 Chem. Educator, Vol. 10, No. X, 2005 Phillip et al.

Level46_14 water samples were generated by the experimental analytical

25.0
5
method. Examples of these chromatograms are shown in
Figures 1 and 2. The experimental analytical method also
20.0 generated the calibration curve for each of the four
concentration levels. Table 1 shows the four concentration
levels, and Figure 3 shows an example of a mixed-standard
15.0
calibration curve.
10
Table 2 depicts the retention times determined by students
µS

10.0 3 for each of the seven anions in the water samples. In order to
accommodate minor fluctuations in anion retention times
5.0 6 8 9 students set the tolerance levels at ±0.2 min for the halide,
12 4
7 nitrite, and nitrate ions and at ±0.5 min for the phosphate and
0
sulfate ions. For each anion, students were required to produce
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 an anion calibration curve with a minimum linear correlation
Minutes coefficient of 0.999. Students failing to meet this criterion had
Figure 1. Ion chromatogram of a level-4 mixed-calibration standard to repeat the procedure with freshly prepared calibration
solution. Peak Assignments: F– (3), Cl– (5), NO2– (6), Br– (7), NO3– standards until they succeeded.
(8), H2PO4– (9), SO42– (10). Students analyzed many drinking-water samples to
determine the concentration of each of the anions present in
Level46_14 bottled drinking water and in laboratory tap water (Table 3)
25.0
5
according to US EPA quality control/quality assurance
protocol [10]. To assess the precision of the analysis, repeated
20.0
measurements of anions in selected samples were carried out.
The relative standard deviation (RSD) for anion analysis falls
within the range of 0.3 to 2.2%.
15.0
Students reported the following: (a) laboratory tap water and
10
bottled water contain mainly chloride, nitrate, and sulfate ions
µS

10.0 3 (Table 3); (b) the chloride concentrations range from 0.89 to
3.35 mg L–1, the nitrate concentrations range from 0.48 to
5.0 6 9
10.39 mg L–1, and the sulfate concentrations range from 2.06 to
8
12 4
7 16.57 mg L–1; (c) concentrations for the fluoride, nitrite, and
phosphate ions were in general below the column detection
0
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0
limits; (d) only the two samples imported from the Caribbean
Minutes islands and the laboratory tap water contained detectable levels
Evian Bottled Water
of fluoride ions (0.56, 0.73, and 1.00 mg L–1, respectively),
10.0 below the EPA maximum allowed level of 4 mg L–1 [10]; (e)
only one bottled water (Deer Park) contained a detectable
8.0 concentration of bromide ions (0.06 mg L–1); and (f) phosphate
3 ions were detected for two water samples: the laboratory tap
6.0 water and one of the Caribbean waters (0.25 and 0.20 mg L–1,
respectively).
µS

4.0 9

Conclusion
2.0 5

12 4 6 78 The drinking-water analysis experiment was developed for

0 the Quantitative Instrumental Analysis course (CHM 37),
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0
which is part of the Pharmaceutical Manufacturing Technology
Minutes A.A.S. program recently introduced at Bronx Community
Figure 2. Ion chromatograms of Dasani (top) and Evian (bottom) College. Preparation of single-anion standard solutions for
bottled waters. Peak Assignments: Cl– (3), NO3– (5), SO42– (9). reference data usually requires 90 min. Another 90 min is
required to obtain reference retention times and calibration
Table 1. The Four Anion-Mixed Calibration-Standard Concentration curves for the seven anions. Unknown samples were analyzed
Levels. during the next three-hour laboratory session. Thus, two three-
hour laboratory periods are sufficient to complete this
Anion Level 1 Level 2 Level 3 Level 4
experiment. A typical run time for each unknown sample is
(mg L–1) (mg L–1) (mg L–1) (mg L–1)
about twenty minutes.
Fluoride 0.20 0.50 2.00 4.00
The experiment utilized readily available samples of bottled
Chloride 0.50 2.00 10.00 20.00
drinking water. The experimental protocol can easily be
Nitrite 0.20 1.00 2.00 5.00
adapted to samples from diverse origins, such as river and lake
Bromide 0.20 0.50 1.00 2.00
water, sea water, treated waste-water, rain, snow, and
Nitrate 0.20 1.00 2.00 5.00
condensed cloud samples. Care must be taken for samples with
Phosphate 2.00 5.00 10.00 20.00
solid particulates in which case appropriate filtration (0.4 µm
Sulfate 2.00 10.00 20.00 40.00

© 2005 The Chemical Educator, S1430-4171(05)0xxxx-x, Published on Web 05/23/2005, 10.1333/s00897050902a, xxxxxxaa.pdf
 Qualitative and Quantitative Anion Analysis of Drinking Water Chem. Educator, Vol. 10, No. X, 2005 3

pore filters) procedures should be included in the sample

preparation.
2x105 This experiment can also serve as the basis for inquiry and
research projects that are integrated with instrumental analysis
1x105 courses for real-world experience. Student research assistants
can use this experimental protocol to begin their training for
environmental and other research projects. This experiment is a
1x105
useful introduction of students to modern instruments and to
Area

important skills and knowledge required in a modern science

8x104 and technology-driven environment.

4x104
Acknowledgment. We are grateful to the National Science
Foundation for the funds to support the development of the
Pharmaceutical Manufacturing Technology program, the new
0 courses and the laboratory experiments (NSF ATE Award
0 1.000 2.000 3.000 4.000 5.000
0202386, 2002-2005).
Amount (mg/L)

Figure 3. Nitrate calibration curve (correlation coefficient r2 = Supporting Materials. The student laboratory handouts
0.999971). with instructions and background notes are provided in a Zip
file (http://dx.doi.org/10.1333/s00897050902a).
Table 2. Reference Anion Retention Times Recorded in the
Experiment Analytical Method References and Notes
– – – – – – 2
Anions F Cl NO2 Br NO3 H2PO4 SO4 1. Weiss, J. Ion Chromatography; VCH: New York, 1995.
–
2. helan, R. J.; Hannon, T. E.; Zare, R. N. J. Chem. Educ. 2004, 81,
Retention 3.68a 6.73a 7.42a 9.42a 11.03a 16.00b 18.3 1299–1302.
Time (min) 3b 3. Sinniah, K.; Piers, K.; J. Chem. Educ. 2001, 78, 358–362.
a
Tolerance ±0.2 min. bTolerance ±0.5 min.
4. Aldhous, P. Nature 2003, 422, 251–253.
Table 3. Anion Concentrations in Drinking-Water Samples (mg L ) –1 5. Clarke, T. Nature 2003, 422, 254–256.
– – – – – – 2 6. Hörold, S.; Tacke, T.; Vorlop, K.-D. Environ. Technol. 1993, 14,
Sample F Cl NO2 Br NO3 H2PO4 SO4 931–939.
Dasani <0.02 1.03 <0.02 <0.02 <0.02 <0.20 14.62
7. Chandrashekar, J.; Anuradha, K. P. Int. Dent. J. 2004, 54, 235–239.
Twin <0.02 0.89 <0.02 <0.02 1.52 <0.20 10.08
8. Bhargavi, V.; Khandare, A. L.; Venkaiah, K.; Sarojini, G. Biol. Trace
Mountain
Elem. Res. 2004, 100, 195–204.
Poland <0.02 2.56 <0.02 <0.02 3.61 <0.20 2.06
Spring
Evian <0.02 2.26 <0.02 <0.02 4.37 <0.20 15.39
Deer Park <0.02 8.37 <0.02 0.06 10.39 <0.20 15.39
Loubiere 0.56 4.07 <0.02 <0.02 2.70 <0.20 3.64
Naturala
TroisPiton 0.73 2.81 <0.02 <0.02 0.48 0.20 16.57
Purea
Vermont <0.02 2.34 <0.02 <0.02 4.76 <0.20 13.27
Pure
BCC Tap 1.00 3.35 <0.02 <0.02 1.14 0.25 7.18
Water
c c
USEPA 4 250 1 10 250
MCLb
a
Bottled Water from the Caribbean Island of Dominica. bDrinking
Water Maximum Contaminant Levels set by the US Environmental
Protection Agency. cNo established USEPA MCL.

© 2005 The Chemical Educator, S1430-4171(05)0xxxx-x, Published on Web 05/23/2005, 10.1333/s00897050902a, xxxxxxaa.pdf

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