Determination of nitrogen species (Nitrate, Nitrite and Ammonia Ions) in environmental samples by ion chromatography

Article (PDF Available)inPolish Journal of Environmental Studies 15(1):5-18 · January 2006with1,600 Reads
Abstract
The necessity of environmental protection has stimulated development of all kinds of methods allowing determination of different pollutants in different elements of the natural environment, including methods for determining inorganic nitrogen ions. Many of the methods used so far have proven insufficiently sensi-tive, selective or accurate and recently much attention has been paid to ion chromatography, which seems most promising. This paper reviews applications of ion chromatography for determining nitrate, nitrite and ammonium ions in environmental samples and in food products along with ISO standards and the relevant methods proposed by the US EPA and Dionex. Literature examples describe the application of ion chromatography for determining NO 3 -, NO 2 -and NH 4 + ions in water, waste water, air, food products and other complex matrix samples. Critical analysis of the methods based on ion chromatography is presented.

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Polish Journal of Environmental Studies Vol. 15, No. 1 (2006), 5-18
Review
*Corresponding author; e-mail: michalski@ipis.zabrze.pl
Determination of Nitrogen Species
(Nitrate, Nitrite and Ammonia Ions) in
Environmental Samples by Ion Chromatography
R. Michalski
1
*, I. Kurzyca
2
1
Institute of Environmental Engineering of Polish Academy of Science,
Sklodowska-Curie Street 34, 41-819 Zabrze, Poland
2
Adam Mickiewicz University, Faculty of Chemistry, Department of Water and Soil Analysis,
Drzymaly Street 24, 60-613 Poznań, Poland
Received: March 4, 2005
Accepted: May 30, 2005
Abstract
The necessity of environmental protection has stimulated development of all kinds of methods allowing
determination of different pollutants in different elements of the natural environment, including methods
for determining inorganic nitrogen ions. Many of the methods used so far have proven insufficiently sensi
-
tive, selective or accurate and recently much attention has been paid to ion chromatography, which seems
most promising. This paper reviews applications of ion chromatography for determining nitrate, nitrite and
ammonium ions in environmental samples and in food products along with ISO standards and the relevant
methods proposed by the US EPA and Dionex.
Literature examples describe the application of ion chromatography for determining NO
3
-
, NO
2
-
and
NH
4
+
ions
in water, waste water, air, food products and other complex matrix samples. Critical analysis of
the methods based on ion chromatography is presented.
Keywords: ion chromatography, nitrate, nitrite, ammonia ions
Introduction
Nitrogen - one of the most commonly occurring elements
in nature - forms many inorganic ionic species, of which the
most important are nitrate, nitrite and ammonium ions.
The main anthropogenic sources of nitrates in the envi-
ronment are municipal and industrial wastes and artificial
fertilizers. Nitrogen oxides present in the air and originat-
ing from natural and anthropogenic sources (combustion,
transportation) after the reactions with water come back to
the earth surface in the form of acid rains [1]. Nitrites ap-
pear as intermediates in the nitrogen cycle. They are un-
stable and, depending on conditions, are transformed into
nitrates or ammonia. Their presence in water can be a result
of water processing or use of nitrite salts as corrosion in
-
hibitors. Nitrites are commonly used in preservatives. To
surface waters they get from the same sources as nitrates,
i.e. in municipal wastes, industrial wastes, mining wastes
and with water flowing in from artificially fertilized fields.
The sources of ammonium ions in surface waters are re-
actions of biochemical decomposition of organic nitrogen
compounds, reduction of nitrites and nitrates by hydrogen
sulfide, iron (II), humus substances (or other reducing
compounds) and, first of all, municipal wastes, industrial
wastes and animal farm wastes. Nitrogen compounds en-
hance eutrophisation of surface waters. Organic nitrogen
compounds undergo biochemical decomposition into ni-
trites later oxidized to nitrates.
Advertisement:
Michalski R., Kurzyca I.
6
The main source of inorganic nitrogen ions in the hu-
man organism is drinking water and food products, in
particular beetroots, celery, lettuce, spinach and preserved
meat. An estimated daily dose of nitrates consumed by man
reaches 75-100 mg, of which 80-90% come from vegeta-
bles and 5-10% from water [2]. The admissible concentra-
tion of nitrates and nitrites in drinking water in the majority
of countries controlling these parameters is 50 mg L
-1
and
0.5 mg L
-1
, respectively. The admissible concentration of
ammonium ions expressed in ammonia is 0.5 mg L
-1
[3,4].
Nitrates and nitrites do not have direct carcinogenic effects
on humans, but it is supposed that neoplasmic diseases in
people are related to the formation of N-nitroso compounds,
of which many are carcinogenic to animals. High concen-
trations of nitrogen ions in drinking water and other food
products can lead to serious problems and diseases. Taken
in excess, the compounds increase the risk of appearance of
methemoglobinemia, especially in infants below 3 months
old, which is directly related to transformation of nitrates in
nitrites in humans [5].
EU countries in 1991 approved the Nitrate Directive
[6] on the protection of water against pollution by nitrates
from agricultural origin. The Directive recommends cer-
tain measures to protect the natural environment against
degradation caused by nitrogen compounds used for agri-
cultural purposes.
General Principles
of Nitrogen Species Determination
Nitrite, nitrate and ammonium ions are determined in
drinking waters, surface waters and underground waters,
as well as in municipal and industrial wastes. Because of
ion instability, the samples should be analyzed immedi-
ately after collection [7,8]. The methods of collection and
storage of water samples for determination of these ions
are described by Gardolinski et al. [9]. Because of low
concentrations of the ions to be determined, their direct
analysis is not always possible. Some preliminary sample
preparation may be needed, including precipitation proce-
dures, ion exchange, distillation, microdiffusion, solvent
extraction or thin layer chromatography [10]. Preparation
of samples with a complex matrix (blood, food products)
is usually time consuming, laborious and, performed in-
correctly, can be a source of significant errors. Prelimi-
nary preparation of samples for analyses by the methods
of ion chromatography and capillary electrophoresis has
been described by Haddad et al. [11].
Nitrogen Determination by Classical Methods
There are a number of methods for determining NO
2
-
,
NO
3
-
and NH
4
+
ions. Determination of these analytes in the
sample often poses analytical problems related to low se-
lectivity of the methods and the presence of many interfer-
ing factors. The classical methods used for these purposes
can be divided into weight, titration, spectrophotometric
(UV/Vis, IR, fluorimetric) and electroanalytical (including
potentiometric based on the use of ion-selective electrodes,
voltamperometric, amperometric, coulometric) [12].
The most important methods for determination of ni
-
trates are colorimetric ones (e.g. determination of nitrate
nitrogen after a reaction with p-fluorophenol), or reduc-
tion in a cadmium column. The method most often used
for routine analyses is based on the reaction of nitrate ni-
trogen with sodium salicylate in an acidic environment,
giving nitrosalicylate acid transformed on alkalization
into the coloured (yellow) ionized form. Nitrate ions can
also be determined by the potentiometric method with an
ion-selective electrode [12,13].
The basic method for determination of nitrites in water
samples (proposed by Griess over 125 years ago), relies
on the reaction of nitrites with sulphanilic acid giving di-
azo compounds, which couples with 1-naphthylamine.
The reaction gives an azo dye of intense red colour. There
are other methods that are modifications of that proposed
by Griess, e.g. that involving the reaction with sulfanil-
amide and N-(1-naphthyl)-ethylenediamine) [12, 13].
The method for determination of ammonia was pro-
posed by Nessler in 1856. In this method the Nessler reagent
(alkaline solution of mercuric potassium iodide - K
2
HgI
4
)
reacts with ammonia to give a colour complex. Unfortunate-
ly, elimination of interfering factors is not always possible
in this method. Ammonium ions are often determined by a
colorimetric indophenol titration method and a potentiomet-
ric method with ion-selective electrode [13].
The US Environmental Protection Agency (EPA)
recommends the methods of ion chromatography, poten-
tiometric and colorimetric methods for determining nitrate
and nitrite ions [14]. The ISO standard methods used for
determinations of nitrates, nitrites and ammonium ions (ex-
cluding ion chromatography method) are presented in Table
1. These methods have some advantages and disadvantag-
es. The latter are related to low selectivity, low sensitivity
and poor repeatability of determinations. Nevertheless, the
search for alternative new methods continues.
Determination of Nitrogen Species
by Ion Chromatography
One of the most commonly used methods for deter-
mining anions (including NO
2
-
and NO
3
-
) and cations (in-
cluding NH
4
+
) is ion chromatography. It offers the pos-
sibility of simultaneous determination of a few ions in a
short time, good reproducibility of results, high sensitiv-
ity, the possibility of simultaneous determinations of an-
ions and cations (including organic and inorganic ions),
small volume samples and the possibility of using differ-
ent detectors (from the most popular conductometric one,
UV, to mass spectrometry) [15, 16]. Ion chromatography
is particularly recommended for speciation analysis. Such
analyses have been performed for simultaneous separa-
tion and determination of nitrate and nitrite ions [17] or
Determination of Nitrogen Species...
7
Table 1. ISO standards for determination of nitrate, nitrite and ammonium ions in water samples.
Method number Method name Range [mg L
-1
] Main interferences
ISO 7890-1
(1986)
Water quality. Determination of nitrate.
Part 1: 2,6-Dimethylphenol spectrometric method
0.006 - 25.0
Strong oxidants, chloride,
turbidity
ISO 7890-2
(1986)
Water quality. Determination of nitrate.
Part 2: 4-Fluorophenol spectrometric method after distillation
0.22 - 45.0
Calcium, magnesium,
turbidity
ISO 7890-3
(1988)
Water quality. Determination of nitrate.
Part 3: Spectrometric method using sulfosalicylic acid
0.003 - 0.2
Chloride, nitrite, calcium,
magnesium
ISO 6777
(1984)
Water quality. Determination of nitrite.
Molecular absorption spectrometric method
0.003 - 0.1
Chloramine, chlorine,
polyphosphates, tiosulphates
ISO 13395
(1996)
Water quality. Determination of nitrite nitrogen and nitrate
nitrogen and the sum of both by flow analysis (CFA and FIA)
and spectrometric detection
NO
2
-
: 0.32 - 20.0
NO
3
-
: 0.01 - 1.0
Organic matter, surfactants
ISO 11905-1
(1997)
Water quality. Determination of nitrogen.
Part 1:Method using oxidative digestion with peroxosulfate
About 0.1 for each
determined ions
Dissolved or suspended
organic matter
ISO 5664
(1984)
Water quality. Determination of ammonium. Distillation
and titration method
0.1 - 10.0
Calcium, magnesium,
aluminium, phosphates
ISO 6778
(1984)
Water quality. Determination of ammonium - Potentiometric
method
0.2 - 50.0
Selected cations present
in high concentration,
unstable temperature
ISO 5664
(1984)
Water quality - Determination of ammonium. Distillation
and titration method.
0.2 - 10.0 Urea and chloramines
ISO 7150-1
(1984)
Water quality - Determination of ammonium.
Part 1: Manual spectrometric method
0.003 - 1.0 Magnesium, calcium
ISO 7150-2
(1986)
Water quality. Determination of ammonium.
Part 2: Automated spectrometric method
0.5 - 50.0 Magnesium, calcium
ISO 11732
(1997)
Water quality. Determination of ammonium nitrogen
by flow analysis (CFA and FIA) and spectrometric detection
0.1 - 10.0
Volatile amines, high
convcentration of metal ions
sulphate and sulphite ions [18]. Recently, ion chromatog-
raphy has been used to determine of side products of wa-
ter disinfection (bromates, chlorates, chlorites) [19] and
metal ion species [20].
Separation and determination of nitrate and nitrite ions
by ion chromatography is carried out in anion-exchange
columns filled with a suitable exchanger and using a prop-
er eluent (e.g. water solution of sodium carbonate and/or
sodium hydrocarbonate) and most often conductometric
or UV detection. Nitrogen ion determination by ion chro-
matography is accompanied by determination of other an-
ions present in the sample, such as: fluorides, chlorides,
phosphates, bromides and sulphates. The main problems
are related to proper separation of NO
2
-
from Cl
-
ions. Ir-
respective of the column used, the retention times of the
ions (related to their structure, ionic radius, selectivity
against the exchanger) are close and in environmental
samples with chloride ions concentrations usually a few
times higher than those of nitrite ions, the peak assigned
to NO
2
-
can be masked by a large peak assigned to Cl
-
ions. Consequently, the quantitative analysis of nitrite ions
can be very difficult or impossible. The retention times of
bromide and phosphate ions are close to nitrate ions but,
fortunately, on the majority of anion-exchange columns
they can be selectively separated. In determination of am-
monium ions, the column is filled with cationic exchanger
and a conductometric detector is most often employed.
As the ammonium ions are usually determined together
with alkali metal ions and alkali earth metal ions, the main
problem is related to the overlapping of the peaks assigned
to sodium ions (often present in much higher concentra
-
tion) and the peak assigned to NH
4
+
.
The problems related to separation of the pairs of
Cl
-
/NO
2
-
and Na
+
/NH
4
+
ions can be solved by optimizing
the conditions of analysis, i.e. changing the composition
of the eluent, type or pH of eluent, intensity of its flow,
type of column and detector. Moreover, the excess ions
interfering in the determination can be removed by spe-
cial cartridges. The effect of eluent and detector on the
determination of nitrite ions in the presence of chloride
ions in high concentrations has been discussed by Pastore
et al. [21]. The use of a classical conductometric detec-
tor and water solution of Na
2
CO
3
/NaHCO
3
as eluent, the
maximum ratio of the concentrations of the ions Cl
-
/NO
2
-
ensuring good performance is 200:1. With water solution
of NaCl as eluent and UV detector, this ratio increases to
200,000:1, and in the system with NaCl as eluent and an
amperometric detector it increases up to 1,000,000:1.
Although ion chromatography has been designed for ion
analyses in water, the recent progress in development of new
fillings, new detection methods and new preliminary proce-
dures of sample preparation has extended the use of this meth-
od to samples with a more complex matrix. A review on the
applications of ion chromatography in analyses of biological
samples has been prepared by Singh et al. [22] in analyses of
food products - by Pereira [23] and Buldini et al. [24]. Compar-
Michalski R., Kurzyca I.
8
Table 2. ISO standards for determination of nitrate, nitrite and ammonium ions in water samples.
Method number Method name Ions determined Detector
Range for
nitrogen ions
[mg L
-1
]
Interferences
ISO 10304 – 1
(1992)
Water quality - Determination
of dissolved fluoride, chloride,
nitrite, orthophosphate, bromide,
nitrate and sulfate ions using
liquid chromatography of ions -
Part 1 : Method for water with low
contamination
F
-
, Cl
-
, NO
2
-
, PO
4
3-
,
Br
-
, NO
3
-
, SO
4
2-
,
Conductivity
NO
2
-
: 0,05 – 20
NO
3
-
: 0,1 - 50
Selected organic ac
-
ids such as: malonic,
maleic and ions in
high concentration
ISO 10304 – 2
(1995)
Water quality - Determination of
dissolved anions by liquid chro-
matography of ions – Part 2 : De-
termination of bromide, chloride,
nitrate, nitrite, orthophosphate and
sulfate in waste waters
Br
-
, Cl
-
, NO
3
-
, NO
2
-
,
PO
4
3-
, SO
4
2-
,
Conductivity
or UV/vis
NO
2
-
: 0,05 – 20
NO
3
-
: 0,1 - 50
ISO 14911
(1998)
Water quality – Determination of
dissolved Li
+
, Na
+
, NH
4
+
,
K
+
, Mn
2+
,
Ca
2+
, Mg
2+
, Sr
2+
and Ba
2+
using
ion chromatography method
Li
+
, Na
+
, NH
4
+
, K
+
,
Mn
2+
, Ca
2+
, Mg
2+
,
Sr
2+
, Ba
2+
Conductivity NH
4
+
: 0,1 - 10
Selected aminoacids,
alifatic amines and
some metal ions such
as: Zn
2+
, Ni
2+
, Cd
2+
.
Table 3. Ion chromatography-based methods for determination of the NO
3
-
, NO
2
-
and NH
4
+
, recommended by selected American organizations.
Method number Method name Ions determined Matrix
United States Environmental Protection Agency
300.0
The determination of inorganic anions in water
by ion chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
,
PO
4
3-
, SO
4
2-
, ClO
2
-
Drinking water, surface water,
300.1
The determination of inorganic anions in
waterby ion chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
, ClO
2
-
, ClO
3
-
, BrO
3
-
Drinking water, ground water,
surface water
300.6
Chlorite, orthophosphate, nitrate and sulphate
in wet deposition by chemically suppressed
ion chromatography
Cl
-
, NO
3
-
, PO
4
3-
, SO
4
2-
Rain water
300.7
Dissolved sodium, ammonium, potassium,
magnesium and calcium in wet deposition by
chemically suppressed ion chromatography
Na
+
, NH
4
+
, K
+
, Mg
2+
, Ca
2+
Rain water
9056 Inorganic anions by ion chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
,
PO
4
3-
, SO
4
2-
Water, solids
Association of Analytical Communities (AOAC)
993.30
Determination of inorganic anions in water
using ion chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
,
PO
4
3-
, SO
4
2-
Water
National Institute for Occupational Safety and Health (NIOSH)
4110
Anions determination by ion chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
,
PO
4
3-
, SO
4
2-
Water
American Society for Testing and Materials (ASTM).
D 4327-97
Anions in water by chemically suppressed
ion chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
,
PO
4
3-
, SO
4
2-
Drinking water, wastewater
D 5085-90
Determination of chloride, nitrate and suplhate
in atmospheric wet deposited by chemically
suppressed ion chromatography
Cl
-
, NO
3
-
, SO
4
2-
Rain water
ison of different methods of nitrates and nitrites determination
in plant samples and biological fluids has been made by Cruiz
and Mam [25] and Everett et al. [26]. Determination of nitrites
and nitrates in preserved meat has been described by Bernini et
al. [27] and in blood serum by Monoghan et al. [28].
Ion chromatography has become a standard method for
determining anions and cations in water, air and solid sam-
ples. In 1984 the American Society for Testing Materials
(ASTM) approved it as the standard method for determin-
ing anions in water [29]. The EPA also has recommended
Determination of Nitrogen Species...
9
Table 4. Methods recommended by Dionex (Dionex Co., Sunnyvale, CA, USA).
Method number Method name Ions determined Matrix
AN 4
Analysis of engine coolants by ion chromatog-
raphy
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
, Na
+
, NH
4
+
, K
+
, Mg
2+
, Ca
2+
Cooling solutions
AN 25
Determination of inorganic ions and organic
aids in non-alcoholic carbonated beverages
Cl
-
, NO
3
-
, PO
4
3-
, SO
4
2-
, selected
organic acids, Na
+
, NH
4
+
, K
+
,
Mg
2+
, Ca
2+
Non-alcoholic beverages
carbonated
AN 31
Determination of anions in acid rain by in
chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
Rain water
AN 51
Method for determination of anions in sodium
hydroxide
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
NaOH solutions
AN 56
Determination of trace anions and key organic
acids in high purity ammoniated and borated
waters found in steam cycle power plants
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
,
selected organic acids
Recylculated water from
power plants
AN 78
Determination of trace anions in concentrated
hydrofluoric acid
Cl
-
, Br
-
, NO
2
-
, SO
4
2-
Fluoric Acid
AN 81
Determination of oxyhalides and other anions by
ion chromatography using a borate-based eluent
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
, ClO
2
-
, ClO
3
-
, BrO
3
-
Drinking water
AN 86
Determination of trace cation in power plant
waters containing morpholine
Na
+
, NH
4
+
, K
+
, Mg
2+
, Ca
2+
Recylculated water from
power plants
AN 93
Determination of trace anions in concentrated
bases using autoNeutralization
TM
pretreatment
and ion chromatography
Cl
-
, Br
-
, NO
3
-
, PO
4
3-
, SO
4
2-
,
ClO
2
-
, oxalate
Concentrated bases
AN 94
Determination of trace cations in concentrated
acids using autoNeutralization
TM
pretreatment
and ion chromatography
Li
+
, Na
+
, NH
4
+
, K
+
, Mg
2+
, Ca
2+
,
ethylamines
Concentrated acids
AN 113
Determination of trace anions in high purity
waters by high volume/direct injection ion
chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
, oxalate
Ultrapure water
AN 114
Determination of trace anions in high purity
waters using direct injection and two-step
isocratic ion chromatography
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
, oxalate
Ultrapure water
AN 136
Determination of inorganic oxyhalide dis
-
infection byproducts anions and bromide in
drinking water using ion chromatography with
the addition of a postcolumn reagent for trace
bromate analysis
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
, ClO
2
-
, ClO
3
-
, BrO
3
-
Drinking water
AU 101
Transition metals in power plant high purity
water
F
-
, Cl
-
, Br
-
, NO
2
-
, PO
4
3-
, SO
4
2-
,
oxalate
Ultrapure water
AU 102
Trace anions in power plant high purity water
and borated water
F
-
, Cl
-
, Br
-
, NO
2
-
, PO
4
3-
, SO
4
2-
,
oxalate
Ultrapure water
AU 103 Trace anions in power plant high purity water
F
-
, Cl
-
, Br
-
, NO
2
-
, PO
4
3-
, SO
4
2-
,
oxalate
Recylculated water from
power plants
AU 106 Trace calcium and magnesium in brine
F
-
, Cl
-
, Br
-
, NO
2
-
, NO
3
-
, PO
4
3-
,
SO
4
2-
, Mg
2+
, Ca
2+
Brines
AU 121 Monovalent cations in explosives Li
+
, Na
+
, NH
4
+
, K
+
Explosives
a number of methods which use ion chromatography in
analyses related to environmental protection [30]. The ISO
standards for anion and cation determination by ion chro-
matography are given in Table 2, while the standards rec-
ommended by select American organizations are given in
Table 3. Table 4 presents the application notes on determi-
nation of ionic nitrogen species recommended by Dionex
- one of the most renowned firms specializing in ion chro-
matography in the world.
Apart from standard methods, literature gives many
examples of applications of ion chromatography in deter-
mination of nitrites, nitrates and ammonium ions in all
kinds of water samples, municipal and industrial wastes,
precipitations, in gases absorbed in solutions, in food
products, biological samples and other samples with com-
plex matrix. Selected examples of ion chromatography
method applications for determination of nitrates and ni-
trites, with specified samples, column, eluent and detec-
tor, are presented in Table 5 (nitrates and nitrites in water
samples), Table 6 (nitrites and nitrates in food products),
Table 7 (nitrites and nitrates in air), and Table 8 (nitrates
and nitrites in complex matrix samples). Examples of the
Michalski R., Kurzyca I.
10
Table 5. Examples of ion chromatography applications for determining nitrates and/ or nitrites in water samples.
Sample matrix Column Eluent Detector References
Waters
Waters IC-Pak
Anion HC
Na
2
CO
3
+ NaHCO
3
Conductivity 31
Reference material Dionex IonPac AS4A
Na
2
CO
3
+ NaHCO
3
Conductivity 32
Environmental
water
TSK guardgel QAE-SW (Tosh) Trimetallic acid-EDTA UV/Vis
33
Polar ice core
Laboratory packed
with resins synthetized
Potassium hydrogenphtalate Conductivity 34
Natural water Dionex IonPac AS4A NaHCO
3
Conductivity 35
Synthetic samples TSK-gel IC anion PWXL (Tosh)
Sodium tetraborate, boric acid,
potassium gluconate
Conductivity, UV
36
Sea water
Column filled
with copper-plated cadmium
Sodium tetraborate, boric acid UV/Vis 37
Rain water Dionex IonPac AS4 Na
2
CO
3
+ NaHCO
3
Conductivity 38
Mineral water Biotronik BT I ANS Na
2
CO
3
+ NaHCO
3
Conductivity 39
Surface water Metrohm IC anion Na
2
CO
3
+ NaHCO
3
Conductivity 40
Drinking water Biotronik BT II AN Na
2
CO
3
+ NaHCO
3
Conductivity 41
Snow Biotronik BT II AN Na
2
CO
3
+ NaHCO
3
Conductivity 42
Drinking water Dionex AS11 NaOH Conductivity 43
Water Dionex IonPac AS9-HC
Na
2
CO
3
+ NaHCO
3
Conductivity/
UV/Vis
44
Water
ODS column Phthalate UV/Vis 45
Drinking water
Metrohm IC
Anion Column Super Sep
Phtalic acid Conductivity 46
Water
Laboratory made
anion-exchange column
NaOH + HClO
4
Conductivity 47
Groundwater Dionex IonPac AS11 NaOH Conductivity 48
Water
Dionex IonPac
AS9-SC
HCl + tris-(hydroxy-methyl)-
-aminomethane
UV/Vis
49
Water
Dionex IonPac
AS9-SC
p-toluenesulfonic acid + tris-
-(hydroxy-methyl)-aminomethane
UV/Vis
49
Water Dionex IonPac AS5A
HClO
4
+ tris-(hydroxy-methyl)-
-aminomethane
UV/Vis
50
Table 5. continues on next page...
Dam water, river
water
Laboratory packed bed Cu-Cd
reductor column
Na
2
B
4
O
7
Conductivity 51
Power plant water Dionex IonPac AS10 NaOH Conductivity 52
Rainwater Dionex IonPac AS11 NaOH Conductivity 53
Reference materi-
als
Dionex IonPac AS4A
Na
2
CO
3
+ NaHCO
3
Conductivity 54
Fog samples Dionex IonPac AS4A Na
2
CO
3
+ NaHCO
3
Conductivity 55
Rain Dionex IonPac AS4A Na
2
CO
3
+ NaHCO
3
Conductivity 56
Waters from
peatlands
Dionex IonPac AS4A
Na
2
CO
3
+ NaHCO
3
Conductivity 57
Atmospheric
aerosols
Dionex IonPac AS4A
Na
2
CO
3
+ NaHCO
3
Conductivity 58
Rainwater Waters IC Pak A HC Gluconic acid + Boric acid Conductivity 59
Drinking water Dionex IonPac AS4A or AS10 NaOH Conductivity 60
Fog samples Dionex IonPac AS14 NaOH Conductivity 61
Rain water
Dionex IonPac AS4
or AS7
Na
2
CO
3
+ NaHCO
3
Conductivity 62
Determination of Nitrogen Species...
11
River water Shimadzu IC-A3
Phthalic acid + tris-(hydroxy-methyl)-
-aminomethane
Conductivity 63
Waters Metrohm Star-Ion A300
Na
2
CO
3
+ NaHCO
3
Conductivity 64
Drinking water Waters IC-Pak C anion PDCA UV/Vis 65
Roof runoff
waters
Dionex IonPac AS14
Na
2
CO
3
+ NaHCO
3
Conductivity 66
Rainwater Dionex IonPac AS14 Na
2
CO
3
+ NaHCO
3
Conductivity 67
Drinking water Dionex IonPac AS17 NaOH Conductivity 68
Atmospheric
aerosols
Metrohm Metrosep SUPP3 Na
2
CO
3
+ NaHCO
3
Conductivity 69
Sea water Dionex IonPac AS4A Na
2
CO
3
+ NaHCO
3
Conductivity 70
Table 6. Examples of ion chromatography applications for determining nitrates and/ or nitrites in food products.
Sample matrix Column Eluent Detector References
Meat products Dionex IonPac AS11 NaOH UV/Vis 71
Coffee
Mixed bed column packed with
anion exchange resin) ICS-A23
and cation exchange resin CH1
Oxalic acid Conductivity 72
Spinach IC anion PRP-X100 Phthalic acid, acetone Amperometric 73
Fruits juice Dionex OmniPac PAX-500 NaOH-ethanol-methanol Conductivity 74
Wine Shimadzu Shim-pack IC-A1 Phthalic acid Conductivity 75
Orange juice Hamilton PRPx100
2,5-dihydroxy-1,4-benzenedisulfonic
acid + EDTA
UV/Vis
76
Food Dionex IonPac AS4, AS9 Na
2
CO
3
+ NaHCO
3
Conductivity or
UV/Vis
77
Frozen food
Yokogawa ICS-A23 and Yokogawa
CH1
Na
2
CO
3
+ NaHCO
3
Conductivity 78
Spinach Dionex IonPac AS4A Na
2
CO
3
+ NaHCO
3
Conductivity 79
Beer Dionex IonPac AS4 Na
2
CO
3
+ NaHCO
3
Conductivity 80
Food extracts Alltech Universal Anion Lithium 4-hydroxbenzoate Conductivity 81
Meats Wescan Anion Exclusion/HS H
2
SO
4
Amperometry 82
Beer Dionex IonPac AS4A Na
2
CO
3
+ NaHCO
3
Conductivity 83
Rice flour Dionex IonPac AS 12A Na
2
CO
3
/NaHCO
3
Conductivity 84
Spinach Dionex IonPac S4A Na
2
CO
3
+ NaHCO
3
Conductivity 85
Vegetables
Laboratory packed anion-exchange
column
Potasium gluconate + borate acid Conductivity 86
Fruits Waters IC-PAK Anion KH
2
PO
4
+ Na
2
HPO
4
UV-Vis 87
Meat extract Dionex IonPac AS-3 Na
2
CO
3
+ NaHCO
3
Conductivity 88
Vegetables and
salads
Wescan 269-001 anion
Phthalate Conductivity 89
Infant food Hamilton PRP-1
Tetrapentyloammonium + aceto
-
nitrile
UV/Vis
90
Cured meat Vydac 302 IC, Waters CN KH
2
PO
4
UV/Vis 91
Cured meat Waters IC-Pak A KH
2
PO
4
UV/Vis 92
Cured meat Biotronik BT II AN Chloromethanesulphonic acid UV/Vis 93
Vegetables Waters IC Pak sodium gluconate + borax Conductivity 94
Edible vegetable
oils, fats
Dionex IonPac AS9
Na
2
CO
3
+ NaHCO
3
Conductivity 95
Michalski R., Kurzyca I.
12
Table 7. Examples of ion chromatography applications for determining nitrates and/ or nitrites in gas samples.
Sample matrix Column Eluent Detector References
Flue gas Dionex IonPac AS4A or AS7
Na
2
CO
3
+ NaHCO
3
or NaOH + p-cyanophenol
Conductivity 96
Stack gases Toyo Soda IC-Anion-PW
Potassium gluconate + sodium
borate + EDTA
Conductivity or
UV/Vis
97
Ambient air Biotronik BT I ANS Na
2
CO
3
+ NaHCO
3
Conductivity 98
Ambient air Dionex IonPac AS14 Na
2
CO
3
+ NaHCO
3
Conductivity 99
Atmospheric
aerosols
RP
18
Tetrabutyl-ammonium hydroxide,
3-(N-morpholine)-propane-sulfonic
acid (zwitterion), Na
2
CO
3
Conductivity 100
Ambient air
Shim-pack IC-A1 or
Dionex IonPac AS9-SC
Phthalic acid +
tris-(hydroxy-methyl)-aminomethane
or Na
2
CO
3
+ NaHCO
3
Conductivity 101
Atmospheric air Dionex IonPac AS4A Na
2
CO
3
+ NaHCO
3
Conductivity 102
Atmospheric air Dionex IonPac AS4A Na
2
CO
3
+ NaHCO
3
Conductivity 103
Atmospheric air Hamilton PRP-X 100 Phthalic acid + acetone Conductivity 104
Table 8. Other examples of ion chromatography applications for determining nitrate and/ or nitrite ions in samples with complex matrix.
Sample matrix Column Eluent Detector References
Blood Dionex IonPac AS12A Na
2
CO
3
+ NaHCO
3
Culometric 105
Pharmaceutical
compounds
Carbon B1-01 (Bio-TechResearch)
TBA, Na
2
CO
3
, acetonitrile Conductivity 106
Urine
A C
18
reversed-phase column
(TSKgel, ODS-100S, i.d., Tosoh,
Tokyo, Japan) modified by
saturation with micelles of 3-( N,
N-dimethylmyristylammonio)prop
anesulfonate (Zwittergent 3–14)
H
3
BO
3
+ Na
2
B
4
O
7
Conductivity 107
Fertilizers Shim-pack IC-A1 Citric acid + NaOH Fluorescence 108
Human plasma
Ion exchanger based on styrene–
divinylbenzene with quarter-
nary amine in the Cl
-
form of the
HEMA-BIO 1000Q type
NaClO
4
UV/Vis 109
Tear fluid, blood
serum
Dionex IonPac AS4A
Na
2
CO
3
+ NaHCO
3
Conductivity 110
Human saliva Dionex IonPac AS12A Na
2
CO
3
+ NaHCO
3
Conductivity 111
Mouse plasma Dionex IonPac AS9-SC Na
2
CO
3
+ NaHCO
3
Conductivity 26
Human serum
Dionex IonPac AS4A, AS9A,
AS12, or Nucleopac-PA 100,
Carbopac PA
Na
2
CO
3
+ NaHCO
3
or NaCl
Conductivity or
UV/Vis
28
Human blood Anion-exchange LC Sykam Acetonitrile + methanol + H
2
O
Electrochemical or
UV/Vis
112
Serum Anion-exchange Hamilton Methanosulphonic acid UV/Vis 113
ion chromatography applications for determination of
ammonium ions are given in Table 9.
An important recent achievement of ion chromatog-
raphy is the use of highly selective microcolumns for
fast determinations of anions and cations [130]. The ap-
plication of a monolithic column covered with didodec-
yldimethylammonium bromide (DDAB) for fast (about
30 seconds) analyses of iodine, chloride, nitrate, nitrite,
phosphate and sulphate ions has been described by Hat-
sis and Lucy [131]. They used 6 mM o-cyanophenol (pH
7.0) at extremely high flow (up to 10 mL/min) as eluent
and a conductometric detector. The limits of detection
Determination of Nitrogen Species...
13
Table 9. Examples of ion chromatography applications for determination of ammonium ions.
Sample matrix Column Eluent Detector References
Beverages
carbonated
Mixed bed laboratory packed
with Yokogawa ICS-A23
and Yokogawa CH1
Oxalic acid Conductivity 114
Tea
Dionex IonPac CS3 HCl + 2,3-diaminopriopionic acid Conductivity 115
Spinach Dionex IonPac CS1 HCl Conductivity 116
Bread, cheese Waters IC-PAK Cation M/D EDTA + HNO
3
Conductivity 117
Food simulants Dionex IonPac CS3 HCl + 2,3-diaminopriopionic acid Conductivity 118
Food extracts Wescan Cation-R Lithium hydrogenphthalate Conductivity 119
Grain Waters IC-PAK Cation HNO
3
Conductivity 120
Foods
Metrohm Supersep
125 IC-Cation
Citric acid + PDCA Conductivity 121
Beer Dionex IonPac CS1 HCl + m-phenylenediamine Conductivity 83
Mineral water Waters IC-PAK CM/D HNO
3
+ EDTA Conductivity 122
Air in cleanrooms Dionex IonPac CS15 H
2
SO
4
+ acetonitrile Conductivity 123
Fog samples Dionex IonPac CS12 Methanesulphonic acid Conductivity 55
Snow and firn
samples
Dionex IonPac CS12 Methanesulphonic acid Conductivity 124
Rain Dionex IonPac CS12 Methanesulphonic acid Conductivity 56
Waters from
peatlands
Dionex IonPac CS10 HCl + 2,3-diaminopropionic acid Conductivity 125
Atmospheric
aerosols
Dionex IonPac CS10 HCl + 2,3-diaminopropionic acid Conductivity 58
Rainwater Waters IC Pak CM/D HNO
3
+ EDTA Conductivity
126
Drinking water Fast Cation HCl + 2,3-diaminopropionic acid Conductivity 127
Fog samples Dionex IonPac CS12 Methanesulphonic acid Conductivity 61
Rain water Dionex IonPac CS2 HCl Conductivity 62
Drinking water Dionex IonPac CS16 Methanesulphonic acid Conductivity 128
Roof runoff
waters
Dionex IonPac CS12A Methanosulphonic acid Conductivity 66
Rainwater Dionex IonPac CS12A H
2
SO
4
Conductivity 67
Atmospheric
aerosols
Metrohm Metrosep Cation1-2 Tartaric acid Conductivity 69
Natural waters Dionex IonPac CG10 + CG10 HCl Conductivity 129
for all these ions were on a level of a few to a few dozen
μg L
-1
.
Kitamaki et al., have described simultaneous determina-
tion of nitrites, nitrates and ammonium ions in river water
samples on microcolumns [132] with NO
3
-
and NO
2
-
detec-
tion by a UV detector at λ=206 nm, ammonium ion detection
by a fluorescence detector after the post-column derivatization
with o-phthaldehyde in the presence of 2-mercaptoethanol.
Ion chromatography as a method applied first of all
for ion separation has also been applied in combination
with other analytical methods and has been a reference
standard as far as sensitivity, repeatability and efficiency
are concerned. A thorough comparison of the methods of
injection flow analysis and ion chromatography in appli-
cation to determine nitrogen ionic species has been made
by Ferree and Shannon [133].
The quality of analyses performed by ion chroma-
tography has been confirmed by the fact that it has been
proved the most versatile and optimal in the analyses of
the contents of the main cations and anions (including
ionic nitrogen species) in water samples, performed in
155 laboratories in 30 countries within the Analytical
Quality Control and Assessment Studies in the Medi-
terranean Basin Project(AQUACON) [134].
Michalski R., Kurzyca I.
14
Usually the contents of nitrate, nitrite and ammoni-
um ions are determined using ion chromatography with
conductometric or UV detection. However, it has been
shown that the sensitivity and selectivity of the deter-
minations can be significantly improved by the post-
column derivatization methods. An exemplary solution
is the use of the reaction of the formation of tri-iodides
with nitrites and their spectrophotometric detection [135,
136]. The method permits determination of nitrites on a
level of a few μg L
-1
, and what is particularly important
there is no interference by the presence of chlorine ions
not oxidized by iodides. Another direction for improv-
ing ionic chromatography is design and development of
new fillings of the ion-exchange columns, e.g. zwitter-
ionic stationary phases [137, 138]. These phases permit
a greater differentiation of the retention times of the ions
determined so a better selectivity of determinations also
of chlorine, nitrite, sodium and ammonium ions, which
has been a basic limitation of their determination by ion
chromatography.
Although this paper is devoted to the applications of
ion chromatography for determinations of inorganic nitro-
gen ions, related methods such as high-performance liquid
chromatography (HPLC) with normal and reversed phase
columns should also be mentioned. A review of the applica-
tions of HPLC with reversed-phase columns in determina-
tion of inorganic ions has been presented by Gennaro and
Angelino [139], and a review of the HPLC applications
with normal phases for simultaneous determinations of ni-
trates and nitrites has been made by Butt et al. [140].
Although ion chromatography has been known and
used for over 30 years, it is still a modern method whose
application has been extended over new groups of com-
pounds and types of samples. The progress in the method
over the years of its application has been described by
Lucy [141, 142].
In conclusion, it should be noted that the majority of
classical methods are much more time-consuming and la-
borious than ion chromatography, and sometimes require
the use of expensive and toxic reagents. Definite advan-
tages of these methods are low cost of analyses, relatively
simple and cheap apparatus, and hence a possibility of use
in most laboratories. The main advantages of ion chro-
matography includes the short time needed for analyses,
possibility of analysis of small volume samples, high sen-
sitivity and selectivity, and most importantly – a possibil-
ity of simultaneous separation and determination of a few
ions, or ions of the same element at different degrees of
oxidation, which provides more comprehensive informa-
tion for the sample studied.
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    • "Ammonium also presents toxicity to living beings, and its toxicity to animals and plants was experimentally demonstrated in laboratory [15]. For the human organism, the admissible concentration of NH 4 + for drinking water was expressed in NH 3 (0.5 mg/L) [16]. Therefore, besides the monitoring of industrial processes, the quantification of the amines and NH 4 + in waters is important to protect human health and the environment. "
    [Show abstract] [Hide abstract] ABSTRACT: A new method was developed for the determination of ammonium ion, monomethylamine and monoethylamine in saline waters by ion chromatography. Steam distillation was used to eliminate matrix interferences. Variables such as distillation time, concentration of sodium hydroxide solution and analyte mass were optimized by using a full two-level factorial (2(3) ) design. The influence of steam distillation on the analytical curves prepared in different matrices was also investigated. Limits of detection of 0.03, 0.05 and 0.05 mg L(-1) were obtained for ammonium, monomethylamine and monoethylamine, respectively. Saline water samples from the Brazilian oil industry, containing sodium and potassium concentrations between 2.0-5.2% w/v and 96-928 mg L(-1) , respectively, were analyzed. Satisfactory recoveries (90-105%) of the analytes were obtained for all spiked samples, and the precision was ≤ 7% (n = 3). The proposed method is adequate for analyzing saline waters containing sodium to ammonium, monomethylamine and monoethylamine concentration ratios up to 28000:1 and potassium to ammonium, monomethylamine and monoethylamine concentration ratios up to 12000:1. This article is protected by copyright. All rights reserved.
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    • "A comparison between the results obtained by using the currently designed biosensor with those reported on GNs-based electrodes (Table S4, is of great importance since nitrite is widely used in the environment, beverages, and food products as a preservative (Ding et al., 2010). Analytical methods developed for determination of nitrite ion are mainly based on spectrophotometry (Kuznetsov and Zemyatova, 2010), separation and chromatography (Michalski and Kurzyca, 2006 ) and electrochemistry (Yue et al., 2011) techniques, however electrochemical techniques are preferred because of their several advantages (Kozub et al., 2010, see also Supporting information, Section 7). "
    [Show abstract] [Hide abstract] ABSTRACT: Thionine (Th) diazonium cation is covalently attached onto the glassy carbon (GC) electrode via graphene nanosheets (GNs) (GC-GNs-Th). The GC-GNs-Th electrode is subjected to further modifications to fabricate (i) glucose and (ii) nitrite sensors. Further modifications include: (i) direct immobilization of glucose oxidase (GOx) and (ii) electrodeposition of gold dendrite-like nanostructures (DGNs) on the GC-GNs-Th surface, constructing GC-GNs-Th-GOx and GC-GNs-Th-DGNs modified electrodes, respectively. The GC-GNs-Th-GOx biosensor exhibited a linear response range to glucose, from 0.5 to 6.0mM, with a limit of detection (LOD) of 9.6μM and high sensitivity of 43.2µAcm(-2)mM(-1). Also, the GC-GNs-Th-DGNs sensor showed a wide dynamic response range for NO2(-) ion with two linear parts, from 0.05μM to 1.0μM and 30.0μM to 1.0mM, a sensitivity of 263.2μAmM(-1) and a LOD of 0.01μM. Applicability of the modified electrodes was successfully tested by determination of glucose in human blood serum and nitrite in water based on addition/recovery tests.
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    [Show abstract] [Hide abstract] ABSTRACT: A novel ultraviolet optical fiber sensor is developed for the determination of nitrate and nitrite in water samples. The absorptivity spectra of nitrate and nitrite are determined at analytical wavelengths of 302 nm and 356 nm. Nitrate and nitrite are measured in the concentration range from 0.0 mg/L to 50 mg/L. The obtained results indicate that a linear relationship between the absorbance with the concentration of nitrate and nitrite in water. The other chemical species present in water do not much interfere with ultraviolet absorbance measurement of nitrate and nitrite. Detection limits are investigated by optical fiber sensor for nitrate is 0.0017 mg/L and nitrite is 0.0014 mg/L. Regression equations for the determination of nitrate and nitrite are presented and successful applied which require the determination concentration nitrate and nitrite in environmental water samples.
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