Determination of Inorganic Anions by Ion Chromatography PDF

Journal of Chromatography A, 881 (2000) 607627
www.elsevier.com/ locate/ chroma

Review
Advances in the determination of inorganic anions by ion
chromatography
*
B. Lopez-Ruiz
Seccion Departamental Qumica Analtica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria s/n,
28040 Madrid, Spain
Abstract
The time period covered for this review includes articles published from 1997 to 1999, with the addition of a few classic
references. The purpose of the review is to include the most relevant works from each topic area of the determination of
inorganic anions by ion chromatography, including new sample pretreatments, new separation methods, new detection
systems and the latest applications in the eld of environmental, water, foods, etc. samples. Experimental conditions such as
stationary phase, eluent, detection mode, as well as matrix are summarized in a table. 2000 Elsevier Science B.V. All
rights reserved.
Keywords: Reviews; Environmental analysis; Water analysis; Food analysis; Ion chromatography; Inorganic anions
Contents
1. Introduction ............................................................................................................................................................................ 608
2. Importance of the determination of inorganic anions .................................................................................................................. 608
3. General reviews ...................................................................................................................................................................... 613
4. Sample pretreatment ................................................................................................................................................................ 613
5. Separation .............................................................................................................................................................................. 615
6. Detection................................................................................................................................................................................ 618
7. Applications of ion chromatographic techniques ........................................................................................................................ 620
7.1. General applications........................................................................................................................................................ 620
7.2. Environmental analysis.................................................................................................................................................... 621
7.3. Water analysis ................................................................................................................................................................ 621
7.4. Food analysis.................................................................................................................................................................. 623
7.5. Theoretical and statistical studies, and computational applications ...................................................................................... 623
References .................................................................................................................................................................................. 624
*Fax: 134-1-394-1754.
E-mail address: bealopru@eucmax.sim.ucm-es (B. Lopez-Ruiz)
0021-9673/ 00/ $ see front matter 2000 Elsevier Science B.V. All rights reserved.
PI I : S0021- 9673( 00) 00244- 2
608 B. Lopez-Ruiz / J. Chromatogr. A 881 (2000) 607627
1. Introduction Chlorine and bromine are considered to be con-
servative elements in ground-water systems and,
When ion chromatography (IC) was introduced in therefore, their concentration in pore-waters can be a
1975, it was basically a chromatographic method for useful tool in constraining the origins of groundwater
the determination of inorganic ions, which consisted salinity. Whole rock determinations for chlorine and
of a low ion-exchange capacity resin as the station- bromine are therefore important in helping to dis-
ary phase and conductimeter as detector and a tinguish between, e.g., saline intrusions and
suppressor column to increase separation speed and palaeosalinity.
detection sensitivity [1]. In 1979, Gjerde et al. [2] Iodine species in seawater exist as iodide and
developed a non-suppressed IC technique by using a iodate. Iodide, which is thermodynamically unstable
low conductivity eluent. This concept of IC was later in oxygenated water, is usually a minor species in
successively widened so that it could also include seawater compared to iodate. Iodine is an essential
organic ions, other separation methods (e.g., ion micronutrient for many organisms. Iodide in sea-
interaction and ion exclusion), simultaneous sepa- water is produced by biologically mediated reduction
ration of anions and cations, and a great variety of of iodate and is also produced under reducing
detectors. conditions. Thus, the distribution of iodide and
Even though IC has become a routine analytical iodate gives clues to understanding the marine
method for the determination of inorganic ions, environment. In addition, the need to determine
especially anions present in various matrices, many iodide and iodate in environmental samples has
papers have been published during the last 2 years arisen because iodine may play a role in taste and
dealing with new modalities in sample pretreatment, odor problems in drinking water. Also, the impor-
separation, detection, etc., for improving the analysis tance from the clinical and epidemiological point of
of the samples. view of iodide determination in biological matrices,
For more immediate information and comparison such as urine and serum, has led to a great interest in
of some of the cited methods, the experimental searching for rapid, simple and specic methods for
conditions are summarized in Table 1. the determination of iodide in those matrices.
The nitrogen, phosphorus and sulfur cycles are of
particular signicance to a number of biological and
2. Importance of the determination of inorganic non-biological processes in the environment. Natural
anions and anthropogenic effects can cause localized inter-
related changes to the cycles. In order to assess the
Bromate is a disinfection by-product of the ozona- impact and extent of the changes, it is essential to
tion of drinking water derived from source water develop analytical methods that allow the simulta-
containing bromide. The bromide in the source water neous determination of two or all three constituents
is oxidized to bromate by the ozone. It is a potential in a wide variety of environmental samples. Phos-
21
carcinogen to rats and mice at mg l levels. New phorus and nitrogen are released into environmental
toxicological studies have led the International waters from many different sources, e.g. animal and
Agency for Research on Cancer (IARC) to classify chemical fertilizer run-off and sewage. Excessive
bromate as a group 2B carcinogen to humans with amounts of these nutrients activate eutrophication,
21
renal tumour risks at concentrations .0.05 mg l . the process of rapid growth of phytoplankton, algae
At the moment the US Environmental Protection and plants. Subsequent decay of these materials
Agency (EPA) recommends a concentration limit of causes dissolved oxygen to be removed from a water
21
10 mg l for bromate in drinking water, while the body and with it the ability to sustain life. A large
World Health Organization (WHO) accepts a limit of number of studies have illustrated the dynamic
21
25 mg l . The Commission of European Union nature of the nitrogen speciation and phosphorus
21
proposes a concentration limit of 10 mg l . For fractionation balances in natural waters, and the
this reason trace analysis of bromate in water has signicance of the organic nitrogen and particulate
received considerable attention in recent years. phosphorus fraction in contributing to the total
B. Lopez-Ruiz / J. Chromatogr. A 881 (2000) 607627 609
Table 1
Experimental conditions of the inorganic anions determination by ion chromatography
Species Matrix Column Eluent Detector Ref.
Total organic carbon Deionized, mineral, Hamilton PRP-X100 KOH, KHP (pH 9.5) Indirect UV at 272 [42]
(TOC) tap and river water
o-Phosphate Water samples Dionex IonPak AS12A NaOH, sodium tetraborate Conductivity [35]
2 42
NO , PO Sea water Dionex AS4A Na CO , NaHCO Conductivity [40]
2 3 2 3 3
2 2
NO , NO Human plasma Exsil SAX KH PO , H PO , acetonitrile UV at 214 nm [38]
2 3 2 4 3 4
Rat blood Dionex IonPac AS12A Na Co , NaHCO Coulometry
2 3 3
2 2
NO , NO Meat products Dionex IonPac AS11 NaOH UV at 225 nm [191]
2 3
42
PO Cola beverages Waters IC-Pak A HR Sodium gluconate, boric Conductivity [184]
3
acid, sodium tetraborate in
glycerinewater
2
BrO Drinking waters Microbore laboratory-packed NH NO (pH 6.0) ICP-MS [55]
3 4 3
packed PSDVB functionalized
with chloromethyloctylether
and AlCl
3
2
BrO Ozonized water Excelpak ACS-A1G/ ICS- Na CO , NaHCO Conductivity [108]
3 2 3 3
A1332
2
BrO Drinking water Dionex IonPac AS9-HC Na CO , NaHCO Conductivity [56]
3 2 3 3
Na CO
2 3
2
BrO Drinking water Dionex IonPac AS9-HC Na CO Conductivity [33]
3 2 3
2
BrO Drinking water Dionex IonPac AS4A-SC Na CO , NaHCO Spectrophotometric [111]
3 2 3 3
at 530 nm
2
BrO Drinking water Dionex IonPac AS12 NaOH ICP-MS [121]
3
2 2
BrO , IO Ozonized water Excelpak ICS-A23 (NH ) CO ICP-MS [124]
3 3 4 2 3
Excelpak ICS-A13
2
BrO Water Dionex IonPac AG9-SC Watermethanol, (NH ) SO MSMS [37]
3 4 2 4
2 2 2
I , IO Mineral and Dionex IonPac AS11 NaBr, NaOH (for I ) UVVis at [110]
3
drinking waters B(OH) , NaOH (for IO ) 288 nm
3 3
2
I Ground water Dionex IonPac AS11 NaOH, in methanolwater Conductivity [155]
and soil
2
I Soil and water Hamilton PRP-X100 NaCl, methanol UV at 230 nm [159]
2
I Sea water TSK-gel SAX (Tosoh) NaClO sodium phosphate UV at 226 nm [32]
4
buffer (pH 6.1)
2
I Urine and serum Water Nova-Pak C KNO Laboratory-made [68]
18 3
reversed-phase coated with iodide ion-selective
N-cetylpyridinium chloride electrode
2 2
Cl (Cl ), Br (Br ) Sedimentary and Dionex IonPac AS12A Na CO , NaHCO UV at 210 nm [52]
2 2 2 3 3
igneous rocks
2
Total nitrogen (NO ), Reference materials Dionex IonPac AS4A Na CO , NaHCO Conductivity [45]
3 2 3 3
32
phosphorus (PO ) Oyster tissue
4
22
and sulfur (SO ) Buffalo River
4
sediments
Table 1 (continued)
Total nitrogen (NO ), Wastewaters Dionex IonPac AS4A Na CO , NaHCO Conductivity [46]
3 2 3 3
32
and phosphorus (PO )
4
Cyanate Gold processing Waters HC IC-Pak A Anthranilic acid (pH 6.7) Indirect UVVis [39]
samples at 355 nm
2 2
CN , SCN Blood TSK-gel IC-Anion-SW Phosphate buffer (pH 6.1) UV at 210 nm [114]
(Tosoh) Fluorimetric l 5418 nm,
ex
l 5460 nm
em
22 22 22 2
S , SO , S O , SCN Hot spring waters TSK-gel IC-Anion-PW Na CO , acetonitrile Photometric at 350 nm [109]
3 2 3 2 3
(Tosoh)
22 22 22 2
S , SO , S O , SCN Samples with Dionex IonPac AS12A NaOH ICP- MS [123]
3 2 3
biological matrices
22 22 2
SO , S O , SCN Hot-spring waters Kaseisorb LC ODS super Phthalate, TPAOH in Conductivity [99]
4 2 3
22 22 22
S O , S O , S O (Tokyo Kasei) acetonitrilewater
2 3 2 6 3 6
22 22 22
S O , S O , S O
4 6 5 6 6 6
Selenite, selenate, Synthetic samples Hamilton PRP X-100 Phosphate buffer (pH 7.0) Hydride generation-quartz [120]
SeCys, SeMet cell atomic absorption
spectrometric
Selenite, selenate, Synthetic sea Dionex IonPac AS4A Na CO or NaOH ICP-AES [117]
2 3
Secystine, water Dionex IonPac AS10
Semethionine Dionex IonPac AS11
Selenite, selenate, Selenium-rich Hamilton PRP-1 reversed Wateracetonitrile ETAAS [118]
Secystine, yeast phase
Semethionine
Trimethylselenonium Synthetic samples ESA Anion III Ammonium citrate ICP-MS or FAAS [126]
iodide, Semethionine,
selenious acid, selenic
acid
Arsenite, arsenate, Highly ferrous/ ferric Dionex IonPac AS4A Na CO , NaOH, ICP-MS [127]
2 3
phenyl arsonate, contaminated methanol
dimethyl arsinate, leachates of
arsenobetaine, lignite spoil
arsenocholine
2 2 2 2 2
F , NO , Cl , Br , NO , Beverages Mixed bed column packed Oxalic acid Conductivity [87]
3 3
acetic, lactic, succinic, with anion-exchange resin
malic, citric, tartaric, ICS-A23 and cation-exchange
1 1 1
Na , NH , K resin CH1
4
2 2 2
Cl , Br , NO Synthetic Two ODS-packed columns, Water Conductivity [78]
3
samples the rst coated with CHAPS Photodiode array UV
micelles and the second with
Zwittergent-314 micelles
2 2 2 2
Cl , Br , NO , SO Water TSK-gel IC-Anion-PW KOH Chemiluminiscence [115]
3 4
(Tosoh)
2 2 2
Cl , NO , SO , acetate, Wines Shimpack IC-Al (Shimadzu) Phthalic acid (pH 4.15) Conductivity [186]
3 4
lactate, succinate, malate,
citrate, tartrate
2 2 22
Cl , NO , SO Plant sap Dionex IonPac AS9-SC Na CO , NaHCO Conductivity [201]
3 4 2 3 3
Dionex IonPac AS11 NaOH
Waters IC-PACK Anion HR Borategluconate (pH 8.5)
Boratetartrate (pH 4.0)
2 2 22 22
Cl , NO , CO , SO , Milk Dionex IonPac AS11 NaOH Conductivity [179]
3 3 4
32
PO , lactate, acetate,
4
propionate, butyrate,
succinate, citrate
Table 1 (continued)
2 2 2
Cl , NO , SO Conc. reagents Hamilton PRP-X100 Phthalate (pH 5.5 or 4.7) UVVis at 298 nm [36]
3 4
2 2 22 22
Cl , NO , CO SO , Milk Dionex IonPacAS11 NaOH Conductivity [179]
3 3 4
32
PO , lactate, acetate,
4
propionate, butyrate,
succinate, citrate
2 2 22 32
Cl , NO , SO , PO , Beverages and Dionex IonPacAS11 NaOH, methanol Conductivity [182]
3 4 4
quinate, formate, malate, citric acids
malonate, oxalate, citrate, fermenting-
isocitrate, aconitate medium
2 2 22
Cl , NO , SO Oil eld waters Laboratory packed Sodium benzoate, Conductivity [57]
3 4
sodium citrate
2 22 32
Cl , SO , PO Edible vegetable Dionex IonPac AS9 Na CO , NaHCO Conductivity [48]
4 4 2 3 3
oils Photometric at 520 nm
2 2 22 32
Cl , NO , SO , PO , Landll leachates Dionex IonPac AS11 NaOH Conductivity [156]
3 4 4
2
SCN ,
2 22 2 2
F , CO , Cl , NO , Power plant waters Dionex IonPac AS10 NaOH Conductivity [91]
3 3
22
SO , acetate, formate,
4
oxalate
2 2 2 22
H PO , Cl , NO , SO , Tea Shimpack IC-A1 Potassium Conductivity [181]
2 4 3 4
acetic, ascorbic, (Shimadzu) hydrogenphthalate,
succinic, malic, malonic phthalic acid
citric, tartaric
2 2 2 22
Cl , NO , NO , SO , Environmental TSK guardgel QAE-SW Trimellitic acidEDTA Indirect UV at [95]
2 3 4
22
CO water (Tosoh) 270 nm
3
2 2 22
Cl , NO , SO Polar ice core Laboratory packed with Potassium Conductivity [163]
3 4
samples resins synthesized hydrogenphthalate,
2 2 2 2 2
F , Cl , Br , I , NO , Natural water Dionex IonPac AS4A NaHCO Conductivity [172]
3 3
2 22 2
NO , SO , HS ,
2 4
22 2
HPO , HCO
4 3
2 2 2 2 2
F , Cl , NO , Br , NO , Pharmaceutical Carbon BI-01 TBA, Na CO , Conductivity [58]
2 3 2 3
22 22 2
SO , HPO , I compounds (Bio-Tech Research) acetonitrile
4 4
2 2 22
Cl , NO , SO Beet sugar Dionex IonPac AS11 NaOH Conductivity [193]
3 4
2 2 22
Cl , NO , SO Rainwater at Dionex IonPac AS11 NaOH Conductivity [164]
3 4
Maracaibo, Venezuela
2 2 2 2
Cl , NO , Br , NO Synthetic samples TSK-gel IC-anion-PWXL Sodium tetraborate, boric Conductivity [84]
2 3
(Tosoh) acid, potassium gluconate UV at 210 or 230 nm
BO H , AsO H Synthetic samples Dionex IonPac AS11 NaOH Conductivity [107]
3 3 3 3
2 2 2
NO , Cl , NO , Vegetables Shimpack IC-Al (Shimadzu) Phthalic acid (pH 4.0) Bulk acoustic wave [134]
3 2
2 2
H PO , SO sensor
2 4 4
2 2 22
Cl , NO , SO Synthetic samples TSKguardgel QAE-SW Pyromellitate (pH 5.4) Conductivity [93]
3 4
(Tosoh)
2
ClO Drinking water Dionex IonPac AS11 NaOH Conductivity [174]
4
and groundwater
22 22 22
SeO , HAsO , SeO , Synthetic samples CS5A Na HPO (pH 9.3) UV at 204 nm [211]
3 4 4 2 4
22 22 22
WO , MoO , GeO ,
4 4 3
22 2 2
CrO , IO , HAsO ,
4 3 3
2 2 2
BrO , NO , NO
3 2 3
nutrient loading in a water body. So a rapid method products by oxidation of sulde and nally oxidized
for the simultaneous determination of total nitrogen to sulfuric acid, which causes the acidication of
(TN) and total phosphorus (TP) is needed, both for natural waters in rivers and lakes. This has created a
environmental studies on natural waters and routine need for their determination.
control of sewage and wastewater. The analysis of cyanide in biological uids is of
Total organic carbon (TOC) has been used suc- interest because cyanide acts not only as an acute
cessfully as a general indicator of organic pollutant toxicant, which binds to and inhibits the activity of
in water for both volatile and nonvolatile organic cytochrome oxidase, but also as a chronic toxicant.
compounds. Due to the need in semiconductor, Cyanide is usually metabolized in vivo to thio-
computer, and other high technology industries for cyanate by rhodanese, which is a mitochondrial
trace organic analysis in deionized water, and the enzyme in liver and kidney. Therefore, an accurate
concern about organic pollution of drinking water and reliable method for simultaneous determination
and various environmental waters, a sensitive meth- of cyanide and thiocyanate has long been sought
od for the determination of trace amounts of TOC in after for studies in forensic science and clinical
water is needed. If TOC is completely oxidized to medicine.
CO , the carbonate anion obtained can be deter- Compounds and forms of arsenic in aquatic,
2
mined. terrestrial, and biological systems have been the
Nitric oxide (NO) is a vital messenger in many target of increasing attention in recent years. Being
cellular communication and control systems. Endo- able to determine different species and compounds of
thelium-derived relaxation factor (EDRF) was iden- arsenic is important if their transport mechanism in
tied nearly 10 years ago as being the free radical the environment, toxicological risks, and inter-rela-
species nitric oxide (NO). It is involved in many tionships are to be specied. IC with inductively
physiological and pathophysiological processes, and coupled plasma MS detection was developed to
in cancer biology. NO has been shown to modify separate either cationic, neutral, and anionic species
tumour vascular tone, metastasis, angiogenesis and or soluble and suspended arsenic species in water
tumour cell proliferation. The assessment of novel samples of environmental interest.
therapeutic approaches, which modulate NO levels In recent years, the chemistry and biology of
within tumours therefore, relies on the accurate selenium and its various species has been the subject
determination of NO within different sample mat- of increasing attention, due to the importance of
ches. Because of the short half-life of NO in aqueous selenium both as an essential and toxic element.
media, assay of NO is performed on its metabolites, However, the identication and determination of the
nitrite and nitrate. The content of nitrite and nitrate many chemical forms of selenium in environmental
in the urine is considered as an index of NO and biological systems is still a major challenge for
production in vivo. analytical chemists, a prerequisite to investigate its
Both nitrite and nitrate must also be monitored pathways in the environment and its mechanism of
regularly because of their toxicity. Nitrite can be action in living organisms. The inorganic selenium
converted to carcinogenic nitrosamines in food prod- species, selenious and selenic acid (selenite and
ucts and within the human digestive system. Nitrate, selenate) are very important in the biochemical cycle
although more stable and less toxic than nitrite, is of selenium. Because of the difference in their
also a concern because it can readily be converted to oxidation states, these two species exhibit quite
nitrite by microbial reduction in food products. different chemical and biological properties. Organic
The endless list of natural and man-made water species of selenium, such as selenoamino acids, take
pollutants also contains inorganic sulfur-containing part in the biological selenium cycle and are incorpo-
22 22 22 22
anions, such as S , SO , SO , S O . These rated into proteins. The main selenoamino acid found
3 4 2 3
anions have been shown to have a diverse impact on in plants is selenomethionine, which is used as a
plants, animals and humans. They can react with one selenium supplement in the diet of man and animals.
another and undergo decomposition or air oxidation. Trimethylselenium ion has been identied in urine
Sulte and thiosulfate, are formed as intermediate and is used as a tracer of selenium levels in humans.
Since the toxicity, bioavailability and transport of substances by IC [29]; the retention models in IC and
selenium depend on different selenium forms and their use in computer optimization of eluent com-
their concentrations, it is essential to selectively position [30]; the application to IC of knowledge
determine selenium species present in the studied discovery in databases [31].
samples.
Phosphate is a nutrient that must usually be
determined in different kinds of samples, such as 4. Sample pretreatment
food, environmental samples, etc.
In most cases, sample pretreatment previous to
determination of inorganic anions by IC techniques
3. General reviews involves only simple operations, such as ltration,
sample dilution, pH adjustment, protein precipitation,
Numerous review articles on the subject of IC extraction of the analyte. However, the analyses of
have appeared during this period in the literature. other kinds of samples require more complex sample
Some of the reviews cover the general aspects of IC preparation procedures. This occurs, e.g., when the
techniques, such as those that include: the theory and concentration of anions in samples is very low, or
methodology of liquid chromatography [3]; the the concentrations of sample matrix anions are high
general aspects of IC [4]; the basic principles of IC relative to the analytes, or when matrix constituents
[5]; the theory and application of the chemical are a source of interferences in the IC separation.
equilibria in IC [6]; the questions that remain Therefore, during the last 2 years papers have
unanswered and unasked in ion analysis [7]; the been published that describe new methods to resolve
recent advances in IC [8], electrostatic IC [9]; the and simplify this decisive analytical step in sample
advances in detection techniques for IC [10,11]; the preparation for IC anion determination.
decomposition method as sample preparation for Ito [32] used a high-capacity anion-exchange resin
simultaneous multielement analysis [12]; the ad- with styrenedivinylbenzene for both preconcentra-
vances in stationary phase development in sup- tion and separation of iodide in seawater. Iodide was
pressed IC [13]; the separation and determination of trapped quantitatively without broadening on a pre-
inorganic anions by reversed-phase high-perform- concentrator column, (TSK gel SAX resin). The
ance liquid chromatography [14]; the design and major anions in seawater, chloride and sulfate ions
application of bulk acoustic wave-based detector for were partially trapped and did not interfere in the
2
IC [15]; the development of suppressed conductivity determination of I . Sodium perchlorate 0.35 M and
detection in IC [16]; the comparison of IC and phosphate buffer (pH 6.1) was selected as eluent
capillary electrophoresis for the determination of with strong eluting power. Colombini et al. [33]
inorganic ions [1719]; the mechanism and applica- supposed that by using a high-capacity anion-ex-
tion of IC for simultaneous analysis [20]; the change column, it should be possible to determine
21
simultaneous determination of anions and cations by bromate at mg l levels by direct injection of a
IC [21]. Other more narrowly focused reviews on very large volume without any sample preconcen-
practical aspects of IC include the chromatographic tration and pretreatment, but experimental results
and electrophoretic methods for inorganic phosphate showed that matrix effect, due to inorganic ions
analysis [22]; the applications of IC to the de- contained in drinking water, strongly inuenced the
termination of inorganic ions in food [23]; the use of chromatographic behavior of the bromate peak.
IC in food and beverage analysis [24]; the develop- Toofan et al. [34] studied the factors affecting the
ment of automatic acid rain monitoring system by IC ion chromatographic preconcentration behavior of
[25]; the applications of anion chromatography in inorganic anions and organic acids.
terrestrial environmental research [26]; the quanti- Mattusch and Wennrich [35] developed a liquid
cation of sulfate and thiosulfate in clinical samples liquid extraction procedure for the elimination of
by IC [27]; the characterization of toxic solutions by high levels of sulfate to determine ppb concen-
IC in biological liquids [28]; the analysis of adhered trations of phosphate in the presence of a 20 000-fold
21
excess of sulfate. The determination of traces of TOC at the mg l level in industrial, environmental,
inorganic contaminants in concentrated reagent by IC and drinking water. Two years later, the same group
requires matrix elimination from the bulk solution in developed a new analytical procedure based on
order to avoid the overloading of the analytical thermal combustionIC for an hourly determination
column. Roeder and Jardy [36] proposed the precipi- of total carbon in air particulate matters using
tation of the predominant anion by means of a cation equipment readily available in the chemistry labora-
preliminary xed on a macroporous cation exchange. tory [43]. A pressurized alkaline decomposition with
Charles et al. [37] proposed an ICMSMS method IC was applied for the determination of trace
to determine bromate ions in water, which requires amounts of chloride in silica [44]. Colina and
sample pretreatment to remove any major ions that Gardiner [45] reported the use of hydrogen peroxide
22
displace bromate, consisting of eliminating SO , at low pH in combination with closed-vessel micro-
4
2 2
Cl and HCO ions respectively with barium-form, wave assisted digestion for the oxidation of various
3
1
silver-form, and acid (H -form) exchange resins. nitrogen, phosphorus, and sulfur containing com-
The three cartridges were successively connected in pounds. The nitrate, phosphate and sulfate ions
the order BaAgH and then installed on the formed were determined by IC. Colombini et al. [46]
vacuum manifold. Stratford et al. [38] reported a proposed the digestion of samples by alkaline persul-
2
means to remove Cl ions from small volumes using fate solution in a microwave oven. A column switch-
1
an Ag resin that facilitates quantication of both ing was used for eliminating sulfate after microwave
nitrite and nitrate in biological samples. Fagan et al. assisted persulfate digestion in order to get a fast
[39] proposed an ion chromatographic analysis of simultaneous determination of total nitrogen and
cyanate in gold processing samples containing large total phosphorus by suppressed ion chromatography
concentrations of metallocyanide complexes. In without any sample preparation. A method for
order to remove the metallocyanide complexes they determining halogens (I, Br, Cl, F) in geological and
developed two procedures: the rst was a manual biological materials with pyrohydrolysis as sample
off-line method which used solid-phase extraction preparation was described [47]; by this process the
cartridges containing a strong anion-exchange resin halogens were separated from the matrix and then
to trap the complexes, while the second approach collected in a receiver solution. Buldini et al. [48]
consisted of an automated on-line method, which showed that saponication followed by oxidative UV
used an anion-exchange guard column to trap the photolysis is a good method to remove completely
complexes and a column switching valve to allow the organic matrix, which strongly interferes in the
back ushing of the cyanate from the guard column. IC determination procedure of some inorganic
Dahllof et al. [40] used a second switching valve species in edible vegetable oils and fats. Kock et al.
between the precolumn and the main column. Inter- [49] presented the use of membranes with a molecu-
ference of a high chloride concentration could be lar-mass-cutoff of M 10 000 for the ultraltration of
r
reduced substantially and detection limits for nitrate blood serum and synovial uid samples previous to
and phosphate lowered ve-fold. Montgomery et al. the determination of sulfates by HPLC. The viscosity
[41] described a new online sample preparation of the synovial uids was reduced by treatment with
technique using electrochemical-regenerated ion sup- hyaluronate lyase before ultraltration. HPLC-grade
pression and sample neutralization. water was evaluated as an alternative extraction
Determination of total organic carbon (TOC) reagent to acid extraction of plant tissue. Cations and
requires two steps. The rst is the conversion of anions were determined by IC, and in about 95% of
organically bounded carbon to a simple molecular occurrences concentration of ions in tissues extracted
form that can be measured quantitatively, and the with HPLC-grade water were equal to, or greater
second step is to detect the CO evolved during the than, those extracted with acids [50]. A diffusion
2
oxidation of the organic compounds. Fung et al. scrubber system equipped with an ion chromatograph
described [42] the applicability and reliability of the was used for collection and determination of low-
hyphenated technique of catalytic thermal combus- concentration (ppb levels) of ammonia and nitric
tionion chromatography for the determination of acid gas [51].
Blackwell et al. [52] described the use of alkaline capacity 510-fold using a standard diameter latex
fusion by sodium peroxide to dissolve chlorine and while maintaining the high chromatographic ef-
bromine in rocks to produce a solution, which is ciency typically associated with pellicular materi-
suitable for analysis by IC. als.
Sanders [53] proposed a procedure for determi- New column packings have been investigated to
nation of total iodine using automated sample prepa- improve the separation conditions of anions. Liu et
ration and IC. The protocol for sample preparation al. [57] prepared an anion stationary phase to analyze
consists of sequentially hydrolyzing the sample, inorganic anions in oil eld waters, which make
oxidizing any organic/ inorganic iodo compounds to possible the use of a single-column IC. Micro silica
iodate, and reduction of iodate to iodide. After beads, g-chloropropyltriethoxysilane, hexamethyldi-
preparation, liberated iodide is analyzed by IC. silazane and N,N-dimethylbenzylamine were used
The detection of small quantities of nitrogen for the synthesis of the required phase. The eluent
oxides in air in a quick and automated way was used was a mixture of sodium benzoate and sodium
carried out by coupling chromatomembrane (CM) citrate. Okamoto et al. [58] developed a new graphit-
cells operating in computer-aided ow injection ized carbon packing, which is sintered from carbonic
analysis systems with IC [54]. material at a high temperature for an ion-interaction
chromatographic method. They employed an ion-
interaction reagent, tetrabutylammonium hydroxide,
5. Separation as the eluent instead of an anion-exchange group,
and sodium carbonate as the eluting agent. Inorganic
This subsection covers publications in the area of anions were successfully separated [59] on a non-
novel or modied stationary phases and also new modied porous graphitic carbon (PGC) column
eluents as well as concentrator pre-columns and with an aqueous eluent containing an electronic
suppressor columns and eluents, due to their implica- modier in the mobile phase such as carboxylic acid.
tion in the separation process. At present, many The addition of organic modier in the mobile phase
research groups are working on this aspect of IC. was without effect in the retention of inorganic
In the method of bromate determination in drink- anions but the addition of pyridine improves the
ing waters proposed by Nowak and Seubert [55], the efciency of the separation. The retention of inor-
use of high-capacity ion exchangers (polystyrene ganic anions on non-modied PGC is dominated by
divinylbenzene copolymer functionalized by chloro- electronic interaction based purely on donoraccep-
methylation), allows both the analysis of water tor interaction between the lone pair electrons of the
samples containing high ion strength (mineral or solute and the p electrons of the PGC. A new
waste water) and the use of large injection volumes metacrylate-based packing with quaternary amine
(.500 ml) without overloading the analytical col- functional groups was proposed for the analysis or
umn. For this reason, no matrix elimination step is inorganic anions by ion chromatography [60]. Col-
required. Also proposed the use of microbore columns packed with this new material work for both
umns (2 mm I.D.) which allow ow-rates up to 500 suppressor-based and single-column ion chromato-
21
ml min . Jackson et al. [56] developed a new graphic methods. Monodisperse agglomerated pel-
high-capacity column to improve the quantitation of licular anion-exchange resins for high-performance
21
bromate at the 10 mg l maximum contaminant ion chromatography have been described. The resins
level currently being proposed by the US EPA. The are stable from pH 0 to 14 [61,62].
production of high-capacity columns requires the use The development of novel stationary phases in-
of latex with a large diameter, which ultimately volves the use of a modied stationary phase.
results in band broadening and decreases chromato- Retention behavior on anion exchangers modied
graphic efciency. They used a superporous resin, with various ionic polymers has been studied; IC-
which allows a thin latex layer to be coated on both Anion-SW columns modied with mucopolysac-
the exterior and interior surfaces of the resin. This charides such as chondroitin sulfate or heparin
approach provides a simple way to increase the resin showed unusual retention behavior [6365], reten-
tion of anions on the anion exchanger was remark- inorganic anions by ion-interaction chromatography.
ably reduced after the modication with heparin An octadecyl-bonded silica column was dynamically
[66]. When silica-based anion exchangers were coated with crystal violet and acetonitrilewater
modied with heparin and dextran sulfate and under buffered with phthalate as the counter-ion was used
the appropriate conditions both anions and cations as the mobile phase. This technique employs a
were simultaneously separated [67]. A C reversed- buffered or unbuffered mobile phase containing a
18
phase column was coated with N-cetylpyridinium hydrophobic positively charged ion. The major ad-
chloride to prepare a low-exchange-capacity ana- vantages of these techniques in comparison with
lytical column and with hexadecyltrimethyl- conventional xed-site ion exchangers are: (i) great-
ammonium bromide to prepare a concentrator pre- er chromatographic efciency and exibility with
column. Both columns were successfully used in the regard to the choice of columns, mobile phases, and
IC determination of iodide in urine and serum [68]. ion-pairing reagent for optimum separation, and (ii)
The surface of gel-type-anion exchange resin was the possibility of controlling the anion-exchange
modied by the adsorption of an anionic polyelec- capacity of the column by varying the mobile phase
trolyte: polycondensation product of sodium naph- composition.
thalenesulfonate and formaldehyde (trade name Electrostatic ion chromatography is a new method
Demo N) was applied to inorganic anions separation of separating ions reported in 1995 by Hu et al.,
[69]. Bohme et al. [70] described an IC method for based on simultaneous electrostatic attraction and
trace analysis of bromate and bromide based on repulsion interactions between analyte ions and xed
coating reversed-phase material with an ionogenic positive/ negative charges of a zwitterionic stationary
agent, tetrakisdecylammonium bromide, to obtain a phase, having the special advantage of using only
pseudo ion-exchange column. Goessler et al. [71] water as the mobile phase [78]. The method uses a
studied the retention behavior of eight selenium conventional reversed-phase ODS stationary phase
compounds with aqueous solutions of pyridine in the modied with a zwitterionic surfactant. The chro-
pH range 2.05.7 on a silica-based strong-cation- matograms with the complicated peaks, derived from
exchange column with strongly acidic sulfonic acid various ion pairs appeared when the sample solu-
groups as exchange sites. The surface of the func- tion contained several kinds of cations and anions,
tionalized silica particles is covered with siloxane were simplied by using a preconditioning cation-
groups, free silanol groups, geminal silanol groups, exchange column. In the preconditioning column,
and associated silanol groups that may interact with various kinds of countercations of the analyte anions
the analyte. The sulfonate exchange sites will inter- were converted to a particular kind of common
act with the cationic selenium compounds, the cation, and thus all analyte anions were separated as
hydrophobic backbore of the column material with the common form cation. The more effective sepa-
uncharged lipophilic selenium compounds, and the ration was achieved by converting to a divalent
compounds with carboxylic acid groups may be cation form than a monovalent cation form, because
retained via hydrogen bonds to siloxane or silanol the anions paired with divalent cation provided
groups. A microcolumn ion chromatography of longer elution times than those paired with mono-
inorganic anions was proposed using bovine serum valent cation [7984]. Mixed micelles obtained by
albumin immobilized on silica gel as a stationary mixing sodium dodecylsulfate (SDS) with
phase [72,73]. The same group described how octa- Zwittergent-314 were used as a dynamic stationary
decylsilica immobilized with bovine serum albumin phase for the simultaneous IC of inorganic cations
was capable of separating inorganic anions [74,75]. and anions [85]. A novel polymer-based zwitterionic
C silica gel dynamically modied with cetyl- separation material was synthesized; the resulting
8
trimethylammonium bromide has been used for the material carried strong/ strong charge zwitterionic
determination of inorganic anions by IC, and the pendant groups, whose charge properties did not
time to separate dihydrogenphosphate, chloride, nit- change over a wide pH range. It was capable of
rite, bromide, nitrate, and sulfate ions was 7 min separating inorganic anions and cations both in-
[76]. Tonelli et al. [77] proposed the separation of dependently and simultaneously using aqueous solu-
tion of perchloric acid or perchlorate salts as eluent diluted solution of alkanesulfonate as eluent com-
[86]. ponents and conductimetric detector [96]. The de-
A mixed-bed column was packed with anion- termination of mixtures of carboxylic acids and
exchange resin ICS-A23 and cation-exchange resin selected inorganic anions proposed by Magyani [97]
CH1. The ion chromatographic method developed involves an ion exclusion separation column with
with this mixed-bed column was used for the sodium octanesulfonate as eluent. The retention of
simultaneous determination of organic acids, inor- these solutes was controlled by a combination of
ganic anions and cations in different food samples ion-exclusion through the Donnan potential and
without any special pretreatment procedure [87]. hydrophobic interactions. The performance of
Mixtures of inorganic ions and neutral organics were cyanuric acid as eluent for suppressed anion chroma-
simultaneously separated in several ion-exchange tography has been investigated [98]. Due to the very
stationary phases that contained both exchange as late elutions of polythionates because of their strong
well as reversed-phase functionality. Mobile phases retentions onto a conventional ion-exchanger sepa-
were a blend of those normally used for ion-ex- ration column, Miura et al. [99] proposed an ion-pair
change separation with those generally used for chromatography using a silica octadecylsilane (ODS)
reversed-phase high-performance liquid chromatog- column with mobile phases of acetonitrile in water
raphy [88]. A hyphenated ICion-exclusion chroma- containing phthalate and tetrapropylammonium salt
tography technique has been reported for determin- as ion pair reagent. The proposed method was
ing organic and inorganic anions [89]. successfully applied to the determination of the
Construction and preliminary characterization of oxyanions of sulfur added to hot-spring waters. The
an open tubular capillary column for ion chromatog- temperature of the mobile phase can be used as an
raphy has been proposed; increasing the column optimization parameter in ion chromatographic anal-
temperature resulted in a dramatic increase in the ysis; the character of the temperature dependence of
column efciency [90]. the retention time for each ion is unique and depends
Toofan et al. developed an anion-exchange col- on the sorbent used [100].
umn for the separation of anions in power plant An electrochemical process called electro-elution
waters. The column was optimized, in terms of ion chromatography was used to generate or moder-
capacity and selectivity, to allow the isocratic sepa- ate the mobile phase composition inside the column
ration of weakly retained organic and inorganic [101]. The main advantage of this process is that
anions, in addition to more strongly retained anions. only water is required as the mobile phase for anion
This new moderate capacity anion-exchange column and cation analysis. Small et al. [102] described how
was utilized for the preconcentration ion chromatog- electrically polarized ion-exchange beds pumped
21
raphy determination of key anions, at low mg l with water could produce electrolytes of steady and
levels [91]. controllable concentration. Such devices make it
Different eluents have been studied including the possible to use water as the pumped phase in IC,
use of vanillic acidN-methyldiethanolamine eluents thus avoiding off-line eluent preparation. Control of
for suppressed ion chromatographic separation of electrical current owing through the devices allows
inorganic anions [92] and the use of pyromellitate precise control of the concentration of eluent that
eluent for the simultaneous determination of com- they deliver. This provides a new way of performing
2 2 22
mon anions (Cl , NO and SO ) and divalent gradient and isocratic elution. Using water as the
3 4
cations [93]. Inorganic cations and anions were carrier and two small beds of resin, one as a
separated simultaneously using sodium sul- generator the other as suppressor, and periodically
fosalicylateEDTA binary eluent on a strong basic reversing their roles through automatically switched
anion-exchange column [94], and inorganic anions, valves, they developed a form of continuous IC that
magnesium and calcium have been separated with involves little intervention by the user. Another
trimellitic acidEDTA as eluent [95]. Common modality of the latter system consisted in the ion
inorganic anions can be separated on an anion- reux, applied to IC. In one embodiment of ion
exchange column of low capacity using a very reux, continuous eluent generation, ion separation,
and continuous suppression are accomplished within the on-line hydrobromic acid generator employing a
a single bed [103]. cation-exchange hollow ber. Miura et al. [109]
An electrochemical process was used to regenerate proposed a method for IC determination of sulde,
the solid-phase ion suppressor for continuous un- sulte, thiosulfate and thiocyanate in their mixtures;
attended operation [104]. Electrolysis of the detector sulfur anions, in the efuent from the column, were
efuent generates hydronium or hydroxide ions, monitored by photometric measurement of the excess
which automatically replace the eluent cations or of iodine (triiodide) for a postcolumn iodineazide
anions on the suppressor. A common micromem- reaction catalyzed by sulde, thiosulfate and thio-
brane suppressor, usually used to chemically sup- cyanate and for a postcolumn reaction of iodine with
press eluent conductance in IC, was successfully sulte. Therefore, chromatograms obtained for the
used to effect ion replacement reactions in sup- sulfur anions gave negative peaks, based on the
pressed eluent stream [105]. A small inexpensive decrease in the absorbance from background. Iodide
system was described that allows high-performance can be determined with ion chromatography and
suppressed anion chromatography on a capillary direct UVvisible detection after preconcentration of
2
scale [106]. The system uses a novel electrodialytic the sample [32] and as IBr , which is formed after
2
NaOH eluent generator that is deployed on the high- the IC separation step in a bromide-containing
pressure side of the pump and thus requires no eluent. The interhalogen compound is formed
special measures for electrolytic gas removal. This through addition of a basic hypobromite solution
device permits both isocratic and gradient operation. with subsequent acidication [110]. Iodate can be
Huang et al. [107] reported preliminary experiments determined by IC and postcolumn reaction with UV
2
and theoretical discussion on the feasibility of a visible detection as I , which is formed in a post-
3
novel approach for the determination of very weak column reaction with an iodide solution and sub-
acids using a commercial micromembrane suppressor sequent acidication [110]. Achilli and Romele [111]
and a low concentration of regenerant. A relatively described a very sensitive bromate IC determination
more concentrated hydroxide ion can be employed as with spectrophotometric detection after post-column
the eluent with low background conductance while reaction with fuchsin in low pH medium, which
the analyte ions were detected as negative peaks. overcomes the interferences commonly found in IC
with conductivity detection. Sub part-per-billion
analysis of bromate, iodate and chloride in drinking
6. Detection water were detected via target-specic, post-column
derivatization; other sample anions were invisible to
Suppressed and non-suppressed conductivity are the detector [112]. Some common inorganic and
the favored detection techniques in IC of inorganic organic anions were separated by high-performance
anions, but the high electrolyte concentration re- ion chromatography coupled with indirect photo-
quired to elute most analyte ions in a reasonable time metric detection and 1,2-dihydroxybenzene-3,5-dis-
is a serious limitation in this detection system. ulfonate and sodium sulfosalicylate, respectively, as
Therefore, other detectors are being made available single-column single-component eluents [113].
for ion separation techniques. A method for the simultaneous determination of
Although it is known that only a limited number cyanide and thiocyanate in blood has been proposed
of common inorganic anions are detectable by direct [114]. After extraction cyanide was derivatized with
photometric detection, the wide use of this technique, 2,3-naphthalenedialdehyde and taurine to give a
due to its analytical qualities, stimulated a search for uorescent product of 1-cyanobenz[ f ]isoindole. This
suitable visualization anions and, in this context, compound was detected with high sensitivity by
various constituents were tested. Inoue et al. [108] uorometry, and the underivatized thiocyanate was
developed a sensitive and selective IC determination detected by UV absorption.
of bromate with postcolumn conversion into tri- A faint chemiluminiscence (CL) from the neutrali-
bromide by hydrobromic acid. A high precision zation reaction of nitric acid and potassium hy-
determination of bromate was performed by using droxide was enhanced by addition of iron(III) to the
acid. The enhanced CL emission was suppressed by anions, the analyte anions were quantied by
adding inorganic anions such as chloride, bromide, measuring their countercations with ICP-AES, where
nitrite, nitrate and sulfate. Based on this, a post- the calibration curve of the countercation measured
column CL detection method [115] was developed by ICP-AES could be used [83].
for the determination of the anions. The decrease in The popularity of ICP-MS is rapidly rising as seen
the CL intensity, which is proportional to the anion by the increasing number of publications. The de-
concentration, can be monitored easily and rapidly in termination of bromate in drinking waters proposed
a ow injection system. A ow-injection chemilumi- by Creed et al. [121] presents the drawback of the
niscence method has been proposed for sensitive co-elution of chloride and bromate, but ICP-MS
determination of arsenate, germanate, phosphate and provided the selectivity to circumvent the co-elution,
silicate. After separation by IC [116], the post-col- a shortcoming of direct conductivity detection. The
umn detection system involved formation of online-coupling of ICICP-MS combined with a
heteropoly acid in H SO medium before the CL high-capacity and high-performance anion exchanger
2 4
reaction with luminol in a NaOH medium. and NH NO -based elution system allowed the
4 3
Various atomic spectroscopy techniques are the determination of bromate in almost every water
predominant choices for analysis of metal. Atomic without any sample pretreatment [122]. Nowak and
absorption spectrometry with ame (FAAS), Seubert [55] developed a method for ultra-trace
graphite furnace (GFAAS) and electrothermal vapor- determination of bromate in drinking waters using
ization (ETVAAS) remain the most popular tech- on-line coupling of IC and ICP-MS. ICP-MS was
niques. Except for some special applications for used as element-specic detector for sulde, sulte,
multielement determination, these instruments are sulfate and thiosulfate after their chromatographic
dedicated to analysis of one specic analyte at a separation [123]. Bromate, iodate and other halogen
time. Inductively coupled plasma atomic emission anions were determined by IC with ICP-MS. The
spectrometry (ICP-AES) is capable of multielement advantages of ICP-MS as an element-selective de-
determination. The ICP-MS technique is generally 1 tection method were evaluated for bromate and
order of magnitude or more sensitive than atomic iodate by considering the comparison with the post-
absorption methods and is capable of simultaneous column derivatization described in a previous paper
multielement determination. These techniques have [124]. For the determination of iodine species an ion
been applied as detectors in anion-chromatographic chromatograph was coupled with an ICP-mass spec-
methods when the analyte anion can be monitored as trometer [125]. Li et al. compared two IC detection
a cation. methods for the determination of four selenium
To minimize interferences by non-selenium anions compounds. Detection was carried out using an on-
in the IC analysis of inorganic selenium anions and line ICP-MS or a FAAS as the selenium-specic
amino acid forms an ICP-AES detector was proposed detector. More powerful selenium detection was
[117]. With the same proposal an electrothermal achieved with an ICP-MS. To increase the nebuliza-
atomic absorption spectrometry detection was tion efciency, an ultrasonic nebulizer replaced the
studied [118] and a speciation of selenium method Meinhard concentric glass nebulizer. The ICP-MS
based on microbore anion-exchange chromatography signal intensity was increased with ultrasonic nebuli-
and a Zeeman-effect electrothermal atomic absorp- zation by a factor of 731 times [126]. Goessler et
tion spectrometry for element specic detection via al. also proposed ICP-MS as a selenium-specic
ultra low volume fraction collection has been de- detector [71] for the determination of inorganic and
scribed [119]. A new on-line method, consisting of organic selenium compounds. In this case, also with
liquid chromatographyUV irradiationhydride gen- the aim of increasing the nebulization efciency, the
erationquartz cell atomic absorption spectrometry Meinhard concentric glass nebulizer was replaced by
was proposed [120]. All these techniques can be a hydraulic high-pressure nebulizer. The determi-
considered as reliable, straightforward systems for nation of anionic, neutral and cationic species of
selenium speciation. When a zwitterionic stationary arsenic in environmental samples was carried out by
phase was used in the determination of inorganic IC with ICP-MS detection, the gradient method was
used to determine arsenic species in highly ferrous/ iodide in urine and serum. The tubular detector
ferric-contaminated leachates of lignite spoil [127]. presents the advantages of being easily connected to
A speciation method using IC coupled with ICP-MS the system and having virtually no dead volume.
was described for simultaneous analysis of eight Chen and Alexander [136] proposed the use of a
halides and oxyhalogens: chloride, chlorite, chlorate, metallic silver wire electrode as potentiometric de-
perchlorate, bromide, bromate, iodite and iodate tector of anions separated by ion and ion-pair
[128]. ICICP-MS has been applied to the determi- chromatography.
nation of halogens, with special reference to iodine, Amperometric detection of inorganic anions in ion
in geological and biological samples [47]. A particle chromatography has been applied by Kolb et al.
2 2 2
beam interface was studied for coupling IC with [137] for the determination of anions (NO , Cl , I ,
2
22 2 22
mass spectrometric detection [129]. Several pre- SO , Br , S ) using a carbon paste working
3
requisites must be fullled, including mobile phases electrode. Casella [138] studied the electrooxidation
containing volatile buffers and high amounts of of thiocyanate on a copper-modied gold electrode
organic solvents at low ow-rates. and proposed its amperometric determination by IC.
Charles et al. [37] developed an electrospray ion An amperometric detector with a glassy-carbon
chromatographytandem mass spectrometry (IC working electrode has been used for the simulta-
MSMS) method for the analysis of bromate at neous determination of sulte, iodite and rhodanide
sub-ppb levels in water; the methanolic sulfate eluent [139]. Liu et al. [140] reported the determination of
permits ICMS coupling via an electrospray inter- sulte in food by exclusion ion chromatography with
face. They proposed two methods for analyzing pulsed amperometric detection. Ion chromatographic
chlorite, chlorate, bromate and iodate by IC coupled detection of nitrite at a dispersed platinum glassy
with electrospray and ionspray tandem mass spec- carbon electrode has been described [141]. Platinum
trometry (ICMSMS) [130,131] and silver / silver chloride electrodes have been
The use of evaporative light scattering detection evaluated for simultaneous amperometric and poten-
(ELSD) has been proposed as an effective alternative tiometric detection [142].
for the determination of ions such as chloride [132].
Indeed, ELSD is commonly referred to as a sensitive
universal detector in liquid chromatography for
7. Applications of ion chromatographic
solutes, which are less volatile than the eluting
techniques
solvents [133]. Different carboxylic anions derived
from volatile acids compatible with ELSD volatility
requirements have been investigated as electronic 7.1. General applications
competitors in order to manage the retention of
inorganic anions [59]. Pohl et al. [143] described the factors controlling
Yang et al. proposed a bulk acoustic wave sensor ion-exchange selectivity in suppressed IC. A new
as an ion chromatographic detector for the simulta- approach to determining each component of a two-
2 2 2 2
neous determination of NO , Cl , NO , H PO component overlapping peak in single-column anion
3 2 2 4
22
and SO [134], and for determination of iodide chromatographic analysis has also been described
4
[135]. [144].
During recent years, simultaneously with the IC Takayanagi et al. [145] reported the ion chromato-
development, there have been great developments in graphic determination of sulfate in a high-salinity
ion selective electrodes (ISEs), which has brought solution. The retention characteristics of condensed
the possibility of having, for the determination of linear phosphates, P2 to P13, on a strongly basic
certain species, feasible as low-cost units. Almeida et quaternary amine anion exchanger were studied
2 2 2 22
al. [68] described the evaluation of a laboratory- [146]. The determination of F , Cl , NO , SO ,
3 4
32
made iodide-ISE with tubular conguration, based and PO by IC with preconcentration has been
4
on a homogeneous crystalline membrane, as detector reported [147]. A study focused on the development
of a chromatographic system for the determination of of a single-column IC method and the use of
capillary electrophoresis for the determination of Cl [157]. The determination of small quantities of
anions has been described [148]. Ding et al. [149] nitrogen oxides in air was developed by IC using a
proposed the simultaneous separation of organic chromatomembrane cell preconcentration [54]. Water
acids, inorganic anions and alkaline earth metal and acid soluble components in atmospheric dust
cations using a single anion-exchange column. were measured by IC and other techniques [158].
Caliamanis et al. [150] demonstrated that the Total carbon in air particulate matters was deter-
conductimetric determination of anions of weak mined by thermal combustionIC [43]. Silver iodide
acids in chemically suppressed ion chromatography was determined by high-pressure ion chromatog-
could be enhanced, by conversion of the acid to a raphy in soil and water matrixes after reduction by
conjugate salt, if the anion was present above what zinc [159]. Inorganic anions in drainage water and
they termed the critical point concentration. soil solutions were analyzed by single-column IC
The conversion of boric acid in a more acidic [160].
complex, using mannitol or sorbitol as ligands, was Although most water analysis publications involve
exploited to obtain a sensitive and accurate method environmental samples, all water analyses have been
for the determination of boric acid by IC [151]. included in the following section.
Chadwick [152] described the use of a laboratory
robot as a tool to prepare multilevel calibration
standards for several online IC systems. 7.3. Water analysis
Two approaches to interfacing a suppressed ion
chromatography system with a suppressed conduc- Seepage water samples from tin ore tailing were
tometric capillary electrophoresis separation system analyzed for arsenic species by an ICICP-MS
have been described [153]. gradient method, as part of a toxicological assess-
ment [161]. Arsenic species were also determined in
7.2. Environmental analysis highly polluted water leachates of lignite spoil using
the ICICP-MS gradient method [127]. The hyphe-
The analysis of NO and SO by IC with the use nated technique of catalytic thermal combustionIC
2 2
of passive samplers for ambient measurements of was applied to the determination of total organic
21
NO and SO . was reported [154]. A rapid ion carbon at the mg l level in industrial, environ-
2 2
chromatographic method, with isocratic separation mental, and drinking water [42]. Dahllof et al. [40]
and micromembrane suppression was performed for reported on an improved ion chromatographic meth-
the analysis of iodide in soils, and oodplain ground od for nitrate and phosphate determination in sea-
waters [155]. The nitrate, phosphate and sulfate ions water, regardless of salinity, developed using ex-
formed after the use of hydrogen peroxide at low pH perimental design. A simple and highly sensitive ion
in combination with closed-vessel microwave-as- chromatographic method with UV detection was
sisted digestion for the oxidation of various nitrogen-, developed for iodide in seawater [32]. Several or-
phosphorus-, and sulfur-containing compounds in ganic and inorganic ions were simultaneous deter-
Buffalo River sediments, were determined by IC [45] mined by UV in snow samples from Shenyang area
and total nitrogen and phosphorus were simultan- [162]. Liu et al. [57] presented a method to de-
eously determined by IC after microwave-assisted termine inorganic ions in oil eld water by single-
persulfate digestion [46]. IC has been used to column IC. A non-suppressed IC system with con-
determine inorganic and organic anions within land- ductivity detection was tested for the determination
ll leachates. Two procedures are operated on split of chloride, nitrate, sulfate, alkali and alkaline-earth
samples, which have multiple dilutions and vary in metal ions in polar ice core samples by use of large
sample treatment: gradient ion-exchange chromatog- injection volumes [163]. A chemically suppressed IC
raphy for inorganic anions and isocratic ion-exclu- system was used for the analysis of major organic
sion chromatography for organic anions [156]. Phos- and inorganic acid in precipitation samples collected
phorous and phosphoric acids in air have been in the city of Maracaibo during a one-year period.
determined by IC and capillary isotachophoresis Two different isocratic method were used, the rst
for inorganic acids, and a second for organic acids tration method, EPA Method 300.1 and a postcolumn
[164]. Two different chromatographic methods have reagent method. Bichsel and Gunten [110] proposed
been reported for the determination of sulfur anions the determination of iodide and iodate in water by
in hot-spring waters samples: the rst [99] with a two methods using anion-exchange chromatography.
silica octadecylsilane column and the second with an Heumann et al. [171] developed an on-line coupling
ion-exchange column [109]. of chromatographic systems (IC, LC, size-exclusion
The determination of bromate has traditionally chromatography, GC) with ICP-MS for accurately
been accomplished using IC, but in response to the determining various element species. These species
need to develop bromate methods with lower de- included iodate, iodide, organo iodine species, and
tection limits, many researchers have proposed new heavy metal complexes with humic substances
2 2 2 22
methods and several works have been published Inorganic anions (Cl , Br , NO , and SO )
3 4
recently in order to improve the sensitivity and were determined in waters by ion-exchange chroma-
selectivity of IC methods for the determination of tography with chemiluminiscence detection [115],
bromate in drinking waters [33,37,55,56,108, and the applications of IC in the determination of
111,121,124,165167]. Two methods involve the use inorganic anions and cations in various waters with
of IC followed by postcolumn derivatization, which elevated mineralization has been discussed by Gros
converts bromate into tribromide, which is then and Gorene [172]. The high content of hydrogen
detected either by conductivity [108] or by UV carbonate anions and dissolved CO in some mineral
2
spectroscopy [112]. Detection limits were 0.35 waters interfere with the determination of anions in
21 21
mg l and 0.2 mg l , respectively. Creed et al. such samples by IC. Novic et al. [173] proposed a
[121] demonstrated bromate detection limits of 0.1 method to avoid peak deformation and overlapping.
21 21
0.2 mg l , which could be lowered to 50 ng l Inorganic anions, magnesium and calcium have been
by coupling the preconcentrator column to an ul- simultaneously determined in various environmental
trasonic nebulizer. water samples, such as rain and river water [95].
Yamanaka et al. [124] described the specic Low-level perchlorate analysis in drinking water and
determination of bromate, iodate and other halogen groundwater by ion chromatography has been re-
2 2 22
species in raw and ozonized water, by direct in- ported [174]. Anions (Cl , NO , and SO ) in
3 4
jection using ICICP-MS and post-column derivati- natural water were determined by low-pressure ion
2 2 2
zation. They achieved detection limits of 0.45 chromatography [175]. Nitrite and F , Cl , NO ,
3
21 21 2 22 22
mg l for bromate and 0.034 mg l for iodate. Br , HPO , SO were determined in wastewater,
4 4
Nowak and Seubert [55] achieved detection limits of groundwater and surface water samples by enhanced
21
5065 ng l for bromate by using a high-capacity, ion chromatography with sequential ow injection
high-performance, microbore anion exchanger with analysis [176].
ICICP-MS, no pretreatment was required, and A few developments in new regulations and
analysis time was only 815 min. Elwaer et al. [166] regulatory methods have taken place in the last 23
used on-line separation with an activated aluminum years that impact on water analysis. Several new
microbore column in a ow injection system coupled regulatory methods for drinking water measurements
21
to ICP-MS to achieve a detection limit of 60 ng l have been published recently by the EPA. EPA
for bromate. A new method which uses IC separation Method 321.8 Determination of Bromate in Drink-
with no pretreatment, followed by a post-column ing Water by Ion Chromatography Inductively Cou-
2
reaction to produce tribromide (Br ) from bromate pled PlasmaMass Spectrometry provides a lower
3
21 21
was applied for determining sub-mg l levels of detection limit for bromate of 0.3 mg l and
bromate in drinking water [168]. Kohler et al. [169] provides a degree of selectivity that was not avail-
described the use of a high-capacity resin with able with former methodology [177]. EPA Method
photometric detection for determining bromate and 300.1, Determination of Inorganic Anions in Drink-
nitrite in drinking water. Wagner et al. [170] com- ing Water by Ion Chromatography is applicable to a
pared three methods for measuring bromate in broad range of inorganic anions in drinking water
drinking water: a modied selective anion concen- [178].
7.4. Food analysis separation of selenite, selenate, selenocystine and
selenomethionine in selenium-rich yeast was studied
IC has been used for the determination of the with ion-exchange chromatography with a selenium-
principal anions of milk, phosphate, citrate and specic detector [118]. Matsunaga et al. [194] de-
chloride [179], for the determination of iodide in scribed the determination of condensed phosphates in
milk and baby formula [180], in dairy products and foodstuffs by IC. Sulte in food was determined by
table salt [135]. Ding et al. [181] proposed a ion-exclusion chromatography with pulsed am-
simultaneous determination of organic acids and perometry [140]. Chen et al. [195] studied an
inorganic anions in tea by IC. Liu et al. [182], analytical method for inorganic anions in food
described the determination of organic acid and colorants by IC with ion-exchange preseparation.
2 2 22
inorganic anions (Cl , NO , SO ) by gradient IC
3 4
in beverages and citric acids fermenting-medium. IC 7.5. Theoretical and statistical studies, and
was proposed as a rapid method to distinguish computational applications
orange juices from second pressure concentrates
[183]. Bello and Gonzalez [184] proposed the de- Ando et al. [196] described a theoretical study of
termination of phosphate in cola beverages using the elution prole of a high-concentration sample
nonsuppressed IC as an experiment that could be anion in non-suppressed IC.
integrated into existing laboratory courses in ana- The statistical comparison of calibration curves
lytical chemistry. A simultaneous determination of from two similar eluents was carried out in the ion
2 2 2
organic acids and inorganic anions (F , NO , Cl , chromatographic quantication of uoride and ace-
2
2 2
Br , NO ) and cations by IC with mixed-bed tate [197]. Statistical quality control has been applied
3
stationary phase has been described in wine, Japan- to ion chromatography calibrations [198]. Detectors
ese sake and instant coffee power without any for IC were classied using principal components
special pre-treatment procedure [87]. The determi- regression and linear discriminant analysis [199].
nation of nitrate in beer by IC has been tested by The use of factorial experimental design was re-
Buckee [185]. Carboxylic acids and inorganic anions ported for the rapid evaluation of main and interac-
2 2 22
(Cl , NO and SO ) have been determined in tive factors affecting linearity in calibration curves
3 4
wines by ion-exchange chromatography [186]. The for sulfate analysis by IC [200].
use of IC in the liqueurvodka industry, for the Madden et al. [201,202] have compared the per-
2 2
determination of inorganic anions (H PO , Cl , formance of several retention models for predicting
2 4
2 22
NO , SO ) has been proposed by Obrezkov et al. the retention factors of inorganic anions in non-
3 4
[187]. Ding et al. [188] proposed a simultaneous suppressed IC and in suppressed IC and for optimi-
analysis of organic acids and inorganic anions in zation of the separation of anions in ion chromatog-
beverage (dongjiu) by IC. The determination of raphy. Janos [203] reported a retention model in ion
alkali metals and inorganic anions in baobab fruit by chromatography considering the role of side equilib-
IC has been described [189]. Buldini et al. [48] ria in ion-exchange chromatography of inorganic
reported the determination of some inorganic species cations and anions. Correlation and digital signal
2 32 22
(Cl , PO , SO ) in edible vegetables oils and processing techniques were applied to the reduction
4 4
fats. Nitrate contents in red beet products was of detection limits of bromate and bromide in model
analyzed by IC [190]. Nitrate and other inorganic water samples by IC with direct UV detection [204].
2 2 2 22
anions (Cl , NO , H PO , and SO ) were mea- Papoff et al. [205] proposed a comparison between
2 2 4 4
sured in vegetables [134]. Nitrate and nitrite have experimental and deconvolved peak parameters in IC
been determined in meat products [191]. A rapid to enhance the quality of information obtained. The
analytical method for nitrite and nitrate in sh by IC pattern-recognition method was applied for modeling
has been proposed [192]. The identication and expert estimation of chromatogram quality [206].
quantication of some organic acids and inorganic Computational chemical analysis was used to study
2 2 22
anions (Cl , NO , SO ) was carried out in beet the highly sensitive detection of bromate in IC [207].
3 4
sugar using an IC method [193]. The simultaneous A classier system based on genetic algorithm
[27] D.E. Cole, J. Evrovski, J. Chromatogr. A 789 (1997) 221.
methodology was developed for the automatic ex-
[28] R.P. Singh, S. Ann Smesko, N.M. Abbas, J. Chromatogr. A
traction of production rules from a database of
774 (1997) 21.
6000 IC method examples; this machine learning
[29] H. Nomura, Bosei Kanri 41 (1997) 62.
strategy generated heuristics that can assist in the
[30] J. Madden, P.R. Haddad, P. Hajos, Trends Anal. Chem. 15
choice for a detection method for a specied set of (1996) 531.
[31] C.H. Bryant, R.C. Rowe, Trends Anal. Chem. 17 (1998) 18.
IC method and solute properties [208]. An empirical
[32] K. Ito, Anal. Chem. 69 (1997) 3628.
study for the effectiveness of recombination in a
[33] S. Colombini, S. Polesello, S. Valsecchi, S. Cavalli, J.
genetic-based classier system has been applied to
Chromatogr. A 847 (1999) 279.
the eld of IC [209]. An expert system for automated
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troubleshooting and plausibility testing in IC has
togr. A 775 (1997) 109.
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(1996) 335.
[36] V. Roeder, A. Jardy, Analusis 24 (1996) 43.
[37] L. Charles, D. Pepin, B. Casetta, Anal. Chem. 68 (1996)
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Journal of Chromatography A, 881 (2000) 607627

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