C197-E004

Ion Chromatography Solutions for

Environmental Analysis
Ion Chromatography Solutions for Environmental Analysis

Contents
Overview of Environment Analysis 3
Relevance of Ion Chromatography in Environmental Analysis 4
Overview of Ion Chromatography 6
Introduction of Ion Exchange Chromatography 6
Shimadzu’s Ion Chromatography Solutions 7
LabSolutions Software 10
Lineup of Columns 10

Applications of Water & Environmental Atmosphere

Analysis of Anions
Analysis of Inorganic Anions in Tap Water According to EPA Method 300.1 Using Ion Chromatography 11
US EPA 300 Method-Compliant Environmental and Water Analysis 12
ASTM D4327-03 Compliant Analysis of Anions in Drinking Water 13
ASTM D4327-03 Compliant Analysis of Anions in Wastewater 14
Analysis of Total Nitrogen and Total Phosphorus in Environmental Water According to ASTM D8001 by Ion Chromatography 15

Analysis Using Dual System

Simultaneous Analysis of Anions and Cations Using Ion Chromatograph Dual Channel System 16

Analysis of Cations
Analysis of Cations in Drinking Water and Wastewater, Conforming to ASTM D6919-03 18
Quantifying NH4 in Industrial Wastewater Using Ion Chromatography (Non-Suppressor System)
+
19
Analysis Method of Dissolved Hexavalent Chromium According to EPA 218.6 20
Analysis of Hexavalent Chromium in Drinking Water According to EPA 218.7 21
Measuring Hexavalent Chromium Compounds in Atmospheric Dust 22

Lineup of Liquid Chromatography Systems 23

 Ion Chromatography Solutions for Environmental Analysis

Overview of Environmental Analysis

Shimadzu has focused on the development of instruments for environmental analysis for decades, helping scientists to detect,
identify and quantify trace-level pollutants and meet environmental testing demands, for both regulatory purposes and to advance
Research & Development. We offer total solutions to support your environmental monitoring of air, water (drinking, wastewater,
surface…), and soil, from regulated contaminants (pesticides, anions, disinfection by-products, dioxins…) to emerging ones, such as
microplastics and PFAS, as well as greenhouse gases (GHG, including CO2, CH4, and N2O) and carbon dioxide capture and storage (CCUS).
These solutions include a wide range of analytical and measuring technologies/instruments including chromatography (GC, LC, and
SFC), mass spectrometry (GC–MS, LC–MS, and MALDI), sum parameter (TOC), and spectroscopy (UV-Vis, FTIR, AAS, and ICP–OES).

Analytical Instruments for Environmental Analysis

Shimadzu offers the most comprehensive portfolio of solutions for the analysis of regulated and emerging contaminants in all types
of environmental samples.

Carbon dioxide
Soil & Capture,
Water Air Solid Waste PFAS Microplastics
Sediments Utilization and
Storage (CCUS)
UV-Vis ✓ ✓
FTIR, Raman ✓ ✓
TOC ✓ ✓ ✓ ✓
IC ✓ ✓ ✓
HPLC ✓ ✓ ✓ ✓
LC–MS ✓ ✓ ✓ ✓
GC ✓ ✓ ✓ ✓ ✓ ✓
GC–MS ✓ ✓ ✓ ✓ ✓ ✓ ✓
ICP–MS ✓ ✓ ✓ ✓
ICP–OES ✓ ✓ ✓ ✓
AA ✓ ✓ ✓ ✓
Particle size ✓

Cyanotoxins HAAs
PFAS LC–MS Herbicides
LC–MS

Pesticides Pesticides

GC
Emerging HPLC GC Phenols
Contaminants Other Organics
Unknowns (QTOF) PCBs

Carbamate
HPLC

Diquat IC GC–MS 1,4-dioxane

Dioxins & Furans
Glyphosate Nitrosamines
GC–MS

Other Organics
Anions Microplastics
Chromium VI LabSolutions™ DB/CS Semivolatiles
IC

Ammonia TOC ICP–MS Taste & Odor

Volatiles
Nitrogen THMs
TOC

Organic Carbon
Phosphorous Customizable Reports
ICP–MS

Connection to LIMS
Metals
FTIR & Raman ICP
Raman
FTIR &

Microplastics

UV-Vis AA
ICP

Chlorine Metals
UV-Vis

UV254 Particle
Others Size
Particle
Size

AA

Solids Metals

OneLabOneEarth.com

index 3
Ion Chromatography Solutions for Environmental Analysis

Relevance of Ion Chromatography in Environmental Analysis:

Regulations and Analytical Methods
Ion chromatography is widely used for water quality monitoring. Anions and cations in a wide variety of water samples, including
drinking water, ground water, wastewater and sea water, can be analyzed. Most countries have established regulations and standards
for these contaminants. Below is a summary of the standards for contaminants that are routinely analyzed by ion chromatography.

Table 1 List of water quality standards using ion chromatography

WHO US EPA EU Japan China

Components National Primary

Standard Standard Standard Standard
Drinking Water Notes
value value value value
Regulations MCL*1

Inorganics

Chloride (Cl−) — 250 mg/L 250 mg/L (indicator parameters) 200 mg/L 250 mg/L

Fluoride (F−) 1500 µg/L 2.0 mg/L 1.5 mg/L 0.8 mg/L 1.0 mg/L

[nitrate]/50 + [nitrite]/3 ≤ 1
10 mg/L
Nitrate (NO3 ) −
50 mg/L 10 mg/L 50 mg/L (Total amount of 10 mg/L (as N)
NO3–N and NO2–N)

Nitrite (NO2−) 3 mg/L 1 mg/L 0.5 mg/L 0.04 mg/L —

(as NO2–N)

Sodium (Na+) — — 200 mg/L 200 mg/L 200 mg/L

Sulfate (SO42−) — 250 mg/L 250 mg/L (indicator parameters) — 250 mg/L

Hexavalent 0.1 mg/L

— — 0.02 mg/L 0.05 mg/L
chromium (Cr6+) (Total chromium)

Disinfectants and disinfectant by-products

Bromate (BrO3−) 10 µg/L 0.01 mg/L 10 µg/L 0.01 mg/L 0.01 mg/L

Chlorate (ClO3−) 700 µg/L — 0.25 mg/L Max concentration of 0.70 0.6 mg/L 0.7 mg/L
mg/L if chlorine dioxide, or
other disinfectants that
0.8 mg/L generate chlorate, is used 0.6 mg/L
Chlorite (ClO2−) 700 µg/L (Chlorine Dioxide 0.25 mg/L for potable water. 0.7 mg/L
(target value)
as ClO2−)

<Reference> https://www.who. https://www.epa.g https://eur-lex.europa.eu/legal-content/EN/ https://www.env.g GB/T 5749-2022

int/publications/i/it ov/ground-water-a ALL/?uri=CELEX:32020L2184 o.jp/water/water_ Standard for
em/97892415499 nd-drinking-water/ supply/kijun/kijunc drinking water
50 national-primary-dr hi.html#01 quality
inking-water-regula (Japanese only) (Chinese only)
tions

*1 MCL: Maximum Contaminant Level.

4
 Ion Chromatography Solutions for Environmental Analysis

Relevance of Ion Chromatography in Environmental Analysis:

Analytical Methods
Table 2 List of EPA methods and ASTM standards of water quality using ion chromatography

Regulations Target Components

Determination of Dissolved Hexavalent Chromium in Drinking Water, Groundwater, and

218.6
Industrial Wastewater Effluents by Ion Chromatography
Hexavalent chromium
Determination of Hexavalent Chromium in Drinking Water by Ion Chromatography with
218.7
Post-column Derivatization and UV-Visible Spectroscopic Detection

Part A: Bromide Chloride

300.0 Determination of Inorganic Anions by Ion Chromatography Fluoride Nitrate Nitrite
Phosphate-P Sulfate

300.1 Determination of Inorganic Anions in Drinking Water by Ion Chromatography Part B: Bromate Chlorate
Chlorite

Determination of Bromate in Drinking Water Using Two-Dimensional Ion

302 Bromate
Chromatography with Suppressed Conductivity Detection
EPA

314.0 Determination of Perchlorate in Drinking Water Using Ion Chromatography

Determination of Perchlorate in Drinking Water Using Inline Column Concentration/

314.1 Perchlorate
Matrix Elimination Ion Chromatography With Suppressed Conductivity Detection

Determination of Perchlorate in Drinking Water Using Two-Dimensional Ion

314.2
Chromatography with Suppressed Conductivity Detection

Determination of Inorganic Oxyhalide Disinfection By-Products in Drinking Water Using

Bromate, Bromide,
317 Ion Chromatography With the Addition of A Post-column Reagent for Trace Bromate
Chlorite, Chlorate
Analysis

Determination of Inorganic Oxyhalide Disinfection By-Products in Drinking Water Using

Bromate, Bromide,
326 Ion Chromatography Incorporating the Addition of A Suppressor Acidified Post-column
Chlorite, Chlorate
Reagent for Trace Bromate Analysis

D2036A Standard Test Methods for Cyanides in Water Cyanides

Fluoride, Chloride, Nitrite,

Standard Test Method for Anions in Water by Chemically Suppressed Ion
D4327-03 Phosphate, Bromide,
Chromatography
Nitrate, Sulfate

Standard Test Method for Dissolved Hexavalent Chromium in Water by Ion

D5257 Hexavalent chromium
Chromatography

ASTM D6850-18 Standard Guide for QC of Screening Methods in Water —

Standard Test Methods for Bromate, Bromide, Chlorate, and Chlorite in Drinking Water Bromate, Bromide,
D6581
by Suppressed Ion Chromatography Chlorate, Chlorite

Lithium, Sodium,
Standard Test Method for Determination of Dissolved Alkali and Alkaline Earth Cations
D6919-03 Potassium, Magnesium,
and Ammonium in Water and Wastewater by Ion Chromatography
Calcium, Ammonium

Standard Test Method for Determination of Total Nitrogen, Total Kjeldahl Nitrogen by
D8001 Nitrogen, Phosphorus
Calculation, and Total Phosphorus in Water, Wastewater by Ion Chromatography

<References> https://www.epa.gov https://www.astm.org

index 5
Ion Chromatography Solutions for Environmental Analysis

Overview of Ion Chromatography

Ion chromatography (IC) is a type of liquid chromatography technique that measures ionic compounds. These chemicals, when
present in solution, are separated and quantified in a packed column with an ion exchange resin as a stationary phase and using
electrolyte solution as eluent. The most common detector is the electrical conductivity detector, which has high sensitivity, selectivi-
ty, and relatively low cost of operation. Other detectors, such as an electrical conductivity detector and a UV-visible absorption
photometric detector, can be used. The detector chosen is based on the physico-chemical properties of the analytes of interest. In
some cases, a post column derivatization step may be used to enhance sensitivity and selectivity of the analytical method.
IC is a reliable measurement method that has been widely adopted in standardized analytical methods for analysis of environ-
mental samples, foods and other materials. In 1986, Shimadzu developed its first ion chromatograph. Shimadzu has since become
a world-leading ion chromatograph manufacturer, developing both suppressor and non-suppressor systems.

Introduction of Ion Exchange Chromatography

Ion exchange chromatography (IEX) is a Anion in Mobile Phase Anion in
(CO32−) Sample
separation method using the difference
of charge states between the eluent
and analytes from the stationary phase
in the column. It is mainly used for the
analysis of ionic compounds. resin resin resin
There are two types of IEX methods: In equilibrium with Sample ion displaces Sample ion is displaced
anion exchange chromatography and anions in mobile phase mobile phase ion and by mobile phase ion,
adsorbs then adsorbs to next
cation exchange chromatography. exchange group

Figure shows how anion exchange chromatography.

In the stationary phase of anion exchange chromatography, packing materials modified with positively charged ion-exchange
groups are used. When the eluent enters the column, it adsorbs onto the ion exchange groups of the stationary phase due to
electrostatic attraction.
The eluent continuously introduces anions into the column, resulting in a repeated adsorption and desorption of anions
between the stationary and eluents, i.e. a state of equilibrium.
When a sample containing anions is introduced into the column during this state, the anions in the sample are adsorbed
through electrostatic interactions with the functional groups of the stationary phase. At the same time, the anions from the eluent
that were previously adsorbed on the stationary phase are desorbed. The sample anions adsorbed on the stationary phase are then
desorbed and adsorbed onto the next ion exchange group.
This exchange phenomenon is repeated until the sample anions completely move through the column and are eluted.

To detector From column H2O The suppressor method of electric conductivity detection
H2CO3 Na+HCO3 from detector
Waste solution changes the eluent composition to a composition with lower
H2O
H2O + O2 ↑
electrical conductivity. When anions are separated, the
presence of sodium ions generates eluted carbonate ions.
OH− + 1/2H2 ↑ Eliminating the sodium ions just before the detector changes
Cation exchange membrane

Cation exchange membrane

Cation exchange membrane

H+ H+ Na+ Na+ OH the eluent to a slightly acidic aqueous carbonate solution,

with lower electric conductivity. Meanwhile, in the regions
Anode +

Cathode −

H+ H+ Na+ Na+ OH where the inorganic anions in the sample elute, the carbon
dissociation equilibrium shifts toward creating more H+ ions
that become pair ions in order to maintain balanced charges.
H+ H+ Na+ Na+ OH
Because hydrogen ions have a higher equivalent electric
2H+ + 1/2O2 ↑
conductivity than other ions, this increases the peak response.

H2O

H2O
from detector Waste solution

* For more details:

Electrode flow path Eluent flow path Electrode flow path
https://www.shimadzu.com/an/service-support/technical-support/analysis-basics/
Structure and principles behind the ICDS™-40A anion suppressor unit liquid-chromatography/ion/64intro/

6 index
 Ion Chromatography Solutions for Environmental Analysis

Shimadzu’s Ion Chromatography Solutions

Anion Suppressor Ion Chromatograph: HIC-ESP

The HIC-ESP is an anion suppressor ion chromatograph with a built-in electrodialytic suppressor, boasting the same low carryover
and excellent injection precision characteristic of Shimadzu HPLCs to bring you highly reliable results. The newly developed anion
suppressor prevents peak spreading and achieves high sensitivity, providing stable functionality even over long periods of use.

Conductivity Detector Anion Suppressor Unit

CDD-10AVP ICDS™-40A
A temperature-regulating device in the detection This is an electrodialytic suppressor unit
cell and the placement of the detection cell in the built into the top part of the column
column oven ensure precise temperature control. oven. It achieves high performance even
This enables analysis with low noise conditions and with low internal volume.
a stable baseline even when using electrical
conductivity detection, which is sensitive to
temperature fluctuations.
Column Oven
CTO-40S
The forced air circulation oven has extremely
Degassing Unit precise temperature regulation, and can be used
DGU-403 with a variety of column lengths up to 300 mm.
Because the unit adopts an online degassing system
with high performance and low internal volume, it
is easy to replace the eluent and more stable analysis
is achieved. Offline degassing of the eluent with
ultrasonic waves or decompression is not necessary.

Autosampler
Solvent Delivery Pump SIL-20A/20AC (Inert kit)
LC-40i The SIL-20A/20AC is a full-volume autosampler with
Although it is a metal-free pump that uses a series very low carryover, which allows high accuracy,
double plunger system, it has stable liquid delivery high-speed injection of volumes from 0.1 µL up.
performance with suppressed pulsation. The wetted parts are made inert using the inert kit.

CDD Cell

Waste liquid

Analysis column
Pump
Autosampler Oven ICDS™-40A
Suppressor
Eluant

Anion Suppressor Unit ICDS™-40A

With a unique design in which the µS/cm
4 F
eluent flow path bends back around,
combined with dialytic membrane the
Shimadzu ICDS-40A
Other vendor’s
1.2×
Cl
2 suppressor
new ICDS-40A anion suppressor unit NO2
achieves higher efficiency and stable
0
suppression while maintaining a small
internal volume (patent pending).
−2

Separation of F ion peak is improved

−4 through narrower waterdip shape.
0.0 2.0 4.0 6.0 min

index 7
Ion Chromatography Solutions for Environmental Analysis

Shimadzu’s Ion Chromatography Solutions

Non-suppressed Anion Ion Chromatograph: HIC-NS

The mobile phase conductivity is affected by temperature changes and solvent delivery pump pressure variations, which can lead to
baseline noise and drift. With suppressors, noise is reduced by reducing mobile phase conductivity, the source of these problems.
With non-suppressor systems, however, this problem must be dealt with by improving basic hardware performance. Shimadzu
accomplishes this using its proprietary high basic performance. This includes pulse-free solvent delivery, which suppresses pressure
variations during solvent delivery to a bare minimum, and double temperature control, featuring detector cells equipped with
thermal control functionality arranged within the column oven.

Solvent Delivery Pump

LC-40i
With the pulse-free solvent delivery pump,
which is capable of solvent delivery at 100
nL/min to 5 mL/min, conductivity detection, Column Oven
which does not require suppressors, can be CTO-40C
performed.
The column oven features forced
air-circulation, which has an established
reputation for HPLC column temperature
Autosampler control. Furthermore, thanks to the electronic
SIL-20A/20AC (Inert kit) cooling function, column temperature can
The SIL-20A/20AC is a full-volume be controlled from an ambient temperature
autosampler with very low carryover, which of −15 °C. In addition to columns, this
allows high accuracy, high-speed injection large-capacity oven can simultaneously
of volumes from 0.1 µL up. The wetted accommodate a suppressor/non-suppressor
parts are made inert using the inert kit. conductivity detector cell assembly.

Dual Flow-Line Analysis System: HIC-ESP/NS

With automatic switching of the sample injection valves, a sample
loop with two flow lines is consolidated into one. Simultaneous
analysis is performed by adding sample to the two sample loops with
a single sample injection. This system is ideal for routine analysis of
anions and cations as in tap water quality analysis. A UV detector can
also be used when the anion suppressor system is used.

Column oven

Autosampler

Column for
Pump B cation analysis Conductivity
detector cell
Eluent

Column for
Pump A anion analysis Conductivity
detector cell
Eluent

Suppressor

UV detector

Flow-line diagram for the dual flow-line analysis system

8
 Ion Chromatography Solutions for Environmental Analysis

Nexera™ Organic Acid Analysis System

This system is ideal for organic acid analysis of samples with matrices. Combining
ion-exclusion chromatography with Shimadzu’s unique detection technique (pH buffered
electric conductivity detection), the system excels in both selectivity and sensitivity.

Column
Solvent
delivery pump Autosampler
Eluent
Plumbing part
MR
Conductivity
detector cell
Solvent
delivery pump Column oven
Buffer
solution

Flow-line diagram for the Nexera organic acid analysis system

pH buffering reagent
pH is adjusted to near neutral
by buffering action.

−
Column CH3CO2H CH3CO2 Detector

At pH 3 in the column, almost At pH 7 at the detector inlet,

no acetic acid is dissociated. almost all is dissociated.

100%

Proportion of
acetic acid pKa = 4.8
dissociation

0%
2 3 4 5 6 7 8 (pH)

pH of solution

Condition of organic acid in pH buffering method

index 9
Ion Chromatography Solutions for Environmental Analysis

LabSolutions Software
Settings for analysis parameters, continuous analysis, auto-shutdown, data processing, and report creation can all be managed
from LabSolutions analysis software. Data integrity can be handled with the addition of LabSolutions DB and LabSolutions CS.

Analysis Analysis
Analysis Auto- Data Report
Start-up method sequence
preparations shutdown analysis creation
settings settings

2 Filter and display standard/control

samples or unknown samples

Data explorer Peak integration

parameter editing

1 Drag and drop batch files to Table of quantitative results

be processed into the results
browser screen
3 Check statistical results for areas or
retention times of each peak in the table

4 Scroll between chromatograms

to check results with mouse
clicks or arrows on the keyboard

Chromatogram display Calibration curve information

Quantitative results browser

Results can be checked and errors or

outliers detected much more quickly,
with the software automatically
judging calibration curve validity,
maximum and minimum limits for
sample values, etc.

Automatic judgments on analytical results

Lineup of Columns
The column type used for ion chromatography differs depending on whether suppressors are used and whether they are used for
anion or cation analysis. Below are the characteristics of each column.

Capable of analyzing inorganic anions. Compatible with acid or basic mobile

Shim-pack™ IC-A1 phases of wide pH range.
Anion Analysis
Provides outstanding separation efficiency in the analysis of inorganic anions
Shim-pack IC-A3 and acid ions, especially when weakly acid mobile phase is used.
Non-Suppressor Type
Capable of analyzing cations such as alkaline metal ions, alkali earth metal ions,
Shim-pack IC-C1 transition metal ions, rare earth metal ions, and alkyl amines.
Cation Analysis
Capable of simultaneous analysis of alkali metal ions and alkaline earth metal
Shim-pack IC-C4 ions. Enhances the separation of sodium and ammonium ions.

Capable of determining fluoride ions, chloride ions, nitrite ions, bromide ions,
Shim-pack IC-SA2 nitrate ions, phosphate ions and sulfuric acid ions.
Suppressor Type Anion Analysis Provides high-resolution performance when analyzing fluoride ions, chloride
Shim-pack IC-SA3 ions, nitrous acid ions, bromide ions, nitric acid ions, phosphate ions and sulfuric
acid ions as well as chlorous acid ions, chloric acid ions and bromic acid ions.

<Reference>: https://www.shimadzu.com/an/service-support/technical-support/analysis-basics/liquid-chromatography/ion/ic-wash/

10 index
 Ion Chromatography Solutions for Environmental Analysis

Analysis of Anions

Analysis of Inorganic Anions in Tap Water According to EPA

Method 300.1 Using Ion Chromatography
Application
Keywords: EPA 300, tap water

Many countries have standards for environmental and drinking water. In the United States, the Environmental Protection Agency
(EPA) provides methods for the analysis of inorganic anions in water by ion chromatography (EPA Method 300.1).
In this article, we introduce examples of the analysis of 10 inorganic anions in accordance with EPA Method 300.1 using
the HIC-ESP.

Benefits • Suppressed ion chromatography can be used for analysis of tap water according to EPA Method 300.1.
• It can measure 10 anions including disinfection byproducts with high sensitivity in about 22 minutes.
• The ICDS-40 reuses the waste liquid from the detector into reclaimed liquid, allowing environmentally
conscious analysis.

■ Flow Path Diagram 3.00

µS/cm
4
2.50 1. ClO2
2.00 2. BrO3
3. Br
1.50 5
4. ClO3
CDD Cell 1.00
5. DCA 1 3
0.50 2
Waste
0
Column −0.50
Pump
Autosampler Oven Suppressor 0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 min
ICDS™-40A
Eluant Fig. 3 Chromatogram of Standard Solution (Part B)
(1, 2, 3: 100 µg/L 4, 5: 1000 µg/L)
Fig. 1 The HIC-ESP Suppressor Ion Chromatograph
Flow Chart for Anion Analysis

■ Sample Analysis of Tap Water

■ Analytical Conditions
µS/cm
1.00
Table 1 Analytical Conditions 0.90 2 6
0.80
Column Shodex SI-52 4E (250 mm × 4.0 mm I.D., 5 µm) 0.70
0.60 4
Guard column Shodex SI-92G (10 mm × 4.6 mm I.D., 9 µm) 0.50 5
1
Mobile phase 5.4 mmol/L sodium carbonate 0.40
0.30
Flow rate 0.8 mL/min 0.20
0.10 3
Column temp. 45 °C
0
Injection volume 50 µL (Part A), 200 µL (Part B) −0.10
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 min
Vial Shimadzu Vial, LC, 4 mL, Polypropylene*1
Detection Conductivity Fig. 4 Chromatogram of Tap Water (Part A)
(Peak: 1. F, 2. Cl, 3. Br, 4. DCA, 5. NO3–N, 6. SO4)
*1 P/N: 228-31537-91

µS/cm
■ Analysis of Standard Solutions and MDL 1.75
1.50
Fig. 2 shows the results of injecting 50 μL of a mixed standard 3
1.25
solution of Part A. Fig. 3 shows the results of injecting 200 μL 1.00
0.75
of a mixed standard solution of Part B. 0.50
0.25 2
µS/cm 1
0
10.0 1. F 5. DCA 2
2. Cl 6. NO3–N 0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 min
8.0
3. NO2–N 7. PO4–P Fig. 5 Chromatogram of Tap Water (Part B)
6.0 4. Br 8. SO4 8
(Peak: 1. Br, 2. ClO3, 3. DCA)
4.0 7
3
1 4 6
2.0
0
5 ■ Conclusion
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 min This article introduced inorganic anion analysis in accordance
Fig. 2 Chromatogram of Standard Solution (Part A) with EPA Method 300.1 using the Shimadzu HIC-ESP with
(1: 0.5 mg/L 2: 10 mg/L 3: 0.5 mg/L 4: 2 mg/L suppressed ion chromatography.
5: 1 mg/L 6: 0.5 mg/L 7: 2.5 mg/L 8: 5 mg/L)

index 11
Ion Chromatography Solutions for Environmental Analysis

Analysis of Anions

US EPA 300 Method-Compliant Environmental and Water Analysis

Application
Keywords: EPA 300

In this article, an EPA 300-compliant quantitative analysis of 7 general inorganic anions in various types of water samples was
conducted using an HIC-ESP, an ion chromatograph equipped with an electrodialytic suppressor.

Benefits
• EPA 300-compliant analysis of inorganic anions with high sensitivity and high reliability is possible by
using the Shimadzu HIC-ESP ion chromatograph system.

■ Analysis of Standard Solution Table 3 Analytical Conditions

Fig. 6 shows the results when a 50 μL mixed standard sample Column: Shim-pack IC-SA2 (250 mm L. × 4.0 mm I.D.)
Mobile phase: 1.8 mmol/L Sodium Carbonate
of the 7 anions prescribed in EPA 300 was injected. 1.7 mmol/L Sodium Hydrogen Carbonate
Flow rate: 1.0 mL/min
Column temp.: 40 °C
Injection volume: 50 μL
Detection: Electro conductivity detector

■ Repeatability and Accuracy

The repeatability of the retention time and peak area was
verified by using a mixed standard sample with 10 mg/L of
each ion.
The repeatability of the retention time and peak area was
verified from the results of 5 continuous analyses each day.
Fig. 6 Chromatogram of Mixed Standard Sample of Anions Table 4 shows the results for the 1st and 4th days. The results
Peaks: 1. F (5 mg/L), 2. Cl (5 mg/L), 3. NO2 (5 mg/L),
showed excellent repeatability of the retention times and peak
4. Br (5 mg/L), 5. NO3 (5 mg/L), 6. PO4 (5 mg/L), 7. SO4 (5 mg/L)
areas of all components during the test period.

■ Linearity and Detection Limit Table 4 Repeatability of Retention Time and Peak Area
(One Day, Day-to-Day Repeatability)
For the detection limit, in accordance with the procedure
described in Method 300, an MDL (Method Detection Limit) 1st day 4th day
Component Retention Peak area Retention Peak area
standard sample was prepared, 7 continuous analyses were time (%RSD) (%RSD) time (%RSD) (%RSD)
carried out, and the MDL was calculated as (t) × (S). Here, t F 0.06 0.07 0.12 0.72
Cl 0.06 0.07 0.15 0.78
means the t value for the 99% confidence level (Student’s
NO2 0.06 0.14 0.18 0.70
t-value in t-test; in 7 continuous analyses, t = 3.14), and S Br 0.07 0.24 0.20 0.75
means the standard deviation of 7 continuous analyses. NO3 0.08 0.20 0.22 0.97
PO4 0.15 0.25 0.24 0.64
Table 2 shows the calibration curve range, linearity, MDL
SO4 0.13 0.18 0.30 0.63
standard concentration, and calculated MDL.
Table 5 Recovery Rates of Blank and Tap Water
Table 2 Linear Calibration Region, Linearity, MDL Standard, Spiked concen- Recovery rate (%)
and MDL Component
tration (mg/L) Ultrapure water Tap water
Calibration Coefficient of MDL standard F 2.0 93.9 99.4
MDL Cl 2.0 94.0 96.2
Component curve range correlation concentration
(μg/L) NO2 2.0 96.1 95.2
(mg/L) (r2) (μg/L)
F 0.05–20 0.9999 10 3.31 Br 2.0 97.1 91.2
Cl 0.1–100 0.9992 5 2.05 NO3 2.0 98.0 106.0
NO2 0.05–20 0.9995 20 1.49 PO4 2.0 98.4 103.0
Br 0.05–20 0.9989 20 3.3 SO4 2.0 98.3 92.6
NO3 0.05–20 0.9991 20 2.69
PO4 0.05–20 0.9995 50 14.38
SO4 0.05–20 0.9992 20 3.63 ■ Conclusion
EPA 300-compliant analysis of inorganic anions with high
■ Analysis Conditions sensitivity and high reliability is possible by using the Shimadzu
Table 3 shows the analytical conditions. HIC-ESP ion chromatograph.

12 index
 Ion Chromatography Solutions for Environmental Analysis

Analysis of Anions

ASTM D4327-03 Compliant Analysis of Anions in Drinking Water

Application
Keywords: drinking water

An ion chromatograph is widely used in detection and quantitative analysis of ion components in aqueous solutions. ASTM
D4327-03 issued by ASTM International (the United States) specifies the test methods for analysis of 7 species of anions in drinking
water or wastewater by suppressed ion chromatography.
This article introduces an ASTM D4327-03 compliant analysis of anions in drinking water using a Shimadzu HIC-ESP anion
suppressor ion chromatograph.

Benefits
• Enables acquisition of data compliant with ASTM D4327-03.
• Applicable to anion analyses of not only drinking water, but also tap water.

■ Analysis of Drinking Water ■ Analysis Conditions

Two types of commercially-available drinking water (A, B) were Table 6 Analytical Conditions
filtered with a 0.2 μm filter prior to the analysis. Fig. 7 shows Column: Shim-pack IC-SA2*1 (250 mm × 4.0 mm I.D., 9 μm)
the analysis results for the two drinking water samples. Guard column: Shim-pack IC-SA2(G)*2 (10 mm × 4.6 mm I.D., 9 μm)
Mobile phase: 0.6 mmol/L Sodium Carbonate
µS/cm 12.0 mmol/L Sodium Hydrogen Carbonate
(a) Cl Flow rate: 1.0 mL/min
10.0
Column temp.: 30 °C
Injection volume: 50 μL
NO3 Vial: Shimadzu Vial, LC, 4 mL, Polypropylene*3
SO4
Detection: Conductivity (CDD-10AVP)
0.0
*1 P/N: 228-38983-91 *2 P/N: 228-38983-92 *3 P/N: 228-31537-91

0.0 5.0 10.0 15.0 min

■ Spike and Recovery Test
µS/cm
(b) Table 7 shows the results of a spike-and-recovery test of the tap
2.0 Cl
water conforming to ASTM D4327-03. The test was conducted
SO4
F by spiking the sample with standard solution. The recovery rate
1.0
NO3 was calculated using the equation shown below the table, as
PO4 specified in ASTM D4327-03.
0.0
Table 7 Percent recovery of the spike
0.0 5.0 10.0 15.0 min F Cl PO4 SO4 NO2 Br NO3
Fig. 7 Chromatograms of Commercial Drinking Water Samples 97.5 100.9 106.3 99.5 106.8 107.9 98.6
(a) Drinking Water A, (b) Drinking Water B Unit: %
P = 100 [A(VS + V) − BVS] / CV
P : Percent recovery of the spike
■ Analysis of Tap Water A :
B :
Analyte concentration (mg/L) in spiked sample
Analyte concentration (mg/L) in unspiked sample
Using this method, a sample of tap water was analyzed after C : Concentration (mg/L) of analyte in spiking solution
VS : Volume (mL) of sample used, and
filtration with a 0.2 μm filter. Fig. 8 shows the analysis results. V : Volume (mL) added with spike

µS/cm
40.0 µS/cm
■ Conclusion
Cl
1.0 SO4 This article introduced analyses of anions contained in drinking
30.0
NO3
water and tap water based on ASTM D4327-03 using a
F
20.0
0.0
Shimadzu HIC-ESP suppressor ion chromatograph.

10.0 0.0 10.0 min

SO4
F NO3 Reference
0.0
1) ASTM D4327-03, Standard Test Method for Anions in Water by
0.0 5.0 10.0 15.0 min
Chemically Suppressed Ion Chromatography, ASTM International,
West Conshohocken, PA, 2003, www.astm.org
Fig. 8 Chromatogram of Tap Water and Enlarged Figure

index 13
Ion Chromatography Solutions for Environmental Analysis

Analysis of Anions

ASTM D4327-03 Compliant Analysis of Anions in Wastewater

Application
Keywords: wastewater

The ion chromatograph is widely used in detection and quantitative analysis of ion components in aqueous solutions. ASTM
D4327-03 1) issued by ASTM International in the United States specifies the test methods for analysis of seven anions (fluoride ion,
chloride ion, nitrite ion, bromide ion, nitrate ion, phosphate ion, sulfate ion) in drinking water or wastewater by suppressed ion
chromatograph.
This article introduces an ASTM D4327-03 compliant analysis of anions in industrial wastewater using a Shimadzu HIC-ESP
anion suppressor ion chromatograph. A high-resolution column, Shim-pack IC-SA3, was used because industrial wastewater has a
high content of contaminants.

Benefits • Enables acquisition of data with excellent linearity and repeatability.

• Separation of contaminant components and target anions in wastewater is possible by using the
Shim-pack IC-SA3.
• This test method is also applicable to anion analyses of drinking water.

■ Analysis of Industrial Wastewater ■ Linearity and Repeatability

Using this technique, industrial wastewater was filtered with a A 4-level calibration curve was created for the seven anions
0.2 μm filter and then diluted 10 times with ultrapure water that are the targets of analysis in ASTM D4327-03 in a concen-
prior to the analysis. Fig. 9 shows the analysis results. Although tration range conforming to the ASTM standard. All the
contaminant peaks appeared in close proximity to some coefficients of determination (r2) of the calibration curves
components, such as the fluoride ion and phosphate ion, showed 0.990 or greater, as specified in ASTM D4327-03.
satisfactory separation of those components was also possible Table 9 shows the employed calibration levels.
by using a Shim-pack IC-SA3 as the analysis column.
Table 9 Calibration Levels of Seven Anions
µS/cm
F Cl PO4 SO4 NO2 Br NO3
5 1. F
10 STD 1 0.20 0.20 1.00 2.00 0.40 0.20 0.60
2. Cl
2 3. NO2 STD 2 1.00 1.00 5.00 10.00 2.00 1.00 3.00
5. NO3 STD 3 5.00 5.00 25.00 50.00 10.00 5.00 15.00
5 6. PO4 STD 4 10.00 10.00 50.00 100.00 20.00 10.00 30.00
1 7 7. SO4
Unit: mg/L
3 6
0
Table 10 Repeatability of Retention Times and
Peak Areas at Lowest Calibration Levels
0 10 20 30 min
F Cl PO4 SO4 NO2 Br NO3
Fig. 9 Chromatogram of Industrial Wastewater
Concentration (mg/L) 0.20 0.20 1.00 2.00 0.40 0.20 0.60
Retention time %RSD 0.01 0.01 0.03 0.03 0.02 0.03 0.04
■ Analysis Conditions Area %RSD 0.33 0.35 0.39 0.19 0.18 0.59 0.21

Table 8 shows the analysis conditions of the standard solution

of the seven anions. ■ Conclusion
Table 8 Analytical Conditions This article introduced analyses of anions based on ASTM
Column: Shim-pack IC-SA3*1 (250 mm × 4.0 mm I.D., 5 μm)
D4327-03 using a Shimadzu HIC-ESP anion suppressor ion
Guard column: Shim-pack IC-SA3(G)*2 (10 mm × 4.6 mm I.D., 5 μm) chromatograph. Satisfactory separation of contaminants
Mobile phase: 3.6 mmol/L Sodium Carbonate contained in industrial wastewater was possible by using this
Flow rate: 0.8 mL/min instrument in combination with a high-resolution Shim-pack
Column temp.: 40 °C*3
IC-SA3 column. This analysis technique is applicable not only to
Suppressor: Electrodialytic suppressor ICDS-40A
Injection volume: 50 μL
industrial wastewater, but also to anion analysis of drinking
Vial: Shimadzu Vial, LC, 4 mL, Polypropylene*4 water.
Detection: Conductivity
*1 P/N: 228-41600-91 Reference
*2 P/N: 228-41600-92
*3 The temperature can be changed according to the separation pattern of the 1) ASTM D4327-03, Standard Test Method for Anions in Water by
components in the analysis sample. In the analysis of the industrial wastewater Chemically Suppressed Ion Chromatography, ASTM International,
used in this experiment, satisfactory separation of contaminants and West Conshohocken, PA, 2003, www.astm.org
phosphate ions was possible at 40 °C.
*4 P/N: 228-31537-91

14 index
 Ion Chromatography Solutions for Environmental Analysis

Analysis of Anions

Analysis of Total Nitrogen and Total Phosphorus in Environmental

Water According to ASTM D8001 by Ion Chromatography
Application
Keywords: ASTM D8001, total nitrogen, total phosphorus

In recent years, the issue of eutrophication of water quality has attracted attention. Measures against eutrophication are included
in Goal 14 of the SDGs, “Life below water.” The major causes of eutrophication are thought to be phosphorus and nitrogen, which
nourish phytoplankton in water. Industrial and domestic wastewater produced by human activities contains a large amount of
nitrogen and phosphorus, which are discharged into rivers, leading to eutrophication. Therefore, it is essential to control the
concentration of phosphorus and nitrogen in wastewater.

Benefits
• Total Nitrogen (TN) and Total Phosphorus (TP) in environmental water can be analyzed in accordance with
ASTM D8001.
• TN and TP can be measured simultaneously in a single alkaline persulfate digestion.

■ Analytical Conditions ■ Digestion and Analysis of Mixed

Table 11 shows the analytical conditions. Digest-check Sample
Table 12 Spike Recoveries of Mixed Digest-check Sample (n=7)
Table 11 Analytical Conditions
TN TP
Column Shodex SI-52 4E (250 mm × 4.0 mm I.D., 5 μm) Average of measured
0.012 N.D.
Guard column Shodex SI-92G (10 mm × 4.6 mm I.D., 9 μm) Digestion concentration (mg/L)
Mobile phase 3.6 mmol/L Sodium carbonate blank Concentration of
0.55 N.D.
stock solution (mg/L)
Flow rate 0.8 mL/min
Glycerol
Column temp. 45 °C Compounds Glycine
phosphate
(FW: 111.5)
Injection volume 200 μL (FW: 306.1)
Vial Shimadzu Vial, LC, 4 mL, Polypropylene*1 Mixed Average of measured 0.11 0.039
digest- concentration (mg/L)
Detection Conductivity check Concentration of 4.97 1.74
*1 P/N: 228-31537-91 sample stock solution (mg/L)
Found concentration (mg/L) 4.42 1.74
Weight (g) 0.42 0.50
Expected concentration (mg/L) 4.22 1.62
■ Analysis of Standard Solution Spike recovery (%) 105.8 107.8
Figure 10 shows the chromatogram (100 μg/L each).
■ Analysis of Environmental Water
µS/cm
2.25 Table 13 Analytical Results (n=3)
2.00
Nitrogen Phosphorus
1.75
NO2–N (μg/L) (μg/L)
1.50
Undigested sample NO2–N NO3–N PO4–P
1.25 NO3–N
Average of measured concentration N.D. *2 N.D. N.D.
1.00 Digested sample NO3–N PO4–P
0.75 Concentration of stock solution *3 0 0
0.50 PO4–P TKN *4 0 —
0.25
*2 Below MDL.
0.00 *3 (Average of measured concentration of digested sample – average of
−0.25 measured concentration of digested blank) × dilution ratio
−0.50 *4 Concentrations of NO3–N and NO2–N in the undigested sample – Actual
concentration of NO3–N in the digested sample
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 min

Fig. 10 Chromatogram of Mixed Standard Solutions

■ Conclusion
(100 μg/L each) This article introduces the analysis of total nitrogen and total
phosphorus in environmental water according to ASTM D8001.
The HIC-ESP was used for measurement in accordance with the
standard. Furthermore, stable analysis is possible by using the
electrodialytic suppressor ICDS-40A.

Reference
1) ASTM D8001, Standard Test Method for Determination of Total
Nitrogen, Total Kjeldahl Nitrogen by Calculation, and Total
Phosphorus in Water, Wastewater by Ion Chromatography, ASTM
International, West Conshohocken, PA, www.astm.org

index 15
Ion Chromatography Solutions for Environmental Analysis

Analysis Using a Dual System

Simultaneous Analysis of Anions and Cations Using Ion

Chromatograph Dual Channel System
Application
Keywords: dual channel system, simultaneous analysis

This dual channel system enables simultaneous analysis of anions and cations. For anions, suppressor and non-suppressor methods
can be selected, and a UV-VIS detector can be used for the suppressor method. This article introduces applications obtained by a
combination of anion analysis with the electrodialytic suppressor system HIC-ESP and cation analysis with a non-suppressor system.

Benefits
• Various kinds of samples can be analyzed.
• Both anion and cation analytical results were obtained in a single run, resulting in improved work
efficiency, and good repeatability was obtained.

■ Flow Path Diagram ■ Analysis of Standard Solutions

Table 15 Composition of Anion Standard Mixture
F− Fluoride ion 0.025 mg/L
Autosampler
SIL-10Ai Cl− Chloride ion 0.025 mg/L
NO2− Nitrite ion 0.1 mg/L
Pump Sample loop Column (Cation)
(SIL-10Ai) Shim-pack IC-C4 Br − Bromide ion 0.1 mg/L
LC-20ADSP Conductivity
Eluent Detector NO3− Nitrate ion 0.1 mg/L
(Cation) Suppressor
ICDS-40 CDD-10AVP PO43− Phosphate ion 0.25 mg/L
SO42− Sulfate ion 0.1 mg/L
Pump Sample loop Column (Anion)
LC-20ADSP (FCV-12AH) Shim-pack IC-SA2
UV detector
Eluent SPD-40A µS/cm
(Anion)
0.25 anions (CDD-10AVP)
Fig. 11 HIC-ESP/NS Ion Chromatograph Dual Channel System NO2−
Br − NO3
−
Flow Path Diagram F− Cl− PO43− SO42−

■ Analytical Conditions
0.00

Analysis was carried out using a Shim-pack IC-SA2 column for

0 5 10 15 min
anions and a Shim-pack IC-C4 column for cations. Mobile phase mAU
composition and flow rate can be changed according to the anions (SPD-40A)
5
analytical purpose, but since the column oven is shared with
NO2−
NO3 −

anion analysis and cation analysis channels, the temperature

Br −
condition must be set to the same value. Here, the sampling
0
volume is set to 1600 μL to completely displace the two sample
loops with standard solution, but the actual injection volume is 0 5 10 15 min
determined by the sample loop volume (50 μL each, here). µS/cm
cations (CDD-10AVP)
Table 14 Analytical Conditions
2 Na+
Anion
Column: Shim-pack IC-SA2 (250 mm × 4.0 mm I.D., 9 µm)*1
Shim-pack IC-SA2(G) (10 mm × 4.6 mm I.D., 9 µm)*2 K+
Mobile phase: 12 mmol/L sodium hydrogen carbonate, 0
0.6 mmol/L sodium carbonate
Flow rate: 1.0 mL/min 0 5 10 15 min

Cation Fig. 12 Chromatograms of Anion Standard Mixture

Column: Shim-pack IC-C4 (150 mm × 4.6 mm I.D., 7 µm)*3
Shim-pack IC-GC4 (10 mm × 4.6 mm I.D., 7µm)*4
Mobile phase: 2.5 mmol/L oxalic acid
Flow rate: 1.0mL/min
Column temp.: 40°C
Injection vol.: 50 µL ea. (Setting: 1600 µL)
Vial: Shimadzu Vial, LC, 4 mL, Polypropylene*5
Detection: Conductivity, UV-VIS (210 nm)

*1 P/N: 228-38983-91 *3 P/N: 228-41616-91 *5 P/N: 228-31537-91

*2 P/N: 228-38983-92 *4 P/N: 228-59900-91

16
 Ion Chromatography Solutions for Environmental Analysis

Table 16 Composition of Cation Standard Mixture

■ Analysis of Mineral Water
Li+ Lithium ion 0.01 mg/L µS/cm
Na+ Sodium ion 0.04 mg/L 10 Cl− anions (CDD-10AVP)
NH4+ Ammonium ion 0.04 mg/L
K+ Potassium ion 0.1 mg/L 5
SO42−
Mg2+ Magnesium ion 0.1 mg/L NO3− PO43−
F−
Ca2+ Calcium ion 0.1 mg/L 0

0 5 10 15 min
µS/cm mAU
5.0 40
Anions (CDD-10AVP) anions (SPD-40A)
NO3−
NO3−
20

0.0
0

0 5 10 15 min 0 5 10 15 min
mAU µS/cm
100
anions (SPD-40A) cations (CDD-10AVP)
NO3−
50 50 Na+

Mg2+ Ca2+
K+
0
0
0 5 10 15 min 0 5 10 15 min
µS/cm
Fig. 14 Chromatograms of Mineral Water
cations (CDD-10AVP)
Na+
Li+ NH4 +
+
0.5
K Mg 2+

Ca2+
■ Analysis of Soil Extracted Water
0.0
µS/cm
0 5 10 15 min
0.5 anions (CDD-10AVP)
Fig. 13 Chromatograms of Cation Standard Mixture NO3−

Cl− SO42−
F−
■ Area Repeatability and Lower Limit of 0.0
Quantification 0 5 10 15 min
Each lower limit of quantification (LOQ, mg/L) was calculated mAU
as the concentration at which the S/N ratio was 10. 10 NO3− anions (SPD-40A)

Table 17 Area repeatability (n = 6) and lower limit of quantification 5

concentration area repeatability LOQ 0

(mg/L) (%RSD) (mg/L)
0 5 10 15 min
F− 0.025 2.45 0.008 µS/cm

Cl− 0.025 2.30 0.011 K+ cations (CDD-10AVP)

1
NO2− 0.1 2.20 0.021 NH4+
Na+ Ca2+
Br − 0.1 1.34 0.034 Mg2+
0
NO3− 0.1 2.88 0.031
0 5 10 15 min
PO43− 0.25 2.48 0.11
Fig. 15 Chromatograms of Soil Extracted Water
SO42− 0.1 3.53 0.042

NO2 (UV-VIS) 0.1 0.35 0.003

■ Conclusion
−

Br − (UV-VIS) 0.1 0.52 0.009

This article introduces applications obtained by a combination
NO3− (UV-VIS) 0.1 0.41 0.003 of anion analysis with the electrodialytic suppressor system
Li+ 0.01 1.26 0.003 HIC-ESP and cation analysis with a non-suppressor system.
Na +
0.04 1.89 0.010 Both anion and cation analytical results were obtained in a
NH4+ 0.04 2.65 0.009 single run, resulting in improved work efficiency, and good
repeatability was obtained.
K +
0.1 1.82 0.022

Mg2+ 0.1 3.05 0.028

Ca 2+
0.1 3.78 0.062

index 17
Ion Chromatography Solutions for Environmental Analysis

Analysis of Cations

Analysis of Cations in Drinking Water and Wastewater,

Conforming to ASTM D6919-03
Application
Keywords: ion chromatograph, wastewater

Ion chromatography can be widely employed for the detection and quantification of ionic components in aqueous solutions. ASTM
D6919-03 1), published by ASTM International, USA, specifies an ion chromatographic method for analyzing the six cations (lithium,
sodium, ammonium, potassium, magnesium, and calcium) in drinking water and wastewater. This article introduces analysis of the
six cations in drinking water and wastewater using a non-suppressor ion chromatograph that conforms to ASTM D6919-03.

Benefits • Data with good linearity and repeatability can be obtained in analysis conforming to ASTM D6919-03.
• Cations in drinking water and wastewater can be quantified.
• Separation of sodium and ammonium ions can be improved by adding 18-crown-6 ether to the mobile phase.

■ Analysis of Standard Solution ■ Analysis Conditions

µS/cm Table 18 Analytical Conditions
20.0 2 1. Li (0.4 mg/L)
Column: Shim-pack IC-C4*1 (150 mm × 4.6 mm I.D., 7 µm)
2. Na (4.0 mg/L)
3. NH4 (0.4 mg/L) Guard column: Shim-pack IC-GC4*2 (8 mm × 3 mm I.D., 7 µm)
4. K (1.2 mg/L) Mobile phase: 2.5 mmol/L Methanesulfonic Acid
5. Mg (2.4 mg/L) Flow rate: 1.0 mL/min
10.0
1 6. Ca (4.0 mg/L) Column temp.: 40°C
5
6 Injection volume: 50 µL
3 4 Vial: Shimadzu Vial, LC, 4 mL, Polypropylene*3
0.0 Detection: Conductivity

0.0 5.0 10.0 15.0 min *1 P/N: 228-41616-91 *2 P/N: 228-59900-91 *3 P/N: 228-31537-91

Fig. 16 Chromatogram of Six Cations

■ Analysis of Factory Wastewater

■ Analysis of Drinking Water and Tap Water µS/cm
120.0
µS/cm 2. Na
2 2. Na 3. NH4
30.0 4. K
4. K 2
20.0 5. Mg 5. Mg
4 6. Ca 60.0 6. Ca
10.0 5 6
3
0.0
4 5
0.0 5.0 10.0 15.0 min
6
0.0
Fig. 17-1 Chromatogram of Commercial Drinking Water A
µS/cm 0.0 5.0 10.0 15.0 min
2 1. Li Fig. 18 Chromatogram of Factory Wastewater
40.0 2. Na
4. K
20.0 5 5. Mg
6. Ca
■ Conclusion
4 6
1 This article introduced the cation analysis of drinking water and
0.0
0.0 5.0 10.0 15.0 min wastewater using a non-suppressor ion chromatograph conform-
Fig. 17-2 Chromatogram of Commercial Drinking Water B ing to ASTM D6919-03.
µS/cm
2 2. Na Reference
40.0
4. K
5. Mg 1) ASTM D6919-03, Standard Test Method for Determination of
20.0 6 6. Ca Dissolved Alkali and Alkaline Earth Cations and Ammonium in
5 Water and Wastewater by Ion Chromatography, ASTM
4
International, West Conshohocken, PA, 2003, www.astm.org
0.0

0.0 5.0 10.0 15.0 min

Fig. 17-3 Chromatogram of Tap Water

18 index
 Ion Chromatography Solutions for Environmental Analysis

Analysis of Cations

Quantifying NH4+ in Industrial Wastewater Using Ion

Chromatography (Non-Suppressor System)
Application
Keywords: wastewater, non-suppressor

Plating solution and wastewater from plating plants contain multiple ions including those of sodium and ammonium. Ion chroma-
tography is used to quantify these types of ions. Ion chromatography employs a conductivity detector to selectively detect only ions.
However, since the eluent contains ions that cause an increased background level, a suppressor which is located between the
column and detector is sometimes used to convert the eluent into pure water by means of ion exchange.
This article compares calibration curves created using suppressor and non-suppressor systems and introduces an example of
measuring cations contained in industrial wastewater using the non-suppressor system.

Benefits
• NH4+ can be analyzed by ion chromatography (non-suppressor system).
• The signal strength is not much different from suppressors, although there is no background noise
reduction effect.

■ Suppressor and Non-Suppressor System Area ×103

1100
The curvature occurs due to the use of a suppressor system in 1000

which the eluent is converted into water that doesn’t have any 900 r2 = 0.9994
800
pH buffering capacity. Consequently, the dissociations of target 700
NH4
ions are suppressed due to the increasing pH value of the 600
500
eluent flowing into the conductivity detector along with the 400
increase of ammonium ions. In other words, the equilibrium 300
200
relationship expressed by the following formula shifts to the
100
left-hand side. 0
0 5 10 15 Conc.
NH3 + H2O NH4 ⇆ OH Fig. 20 NH4 Calibration Curve Obtained Using the
Non-Suppressor System (First-order approximation)
This leads to a reduction in responsiveness to conductivity
as the concentration of ammonium ions increases, and a
curved line is obtained for the calibration curve. ■ Chromatogram of Industrial Wastewater
Industrial wastewater was filtered through a membrane filter
■ Analysis Conditions with a pore size of 0.2 μm dedicated to ion chromatography,
and then analyzed using a non-suppressor system.
Column: Shim-pack IC-C4 (150 mm L. × 4.6 mm I.D.)
Fig. 21 shows the corresponding chromatogram. Favorable
Mobile phase: 3 mmol/L methanesulfonic acid
Flow rate: 1.0 mL/min separation is achieved even for samples that contain significantly
Column temp.: 40 °C more sodium ions than ammonium ions and the high linearity
Detection: Conductivity detector (CDD-10AVP) of the calibration curve enables accurate quantitation.
Injection vol.: 50 μL

Area ×103
450
400
350 r2 = 0.9996
300 NH4
250
200
150
100
50
0
0 5 10 15 Conc.

Fig. 19 NH4 Calibration Curve Obtained Using the

Suppressor System (Second-order approximation) Fig. 21 Chromatogram of Industrial Wastewater

index 19
Ion Chromatography Solutions for Environmental Analysis

Analysis of Cations

Analysis Method of Dissolved Hexavalent Chromium According

to EPA 218.6
Application
Keywords: hexavalent chromium, EPA 218.6

The method for analyzing dissolved Cr (VI) in drinking water, ground water, and industrial wastewater is described in EPA 218.6.
This article demonstrates analysis of Cr (VI) with the Shimadzu Prominence™ Inert System. Dissolved Cr (VI) is separated by an anion
exchange column. The colored complex formed between Cr (VI) and diphenyl carbazide in the post-column derivatization is then
detected at 530 nm.

Benefits
• Hexavalent chromium Cr (VI) could chromatographically be separated from potential interferences and
selectively detected using post-column derivatization.
• Trace concentrations of Cr (VI) can be analyzed according to EPA 218.6

■ Flow Path Diagram ■ Calculation of Method Detection Limit

Shim-pack IC-SA3
The MDL was calculated from the results of the seven repeated
3 port UV-VIS
Shim-pack IC-SA3(G) connector detector analyses of a 1 μg/L Cr (VI) standard sample.
(inert cell)
Degassing unit mAU
Autosampler 2.5
Metal-free Reaction coil
chamber SIL-40C 1 1. Cr (VI)
(PEEK, 10 m) Waste 2.0

1.5
Pump
LC-40D Column oven 1.0
Eluent
0.5
Pump 0.0
LC-20Ai
Reaction reagent

Fig. 22 Flow Path Diagram of Cr (VI) Analysis System 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 min

Fig. 23 Seven Repeated Analyses of a 1 µg/L Standard Sample

■ Analytical Conditions
Table 19 Analytical Conditions ■ Analysis of Sample
Column: Shim-pack IC-SA2* (250 mm × 4.0 mm I.D., 9 μm)
1 Simulated wastewater and the sample obtained by adding a
Guard column: Shim-pack IC-SA2(G)*2 (10 mm × 4.6 mm I.D., 9 μm) 1 µg/L Cr (VI) standard to the simulated wastewater were
Mobile phase: 25 mmol/L Ammonium sulphate, analyzed according to the procedure described in EPA 218.6.
10 mmol/L Ammonium hydroxide
Mobile phase flow rate: 1.5 mL/min The percent recovery calculation method was in accordance
Post column reagents: 2 mmol/L Diphenylcarbohydrazide with EPA 218.6.
10 %(v/v) Methanol
0.5 mmol/L Sulfuric acid Table 21 Percent Recovery
Post column reagents flow rate: 0.5 mL/min
Column temp.: 40 °C R: 106.7 %
Injection volume: 250 μL CF − C
Vial: Shimadzu Vial, LC, 4 mL, Polypropylene*3 R= — × 100
F
Detection: UV-VIS (530 nm, Inert cell) R = percent recovery
Reaction coil: 10 m × 0.5 mm I.D. (PEEK) CF = fortified sample concentration
C = sample background concentration
*1 P/N: 228-38983-91 *2 P/N: 228-38983-92 *3 P/N: 228-31537-91 F = concentration equivalent of Cr (VI) added to sample

■ Analysis of Repeatability ■ Conclusion

Table 20 shows the repeatability of area and retention time for The analysis of Cr (VI) according to EPA method 218.6 is
seven repeated analyses of each standard sample. introduced in this article. Cr (VI) can be selectively analyzed
with the post-column reaction.
Table 20 Repeatability of Area and Retention Time
concentration Retention time Area repeatability
(mg/L) repeatability (%RSD) (%RSD) Reference
5 µg/L 0.04 2.16 1) EPA Method 218.6: Determination of Dissolved Hexavalent
20 µg/L 0.02 0.56 Chromium in Drinking Water, Groundwater, and Industrial
50 µg/L 0.04 0.16 Wastewater Effluents by Ion Chromatography, Rev. 3.3

20 index
 Ion Chromatography Solutions for Environmental Analysis

Analysis of Cations

Analysis of Hexavalent Chromium in Drinking Water According

to EPA 218.7
Application
Keywords: hexavalent chromium, EPA 218.7

In EPA Method 218.7, the hexavalent chromium is separated by an anion exchange column. The colored complex formed between
hexavalent chromium and 1,5-diphenylcarbazide in the post-column derivatization is then detected at 530 nm. Compared to EPA
Method 218.6, the sample injection volume is larger, and a lower detection limit is required.
This article introduces an example of hexavalent chromium analysis for several types of drinking water in accordance with EPA
Method 218.7 using the Shimadzu Nexera lite inert system.

Benefits
• Hexavalent chromium in drinking water can be analyzed according to EPA Method 218.7.
• Hexavalent chromium can be chromatographically separated from potential interferences and selectively
detected using post-column derivatization.

■ Flow Path Diagram ■ Method Detection Limit

mAu
Shodex SI-90 0.45
0.40 Cr (VI)
3 port 0.35
Shodex SI-90(G) n=1
connector UV-VIS 0.30 n=2
Degassing unit (PEEK) detector 0.25
n=3
DGU-403 Autosampler SPD-40V 0.20
n=4
SIL-20AC with 0.15 n=5
Metal-free (inert cell) 0.10
100 μL inert kit & n=6
chamber 2 mL sample loop 0.05
n=7
0
Reaction coil Waste −0.05
(PEEK, 0.5 −0.10
mm × 1 m) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 min

Pump Fig. 25 Chromatograms of Seven Replicated Analyses

LC-40i of a 0.02 µg/L Hexavalent Chromium Standard
Eluent Column oven
CTO-40C
Table 23 MDL calculation

MDL: 0.003 µg/L

Pump Resistance tube
LC-40i (PEEK, 0.1 mm × 2 m)
Reaction MDL = (t) × (s)
reagent
t = Student’s t value for n−1 degrees of freedom
at the 99% confidence level;
Fig. 24 Flow Path Diagram of Cr (VI) Analysis System t = 3.143 for seven degrees of freedom
s = standard deviation of the replicate analyses

■ Analytical Conditions
■ Analysis of Sample
Table 22 Measurement Conditions
Column: Shodex SI-90 (250 mm × 4.0 mm I.D., 9 µm) Table 24 Analytical Result of Samples
Guard column: Shodex SI-90(G) (10 mm × 4.6 mm I.D., 9 µm) Mineral Mineral Mineral Tap
Sample
Mobile phase: 50 mmol/L Ammonium sulfate water A water C water S water
20 mmol/L Ammonium hydroxide Mean measured
value (µg/L) N.D.*1 0.80 0.0095 0.021
Mobile phase flow rate: 0.8 mL/min
Relative standard
Post column reagents: 2 mmol/L 1,5-diphenylcarbazide 0.37 3.74 6.14
deviation (%RSD)
10 % (v/v) Methanol
0.5 mol/L Sulfuric acid *1 Not Detected (< MDL)
Post column reagents flow rate: 0.3 mL/min
Column temp.: 45 °C ■ Conclusion
Injection volume: 1000 µL
Vial: Shimadzu Vial, LC, 4 mL, Polypropylene*1 Hexavalent chromium in water can be chromatographically
Detection: UV-VIS (530 nm, inert cell) separated from potential interferences and selectively detected
Reaction coil: 1 m × 0.5 mm I.D., (PEEK) using post-column derivatization.
*1 P/N: 228-31537-91

Reference
1) EPA Method 218.7: Determination of Hexavalent Chromium in
Drinking Water by Ion Chromatography with Post-Column
Derivatization and UV-Visible Spectroscopic Detection, Version 1.0
Public Health Goal for Hexavalent Chromium in Drinking Water.
https://oehha.ca.gov/water/public-health-goals-phgs

index 21
Ion Chromatography Solutions for Environmental Analysis

Analysis of Cations

Measuring Hexavalent Chromium Compounds in Atmospheric Dust

— Ion Chromatography Post-Column Absorption Spectroscopy Method —
Application
Keywords: hexavalent chromium, post-column method

In March 2018, Japan’s Ministry of the Environment issued the “Manual of measurement methods for hazardous air pollutants—
Measurement method for hexavalent chromium compounds in atmospheric dust”. In this manual, hexavalent chromium compounds
are measured using the alkali impregnated filter collection – ion chromatography post-column derivatization spectroscopic absorp-
tion method. Diphenyl carbonohydrazide, which specifically reacts with hexavalent chromium, is used as the post-column derivat-
ization reagent.

Benefits
• It is possible to analyze according to the “Manual of measurement methods for hazardous air pollutants—
Measurement method for hexavalent chromium compounds in atmospheric dust”.
• Hexavalent chromium can be measured in accordance with EPA 218.6 with the same instrument configuration.

■ Analytical Conditions Table 26 Repeatability of Area and Retention Time

Concentration Accuracy
Measurement Area
Table 25 Measurement Conditions (ng/mL) (%)
1 724 0.099 99.1
■ Separation 2 719 0.098 98.5
Column: Shim-pack IC-SA2 (250 mm L., 4.0 mm I.D.) 3 743 0.102 101.7
Guard column: Shim-pack IC-SA2G (10 mm L., 4.6 mm I.D.) 4 731 0.100 100.0
Eluent: 10 mmol/L Sodium Carbonate / 5 736 0.101 100.8
10 mmol/L Sodium Bicarbonate Average 731 0.100
Flow rate: 1.0 mL/min %RSD 1.3 1.6
Column temp.: 40 °C
■ Injection vol.: 0.25 mL
■ Post Column Derivatization ■ Influence of Sample Matrix
Reaction reagent: 2 mmol/L Diphenyl carbonohydrazide – Fig. 27 compares the chromatograms of the standard solution
10 %-Methanol – 0.5 mol/L Sulfate
Flow rate: 0.2 mL/min
when diluted, respectively, with water and with sodium
Reaction temp.: 40 °C bicarbonate solution, which is used to prepare the alkali
Reaction coil: 0.5 mm I.D. × 8 mL. (PTFE) impregnated filter. Sodium carbonate released from the
■ Detection: UV-VIS detector at 540 nm alkali-impregnated filter is a matrix and the elution strength
(SPD-20AV, W lamp, Inert Cell)
becomes slightly stronger, causing a change in the elution time
by a few seconds. However, we can see that the peak shapes
■ Analysis of Standard Samples are the same.
µV
Fig. 26 shows the chromatograms of potassium dichromate
standard solutions diluted to between 0.1 and 5.0 ng/mL using 500000 Diluted with a sodium Diluted with water
bicarbonate solution
ultra-pure water. 400000

300000
µV
1800 200000
1600 5.0 ng/mL 100000
1400
0
1200 2.0 ng/mL 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 min
1000 (a) Before retention time alignment
800 1.0 ng/mL
µV
600 0.5 ng/mL
400 0.2 ng/mL 500000
200 0.1 ng/mL 400000
0
300000
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 min
200000
Fig. 26 Chromatograms of Standard Solutions 100000

0
■ Repeatability of the Standard Solutions 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 min
(b) After retention time alignment
Table 26 lists the peak area, quantitation value (concentration),
Fig. 27 Comparison of Dilution Solvents with
and accuracy of each measurement. a 1000 ng/mL Standard Solution

22 index
 Ion Chromatography Solutions for Environmental Analysis

Lineup of Liquid Chromatography Systems

Liquid chromatography (LC) is a separation technique used to separate and analyze each component in a mixture.
Shimadzu provides a range of liquid chromatography systems from HPLC (High Performance Liquid Chromatography) to UHPLC,
preparative systems, and more. We also offer solutions for supercritical fluid chromatography and ion chromatography.
LabSolutions dedicated software simplifies method development and routine workflows for quantitative and qualitative analysis.
Shimadzu’s Shim-pack columns ensure high-quality analysis data over for a multitude applications.

Liquid Chromatography Products

HPLC/UHPLC/SFC System HPLC/UHPLC/SFC System

Nexera™ Series i-Series

The Nexera series is a family of The integrated i-Series LC system
HPLC systems that marries AI and excellent performance while
IoT enhancements to set new addressing the need for automa-
industry standards. tion efficiency.

Application Specific LC System HPLC/UHPLC/SFC System

Nexera™ XS inert Nexera™ lite inert

The Nexera XS inert system offers Nexera lite inert is a robust HPLC
the ideal solution for the separation system that eliminates the risk of
of biomolecules by combining the corrosion by high-salt mobile phases
elevated pressure tolerance of a and sample adsorption onto metal
UHPLC system with complete surfaces. It improves the data quality
inertness of the sample flow path, of protein analysis in biological
ensured by the absence of wetted samples with superior reproducibility,
metal surfaces and offering without any special considerations
ultra-high resistance to corrosion. for stable and long-term use.

HPLC/UHPLC/SFC System HPLC/UHPLC/SFC System

Nexera™ UC LC-2030C NT
Nexera UC improves your The LC-2030C NT is an integrated
analytical workflow by high-performance liquid chroma-
utilizing a completely new tography system. The intuitive
separation technology, touch-screen interface and stable
Unified Chromatography, column performance over many
which unites sample continuous injections ensure reliable
separation, analysis with data every time, whether you are
various separation modes, an HPLC beginner or an expert.
and high-sensitivity
detection.

index 23
 Ion Chromatography Solutions for Environmental Analysis

LabSolutions, ICDS, Nexera, Shim-pack and Prominence are trademarks of Shimadzu Corporation or its affiliated companies in Japan and/or other countries.

For Research Use Only. Not for use in diagnostic procedures.

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© Shimadzu Corporation, 2024 / First Edition: June 2024, 3655-11313-PDFNS, C197-E004