Ion Chromatography - Municipal Water Analysis Applications

Ion Chromatography
Municipal Water Analysis
Applications Summary
Inorganic Anions and Cations • Toxic Contaminants • Disinfection Byproducts
Table of Contents
Introduction................................................................................................................................................................................................................ 3
How are you ensuring the safety of your community’s drinking water?......................................................................................................................... 3
Ion Analysis................................................................................................................................................................................................................ 4
High-Pressure Ion Chromatography (HPIC).................................................................................................................................................................. 5
Reagent-Free Ion Chromatography (RFIC).................................................................................................................................................................... 5
Reagent-Free Ion Chromatography – Eluent Regeneration............................................................................................................................................ 5
Reagent-Free Ion Chromatography – Eluent Generation............................................................................................................................................... 6
Capillary Ion Chromatography...................................................................................................................................................................................... 7
Automated Titration Ion Chromatography................................................................................................................................................................ 8
Application Briefs: Inorganic Anions and Cations....................................................................................................................................................... 10
Low-Cost Determination of Anions in Municipal Drinking Water Using EPA Method 300.0 and the Dionex ICS-900 IC System.............................. 10
Efficient and Fast Separations of Inorganic Anions in Water Samples Using a 4 µm Particle Size Microbore Column with a
High-Pressure Ion Chromatography System................................................................................................................................................................ 11
Determination of Inorganic Anions in Municipal Drinking Water Using a Modular High-Pressure
Capillary Ion Chromatography System........................................................................................................................................................................ 12
Fast Determinations of Inorganic Cations in Municipal Wastewater Using High-Pressure Capillary IC...................................................................... 13
Determination of Nitrite and Nitrate in Wastewater Using Capillary IC with UV Detection....................................................................................... 14
Application Briefs: Disinfection Byproducts................................................................................................................................................................ 15
Determination of Trace Concentrations of Oxyhalides and Bromide in Municipal and Bottled Waters Using a
Hydroxide-Selective Column with a Reagent-Free Ion Chromatography System......................................................................................................... 15
Determination of Trace Concentrations of Disinfection Byproduct Anions and Bromide in Drinking Water Using a Reagent-Free
Ion Chromatography System Followed by Postcolumn Addition of an Acidified On-Line Generated Reagent for Trace
Bromate Analysis......................................................................................................................................................................................................... 17
Determination of Sub-µg/L Bromate in Municipal and Natural Mineral Waters Using Preconcentration with Two-Dimensional
Ion Chromatography and Suppressed Conductivity Detection..................................................................................................................................... 19
Application Briefs: Toxic Contaminants....................................................................................................................................................................... 21
Sensitive Determination of Hexavalent Chromium in Drinking Water ........................................................................................................................ 21
Determination of Metal Cyanide Complexes by Ion Chromatography with On-Line Sample Preconcentration and
UV Absorbance Detection............................................................................................................................................................................................ 23
Direct Determination of Cyanide in Drinking Water by Ion Chromatography with Pulsed Amperometric Detection ICE-PAD.................................. 24
Determination of Total Cyanide in Municipal Wastewater and Drinking Water Using Ion-Exclusion Chromatography with
Pulsed Amperometric Detection (ICE-PAD)................................................................................................................................................................. 26
Determination of Perchlorate in Drinking Water Using Reagent-Free Ion Chromatography........................................................................................ 28
Literature References.................................................................................................................................................................................................... 29
I nt rodu c t i on to
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Introduction
How are you ensuring the safety of your community’s drinking water?
Drinking water quality is a universal health concern
with global impact. The water discharged by
municipal waste water treatment plants and
industrial facilities must be monitored to ensure strict
compliance with global regulatory requirements.
These agencies have developed standards for water
analysis to assure that the community is consuming
only safe drinking water.
EPA decided to develop a national primary drinking
water regulation for perchlorate. This effort is still in
progress. Similarly, also in 2011 they recommended
enhanced monitoring for Cr(VI) based on results from
an independent survey showing that 35 drinking
water samples exceeded the regulatory limits for
Cr(VI). Hexavalent chromium (Cr(VI)) is of
particular concern since it is a highly toxic carcinogen.
The Safe Drinking Water Act (SDWA) is a US federal
law which sets legal limits on the levels of certain
contaminants in drinking water. Under the SDWA,
the United States Environmental Protection Agency
(EPA) enforces the National Primary Drinking Water
Regulations (NPDWRS or primary standards) that
apply to all public water systems. The NPDWR
mandates maximum concentration levels of certain
drinking water contaminants, also called “maximum
contaminant levels” or “MCLs”. The EPA also
provides a list of acceptable techniques for treating
drinking water to reduce regulated contaminants to
acceptably low levels. In Europe, the Drinking Water
Directive provides the essential quality standards.
These quality standards were developed using
guidelines from the World Health Organization
(WHO) and the European Commission’s Scientific
Advisory Committee. Member States of the European
Union can add additional requirements for substance
regulation; however they cannot set lower standards
for these substances. Drinking water must be
reported to the European Commission every three
years.
Thermo Fisher Scientific is committed to enhancing
the quality of our global water resources. Our
Thermo Scientific™ Dionex™ ion chromatography
(IC) instruments are used by government and
industry to provide solutions for environmental
water testing for a wide range of regulated and
emerging inorganic elements and organic compounds.
These analytical instruments have evolved over many
generations, each providing enhanced performance,
greater reliability, and easier operation.
Contaminant levels in drinking water are continuously subject to reassessment by the above regulatory
bodies, both in regard to revised levels, as well as the
addition of new contaminants to the list of existing
regulated substances. For example, perchlorate has
been recently identified as an environmental
contaminant found in drinking water which impairs
normal thyroid function by interfering with iodine
uptake by the thyroid gland. In February, 2011 the
Ground and surface waters are a vital resource for a
healthy environment. They are also the largest source
of fresh water. These waters can comprise complex
matrices that interfere with detection of analytes of
interest. Another major challenge for qualifying
drinking water is the analysis of disinfection
byproducts (DBP). Drinking water is treated with
disinfectants to remove potentially harmful bacteria.
These disinfectants also react with ions and residual
organic matter resulting in the formation of DBPs.
DBPs are highly toxic, are regulated, and require
mitigation of their concentrations prior to distribution of treated water. As the technology leader in ion
chromatography, we have developed innovative
techniques which overcome common challenges in
the analysis of drinking water contaminants and
DBPs.
As your partner for drinking water analysis, we
promise to deliver the technology, experience, and
support necessary for you to provide safe drinking
water and ultimately protect our environment.
3
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Ion Analysis
New and Innovative IC Systems
Since the development of ion chromatography (IC)
analysis over 30 years ago, Thermo Fisher Scientific
has continually pioneered the development of new
and innovative IC systems.
Our High-Pressure™ Ion Chromatography (HPIC™)
systems include the Thermo Scientific Dionex
ICS-5000+ HPIC system which is optimized for
flexibility, modularity and ease-of-use, combining the
highest chromatographic resolution with convenience.
In addition, the Thermo Scientific Dionex ICS-4000
Capillary HPIC system is the world’s first dedicated
capillary Reagent-Free™ IC (RFIC™) system that is
commercially available. The Dionex ICS-4000 system
is always ready for the next analysis delivering
high-pressure IC on demand.
Reagent-Free IC eliminates daily tasks of eluent and
regenerant preparation, saving time, preventing
errors, and increasing convenience. RFIC-EG systems
use electrolytic technologies to generate eluent on
demand from deionized water, and to suppress the
eluent back to pure water, delivering unmatched
sensitivity. RFIC-ER systems are designed to use
carbonate, carbonate/ bicarbonate, or MSA eluents
for isocratic separations.
At the heart of our ion chromatography systems is a
unique set of column chemistries that provide high
selectivities and efficiencies with excellent peak shape
and resolution. Thermo Scientific™ Dionex™ IonPac™
polymeric columns address a variety of chromatographic separation modes including ion exchange, ion
exclusion, reversed-phase ion pairing, and ion
suppression. Our column chemistries are designed to
solve specific applications, and we offer a variety of
selectivities and capacities for simple and complex
sample matrices. Additionally, our Dionex IonPac
column line is available in standard bore, microbore
and capillary formats for the ultimate application
flexibility. Learn more about our innovations in IC at
www.thermoscientific.com/IC.
The complete Thermo Scientific Dionex IC Systems Family
4
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Innovative Solutions for All Application
and Performance Needs
High-Pressure Ion Chromatography
RFIC – Eluent Regeneration (RFIC-ER)
High-pressure ion chromatography systems allow
continuous operation up to 5000 psi when configured
as a Reagent-Free (RFIC) system for standard,
microbore and capillary scale flow rates. As a result,
these instruments can use high resolution 4 µm
particle ion exchange columns which create higher
back pressures. Higher backpressures are possible
with the Dionex ICS-5000+ system and the Dionex
ICS-4000 systems .
RFIC systems with Eluent Regeneration (RFIC-ER
systems) are designed to use carbonate, carbonate/
bicarbonate, or MSA eluents for isocratic separations.
Eluent regeneration uses the suppressor to reconstitute
the starting eluent, allowing use of a single 4 L bottle
of eluent for up to four weeks. Because the system is a
closed loop, it can run continuously, eliminating the
need for recalibration or re-equilibration during the 28
days of non-stop operation. The same electrolytic
process that suppresses eluent for detection is used to
regenerate eluent for reuse.
The Dionex IonPac 4 μm particle-size columns as in
the case of reversed phase HPLC columns with
smaller particles, higher system operating pressures
are necessary to utilize these small particle columns.
High pressure IC systems enable the use of the 4 µm
columns, thus yielding yield fast separations with
short (150 mm) columns, and high resolution with
standard length (250 mm) columns.
Reagent-Free Ion Chromatography (RFIC)
Minimize unintentional variations in the
preparation of eluents and regenerants
Advances in eluent generation and electrolytic
suppression technologies are enabling a wider variety
of applications and increased productivity. RFIC
systems are available with eluent generation (RFICEG) or with eluent regeneration (RFIC-ER), such as
the Thermo Scientific Dionex ICS-2100, the Dionex
ICS-4000, and the Dionex ICS-5000+ systems. These
systems combine automated eluent generators and
electrolytically regenerated suppressors to electrolytically create the required eluents and regenerants used
for IC applications. Laboratories using RFIC systems
spend less time on equilibration, calibration, method
verification, troubleshooting, and consistency checks
because the systems minimize unintentional variations in the preparation of eluents and regenerants.
After detection, suppressed eluent is passed through
an analyte trap column to remove the analyte ions.
The suppressed eluent is then returned to the
suppressor to provide the water for electrolytic
suppression. The effluent from the suppressor
contains the eluent ions and H2 and O2 gases. A
catalytic column recombines the oxygen and
hydrogen to form water. The suppressor effluent is
then returned to the eluent reservoir for reuse.
Because the electrolysis gases are recombined
stoichiometrically, no water is lost in the system and
eluent concentration remains constant. A purification
column is plumbed after the pump to further assure
eluent purity. Stable eluent concentration yields
reproducible results, with little variability in peak
retention times or areas.
Continuous operation eliminates the need to reequilibrate, and with no need to prepare eluent; all the
operator has to do is load a sample. This means higher
sample throughput and more time for operators to
pursue other tasks. Pump maintenance is also reduced,
because the flowing eluent has no opportunity to
crystallize on pump surfaces. Eluent can be regenerated for up to four weeks for analysis of samples with
low- to moderate-ionic strength, such as drinking
water. Higher injection volumes or heavy workloads
may require more frequent replacement or regeneration of trap and purification columns and eluent.
Learn more about our eluent regeneration solutions at:
www.thermoscientific.com/eluentregeneration.
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RFIC -Eluent Generation (RFIC-EG)
Just Add Water
The Thermo Scientific Dionex Eluent Generator
Cartridge (EGC) is at the core of the patented eluent
generation technology used in RFIC-EG systems. A
range of Dionex EGC cartridges are available for
the production of hydroxide, carbonate, and
methanesulfonic acid eluents. For cation-exchange
applications, the Dionex EGC III MSA, Dionex EGC
MSA (Capillary) and Dionex EGC 500 MSA
cartridges produce methanesulfonic acid eluents. For
anion-exchange applications, the Dionex EGC III
KOH, Dionex EGC NaOH, or Dionex EGC LiOH,
Dionex EGC KOH (Capillary) and Dionex EGC 500
KOH cartridges produce potassium, sodium, or
lithium hydroxide eluents. The Dionex EGC III
K2CO3 cartridge produces carbonate-only eluent,
and the Electrolytic pH Modifier (EPM III) can be
added for generating carbonate/bicarbonate eluents..
Eluent generation allows the automatic production of
high-purity IC eluents. This is made possible through
precise control of the electric current applied to the
electrolysis of water to generate hydroxide and
hydronium ions. Eluent generation eliminates the
need to manually prepare eluents from concentrated
acids and bases. The only routine reagent needed is
deionized water. Furthermore, because the instrument
pump seals and pistons only come in contact with
deionized water, overall pump maintenance is
significantly reduced.
With eluent generation, a pair of electrodes is
positioned with an ion exchange membrane separating them; when a current is applied to the electrodes,
electrolysis of water generates hydroxide at the
cathode and hydronium at the anode. The ion
exchange membrane prevents the species from
recombining into water, and allows a counter-ion
from the Eluent Generation Cartridge to migrate
across the membrane to form the eluent. The eluent
concentration is varied by changing the applied
current to within a given range 0–100 mM or 0–200
mM (cap). This entire process can be done without
the use of extra pumps, fittings, valves or any moving
parts.
RFIC-EG systems have redefined IC by making it
possible to just add water to operate an IC system.
These systems allow for a simpler and more reliable
way to help deliver superior results while simultaneously saving time and labor. RFIC-EG systems
facilitate drinking, waste, and groundwater analyses
for regulatory compliance. Furthermore, they provide
the accuracy and reproducibility needed for the
analysis of high-purity water. Learn more about our
eluent generation solutions at:
www.thermoscientific.com/eluentgeneration.
Anode
H+
Electrolyte Reservoir
K+
K+
K+
K+
K+
K+
Ion-Exchange Connector
KOH Generation Chamber
Eluent Stream
OH-
H2O
+
K OH-
Cathode
Hydrogen
6
Oxygen
Potassium
The Dionex EGC III KOH cartridge consists of a KOH generation chamber and a K+ electrolyte reservoir,
connected by a cation exchange connector. A high-pressure connector permits the passage of K+ ions from
the K+ electrolyte reservoir into the electroytic chamber.
I nt rodu c t i on to
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Capillary IC
Always Ready
Column size, injection volumes, and flow rates are
scaled down by a factor of 10 to 100 in capillary IC.
A capillary IC system can be left always ready to run
samples as soon as they are prepared. This helps
improve system stability and reduces the need for
recalibration. A continuous mode of operation is
possible because capillary IC systems only consume
15 mL of water a day, translating into 5.2 L a year.
The waste produced by a capillary IC system is
dramatically minimized which in turn reduces
disposal costs. When operated as a RFIC system, the
Eluent Generation Cartridge lasts for 18 months
under continuous operation. Using eluent generation,
only water flows through the pumps which greatly
extends the life of seals and decreases the cost of
maintenance.
The Dionex ICS-5000+ and the Dionex ICS-4000
systems represent our latest innovations in capillary
ion chromatography. As mentioned, they are also
RFIC systems, which allow continuous operation up
to 5000 psi when configured as an RFIC system.
Dionex ICS-4000 and ICS-5000+ capillary IC systems.
7
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Automated Titration IC
Streamlined workflows to save time and improve reliability
The U.S. EPA lists a set of secondary water quality
standards in addition to the National Primary
Drinking Water Regulations. These secondary
standards recommend maximum levels of certain
analytes in drinking water that can cause a variety of
issues ranging from poor taste and appearance to
detrimental health effects. Some parameters, such as
water hardness, can cause system problems related to
scale formation. As a result, drinking water consumers and industries that use water may need to
understand the secondary qualities of the water they
source. Titration IC systems are fully automated to
quickly and easily provide the levels of many of the
secondary analytes suggested by the U.S. EPA.
Titration and IC can, as separate systems, provide the
results of several different types of analyses automati-
cally. Automated titration can be implemented to
provide values such as conductivity, pH, alkalinity and
carbonate hardness. Ion chromatography provides
automated analysis of the individual anion and cation
concentrations. Operation of these systems separately
involves loading at least two autosamplers and
operating at least two instrument control/data
acquisition software packages. Additionally there is
the issue of data compilation. Utilizing separate IC
and Titration data systems requires results from the
ion chromatographs and the titrator to be combined
by manual entry into a spreadsheet to calculate ion
balance and permanent (or calcium) hardness.
Unfortunately, this process of manual data entry
increases required labor time and introduces the
possibility of transcription errors, compromising the
accuracy of results.
Manual versus automated sample handling time with water quality analysis
Manual Operation
Automated
Operation
Automated Labor Time10 Samples (min)
Time Saved
(min)
Measure 50 mL sample
4
Fill sample beakers
1
3
Add indicator
5
Automatic
0
5
Enter sample ID,
Situate beaker
3
Load autosampler
3
0
20
Titrate
0
20
Rinse and change sample
5
Remove samples
from autosampler
1
4
Total labor time, manual
37
Total labor time
with automation
5
32
Titrate
8
Manual Labor Time10 samples (min)
I nt rodu c t i on to
I C Te ch nolog i es
Fully automated water analysis system
The METTLER TOLEDO™ titration system and
liquid handler combined with two Dionex ion
chromatography systems creates a fully automated
water analysis system. The system can automatically
dilute ion standards, removing the need for manual
standards dilutions. These standards are then used to
automatically build a multilevel calibration curve
enabling analysis of a wide variety of drinking,
surface, and ground water samples. The system can
determine anions, cations, conductivity, and temperature values. Automated titration produces acid
capacity numbers; total hardness and ion balance are
automatically calculated for each sample.
The IC part of the solution comprises either two
Dionex ICS-1100 systems or two Dionex ICS-1600
systems; one each for anion and cation analysis. IC
analysis is performed simultaneously with titration for
a completed analytical procedure in approximately 20
min. Additional features that enhance the productivity
and accuracy of the system include automated, user
selectable pH electrode calibration and verification.
The Thermo Scientific Dionex AS-AP Autosampler
provides high-performance, automated sample
processing for ion chromatography applications. In
addition, the Thermo Scientific Dionex AS-AP Sample
Conductivity and pH Accessory—the first ever in an
IC autosampler—allows in-line measurement of the
sample conductivity and pH prior to injection. Thermo
Scientific™ Dionex™ Chromeleon™ Chromatography
Data System (CDS) software triggers can then be used
to either inject the sample or modify the sample prior
to injection.
For anion analysis by IC, automatic selection of the
correct sample loop size based on a conductivity value
is also enabled. This eliminates time-consuming and
costly rework of samples. Chromeleon Chromatography Data System software manages the entire system
and integrates all results into a single convenient
report ensuring automatic data analysis and reporting.
The combined Titration IC system provides traceable
ion analysis of water samples using the audit trail
feature of Chromeleon CDS. Automating these
analyses results in significant reductions in the amount
of costly manual labor Results are more reliable and
precise due to the removal of any need for manual
data entry and calculations.
Learn more about our Titration IC solutions at:
www.thermoscientific.com/TitrationIC.
The METTLER TOLEDO titration system and liquid handler combined with two Dionex IC systems
9
Br i e f of
Appli cat i on Br i e f 1 2 1
Low-Cost Determination of Anions in Municipal
Drinking Water Using EPA Method 300.0 and
the ICS-900 IC System
Anions in Municipal Drinking Water
Equipment
• Dionex ICS-900 System
Analysis
Ion-Chromatography
Results
Summary
U.S. EPA 300.01 is an ion
chromatography (IC) method
approved by the United States
Environmental Protection
Agency (EPA) to determine
inorganic anions (fluoride,
chloride, nitrite, sulfate, bromide,
nitrate, and phosphate) in
municipal drinking water and
wastewater. Three of these
anions (fluoride, nitrite, and
nitrate) are considered contaminants in drinking water under
the EPA’s National Primary
Drinking Water Regulations.
High levels of fluoride cause
bone disease; nitrite and nitrate
can cause birth defects. Chloride
and sulfate are not harmful to
public health but should not
exceed 250 mg/L for the proper
taste of water, according to the
EPA’s National Secondary
Drinking Water Regulations. The
EPA enforces these regulations to
ensure use of approved analytical
methods when analyzing water
samples to meet federal monitoring requirements or to comply
with drinking water regulations.
The Thermo Scientific Dionex
ICS-900 provides a complete
solution for routine analysis of
inorganic anions in water and
meets all requirements specified
in EPA method 300.0.
Download the full version of
Application Brief 121
10
See chromatogram below.
Column:
Eluent:
Dionex IonPac AG22/AS22, 4 mm
4.5 mM Sodium Carbonate
1.4 mM Sodium Bicarbonate
Ambient
1.2 mL/min
25 µL
Conductivity, Suppressed Conductivity
Thermo Scientific™ Dionex™ AMMS™ 300 Anion
MicroMembrane suppressor, 50 mM Sulfuric Acid
Column Temp.:
Flow Rate:
Inj. Volume:
Detection:
Peaks:
1. Fluoride
2. Chloride
3. Nitrite
4. Bromide
5. Nitrate
6. Phosphate
7. Sulfate
0.19 mg/L
98.1
0.54
1.22
2.43
3.12
48.2
2
15
7
µS
3
1
5
4
6
–1
0
5
Minutes
10
Separation of anions in municipal drinking water sample on the Dionex
IonPac AS22 column using the Dionex ICS-900 system.
15
Br i e f of
Te ch ni cal N ote 1 2 7
Efficient and Fast Separations of Inorganic
Anions in Water Samples Using a 4 µm
Particle Size Microbore Column with a
High-Pressure Ion Chromatography System
Inorganic Anions in Municipal Drinking and Wastewater
Equipment
Results
• Dionex High-Pressure ICS-5000+ HPIC ReagentFree system including:
See chromatograms below.
– Dionex SP/DP Pump module
Summary
The Dionex IonPac AS18-4µm
column is a newly developed high
capacity column with AS18
chemistry using 4 µm resin
particles. The Dionex IonPac
AS18 column was developed as
an alternative to the AS4A
column; the Dionex IonPac AS18
is designed for use with EPA
Method 300.0 (A) using
electrolytically generated
hydroxide eluents. These smaller
resin particles allow an optimal
combination of fast speed and
high resolution. For the determination of inorganic anions in
water samples, a comparison of
the new 4 µm versus the previous
7.5 μm resin Dionex IonPac
AS18 column is performed. This
technical note presents the
advantages of using the smallparticle size microbore (2 mm
i.d.) Dionex IonPac AS18-4µm
column, in combination with the
Dionex ICS-5000+ HPIC system,
to obtain fast and efficient
separation of inorganic anions in
municipal drinking and wastewater samples.
Download the full version of
Technical Note 127
Peaks:
1. Fluoride
2. Chlorite
3. Chloride
4. Nitrite
5. Carbonate
– Dionex EG Eluent Generator module with
high-pressure degas module
– Dionex DC Detector/Chromatography module
25
C: 0.38 mL/min
3600 psi
3
4
– Dionex AS-AP Autosampler
• Chromeleon CDS software ver. 6.8 or 7.1
1
Reagents and Standards
• 18 MΩ-cm degassed deionized water
• Fisher Scientific reagents, ACS Grade
0.5 mg/L
1.0
3.0
5.0
–
6. Bromide
7. Sulfate
8. Nitrate
9. Chlorate
10.0 mg/L
10.0
20.0
10.0
6
78
9
2
5
B: 0.30 mL/min
3000 psi
µS
Conditions
Columns:
Dionex IonPac AG18-4µm column, 2 × 50 mm
Dionex IonPac AS18-4µm column, 2 × 150 mm
Eluent Source:
Dionex EGC 500 KOH Eluent Generator
Cartridge, Thermo Scientific Dionex CR-ATC
500 Continuously Regenerated Anion
Trap Column
Eluent: 23 mM KOH
Flow Rate:
0.25, 0.30, 0.38 mL/min for
flow rate experiments
0.38 mL/min for samples
Column Temp.:
30 °C
Inj. Volume:
5 µL
Detection:
Suppressed conductivity, Thermo Scientific™
Dionex™ ASRS™ 300 Anion Self-Regenerating
Suppressor, recycle mode; 15, 18, 22 mA
Background
Conductance:
< 1.0 µS
Noise:
< 3 nS
System
backpressure:
A: 0.25 mL/min
2500 psi
0
0
1
2
3
4
5
Minutes
6
7
8
9
Comparison of the separation of inorganic anions using increasing flow
rates.
Samples:
A: Municipal Drinking Water
B: Municipal Wastewater
Sample Prep: A: 5-fold diluted, filtered 0.45 µm
B: 10-fold, filtered 0.45 µm
2 Peaks (mg/L):
A
B
1. Fluoride
0.11
0.56
2. Chloride 36.0
160
3. Carbonate –
–
4. Sulfate 38.0
110
5. Nitrate
2.90
43.0
31
4
µS
2500–3600 psi
5
Analysis
High-Pressure Ion Chromatography
3
1
B
A
0
0
1
2
3
4
5
Minutes
6
7
8
Determination of inorganic anions in municipal drinking and waste water
samples
11
Br i e f of
Te ch ni cal N ote 1 3 2
Determination of Inorganic Anions in Municipal Water
Using High-Pressure Modular Capillary
Ion Chromatography
Inorganic Anions in Municipal Drinking Waters
Equipment
Results
• Dionex High-Pressure ICS-5000+ HPIC capillary
Reagent-Free system including:
See chromatograms below.
– Dionex ICS-5000+ DP Dual Pump module
with high-pressure capillary pumps
Summary
Ion chromatography (IC) has
been widely adopted to determine inorganic anions in
environmental waters, including
surface, ground, drinking and
wastewaters. This Technical Note
describes the determination of
inorganic anions in municipal
drinking water samples using the
Dionex ICS-5000+ HPIC
capillary system in combination
with the Dionex IonPac
AS18-4μm column, which is the
column of choice for compliance
monitoring of water samples in
accordance with U.S. EPA
Methods 300.0 (A) and 300.1.
Download the full version of
Technical Note 132
– Dionex ICS-5000+ EG Eluent Generator
module
– Dionex ICS-5000+ DC Detector/
Chromatography module with a Dionex
IC Cube and high-pressure degas cartridge
Sample Prep: A, C: Diluted 5-fold
B, D: Undiluted
Peaks:
1. Fluoride
2. Chloride
3. Carbonate
4. Sulfate
140 5. Nitrate
B
0.95
5.76
–
18.00
0.16
C
0.05
38.80
–
66.90
17.00
D
1.14 mg/L
13.90
–
20.30
–
2
– Dionex AS-AP Autosampler
• Chromeleon CDS software
4
Reagents and Standards
• 18.2 MΩ-cm degassed deionized water
µS
D
• Anion Standard solution made from 1000 mg/L
stocks
C
Samples
B
• Municipal drinking and wastewater diluted as
indicated with deionized water
Column:
Dionex IonPac AS18-4µm column, 0.4 × 150 mm
Eluent Source:
Dionex EGC-KOH Cartridge (Capillary)
with Dionex CR-ATC Continuously Regenerated
Anion Trap Column
Eluent:
23 mM KOH
Flow Rate:
0.025 mL/min
Inj. Volume:
0.4 µL
Detection:
Suppressed conductivity, Thermo Scientific™ Dionex™
ACES 300 Anion Capillary Electrolytic suppressor,
recycle mode
Less than 3 nS
2
Minutes
1
4
3
Sample Prep: Diluted 1000-fold, filtered, 0.2 µm
Peaks:
A
1. Chloride
76.5
2. Nitirite
1.5
3. Carbonate
–
4. Sulfate
41.6
5. Nitrate
28.8
1.7
1
B
146.0
2.1
–
88.9
7.2
C
154.0
37.4
–
84.8
31.7
D
130.0
1.6
–
91.8
128.0
mg/L
3
4 5
D
2
µS
C
System
Backpressure: ~ 3500 psi
B
Analysis
Capillary Ion Chromatography
5
Determination of inorganic anions in municipal drinking water samples
using high-pressure capillary IC.
Background
Conductance: 0.3–0.5 µS
Noise:
3
A
0
Conditions
1
0
Column Temp.: 30 °C
A
0
0
12
A
0.61
8.36
–
50.10
7.09
1
2
Minutes
3
Determination of inorganic anions in municipal wastewater using highpressure capillary IC.
4
Br i e f of
Te ch ni cal N ote 1 2 1
Fast Determinations of Inorganic Cations in Municipal
Wastewater Using High-Pressure Capillary IC
Inorganic Cations in Municipal Wastewater
Equipment
Analysis
• Dionex ICS-5000+ HPIC Reagent-Free capillary
system including:
Capillary Ion Chromatography
– Dionex ICS-5000+ SP Single Pump module
with high-pressure capillary pumps
See chromatogram below.
Summary
– Dionex ICS-5000+ EG Eluent Generator module
Analysis of cations and anions
are important to municipal
drinking water and wastewater
treatment plants for compliance
monitoring. Cationic determinations are necessary as part of the
water monitoring program’s
secondary water specification of
acceptable taste. In municipal
wastewater, cation determinations ensure that no
environmental effects occur as a
result of discharging high-salt
concentrations into the water
system. This application
demonstrates the advantages of
high-pressure capillary IC using
the high capacity Dionex IonPac
CS16 capillary cation-exchange
column to provide high sample
throughput by simply increasing
the flow rate on a high-pressure
capable Dionex ICS-5000+ HPIC
capillary IC, saving time and
money.
– Dionex ICS-5000+ DC Detector/
Chromatography module with Dionex
IC Cube and high-pressure degas cartridge
Download the full version of
Technical Note 121
Results
14
1
1
Peaks:
– Dionex AS-AP Autosampler
• Chromeleon CDS software
Reagents and Standards
B 2
Columns: Dionex IonPac CS16 column, 0.5 × 250 mm
Eluent Source: Dionex EGC-MSA capillary cartridge with
Dionex CR-CTC Continuously Regenerated
Cation Trap Column
Eluent:
30 mM MSA
Flow Rate: A: 0.010 mL/min
B: 0.030 mL/min
IC Cube Temp.:* 40 °C
34
0.030 mL/min, 3720 psi
4
• Thermo Scientific Dionex Combined Six Cation II
Standard (Dionex P/N 046070)
A
–2
96 mg/L
0.80
11.6
38.0
52.9
5
µS
• 18 MΩ-cm degassed deionized water
Conditions
1. Sodium
2. Ammonium
3. Potassium
4. Magnesium
5. Calcium
0
2
3
10
Minutes
5
0.010 mL/min,
1250 psi
20
30
Fast, high-pressure cation separations in a wastewater sample using
capillary IC.
Compartment Temp.: 15 °C
Inj. Volume: 0.4 μL
Detection: Suppressed conductivity, Thermo Scientific™
Dionex™ CCES™ 300 Cation Capillary Electrolytic
Suppressor, recycle mode;
A: 8 mA; B: 13 mA
Background
Conductance: 0.3–0.8 μS
Noise: < 0.3 nS
System
Backpressure: A: 1250 psi; B: 3720 psi
* The Dionex IC Cube heater controls the separation
temperature by controlling the column cartridge
temperature. The original term of “column
temperature” refers to the temperature in the bottom
DC compartment which is not used for capillary IC.
13
Br i e f of
Appli cat i on Update 1 8 5
Determination of Nitrite and Nitrate in Wastewater
Using Capillary IC with UV Detection
Nitrite and Nitrate in Wastewater
Equipment
• Dionex ICS-5000 Capillary IC system* including:
– DP Dual Pump module (Capillary)
Summary
Ion chromatography with
suppressed conductivity
detection is an effective technique to simultaneously
determine common inorganic
anions in environmental water
and drinking water. However in
some samples such as mineral
water, wastewater, and brine,
accurate quantification of some
anions present at low concentrations can be challenging due to
the high ionic strength of the
sample. Ion chromatography
with UV detection provides an
alternate approach for determining nitrite and nitrate without
compromising sensitivity. By
combining suppressed conductivity with UV detection, the
suppressor reduces the background noise. The Dionex
Capillary RFIC system delivers
fast turnaround by reducing
eluent preparation, system
startup, and equilibration times.
This method is a solution for
nitrite analysis when high
concentrations of chloride can
mask the presence of nitrite.
Download the full version of
Application Update 185
14
–
Dionex EG Eluent Generator
module with Thermo Scientific Dionex EGC
Cartridge (Capillary) and Thermo Scientific
Dionex CR-TC Continuously Regenerated
Trap Column (Capillary)
–
Thermo Scientific Dionex DC Detector/
Chromatography Compartment with
Thermo Scientific™ Dionex™ IC Cube™ module
and Capillary CD Conductivity Detector
– Dionex AS-AP Autosampler
– Thermo Scientific Dionex ICS-Series VWD
Variable Wavelength Detector with PEEK
capillary cell (P/N 076072)
• Chromeleon CDS Software
Conditions
Column:
Dionex IonPac AS18-Fast column, 0.4 × 150 mm
Eluent:
33 mM KOH
Flow Rate: 0.015 mL/min
Inj. Volume: 0.4 µL
Detection: A: Suppressed conductivity, Dionex ACES 300 suppressor,
recycle mode
B: UV, 210 nm, capillary
Analysis
Capillary Ion Chromatography
Results
See chromatogram below.
1. Fluoride
2. Chloride
3. Nitrite
4. Sulfate
5. Bromide
6. Nitrate
*Dionex ICS-4000 system and Dionex ICS-5000 +
system can be used for equivalent results
Reagents and Standards
• Nitrite, 1000 mg/L (Fisher Scientific
P/N AS-NO29-27)
A
—
—
—
—
—
—
Peaks:
B mg/L
—
—
0.030
—
—
48.7
30
• Nitrate, 1000 mg/L (Fisher Scientific
P/N AS-NO3N9-2y)
4
2
6
mAu
1
A
3
-9
0
5
4
Minutes
B
8.5
Separation of inorganic anions in a municipal wastewater sample spiked
with 0.030 mg/L nitrite.
Br i e f of
Appli cat i on N ote 1 6 7
Determination of Trace Concentrations of Oxyhalides
and Bromide in Municipal and Bottled Waters Using
a Hydroxide-Selective Column with a Reagent-Free
Ion Chromatography System
Oxyhalides and Bromide in Municipal and Bottled Water
Equipment
• Thermo Scientific Dionex ICS-2000 RFIC*
System** consisting of:
– Eluent Generator
Summary
– Column Heater
Previous methods developed for
determining low μg/L concentrations of bromate by direct
injection have focused primarily
on using columns specifically
designed for carbonate eluents.
Columns designed for use with
hydroxide eluents have not been
widely used for the determination of trace bromate in
environmental waters due to
their lack of appropriate
column selectivity and the
difficulty in preparing contaminant-free hydroxide eluents. The
introduction of electrolytic
eluent generation has not only
eliminated the difficulty in
preparing hydroxide eluents,
but has simplified the development of optimized methods. In
this application note, we use the
Dionex IonPac AS19 column, a
column specifically designed for
use with hydroxide eluents and
developed with an optimized
selectivity for the determination
of trace disinfection byproducts
(DBPs) and bromide in
environmental waters.
– Pump with Degasser
Download the full version of
Application Note 167
– Dionex EluGen EGC II KOH Cartridge
(P/N 058900)
– Dionex CR-ATC Continuously Regenerated
Anion Trap Column (P/N 060477)
Conditions
Columns:
Dionex IonPac AS19 Analytical column, 4 × 250 mm
(P/N 062885)
Dionex IonPac AG19 Guard column, 4 × 50 mm
(P/N 062887)
Eluent:
10 mM KOH from 0 to 10 min,
10–45 mM from 10 to 25 min*
Eluent Source: Dionex ICS-2000 EG Cartridge with Dionex CR-ATC
Trap Column
Flow Rate:
1.0 mL/min
• Thermo Scientific Dionex AS50 Autosampler
Temperature: 30 °C
• Chromeleon CDS Software
Injection:
*Also applicable to other RFIC systems.
**Dionex ICS-5000 + HPIC system can be used for
equivalent or improved results
Reagents and Standards
• Deionized water, Type I reagent grade, 18 MΩ-cm
resistivity or better
• Sodium and Potassium salts, A.C.S. reagent grade
or better, for preparing anion standards (VWR or
other)
• Fluoride standard 1000 mg/L, 100 mL
(P/N 037158)
• Chloride standard 1000 mg/L, 100 mL
(P/N 037159)
• Sulfate standard 1000 mg/L, 100 mL
(P/N 037160)
250 µL
Detection:
Suppressed conductivity, Thermo Scientific™
Dionex™ ASRS™ ULTRA II Suppressor, 4mm
(P/N 061561), Autosuppression, Recycle Mode,
130 mA current
Background
Conductance: <1 µS
System
Backpressure: ~2200 psi
Run Time:
30 min
*Method returns to 10 mM KOH for 3 min prior to
injection
Analysis
Reagent-Free IC
Results
See chromatogram and table.
• Bromide standard 1000 mg/L, 100 mL (Ultra
Scientific, VWR P/N ICC-001)
• Sodium Chlorite, 80% (Fluka Chemical Co.)
• Sodium Bromate (EM Science, VWR
P/N EM SX0385-1)
• Ethylenediamine, 99% (Sigma-Aldrich)
15
Column:
Eluent:
Eluent Source:
Flow Rate:
Temperature:
Inj. Volume:
Detection:
3.00
Dionex IonPac AG19 and
Peaks:
AS19 columns, 4 mm
10 mM KOH 0–10 min,
10–45 mM 10–25 min
Dionex ICS-2000 EG cartridge
with Dionex CR-ATC trap column
1 mL/min
30 °C
500 µL
Dionex ASRS ULTRA II suppressor, 4 mm
recycle mode, 130 mA
1. Chlorite 23 µg/L
2. Bromate
5
3. Chlorate 190
4. Bromide 77
3
µS
4
1
2
–0.10
0
5
10
15
Minutes
20
25
Determination of DBP anions and bromide spiked in drinking water A using a 500 µL injection
volume.
Recoveries of trace oxyhalides and bromide spiked into environmental waters.
:
16
30
Br i e f of
Appli cat i on N ote 1 7 1
Determination of Disinfection Byproduct Anions and
Bromide in Drinking Water Using a Reagent-Free
Ion Chromatography System Followed by Postcolumn
Addition of an Acidified On-Line Generated Reagent
for Trace Bromate Analysis
Disinfection Byproduct Anions and Bromide in Drinking Water
Equipment
• Ethylenediamine (EDA) (Aldrich, 24,072-9)
• Dionex ICS-3000 RFIC System* consisting of:
• Sulfuric Acid, 36 N (J.T. Baker® Instra-Analyzed®
9673-33)
– DP Dual Pump or SP Single Pump
Summary
Considerable efforts have
focused on developing improved
analytical methods for determining trace concentrations of
inorganic DBPs in drinking water
to meet current regulatory
requirements. Traditionally, IC
with suppressed conductivity
detection has been used to
determine chlorite, bromate, and
chlorate in environmental waters,
as described in EPA Method
300.0 (B). In this application
note, we demonstrate the
performance of the Dionex
IonPac AS19 column for EPA
Method 326.0. This method
allows quantification of bromate
to 1 µg/L by suppressed
conductivity detection with a
hydroxide eluent and 0.5 µg/L
using postcolumn reaction with
UV detection.
Download the full version of
Application Note 171
–
DC Dual Compartment with a CD
conductivity detector and an Automation
manager (PN 061962) equipped with a
RCH-1 Postcolumn Reaction Heater
(P/N 079944)
– VWD UV/Vis Absorbance Detector with a
PEEK™ analytical flow cell (PN 6074.0200)
– Dionex AS Autosampler
– EG Eluent Generator with a Dionex EluGen
EGC II KOH Cartridge (P/N 058900)
– Dionex CR-ATC Continuously Regenerated
Anion Trap Column (P/N 060477)
– PC10 Postcolumn Pneumatic Delivery Module
(P/N 050601)
– Knitted Reaction Coil, 500 µL, potted (for
RCH-1) (P/N 039349)
– PEEK Mixing Tee (P/N 048227)
– Four 4 L plastic bottle assemblies
(P/N 063292)
– Three bottles for external water mode of
suppression
• Bromide Standard, 1000 mg/L, 100 mL (Ultra
Scientific, VWR P/N ICC-001)
• Sodium Chlorite (NaClO2) (Fluka 71388,
80% pure)
• Bromate Standard, 1000 mg/L, 100 mL (Ultra
Scientific,VWR P/N ICC-010)
• Sodium Bromate (NaBrO3) (EM SX 03785-1)
• Sodium Chlorate (NaClO3) (Aldrich, 24,414-7)
• DL-Malic Acid, Disodium salt (Sigma-Aldrich,
M6773)
Conditions
Columns:
Dionex IonPac AS19 Analytical column, 4 × 250 mm
(P/N 062885)
Dionex IonPac AG19 Guard column, 4 × 50 mm
(P/N 062887)
Eluent:
10 mM KOH from 0–10 min,
10–45 mM from 10–25 min
45 mM from 25–30 min*
Eluent Source: Dionex EG50 cartridge with
Dionex CR-ATC trap column
Flow Rate:
1.0 mL/min
Temperature: 30 °C
Inj. Volume:
250 µL
• Polystyrene Autoselect vials with caps and septa,10
mL (P/N 055058)
Detection:
Suppressed conductivity, Dionex ASRS 300
suppressor, 4mm (P/N 064554), Autosuppression,
external water mode, 112 mA current
• Nalgene Filter Unit, 0.2 µm nylon membrane,
1000 mL (VWR P/N 28198-514)
Background
Conductance: <1 µS
*Dionex ICS-5000 + HPIC system can be used for
equivalent or improved results
System
Backpressure: ~2200 psi
– One bottle for 0.3 N sulfuric acid for the
online conversion of KI to I3–
• Chromeleon CDS Software
Reagents and Standards
Run Time:
• Deionized water, Type I reagent grade, 18 MΩ-cm
resistivity or better
Postcolumn Reaction Conditions
30 min
• Potassium Iodide (KI) (VWR
P/N BDH0264-500g)
UV Detection:
Absorbance at 352 nm (deuterium lamp)
PCR Flow:
0.26 M potassium iodide at 0.3 mL/min
• Ammonium Molybdate
Tetrahydrate[(NH4)6Mo7O24•4H2O] (SigmaAldrich, A7302)
AMMS III:
0.3 N sulfuric acid at 2.5 mL/min
Postcolumn
Heater Temp: 80 °C
UV Noise:
<0.1 mAU
*Method returns to 10 mM KOH for 3 min prior to
injection.
17
Analysis
Column:
Eluent:
Bromate (conductivity)
0.32
1.0
95.5
Dionex IonPac AG19/AS19 columns, 4 mm
10 mM potassium hydroxide for 0–10 min,
10–45 mM potassium hydroxide for 10–25 min
45 mM potassium hydroxide for 25–30 min
Eluent Source:
Dionex EG50 cartridge with Dionex CR-ATC trap column
Temperature:
30 ºC
Flow Rate:
1 mL/min
Inj. Volume:
250 µL
Detection:
(A) Dionex ASRS 300 suppressor,
4 mm, external water mode
(B) Absorbance, 352 nm
Postcolumn Reagent: Acidified potassium iodide (KI)
PCR Flow Rate:
0.3 mL/min
Postcolumn Heater: 80 ºC
Bromate (UV/Vis)
0.35
1.0
98.1
Peaks (A):
1. Unknown
2. Bromate
3. Chlorate
4. Bromide
Peaks (B):
1. Unknown
2. Bromate
Reagent-Free IC
Results
See table and chromatogram below.
Amount
Found
Recoveries of trace DBP anions spiked
into water
samples Amount Added
Analyte
(µg/L)
(µg/L)
Recovery
(%)
Tap Water A
Chlorite
4.6
6.9
95.9
Chlorate
74.7
80.1
97.5
Bromide
34.6
39.9
95.4
< MDL
4.6
108.0
Bromate (conductivity)
2.4
3.0
102.8
Bromate (UV/Vis)
2.8
3.0
94.7
62.4
69.7
96.7
17.5
19.9
92.3
4.9
105.3
101.1
Tap Water B
Chlorite
Chlorate
Bromide
Bottled Water A-1
Chlorite
Bromate (conductivity)
Bromate (UV/Vis)
Chlorate
Bromide
< MDL
9.5
9.7
10.8
9.7
97.3
< MDL
6.2
99.8
19.0
19.9
95.0
<MDL
6.4
95.9
Bromate (conductivity)
8.7
9.7
95.7
Bromate (UV/Vis)
Chlorate
Bromide
8.5
9.7
98.4
< MDL
6.4
107.6
3.2
6.4
111.8
–
2.8
A
µS
Bottled Water A-2
Chlorite
1.5
– µg/L (ppb)
2.4
62.4
17.5
3
1
4
2
0.7
0.025
B
AU
1
Bottled Water B
Chlorite
< MDL
4.9
Bromate (conductivity)
< MDL
1.0
108.3
102.4
Bromate (UV/Vis)
< MDL
1.0
104.5
Chlorate
< MDL
5.2
101.5
Bromide
10.4
9.9
90.8
2
–0.013
0
5
10
15
Minutes
20
25
Determination of trace DBP anions and bromide in tap water B using suppressed conductivity
detection and UV absorbance after PCR with acidified iodide.
:
18
30
Br i e f of
Appli cat i on N ote 1 8 7
Determination of Sub-μg/L Bromate in Municipal
and Natural Mineral Waters Using Preconcentration
with Two-Dimensional Ion Chromatography and
Suppressed Conductivity Detection
Bromate in Municipal and Natural Mineral Water
Equipment
• Dionex ICS-3000 RFIC System* consisting of:
– EG Eluent Generator module with a dual
setup
Columns:
Dionex IonPac AG19 Guard column, 4 × 50 mm
(P/N 062887)
Dionex IonPac AS19 Analytical column, 4 × 250 mm
(P/N 062885)
– DC Detector/Chromatography module (single
or dual temperature zone configuration)
Eluent:
10 mM potassium hydroxide 0–12 min,a
step to 65 mM at 12 min, 65 mM 12–35 minb
• Dionex AS Autosampler with a 5 mL syringe
(P/N 053915), 8.2 mL sampling needle assembly
(P/N 061267)
Eluent Source: Dionex EGC II KOH cartridge with
Dionex CR-ATC trap column
Flow Rate:
1 mL/min
• Dionex EluGen EGC II KOH cartridges
(P/N 058900)
Temperature:
30 °C (lower compartment)
30 °C (upper compartment)
• Two Dionex CR-ATC Continuously Regenerated
Anion Trap Columns (P/N 060477)
Injection Vol:
1000 μL
Detection:
Suppressed conductivity, Dionex ASRS ULTRA II
suppressor, 4mm (P/N 064554), Autosuppression,
external water mode, (Flow rate: 3–5 mL/min)
Current setting: 161 mA
– DP Dual Pump module
Summary
Determining low concentrations
of bromate in high-ionicstrength matrices using
suppressed conductivity
detection is subject to potential
interferences and loss of
sensitivity. Although postcolumn
reaction methods do not
generally suffer from interferences by common anions,
column overloading with
high-ionic-strength samples can
still cause peak broadening and
an associated loss of response. In
this application note, we
demonstrate the use of a
two-dimensional (2-D) IC
system for the determination of
trace concentrations of bromate
in municipal and natural
mineral waters with high-ionicstrength matrices. This 2-D IC
method achieves bromate
detection limits equivalent to or
better than postcolumn addition
methods. The 2-D IC method
avoids the cost and disposal of
the chemicals required for
postcolumn configurations and
simplifies the experimental
setup.
Download the full version of
Application Note 187
First-Dimension Conditions
• Four 4 L plastic bottle assemblies for external
water mode of operation
• Chromeleon CDS Software, version 6.8
*Dionex ICS-5000 + HPIC system can be used for
equivalent or improved results.
Reagents and Standards
• Deionized water,Type I reagent grade, 18 MΩ-cm
resistivity or better
• Bromate standard (1000 mg/L, ULTRA Scientific,
N. Kingstown, RI, USA, VWR P/N ULICC-010)
• Sodium bromate (NaBrO3) (EM Science, EMD
Millipore, Billerica, MA, USA, SX0385-1)
System
Backpressure: ~2300 psi
Expected
Background
Conductance: <0.5 μS
Noise:
~1–2 nS/min peak-to-peak
Run Time:
35 min
The step change described here should occur after the valve on system #2
has switched from the load to inject position.
a
The method equilibrates for 5 min at 10 mM KOH prior to injection.
b
• Sodium chloride (NaCl) (J.T. Baker®, Center
Valley, PA, USA VWR P/N JT3625-1)
• Sodium nitrate (NaNO3) (Fisher Scientific
S343-500)
• Sodium bicarbonate (NaHCO3) (EM Science
SX0320-1)
• Sodium sulfate (Na2SO4) (Sigma-Aldrich, St. Louis,
MO, USA, 29,931-3)
• Sodium phosphate, dibasic, anhydrous(Na2HPO4)
(J.T. Baker 4062-1)
19
Second-Dimension Conditions
Columns:
Dionex IonPac AG24 Guard column, 2 × 50 mm (P/N 064151)
Dionex IonPac AS24 Analytical column, 2 × 250 mm (P/N 064153)
Eluent:
10 mM potassium hydroxide 0–24 min,
step to 65 mM at 24 min, 65 mM 24–35 minb
Bromate recoveries from fortified reagent water, LSSM, and municipal drinking water matrices.
Matrix
Amount
Found
(µg/L)
Reagent Water
—
LSSMa
—
Eluent Source: Dionex EGC II KOH cartridge with Dionex CR-ATC trap column
Flow Rate:
0.25 mL/min
Temperature:
30 °C (lower compartment)
30 °C (upper compartment)
Cut Volume:
2 mL (on the concentrator column)
Concentrator:
Dionex IonPac TALC-ULP1 column, 5 × 23 mm (P/N 061400)
Detection:
Suppressed conductivity, Dionex ASRS ULTRA II suppressor, 2 mm,
auto-suppression, external water mode (flow rate: 1–3 mL/min)
Current setting: 41 mA
System
Backpressure: ~2400 psi
Expected
Background
Conductance: <0.5 μS
Noise:
~2–3 nS/min peak-to-peak
Run Time:
35 min
The method equilibrates for 5 min at 10 mM KOH prior to injection.
b
:
20
Drinking Water A
Drinking Water B
0.45
1.19
Amount
Added
(µg/L)
Replicates
Average
Recovery
(%)
Peak Area
Precision
(RSD)
0.5
7
101.5
1.98
5.0
7
105.6
0.66
0.5
7
96.1
5.75
5.0
7
106.7
1.66
0.5
7
98.2
6.06
5.0
7
104.5
1.71
0.5
7
98.7
2.51
5.0
7
105.6
1.91
LSSM = Laboratory synthetic sample matrix containing 100 mg/L each of chloride, sulfate, and bicarbonate and 10 mg/L
each of nitrate-N and phosphate-P
a
Br i e f of
Appli cat i on Update 1 7 9
Sensitive Determination of Hexavalent Chromium in
Drinking Water
Hexavalent Chromium in Drinking Water
Equipment
• Thermo Scientific Dionex ICS-2100, Dionex
ICS-1600, Dionex ICS-1100,* or Dionex
ICS-5000+ system including:
– SP Single Pump or DP Dual Pump module**
Summary
– DC Detector/Chromatography module**
Chromates are oxyanions (e.g.,
–
–
CrO42 , Cr2O72 ) of chromium in
oxidation state +6. All hexavalent chromium Cr(VI)
compounds are strong oxidizing
agents and considered toxic and
potentially carcinogenic. Hence,
chromates are regulated in the
environment and are a primary
drinking water contaminant in
the United States. For example,
in 1999, the state of California
established a public health goal
(PHG) of 0.2 μg/L (ppb) for
Cr(VI) and 2.5 μg/L for total
chromium. The PHG is based on
an estimated one-in-one-million
lifetime cancer risk level. This
method allows modifications to
the existing U.S. EPA Method
218.6 to allow sufficient
sensitivity for determining
hexavalent chromium (i.e.,
Cr(VI) as CrO42−) at the
proposed California PHG level
of 0.02 μg/L.
– Injection loop, 1000 μL
– Reaction coil, 125 μL (P/N 053640), 375 μL
(P/N 043700)
– Sample syringe, 5 mL
– Dionex ICS Series VWD UV-vis Absorbance
Detector (P/N 069117, 4 wavelength or
P/N 069116, single wavelength) with PEEK
semi-micro flow cell, 2.5 μL, 7 mm (Victrex
P/N 6074-0300) or PEEK standard flow cell,
11 μL, 10 mm (Victrex P/N 6074.0200)
• Polypropylene injection vials with caps (0.3 mL
vial kit,P/N 055428)
•Nalgene™ 125 mL HDPE narrow mouth bottles
(VWR P/N 16057-062)
• Nalgene 250 mLHDPE narrow mouth bottles
(VWR P/N 16057-109)
• Nalgene 250 mL 0.2 µm nylon filter units (VWR
P/N 28199-371)
• Nalgene 1000 mL 0.2 µm nylon filter units (VWR
P/N 28198-514)
*With addition of the optional column heater
**For the Dionex ICS-3000 or ICS-5000 +
Reagents
•
Prepare all solutions from analytical reagentgrade chemicals (when commercially available).
Note: There is a possibility of the presence of
trace levels of chromate in some commercially
available chemicals.
•
Deionized (DI) water, 18 MΩ or better
•
Ammonium sulfate (Mallinckrodt General
P/N AR 7725)
•
Ammonium hydroxide (Sigma P/N A6899)
•
Sulfuric acid, 95–98% (J.T. Baker® InstraAnalyzed® P/N 9673)
• Chromeleon CDS software
•
• Eluent Organizer, including 2 L plastic bottles
(P/N 072057) and pressure regulator (P/N 038201)
Methanol, HPLC grade (Fisher Optima
P/N A454-4)
•
Potassium dichromate (J.T. Baker P/N 4765-01)
•
Sodium and potassium salts, A.C.S. reagent
grade, for preparing the anion standards
• Postcolumn Delivery Configuration:
– DP** or PC10 Postcolumn Pneumatic Delivery
Package or the Thermo Scientific Dionex
AXP Auxiliary Pump (P/N 063973) or
Thermo Scientific Dionex AXP-MS Metering Pump (P/N 060684)
• Dionex AS-AP Autosampler
Download the full version of
Application Update 179
21
Analysis
Conditions
Reagent-Free Ion Chromatography
Method
Columns:
Dionex IonPac AG7 Guard, 2 × 50 mm (PN 063099),
Dionex IonPac AS7 Analytical, 2 × 250 mm (PN 063097)
Eluent:
250 mM Ammonium sulfate and 100 mM ammonium hydroxide
Eluent Flow Rate: 0.36 mL/min
Inj. Volume:
1000 μL (Full loop)
Temperature: 30 °C
Back Pressure:
1700–2000 psi
Results
See chromatogram below.
3.3
Column:
Dionex IonPac AG7,
2 × 50 mm,
Dionex IonPac AS7, 2 × 250 mm
Eluent:
250 mM (NH4)2 SO4,
100 mM NH4OH
Flow:
0.36 mL/min
Inj. Vol.:
1000 µL
Postcolumn Reagent: 2 mM diphenylcarbazide
10% methanol
1 N sulfuric acid
Reaction Coil:
125 µL
UV Cell:
Semi-micro (PEEK), 2.5 µL
Postcolumn Reagent (PCR):
2 mM diphenylcarbazide, 10 % methanol, 1 N sulfuric acid
PCR Flow Rate:
0.12 mL/min
Detection:
Visible absorbance, 530 nm
Noise: 6–8 μAU
Run Time: 10 min
mAU
A:
B:
0.1 µg/L Cr(VI) in DI water
0.1 µg/L Cr(VI) in HIW
B
A
-0.7
Signal offset 5%
0
2
4
Minutes
6
8
10
Determination of chromate (0.1 µg/L) in A) DI water and B) HIW on a Dionex ICS-2100 system.
Postcolumn reagent delivered by an AXP pump. Flow cell: semi-micro (PEEK).
:
22
Br i e f of
Appli cat i on N ote 1 6 1
Determination of Metal Cyanide Complexes by
Ion Chromatography with On-Line Sample
Preconcentration and UV Absorbance Detection
Metal Cyanide Complexes in Water Samples
Equipment
• Thermo Scientific Dionex ICS-2500* IC system
consisting of:
– Thermo Scientific Dionex GS50 Gradient Pump
Summary
Several methods measure free
cyanide, but rely on some
operational definition to
distinguish between weak and
strong cyanide complexes. Ion
chromatography resolves each
individual metal cyanide complex
during an automated, 30 min
separation. IC thus allows a
precise differentiation of
complexes of limited toxicity
from those of greater toxicity.
This method of on-line preconcentration allows determination
of metal cyanide complexes at
µg/L concentrations in a variety
of environmental water matrices.
This method provides good
recoveries for the gold, iron, and
cobalt cyanide complexes in all
matrices studied, and for the
nickel cyanide complex in all
matrices except wastewater. This
method shows increased bias for
the silver and copper cyanide
complexes, especially in
higher-ionic strength matrices.
Download the full version of
Application Note 161
– Thermo Scientific Dionex AD25 Absorbance
Detector
– Thermo Scientific Dionex AS50 AutoSelect,
PEEK, with Chromatography Compartment and
Chemistry Switching Option
– Thermo Scientific Dionex AS50 Dual-Valve
Needle Assembly (P/N 061267-01)
– Thermo Scientific Dionex Sample PREP
Syringe, 10-mL (P/N 055068)
• Chromeleon CDS Workstation
• Thermo Scientific Dionex DQP-1 Sample/Reagent
Pump (P/N 035250)
• Syringe filters (Gelman IC Acrodisk® 0.2-µm,
PN 4483)
Conditions
Columns:
Dionex IonPac AS11 Analytical column, 2 × 250mm
Dionex IonPac AG11 Guard column, 2 × 50 mm,
2 each
Dionex IonPac ATC-3 column
Temperature: 30 °C
Injection: 5 mL
Detection: Absorbance at 215 nm
Expected System
Backpressure: 850 psi
Noise: 1–5 mAU
Run Time: 32 min
Flow Rate: 0.25 mL/min
Eluent: (A) 20 mM sodium hydroxide/150 mM sodium
cyanide
(B) 20 mM sodium hydroxide/300 mM sodium
perchlorate
(C) 20 mM sodium hydroxide
• Storage bottles, amber HDPE
(VWR IRN301-0125 or 16172-144)
Analysis
• Thermo Scientific Dionex Trap Columns, MetalFree MFC-1, 2 each (P/N 037017)
Results
• Thermo Scientific Dionex Vial Kit 10-mL polystyrene (P/N 055058)
*Dionex ICS-5000 + system can be used for equivalent or
improved results
Ion Chromatography
See chromatogram below.
Peaks:
1. [Ag(CN)2]–
2. [Cu(CN)3]2–
3. [Au(CN)2]–
4. [Ni(CN)4]2–
5. [Fe(CN)6]4–
6. [Co(CN)6]3–
0.4
Reagents and Standards
• Copper cyanide (AlfaAesar 12135)
• Potassium dicyanoargentate (I) (AlfaAesar 12551)
1
• Potassium dicyanoaurate (I) (AlfaAesar 12552)
• Potassium ferrocyanide (II) trihydrate
(Aldrich 22,768-4)
A
8.6
1.1
B
79.5 μg/L
16.1
83.7
60.8
6
10.1
10.7
0.1
1.2
2
3 4
AU
5
B
• Potassium hexacyanocobaltate (III)
(AlfaAesar 23126)
• Potassium tetracyanonickelate (II) hydrate
(Strem 93-2836)
• Sodium cyanide, 99.99% (Aldrich 43,159-1)
• Sodium hydroxide solution 50% w/w (Fisher
SS254)
• Sodium perchlorate monohydrate, HPLC-grade
(Fisher S490)
A
2
1
5
6
–0.3
10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
Minutes
Anion-exchange separation with preconcentration and absorbance
detection at 215 nm of metal cyanide complexes in drinking water from
a municipal well. Drinking water matrix blank (A) and matrix spiked with
metal cyanide complexes (B) as shown.
23
Br i e f of
Appli cat i on N ote 1 7 3
Determination of Cyanide in Drinking Water by
Ion Chromatography with Pulsed Amperometric
Detection (ICE-PAD)
Cyanide in Municipal Drinking Water
Summary
Cyanide occurs naturally in
many foods (cassava, sorghum,
African lima beans, bamboo
shoots, bitter almonds, and
apricot, cherry, and peach pits)
and is naturally generated by
microorganisms. Cyanide is used
in many industries (e.g., plating
and mining) and it can be
released into the air from
burning coal and plastics. In the
U.S., drinking water contamination with cyanide is typically
from an industrial source or
leached from waste sites This
Application Note demonstrates
fast, accurate determinations of
free cyanide in drinking water
samples using IC-PAD with a
waveform optimized for cyanide,
and use with disposable silver
working electrodes. This method
is compatible with the basic
solutions used to preserve
drinking water samples for
cyanide analysis and is unaffected by other compounds
typically found in drinking water.
Download the full version of
Application Note 173
Equipment
Reagents and Standards
• Thermo Scientific Dionex ICS-3000* IC system
consisting of:
Use only ACS reagent grade chemicals for all reagents
and standards.
– Single Gradient Pump (SP) or Dual Gradient
Pump (DP) module with degas option and
gradient mixer (P/N 049135)
• Deionized water, Type 1 reagent-grade,
18.2 MΩ-cm resistivity or better, freshly degassed
by vacuum filtration
– Detector and Chromatography Module (DC)
with a single temperature zone and one
injection valve
• Sodium cyanide, anhydrous (Aldrich,
P/N 20,522-2)
–
Electrochemical Detector ED (P/N 061718)
with an electrochemical cell containing a
combination pH-Ag/AgCl reference electrode
(cell and reference electrode, P/N 061756,
reference electrode P/N 071879) and a Certified
Disposable Silver (Ag) working electrode
(Package of 6 electrodes, P/N 063003)
– Dionex AS Autosampler with Sample Tray
Temperature Controlling option and 1.5 mL
sample tray
• Chromeleon CDS software version 6.7 or higher
• Filter unit, 0.2-µm nylon (Nalgene Media-Plus with
90-mm filter, Nalge Nunc International,
P/N 164-0020) or equivalent nylon filter
• pH 7 (yellow) and pH 10 (blue) buffer solutions
(VWR International, P/N 34170-130, 34170-133)
Used for experiments that determined retention times
and possible interferences:
• Copper reference standard, Certified 1000 ppm
±1% (Fisher Chemical, P/N SC194-100)
• Iron reference standard, Certified 1000 ppm ±1%
(Fisher Chemical, P/N SI124-100)
• Nickel reference standard, Certified 1000 ppm ±1%
(Fisher Chemical, P/N SN70-100)
• Sodium bromide, anhydrous (Aldrich,
P/N 310506)
• Vacuum pump
• Sodium iodide, anhydrous (Aldrich, P/N 383112)
• 1.5-mL polypropylene sample vials, with caps and
slit septa (vial kit, P/N 061696)
• Sodium sulfide, nonahydrate, >99.99%
(Aldrich, P/N 431648)
• Disposable polystyrene 10-mL and 25-mL
graduated pipettes
• Sodium sulfite, anhydrous (Aldrich, P/N 239321)
• Micropipettor and tips for preparing samples,
standards, and pipetting samples into vials
• Thermo Scientific™ Dionex™ OnGuard™ II H
cartridges (2.5 cc, package of 48, P/N 057086)
• Black PEEK (0.254-mm or 0.010-in. i.d.) tubing,
used for eluent connections to cell, Pump 1, and
columns (5 ft, P/N 052306)
• Red PEEK (0.127-mm or 0.005-in. i.d.) tubing,
installed in DC heat exchanger (5 ft, P/N 052310)
• Green PEEK (0.76-mm or 0.030-in. i.d.) tubing,
installed in Dionex AS Autosampler (5 ft,
P/N 052305)
*Dionex ICS-5000 + system can be used for equivalent or
improved results
24
• Sodium hydroxide, 50% (w/w) (Fisher Chemicals,
P/N SS254-500)
• Sodium thiocyanate, (Aldrich, P/N 251410)
• Sodium thiosulfate, pentahydrate (Aldrich,
P/N 2929)
Analysis
Conditions
Columns:
Dionex IonPac AS15 Analytical column, 2 × 250 mm
Dionex IonPac AG15 Guard column, 2 × 50 mm
Flow Rate:
0.25 mL/min
Eluent:
(A) 63 mM Sodium hydroxide (31.5%)
(B) 200 mM sodium hydroxide)
Column Temp:
30 ºC
Tray Temp: 10 ºC
Inj. Volume: 10 µL (PEEK sample loop, P/N 042949), full-loop injection
Detection:
Pulsed Amperometric Detection (PAD)
Electrodes:
Reference: pH-Ag/AgCl electrode (P/N 061879) in AgCl mode
Working electrode: Certified disposable Ag working
Background:
3–13 nC versus Ag/AgCla
Backpressure:
~1100 psi
Noise: <7 pC
Run Time:
25 min
Syringe Speed: 4
Flush Volume:
250 µL
ICE-PAD
Results
See chromatogram below.
Columns:
Eluent:
7.20
3
4
nC
Dionex IonPac AS15 and Guard Columns, 2 mm
63 mM Sodium hydroxide (31.5% Eluent B,
200 mM sodium hydroxide)
Column Temp: 30 °C
Tray Temp:
10 °C
Samples:
(A) City of Sunnyvale drinking water, sampled
during the summer and treated with
sodium hydroxide
(B) Sample A Spiked with 10 µg/L cyanide
Flow Rate:
0.25 mL/min
Inj. Volume: 10 µL
Detection:
PAD, Cyanide waveform
Peaks:
1. Unknown
2. Unknown
3. Chloride
4. Cyanide
10 µg/L
5. Bromide
5
1
The disposable silver electrodes have a background specification of – 45 to
a
B
2
+55 nC versus Ag/AgCl with a recommended waveform.
A
6.45
2
5
10
Minutes
15
20
25
City of Sunnyvale drinking water with and without spiked cyanide.
25
Br i e f of
Appli cat i on N ote 2 2 7
Determination of Total Cyanide in Municipal Wastewater
and Drinking Water Using Ion Exclusion Chromatography
with Pulsed Amperometric Detection (ICE-PAD)
Total Cyanide in Municipal Waste and Drinking Water
Equipment
• PEEK Tubing:
• Dionex ICS-3000* IC system consisting of:
– Red (0.127 mm or 0.005 in i.d., P/N 052310
for 5 ft) tubing used for liquid line connections
from injection valve to the guard and analytical
columns, and cell.
– Single Gradient Pump (SP) module with
degas option
Summary
Total cyanide is defined by the
US EPA as free cyanide ion and
complex cyanides that are
converted to hydrocyanic acid
(HCN) during strong acid
digestion. For drinking and
surface waters, the US EPA has
established a maximum
contamination level (MCL) of
200 µg/L free cyanide determined
by a total cyanide assay. In
wastewater, the EPA specifies
cyanide discharge limits by
industry and size of the facility.
In this Application Note, the
authors describe a method with
PAD using a Pt disposable
working electrode and a
waveform optimized for
determination of total cyanide in
drinking and wastewater. The
authors also demonstrate
linearity, detection limits,
accuracy, and precision for
determination of total cyanide in
drinking water and wastewater
samples using the EPA-approved
MICRO DIST™ system and
ICE-PAD.
Download the full version of
Application Note 227
– Detector and Chromatography Module (DC)
with single or dual heating zone, and 6-port
injection valve
– Electrochemical Detector ED (P/N 061718)
– Dionex AS Autosampler with Sample Tray
Temperature Controlling option and 1.5 mL
sample tray
• 50 µL PEEK sample loop (P/N 042950)
– Dionex AS Autosampler with Sample Tray
Temperature Controlling option, and
10 mL sample tray
Reagents and Standards
–
An electrochemical cell containing a
combination pH–Ag/AgCl reference electrode
(cell and reference electrode, P/N 061756)
and a disposable (Pt) working electrode
(P/N 064440 package of six)
• Chromeleon CDS 6.8 Workstation
• Vial Kit, 10 mL polystyrene with caps and septa
(P/N 055058)
• Knitted reaction coil, 375 µL, (P/N 043700) with
two PEEK™ unions (¼-28 thread female to 10-32
thread female, P/N 042806)
*Dionex ICS-5000 + can be used for equivalent or
improved results
• Deionized water, Type 1 reagent grade,
18.2 MΩ-cm resistivity, freshly degassed by
ultrasonic agitation and applied vacuum
• Use only ACS reagent grade chemicals for all
reagents and standards
• Magnesium chloride, hexahydrate
(VWR, P/N JT2444-1)
• Methanesulfonic acid (Aldrich, P/N 64280; Dionex,
P/N 033478)
• pH 7 (yellow) buffer solution (VWR International,
P/N BDH5046)
• pH 4 (red) buffer solution (VWR International,
BDH5018)
• MICRO DIST System for sample distillation
(Lachat Instruments/Hach Company,
P/N MDD001) with user filled tube kit (Hach
Company, P/N A17117 package of 100), heating
block, protective gloves, test tube racks, and a
small mechanical press
• Sodium cyanide, anhydrous (Aldrich,
P/N 20,522-2)
• Filter unit for vacuum filtration, 0.2 µm nylon
(Nalgene™ Media-Plus with 90 mm filter, Nalge
Nunc International, P/N 164-0020) or equivalent
nylon filter
For Interference Experiments
• Vacuum pump
• Syringe filter (Pall Life Sciences, GHP Acrodisc®
25 mm with 0.45 µm GHP membrane,
P/N 4560T) or filter unit for sample filtration,
0.45 µm nylon (Nalgene Media-Plus with 50 mm
filter, Nalge Nunc International, P/N 153-0045) or
equivalent nylon filter
26
– Yellow (0.76 mm or 0.003 in i.d., P/N 052301
for 5 ft) tubing used for system backpressure
loop.
• Sodium hydroxide, 50% (w/w) (Fisher Chemicals,
P/N SS254-500)
• Sulfuric acid (VWR, P/N JT9681-33)
• Ammonium chloride (Aldrich, P/N 213330,
FW 53.49)
• Sodium cyanate (Aldrich, P/N 185086, FW 65.01)
• Sodium sulfide, nonahydrate, > 99.99% (Aldrich,
P/N 431648, FW 240.18)
• Sodium thiocyanate, (Aldrich, P/N 251410,
FW 81.07)
• Sodium nitrate (Aldrich, P/N SS506, FW 84.99)
• Sodium sulfate (Aldrich, P/N 239313, FW 142.04)
Average cyanide determinations over three days.
Conditions
Columns:
Dionex IonPac ICE-AG1 Guard column, 4 × 50 mm (P/N 067842)
Dionex IonPac ICE-AS1 Analytical column, 4 × 250 mm (P/N 064198)
Flow Rate:
0.2 mL/min
50 mM Methanesulfonic acid
Eluent:
Column Temperature: 30 °C
Amount Found
(µg/L)a
Amount Added
(µg/L)
Average
Recoverya (%)
100 mM sodium hydroxide
<LOD
1.06
110 ± 6.4
Filtered 100 mM sodium
hydroxide
<LOD
5.02
102 ± 1.0
4.25 ± 0.07
4.99
102 ± 0.9
0.67 ± 0.02
0.99
97.4 ± 2.0
Sample
Tray Temperature:
10 °C
Inj. Volume: 50 µL
10-fold dilution of certified
cyanide wastewater sample (4.0
µg/L total cyanide)
Detection:
Pulsed Amperometric Detection (PAD)
Municipal drinking water
Reference Electrode:
pH-Ag/AgCl electrode (P/N 061879) in AgCl mode
Filtered municipal wastewater
effluent without base
<LOD
Not Tested
—
Working Electrode: Disposable Platinum
Typical Background:
70–120 nC
Filtered municipal wastewater
effluent with base
5.99 ± 0.09
4.97
99.5 ± 1.0
a
Typical System
Backpressure:
2200 psi
Noise:
20–30 pC
Typical pH:
1.2–1.3
Run Time:
30 min
n=6
Analysis
ICE-PAD
Results
See chromatogram and table below.
Columns:
Eluent:
Temperature:
Flow Rate:
Inj. Volume:
Detection:
Sample Prep.:
Samples:
Dionex IonPac ICE-AG/S1 columns, 4 mm
50 mM Methanesulfonic acid
30 °C
0.2 mL/min
50 µL
PAD, Pt (Disposable)
Micro Dist acid digestion
A: Municipal drinking water + base
B: Sample A + 1 µg/L cyanide
Peaks:
A
—
0.67
—
1. Unknown
2. Cyanide
3–5. Unknown
B
— µg/L
1.61
—
106.8
2
112
nC
B
A
106.5
15.40
nC
B
Minutes
1
2 34
16.60
5
A
106
0
10
Minutes
20
30
Comparison of (A) Municipal drinking water, and (B) Sample A with 1 µg/L cyanide added.
27
Br i e f of
Appli cat i on Update 1 4 8
Determination of Perchlorate in Drinking Water Using
Reagent-Free Ion Chromatography
Perchlorate in Drinking Water
Equipment
Summary
Perchlorate (ClO4–) is an
environmental contaminant and
has been found in drinking,
ground, and surface waters in
several states in the U.S.
However, most contaminated
sites appear to be geographically
confined, particularly in the
western U.S., and linked to
identifiable sources, such as
military installations and
manufacturing sites. Because
perchlorate targets the thyroid
gland at sufficiently high
concentrations, in 1998 the EPA’s
Office of Groundwater and
Drinking Water placed this anion
on its Contaminant Candidate
List (CCL) for drinking water.
Currently, the EPA has not
established any enforceable
health regulations for perchlorate
in drinking water or related
matrices, although some states
have set individual action levels.
This application update
demonstrates an approved
approach compared to Application Note 134 for the
determination of perchlorate in
environmental samples using
U.S. EPA Method 314.0.
The results meet or exceed
the performance requirements
specified in U.S. EPA
Method 314.0.
Download the full version of
Application Update 148
Conditions
• A Dionex ICS-2000* RFIC System was used in this
work. The Dionex ICS-2000 system is an integrated ion chromatograph that includes:
– Eluent Generator
Columns: Dionex IonPac AS11 Analytical, 4 × 250 mm
(P/N 055376)
Dionex IonPac AG16 Guard, 4 × 50 mm
(P/N 055377)
– Column Heater
Eluent: 65 mM potassium hydroxide
– Pump Degas
Eluent Source: Dionex ICS-2000 EG with
Dionex CR-ATC column
Flow Rate: 1.2 mL/min
Temperature: 30 °C
Injection: 1000 μL (with 10 μL cut volume from a
1100 μLsample loop)
Detection: Suppressed conductivity, Dionex ASRS
ULTRA II suppressor, 4 mm,
auto-suppression external water mode
Power setting, 193 mA
System Backpressure:
~2500 psi
– Dionex EluGen EGC II KOH Cartridge
(P/N 058900)
– Dionex CR-ATC Continuously Regenerated
Anion Trap Column (P/N 060477)
• Dionex AS50 Autosampler
• Dionex Chromeleon 6.5 CDS Workstation
• Suppressor External Regen Installation Kit for
ExternalWater Mode (P/N 038018)
• Conductivity Meter (Thermo Scientific™ Orion,™
Model 105)
• This application update is also applicable to other
RFIC systems.
* Equivalent or improved results can be achieved using
the Dionex ICS-2100 system.
Reagents and Standards
• Deionized (DI) water, Type I reagent grade,
18 MΩ-cmresistance or better
• Sodium Perchlorate (NaClO4) (Aldrich 41,024-1)
• Sodium Chloride (NaCl) (J. T. Baker; VWR
P/N JT3625-1)
BackgroundConductance: ~1–2 μS μS
Noise: ~1–2 nS/min peak-to-peak
Run Time: 15 min
Analysis
Ion Chromatography
Results
See chromatogram on below.
1.5
Columns:
Dionex IonPac AG16/AS16,
4 mm
Eluent:
65 mM KOH
Eluent Source: Dionex ICS-2000 EG with
Dionex CR-ATC column
Temperature: 30 °C
Flow Rate:
1.2 mL/min
Inj.Volume:
1000 µL
Detection:
Dionex ASRS ULTRA II suppressor
external water mode
• Sodium Sulfate (Na2SO4) (Aldrich 29,931-3)
• Sodium Carbonate Monohydrate (Na2CO3 • H2O)
(Fisher S262-3)
µS
Peaks:
1. Perchlorate 1 µg/L
1
1.1
0
2
4
6
8
10
Minutes
28
Determination of 1 μg/L perchlorate in deionized water.
12
15
Literature References
Useful Links
References for Application Brief 121
•
U.S. Environmental Protection Agency (EPA). Current Drinking
Water Regulations.
http://water.epa.gov/lawsregs/rulesregs/sdwa/currentregulations.cfm
(accessed March 5, 2014).
•
The Determination of Inorganic Anions in Water by Ion Chromatography; Method 300.0, Revision 2.1; U.S. Environmental
Protection Agency: Cincinnati, OH, 1993.
•
•
U.S. Environmental Protection Agency (EPA). Safe Drinking Water
Act (SDWA).
http://water.epa.gov/lawsregs/rulesregs/sdwa/
(accessed March 5, 20014).
Dionex (now part of Thermo Scientific). Determination of
Inorganic Anions in Drinking Water by Ion Chromatography.
Application Note 133, LPN 1192; Sunnyvale, CA, 2004.
References for Technical Note 127
•
European Commision. The Directive Overview.
http://ec.europa.eu/environment/water/water-drink/legislation_en.
html
(accessed March 5, 2014).
•
U.S. EPA Method 300.0, rev 2.1, Determination of Inorganic Anions
in Water by Ion Chromatography, U.S. Environmental protection
Agency, Cincinnati, OH, 1993.
•
•
Dionex (now part of Thermo Scientific) Product Specification Sheet:
Reagent-Free Ion Chromatography Systems with Eluent Regeneration. Sunnyvale, CA, 2010. [Online]
http://www.thermoscientific.com/content/dam/tfs/ATG/CMD/
CMD%20Documents/Product%20Manuals%20&%20Specifications/Chromatography/Ion%20Chromatography/IC%20and%20
RFIC%20Columns/65844-DS-RFIC-ER-IC-05Apr2010LPN2022-03.pdf
(accessed March 5, 2014).
Thermo Scientific Dionex IonPac AS18-4µm Hydroxide-Selective
Anion-Exchange Capillary Column, http://www.dionex.com/en-us/
products/columns/ic-rfic/hydroxide-selective-packed/ionpac-as184um/lp-111535.html
•
Thermo Fisher Scientific. Dionex Technical Note 129, Configuring
High-Pressure IC Systems for Analytical Flow Rates. Doc No.
TN70317, Sunnyvale, CA, 2012.
•
Thermo Fisher Scientific. Dionex Product Manual for Anion
Self-Regenerating Suppressor 300 and Cation Self-Regenerating
Suppressor 300. Doc No. 031956, Sunnyvale, CA, 2009.
•
Thermo Fisher Scientific. Dionex ICS-5000+ Installation instructions.
Doc No. 065447, Sunnyvale, CA, 2011.
•
Thermo Fisher Scientific. Dionex AS-AP Operator’s Manual. Doc
No. 065361, Sunnyvale, CA, 2012.
•
Thermo Fisher Scientific. Dionex Application Note 154, Determination of Inorganic Anions in Environmental Water Using a
Hydroxide-Selective Column. LPN 1539, Sunnyvale, CA 2003.
•
Thermo Fisher Scientific. Dionex Application Brief 132, Determination of Anions in Municipal Drinking Water by Fast IC Using a
Hydroxide Eluent. LPN 2874, Sunnyvale, CA 2011.
•
•
•
•
U.S. Environmental Protection Agency (EPA). Basic Information
about Chromium in Drinking Water.
http://water.epa.gov/drink/contaminants/basicinformation/
chromium.cfm
(accessed March 5, 2014).
Dionex (now part of Thermo Scientific) Brochure LPN2527: Water
Analysis for a Global Market. Sunnyvale, CA, 2010. [Online]
http://www.dionex.com/en-us/webdocs/86525-Bro-Water-Analysis03May2010-LPN2527.pdf
(accessed March 5, 2014).
Jack, Richard., Rohrer, Jeffrey., Chen, Lillian., De Borba, Brian.
Review of U.S. EPA Methods for Perchlorate Using Suppressed
Conductivity Detection. American Laboratory. [Online]
Jan 22, 2013
http://www.americanlaboratory.com/913-TechnicalArticles/129226-Review-of-U-S-EPA-Methods-for-PerchlorateUsing-Suppressed-Conductivity-Detection/
(accessed March 5, 2014).
Jack, Richard., Rohrer, Jeffrey., Basumallick, Lipika. Changes from
EPA Method 218.6 to 218.7 Yield Improved Detection Limits for
Hexavalent Chromium. LCGC ChromatographyOnline. [Online]
Feb 22, 2012
http://digital.findanalytichem.com/nxtbooks/advanstaruk/thecolumn022212/#/12
(accessed March 5, 2014).
References for Technical Note 132
•
Greenberg, A. E.; Clesceri, L. S.; Eaton, A. D., Eds.; Standard
Methods for the Examination of Water and Wastewater, 18th ed.;
Am. Public Health Assoc.; Washington, DC, 1992.
•
American Society for Testing and Materials. Standard Test Methods
for Anions in Water by Chemically Suppressed Ion Chromatography,
D4327-97, Vol. 11.01, West Conshohocken, PA, 1999, 420-427.
•
Environmental Protection Agency. Fluoride: Dose-Response Analysis
for Non-cancer Effects, EPA Report No. 820-R-10-019, Washington,
CD, 2010.
•
Environmental Protection Agency. Monitored Natural Attenuation
of Inorganic Contaminants in Ground Water, EPA Report No.
600-R-07-140, Cincinnati, OH, 2007.
•
U.S. EPA Method 300.0, rev 2.1, Determination of Inorganic Anions
in Water by Ion Chromatography, U.S. Environmental protection
Agency, Cincinnati, OH, 1993.
•
U.S. EPA Method 300.1, rev 1.0, Determination of Inorganic Anions
in Drinking Water by Ion Chromatography, U.S. Environmental
Protection Agency, Cincinnati, OH, 1997.
•
Thermo Fisher Scientific. Dionex Technical Note 113, Practical
Guidance for Using Capillary Anion Chromatography, LPN 3043,
Sunnyvale, CA, 2012.
29
Thermo Fisher Scientific. Technical Note 131, Configuring HighPressure Capillary IC on the Modular IC System, Document No.
TN70352, Sunnyvale, CA, 2012.
References for Application Note 167
Thermo Fisher Scientific. Dionex ICS-5000+ Ion Chromatography
System Installation Instructions. Document No. 065447, Sunnyvale,
CA, 2012.
•
World Health Organization. Disinfectants and Disinfection
By-Products; International Programme on Chemical Safety-Environmental Health Criteria 216; Geneva, Switzerland, 2000.
•
Wagner, H. P.; Pepich, B. V.; Hautman, D. P.; Munch, D. J.
J. Chromatogr., A 1999, 850, 119–129.
•
World Health Organization. Draft Guideline for Drinking Water
Quality; Third ed., 2003.
•
Fed. Regist. 1996, 61 (94), 24354.
•
Fed. Regist. 1998, 63 (241), 69389.
•
U.S. EPA Method 300.1; U.S. Environmental Protection Agency;
Cincinnati, OH, 1997.
•
European Parliament and Council Directive No. 98/83/EC, Quality
of Water Intended for Human Consumption, 1998.
•
Fed. Regist. 2003, 68 (159), 49647.
•
Posnick, L. M.; Henry, K. Food Safety Magazine, Aug/Sept 2002.
•
Fed. Regist. 2001, 66 (60), 16858.
Thermo Fisher Scientific. Dionex Application Update 132, Determination of Nitrite and Nitrate in Drinking Water Using Ion
Chromatography with Direct UV Detection. LPN 034567,
Sunnyvale, CA, 1991.
•
Jackson, L. K.; Joyce, R. J.; Laikhtman, M.; Jackson, P. E.
J. Chromatogr., A 1998, 829, 187–192.
•
Thermo Fisher Scientific. Dionex Application Note 81.
LPN 034732-02, Sunnyvale, CA.
•
Thermo Fisher Scientific. ICS-5000 Installation Instructions.
Document No. 065343, Sunnyvale, CA, 2011.
•
U.S. EPA Method 300.0; U.S. Environmental Protection Agency;
Cincinnati, OH, 1993.
•
Thermo Fisher Scientific. ICS-Series Variable Wavelength Detector
Operator’s Manual. Document No. 065141, Sunnyvale, CA, 2006.
•
Thermo Fisher Scientific. Dionex Application Note 154, LPN 1539,
Sunnyvale, CA.
•
Thermo Fisher Scientific. Dionex Product Manual for IonPac AG19
and IonPac AS19 Columns. Document No. 065003-06, Sunnyvale,
CA, 2010.
•
Thermo Fisher Scientific. Dionex IonPac AS19 Anion-Exchange
Column (data sheet). LPN 1616, Sunnyvale, CA.
•
Lo, B.; Williams, D. T.; Subramanian, K. S. Am Lab. Feb. 1999,
160–161.
Letter to Dionex Corporation (now a part of Thermo Fisher
Scientific). U.S. Environmental Protection Agency, Office of Water;
November 19, 2002.
•
•
•Thermo Fisher Scientific. Product Manual for the Dionex Continuously Regenerated Trap Column (CR-TC). Doc No. 031910,
Sunnyvale, CA, 2010.
•
Thermo Fisher Scientific. Dionex CES 300 Product Manual.
Document No. 065386, Sunnyvale, CA, 2012.
•
Thermo Fisher Scientific. AS-AP Operator’s Manual. Document No.
065361, Sunnyvale, CA, 2012.
•
•
Thermo Fisher Scientific. Application Note 130, Fast Determinations
of Inorganic Ions in Salton Sea Samples Using a High-Pressure IC
System, Document No. TN70351, Sunnyvale, CA, 2013.
Thermo Fisher Scientific. Dionex Application Note 154, Determination of Inorganic Anions in Environmental Waters Using a
Hydroxide-Selective Column. LPN 1539, Sunnyvale, CA, 2003.
References for Application Update 185
•
References for Technical Note 121
•Drinking Water Treatment; EPA 810-F-99-013; U.S. Environmental
Protection Agency, 1999.
•
Thermo Fisher Scientific. Dionex Application Brief 133, CostEffective of Inorganic Anions and Cations in Municipal Drinking
Water Using Capillary Ion Chromatography. LPN 2878, Sunnyvale,
CA, 2011.
•
•
Thermo Fisher Scientific. Dionex Technical Note 113, Practical
Guidancefor Using Capillary Anion Chromatography. LPN 3043,
Sunnyvale, CA, 2012.
•
Drinking Water Treatment. EPA-810/F-99/013; U.S. Environmental
Protection Agency, U.S. Government Printing Office: Washington,
DC, 1999.
•
Thermo Fisher Scientific. Dionex ICS-5000 Installation manual. Doc
No. 065343, Sunnyvale, CA, 2011.
•
Thermo Fisher Scientific. Dionex Product Manual for CES 300
Suppressors. Dionex Doc No. 065386, Sunnyvale, CA, 2010.
•
Thermo Fisher Scientific. Technical Note 131, Configuring HighPressure Capillary IC on the Modular IC System. Document No.
TN70352, Sunnyvale, CA 2012.
•
Thermo Fisher Scientific. Dionex AS-AP Operator’s Manual. Doc
No. 065361, Sunnyvale, CA, 2012.
•
Thermo Fisher Scientific. Dionex Application Brief 141, Fast
Determination of Inorganic Anions in Municipal Drinking Water
Using Capillary Ion Chromatography. LPN 3059, Sunnyvale, CA,
2012.
•
Thermo Fisher Scientific. Environmental Capillary IC Applications
in the Capillary IC Library, website, 2011.
•
Thermo Fisher Scientific. Dionex Application Note 141, Determination of Inorganic Cations and Ammonium in Environmental Waters
By Ion Chromatography Using the Dionex IonPac CS16 Column.
LPN 1404, Sunnyvale, CA 2001.
:
30
References for Application Note 171
•
Disinfectants and Disinfection By-Products; World Health Organization, International Programme on Chemical Safety–Environmental
Health Criteria 216: Geneva, Switzerland, 2000.
•
Wagner, H. P.; Pepich, B. V.; Hautman, D. P.; Munch, D. J.
J. Chromatogr., A. 1999, 850, 119–129.
•
Fed. Regist. 1994, 59 (145), 38709.
•
Fed. Regist. 1996, 61 (94), 24354.
•
Quality of Water Intended for Human Consumption. European
Parliament and Council Directive No. 98/83/EC, 1998.
•
Draft Guideline for Drinking Water Quality. World Health
Organization, WHO Technical Report; 3rd edition, 2003.
•
U.S. EPA Method 300.0, U.S. Environmental Protection Agency,
Cincinnati, OH, 1993.
•
U.S. EPA Method 300.1, U.S. Environmental Protection Agency,
Cincinnati, OH, 1997.
•
Joyce, R. J.; Dhillon, H. P. J. Chromatogr., A. 1994, 671, 165–171.
•
Weinberg, H. J. Chromatogr., A. 1994, 671, 141–149.
•
Fed. Regist. 2003, 68 (159), 49647.
•
U.S. EPA Method 317.0, U.S. Environmental Protection Agency,
Cincinnati, OH, 2000.
•
Delcomyn, C. A.; Weinberg, H. S.; Singer, P. C. J. Chromatogr., A,
2001, 920, 213-219.
•
U.S. EPA Method 326.0, U.S. Environmental Protection Agency,
Cincinnati, OH, 2002.
•
Thermo Fisher Scientific. Dionex Application Note 167, Determination of Trace Concentrations of Oxyhalides and Bromide in
Municipal and Bottled Waters Using a Hydroxide-Selective Column
with a Reagent-Free™ Ion Chromatography System. Sunnyvale, CA,
2004.
•
De Borba, B. M.; Rohrer, J. S.; Pohl, C. A.; Saini, C. Determination
of Trace Concentrations of Bromate in Municipal and Bottled
Drinking Waters Using a Hydroxide-Selective Column with Ion
Chromatography. J. Chromatogr., A. 2005, 1085, 23–32.
•
Thermo Fisher Scientific. Dionex Application Note 168, Determination of Trace Concentrations of Disinfection By-Product Anions and
Bromide in Drinking Water Using Reagent-Free™ Ion Chromatography Followed by Postcolumn Addition of o-Dianisidine for Trace
Bromate Analysis. Sunnyvale, CA, 2005.
References for Application Note 187
• Bonacquisti, T. A Drinking Water Utility’s Perspective on Bromide,
Bromate, and Ozonation. Toxicology 2006, 221, 145–148.
• Thermo Fisher Scientific. Dionex Application Note 168, Determination of Trace Concentrations of Disinfection By-Product Anions and
Bromide in Drinking Using Reagent-Free Ion Chromatography
Followed by Postcolumn Addition of o-Dianisidine for Trace
Bromate Analysis. LPN 1706, Sunnyvale, CA, 2005.
• Thermo Fisher Scientific. Dionex Application Note 171, Determination of Trace Concentrations of Disinfection By-Product Anions and
Bromide in Drinking Using a Reagent-Free Ion Chromatography
System Followed by Postcolumn Addition of an Acidified On-Line
Generated Reagent for Trace Bromate Analysis. LPN 1767,
Sunnyvale, CA, 2006.
• Thermo Fisher Scientific. Dionex Application Note 184, Determination of Trace Concentrations of Chlorite, Bromate, and Chlorate in
Bottled Natural Mineral Waters. LPN 1890, Sunnyvale, CA, 2007.
• U.S. Environmental Protection Agency, Statistical Approach for the
Determination of the Single-Laboratory Lowest Concentration
Minimum Report Level (LCMRL) and Validation of Laboratory
Performance At or Below the Minimum Reporting Level, EPA
Document No. 815-R-05-006, November 2004, available at http://
www.epa.gov/ogwdw/methods/pdfs/methods/methods_lcmrl.pdf.
References for Application Update 179
•
Drinking Water Contaminants; U.S. Environmental Protection
Agency, Cincinnati, OH http://water.epa.gov/drink/contaminants/
index.cfm (accessed Jan 31, 2011). Basic Information about
Chromium in Drinking Water; U.S. Environmental Protection
Agency, Cincinnati, OH http://water.epa.gov/drink/contaminants/
basicinformation/chromium.cfm (accessed Feb 2, 2011).
World Health Organization, Bromate in Drinking Water–Background document for the development of WHO Guidelines for
Drinking Water Quality, 2005.
•
Public Health Goal for Chromium in Drinking Water. Feb 1999,
http://oehha.ca.gov/water/phg/pdf/ chrom_f.pdf (accessed Feb 28,
2011).
•
U.S. EPA. National Primary Drinking Water Regulations. Disinfectants and Disinfection By-Products. Fed. Reg. 1998, 63 (241),
69389–69476.
•
Planned National Toxicology Program Studies on Hexavalent
Chromium. http://ntp.niehs.nih.gov/ntp/htdocs/Studies/HexChromium/HexChromiumStatement.pdf (accessed Jan 30, 2011).
•
Fawell, J.; Walker, M. Approaches to Determining Regulatory Values
for Carcinogens with Particular Reference to Bromate. Toxicology
2006, 221, 149–153.
•
Public Health Goal for Hexavalent Chromium in Drinking Water.
http://www.oehha.ca.gov/water/phg/pdf/Cr6PHGdraft082009.pdf
(accessed Jan 31, 2011).
•
Toxicological Review of Hexavalent Chromium; Federal Register;
September 30, 2010, http://cfpub.epa.gov/ncea/iris_drafts/recordisplay.cfm?deid=221433 (accessed Jan 31, 2011).
•
Public Health Goal for Hexavalent Chromium in Drinking Water.
http://oehha.ca.gov/water/phg/pdf/123110Chrom6.pdf (accessed
Feb 28, 2011).
•
• U.S. EPA Method 300.1, The Determination of Inorganic Anions in
Drinking Water by Ion Chromatography, U.S. Environmental
Protection Agency, Cincinnati, OH, 1997.
Determination of Dissolved Hexavalent Chromium in Drinking
Water, Groundwater, and Industrial Wastewater Effluents by Ion
Chromatography; U.S. Environmental Protection Agency, Method
218.6; Cincinnati, OH, 1991.
•
• U.S. EPA Method 317.0, rev 2.0, Determination of Inorganic
Oxyhalide Disinfection By-Products in Drinking Water Using Ion
Chromatography with the Addition of a Postcolumn Reagent for
Trace Bromate Analysis, U.S. Environmental Protection Agency,
Cincinnati, OH, 2001.
Dionex Corporation (now part of Thermo Scientific), Determination of Hexavalent Chromium in Drinking Water Using Ion
Chromatography. Application Update 144; LPN 1495, 2003,
Sunnyvale, CA.
•
Dionex Corporation (now part of Thermo Scientific), Determination of Cr(VI) in Water, Waste Water, and Solid Waste Extracts.
Technical Note 26, LPN 034398-02, 2007, Sunnyvale, CA.
•
•
Determination of Inorganic Anions in Drinking Water by Ion
Chromatography; U.S. Environmental Protection Agency, Method
300.1; Cincinnati, OH, 1997.
•
Dionex Corporation (now part of Thermo Scientific), AXP/
AXP-MS Metering Pump Operator’s Manual. Doc. No. 031897,
2006, Sunnyvale, CA.
•
Dionex Corporation (now part of Thermo Scientific), PC10
Postcolumn Delivery System. LPN 1711, 2005, Sunnyvale, CA.
•
Analytical Methods Developed by the Office of Ground Water and
Drinking Water, Lowest Concentration Minimum Reporting Level;
U.S. Environmental Protection Agency, Cincinnati, OH http://water.
epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogwdw.
cfm (accessed Feb 6, 2011).
•
U.S. Environmental Protection Agency, Water Health Series: Bottled
Water Basics, Sept 2005.
•
U.S. Environmental Protection Agency, Occurrence Assessment for
the Final Stage 2 Disinfectants and Disinfection Byproducts Rule,
Document No. 815-R-05-011, December 2005.
•
• Food and Drug Administration. Beverages: Bottled Water. Fed. Reg.
2001, 66 (60), 16858–16868.
• European Parliament and Council Directive No. 2003/40/EC,
Establishing the List, Concentration Limits and Labeling Requirements for the Constituents of Natural Mineral Waters and the
Conditions for Using Ozone-Enriched Air for the Treatment of
Natural Mineral Waters and Spring Waters, 2003.
• Toxicological Review of Bromate, U.S. Environmental Protection
Agency, Washington, D.C., 2001.
U.S. EPA Method 326.0, Determination of Inorganic Oxyhalide
Disinfection By-Products in Drinking Water Using Ion Chromatography Incorporating the Addition of a Suppressor Acidified
Postcolumn Reagent for Trace Bromate Analysis, U.S. Environmental
Protection Agency, Cincinnati, OH, 2002.
• Thermo Fisher Scientific. Dionex Application Note 167, Determination of Trace Concentrations of Oxyhalides in Municipal and
Bottled Waters Using a Hydroxide-Selective Column with a
Reagent-Free Ion Chromatography System. LPN 1662, Sunnyvale,
CA, 2004.
31
References for Application Note 161
•
Standard Methods for the Examination of Water and Wastewater.
17th Edition, 1989. APHA-AWWAWPCF. 4500-CN B., pp 4–34.
•
Thermo Fisher Scientific. Dionex Application Update 147;
Sunnyvale, CA.
•
WK2791 Standard Test Method for Determination of Metal
Cyanide Complexes in Wastewater, Surface Water, Groundwater
and Drinking Water using Anion Exchange Chromatography with
UV Detection; ASTM International; West Conshohocken, PA.
•
Standard Methods for the Examination of Water and Wastewater.
17th Edition, 1989. APHA-AWWAWPCF. 4500-CN B.,
pp 4–25.
References for Application Note 173
•
•
•
Simeonova, P. Prof., Fishbein, L. Dr. Concise International
Chemical Assessment Document 61, Hydrogen Cyanide and
Cyanides: Human Health Aspects, Executive Summary section.
Jointly by United Nations Environment Programme, International
Labour Organization, and the World Health Organization in
Inter-Organization Programme for the Sound Management of
Chemicals. Geneva, 2004, 10–11.
Maximum Contaminant Levels for Inorganic Contaminants. Fed.
Regist. Code of Federal Regulations, Section 162, Title 40,
Revised July 1, 2002, 428–429.
Simeonova, Prof. P., Fishbein, Dr. L. Concise International
Chemical Assessment Document 61, Hydrogen Cyanide and
Cyanides: Human Health Aspects, Environmental Levels and
Human Exposure, section 5. Jointly by United Nations Environment Programme, International Labour Organization, and the
World Health Organization in Inter-Organization Programme for
the Sound Management of Chemicals, Geneva, 2004, 1.
•
Thermo Fisher Scientific. Operator’s Manual for Dionex ICS-3000
Ion Chromatography System, Sections 9.25.1, Disconnecting the
Amperometric Cell and 9.25.5, Calibrating the Reference
Electrode. LPN 065031, 242, 252–253, Sunnyvale, CA, 2005.
•
Thermo Fisher Scientific. Dionex Product Manual for Gold and
Silver Disposable Electrodes. LPN 065040, Sunnyvale, CA, 2005.
•
Thermo Fisher Scientific. Product Manual for Dionex AminoPac
PA10, AAA-Direct. Section 5 Eluent Preparation, p. 14.
LPN 031481, Sunnyvale, CA, 2005.
•
Thermo Fisher Scientific. Product Manual for Dionex OnGuard II
Cartridges. LPN 031688, Sunnyvale, CA, 2004.
•
Thermo Fisher Scientific. Operator’s Manual for Dionex ICS-3000
Ion Chromatography System. LPN 065031, Sunnyvale, CA, 2005.
•
Thermo Fisher Scientific. Installation Manual for Dionex
ICS-3000 Ion Chromatography System. LPN 065032, Sunnyvale,
CA, 2005.
•
Thermo Fisher Scientific. Product Manual for Dionex IonPac
AG15 Guard Column, Dionex IonPac AS15 Analytical Columns.
LPN 031362, Sunnyvale, CA, 2002.
•
Thermo Fisher Scientific. Dionex AS Autosampler Operator’s
Manual. LPN 065051, Sunnyvale, CA, 2005.
•
Thermo Fisher Scientific. Operator’s Manual for Dionex ICS-3000
Ion Chromatography System, Figure 2-22 Amperometric Cell,
Section 2.16.1 Amperometric Cell. LPN 065031,
p. 54, Sunnyvale, CA, 2005.
•
Thermo Fisher Scientific. Dionex Disposable Electrode Ag
Installation Guide. LPN 065086, Sunnyvale, CA, 2005.
•
Thermo Fisher Scientific. Product Manual for Dionex IonPac AS7
Analytical Column and Dionex IonPac AG7 Guard Column. LPN
031299, Sunnyvale, CA, 2005.
•
U.S. EPA Method 335.2, U.S. Environmental Protection Agency:
Cincinnati, OH, 1980.
•
•
U.S. EPA Method 335.1, U.S. Environmental Protection Agency:
Cincinnati, OH, 1974.
Montgomery, J. M. Water Treatment Principles and J. Wiley, New York, 1985, 11–13.
•
•
U.S. EPA Method 335.3, U.S. Environmental Protection Agency:
Cincinnati, OH, 1978.
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Standard Methods SM-4500-CN-F. American Public Health
Association, American Water Works Association, and Water
Environment Federation, Washington, D.C., 1998.
Liang, L., Cai, Y., Mou, S., Cheng, J. Comparisons of Disposable
and Conventional Silver Working Electrodes for the Determination of Iodide using High-Performance Anion-Exchange
Chromatography with Pulsed Amperometric Detection. J.
Chromatogr., A 2005, 1085, 37–41.
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Thermo Fisher Scientific. Dionex Application Update 107,
Determination of Cyanide in Strongly Alkaline Solutions. LPN
0754, Sunnyvale, CA, 2003.
•
Heckenberg, A., Cheng, J., Jandik, P., Cavalli, S., Abballe, F.
Determination of Sulfide and Cyanide Using Integrated Pulsed
Amperometric Detection on a Disposable Silver Electrode.
LC-GC, The Application Notebook, September 2004, 32.
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Giuriati, C., Cavalli, S., Gorni, A., Badocco, D., Pastore, P. Ion
Chromatographic Determination of Sulfide and Cyanide in Real
Matrices by Using Pulsed Amperometric Detection on a Silver
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Cheng, J., Jandik P., Avdalovic, N. Pulsed Amperometric Detection
of Sulfide, Cyanide, Iodide, Thiosulfate, Bromide and Thiocyanate
with Microfabricated Disposable Silver Working Electrodes in Ion
Chromatography. Anal. Chim. Acta. 2005, 536, 267–274.
Design.
References for Application Note 227
•
Simeonova, P. Prof.; Fishbein, L. Dr. Concise International
Chemical Assessment Document 61, Hydrogen Cyanide and
Cyanides: Human Health Aspects, Executive Summary section,
jointly by United Nations Environment Programme, International
Labour Organization, and the World Health Organization in
Inter-Organization Programme for the Sound Management of
Chemicals: Geneva, 2004, pp. 1–5, 10–11.
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U.S. Department of Health and Human Services, Public Health
Service, Agency for Toxic Substances and Disease Registry.
Toxicological Profile for Cyanide, PB2007-100674. Agency for
Toxic Substances and Disease Registry: Atlanta, GA, 2006,
pp. 153–159.
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National Primary Drinking Water Regulation. Code of Federal
Regulations, Part 141, Title 40, 2008; Fed Regist. 2008, 22, 448.
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Water Quality Standards. Code of Federal Regulations, Part 131,
Title 40, 2008; Fed Regist. 2008, 21, 451–463.
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Water Quality Guidance for the Great Lakes System. Code of
Federal Regulations, Part 132, Title 40, 2008; Fed Regist. 2008,
21, 493–494.
•
EPA Method 335.2 Determination of total cyanide in water
(titrametric, spectrophotometric), EPA/600/4-79-020, U.S. Environmental Protection Agency National Exposure Research Laboratory;
Cincinnati, OH, 1980.
•
Weiss, J.; Ion-Exclusion Chromatography (HPICE). In Handbook of
Ion Chromatography, 3rd ed.; Wiley-VCH Verlag GmbH & Co.:
KGaA, Weinheim 2004; pp. 359–391.
•
•
Final Administrative Determination on Ferric and Ferrocyanide. Fed.
Regist. 2003, 68 (193), 57690–57691.
Fritz, J. S.; Gjerde, D. T. Ion Chromatography, Wiley-VCH Verlag
GmgH, Weinheim, 2000; pp. 165–186.
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•
Electroplating Point Source Category. Code of Federal Regulations,
Part 413, Title 40, 2008; Fed Regist. 2008, 28, 216–217.
•
Carr, S. A.; Baird, R. B.; Lin, B. T. Wastewater derived interferences
in cyanide analysis, Water Res., 1997, 31(7), 1543–1548.
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Watershed Investigations, Laboratory Staff Watershed Protection
Group Environmental Services Department, City of San Jose.
Cyanide Attenuation Study Report, 2004, 1–45.
American Public Health Association (APHA), American Water Works
Association (AWWA), Water Environment Federation (WEF).
Method 4500-CN- Cyanide, Preliminary Treatment of Samples. In
Standard Methods for the Examination of Water and Wastewater,
20th ed.; Clesceri, L. S., Greenberg, A. E., Eaton, A. D., Franson, M.
A. H.; APHA: Washington, DC, 1998; pp. 35–36.
•
•
U.S. EPA Method 335.3, EPA/600/4-79/020, U.S. Environmental
Protection Agency National Exposure Research Laboratory;
Cincinnati, OH, 1978.
Thermo Fisher Scientific. Dionex Application Note 154, Determination of Inorganic Anions in Environmental Waters Using a
Hydroxide-selective Column. LPN 1539, Sunnyvale, CA, 2003.
•
•
U.S. EPA Method 335.4, EPA/600/R-93/100, U.S. Environmental
Protection Agency National Exposure Research Laboratory;
Cincinnati, OH, 1993.
Thermo Fisher Scientific. Dionex Application Note 138, Determination of Thiosulfate in Refinery and other Wastewaters. LPN 1237,
Sunnyvale, CA, 2001.
•
•
Weinberg, H.S.; Cook, S. J. Segmented flow injection, UV digestion,
and amperometric detection for the determination of total cyanide in
wastewater treatment plant effluents, Analy. Chem., 2002, 74(23),
6055–6063.
Thermo Fisher Scientific. Dionex Application Note 200, Direct
Determination of Cyanate in a Urea Solution and a Urea-containing
Protein Buffer. LPN 2034, Sunnyvale, CA, 2008.
References for Application Update 148
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Jackson, P. E.; Gokhale, G. T.; Streib, T.; Rohrer, J. S.; Pohl, C. A.
J. Chromatogr. A 2000, 888, 151.
Thermo Fisher Scientific. Dionex Application Update 107, Determination of Cyanide in Strongly Alkaline Solutions. LPN 0754, 2003.
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Urbansky, E. T.; Collette, T. W. J. Environ. Monit. 2001, 3, 454.
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Urbansky, E. T. Biorem. J. 1998, 2, 81.
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Perchlorate and Drinking Water: Action Level and Public Health
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Services: www.dhs. ca.gov/ps/ddwem/chemicals/perchl/actionlevel.
htm.
•
Dionex Corporation (now part of Thermo Scientific).Determination
of Low Concentrations of Perchlorate in Drinking and Groundwaters Using Ion Chromatography. Application Note 134; Sunnyvale,
CA.
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Dionex Corporation (now part of Thermo Scientific).
Determination of Perchlorate inEnvironmental Waters by Ion
Chromatography Coupled with Electrospray Mass Spectrometry
(ICMS). Application Note 151; Sunnyvale, CA.
•
Dionex Corporation (now part of Thermo Scientific). Determination
of Perchlorate in Drinking Water by Ion Chromatography. Application Update 145; Sunnyvale, CA.
•
Determination of Perchlorate in Drinking Water Using Ion
Chromatography. Method 314.0; U.S. Environmental Protection
Agency; Cincinnati, Ohio, 1999.
•
•
Thermo Fisher Scientific. Dionex Application Note 188, Determination of Glycols and Alcohols in Fermentation Broths by
Ion-exclusion Chromatography and Pulsed Amperometric Detection. LPN 1944, Sunnyvale, CA, 2008.
•
Cheng, J.; Jandik, P. Highly sensitive and direct analysis of chelating
agents using integrated pulsed amperometric detection and
disposable platinum electrodes, The Application Notebook, LCGC,
2006, 53.
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Cheng, J.; Jandik, P.; Liu, X.; Pohl, C. Pulsed amperometric detection
waveform with disposable thin-film platinum working electrodes in
high performance liquid chromatography, J. Electroanal. Chem.,
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