Chromatographia (2011) 73 (Suppl 1):S15–S28

DOI 10.1007/s10337-011-1967-9

REVIEW

The Challenging Role of Chromatography in Environmental

Problems
M. C. Bruzzoniti • R. M. De Carlo •

C. Sarzanini

Received: 29 November 2010 / Revised: 18 January 2011 / Accepted: 4 February 2011 / Published online: 4 March 2011
Ó Springer-Verlag 2011

Abstract This review details the contribution of ion TCA Trichloroacetic acid
chromatography (IC) to environmental analysis. With ref- DBA Dibromoacetic acid
erence to the problems usually encountered in environ- BCA Bromochloroacetic acid
mental analysis (low concentrations to be detected and BDCA Bromodichloroacetic acid
matrix interference), applications of IC in the analysis of CDBA Chlorodibromoacetic acid
inorganic cations in water and in the analysis of the platinum CIA Chloroiodoacetic acid
group elements (PGEs) in air particulate matter, and the BIA Bromoiodoacetic acid
advantages of this technique over more traditionally accep- TBA Tribromoacetic acid
ted analytical techniques will be discussed. Other current
environmental topics, for example the occurrence of halo-
acetic acids (HAAs) in drinking water, will be covered, Introduction
highlighting the importance of IC as an emerging powerful
tool for monitoring HAAs, recognized also by the EPA that The analysis of pollutants in environmental matrices is
recently adopted it in a regulated method (Method 557). difficult for two reasons:
1 the low concentrations in which they are present which
Keywords Ion chromatography
Platinum group can, even so, be hazardous to the environment and to
elements (PGEs)
Haloacetic acids (HAAs)
living organisms; and
Environmental control 2 strong interference from other components of the
matrices that hamper correct quantification of each
Abbreviations pollutant.
MCA Monochloroacetic acid
MBA Monobromoacetic acid The use of analytical methods in environmental science
MIA Monoiodoacetic acid has therefore become crucial; among those analytical
DIA Diiodoacetic acid methods, chromatographic approaches are necessary to
DCA Dichloroacetic acid solve some problems.
In this paper, the contribution of liquid separation meth-
ods, focusing mainly on those based on the ion-exchange
mechanisms, to the analysis of specific classes of inorganic
compounds (i.e. ammonium, alkaline earth metals, and
Presented at: 16th International Symposium on Separation Science,
Recent Advancements in Chromatography and Capillary PGEs) and organic compounds (e.g. haloacetic acids) in
Electromigration Techniques. Rome, Italy, September 6–10, 2010. environmental matrices will be discussed. For easier com-
prehension, Tables 1, 2, 3 summarize the most important
M. C. Bruzzoniti (&)
R. M. De Carlo
C. Sarzanini analytical conditions and the main results achieved by use of
Department of Analytical Chemistry,
University of Torino, Via P. Giuria 5, 10125 Turin, Italy the methods reviewed for each of the three classes of
e-mail: mariaconcetta.bruzzoniti@unito.it analytes.

123
 Table 1 Main chromatographic approaches for analysis of alkali metals, alkaline earths, and ammonium
S16

Column Eluent Flow rate Ions studied (injection volume) Detection Ref. Comments
(mL min-1)

123
Zr silica (150 9 4.6 mm) 10 mM tartaric acid 1.0 Li?, Na?, NH4?, K?, Rb? Cs? (20 lL) Indirect [12] Detection limits from 1.9 lg L-1 (Li?) to 109 lg L-1 (Cs?).
Silica functionalized with conductivity Separation within 22 min
Zr(OCH2CH2CH2CH3)4 Because the cation-exchange capacity of Zr is high, the
simultaneous elution of alkaline earth metal cations is not
feasible. Na?:NH4? *30. River water applications are
shown
IonPac CS10 20 mM H2SO4 1 Li?, Na?, NH4?, K?, Rb?, Conductometric [13] Detection limits not provided. Separation within 25 min. The
(250 9 4 mm) monoethanolamine, diethanolamine, with CSRS simultaneous elution of alkaline earth metal cations is not
Ion-exchange group: triethanolamine, feasible. Several applications in industrial samples are
sulfonic monomethylethanolamine, shown
morpholine (25 lL)
IonPac CS15 5 mM H2SO4 9% CH3CN 1.2 Li?, Na?, NH4?, K?, Mg2?, Ca2? Conductometric [14] Detection limits not provided. Separation within 18 min.
(250 9 4 mm) (25 lL) with CSRS in 4,000:1 sodium-to-ammonium concentration ratios; for
Ion-Exchange group: the external larger ratios, an eluent step change or gradient elution is
carboxylic acid, water mode needed
phosphonic acid, and
crown ether
IonPac CS16 26 mM methanesulfonic 1.5 Li?, Na?, NH4?, K?, Mg2?, Ca2? Conductometric [15] Detection limits between 0.2 lg L-1 (Li?) and 2.6 lg L-1
(250 9 5 mm) acid (25 lL) with CSRS (K?). Separation in 25 min. Cations (especially K) are
Ion-exchange group: grafted Ultra in the sensitive to temperature variations. Temperature control
carboxylic acid. High recycling mode (30 °C) is needed. Separation with 6,000:1 sodium-to-
capacity column, see text ammonium concentration ratio is shown
Two columns connected in 3 mM methanesulfonic acid 1 Li?, Na?, NH4?, K?, Mg2?, Ca2?, Non-suppressed [17] Detection limits not provided. Two retention mechanisms
series or mixed in a single ethanolamine, triethanolamine conductivity (cation-exchange and complexation) can be exploited
column: (100 lL) (indirect mode)
(1) Silica gel coated with a
polybutadiene–maleic
acid copolymer
(100 9 4.6 mm)
(2) 18-Crown-6 ether The crown ether column can separate only Na?, NH4?, K?.
chlorosilane bonded to Crown ether column before the cation-exchange column
silica (100 mm or enhances separation between analytes. System peaks are
250 mm observed. Separation within 28 min. Separation with 5,000:1
length 9 4.6 mm) sodium-to-ammonium concentration ratio is shown
IonPac CS15 10.8 mM H2SO4 and 1 Li?, Na?, NH4?, K?, Sr2?, Mg2?, Conductometric [18] NH4?, K?, Sr2?, CH3NH? largely affected by 18-crown-6
(250 9 4 mm) 10.0 mM 18-crown-6 Ca2?, CH3NH?, (CH3)3NH?, with CSRS concentration. Several mechanisms (ion pairing, adsorption,
Ion-exchange group: (CH3)2NH2? external water association) acting on retention of the cations are invoked.
carboxylic acid, mode Separation within 18 min. Separation with 60,000:1 sodium-
phosphonic acid, and to-ammonium concentration ratio is shown. Detection limit
crown ether for NH4?: 0.0023 mmol L-1
M. C. Bruzzoniti et al.
The Challenging Role of Chromatography in Environmental Problems S17

20 min (Cs?, Rb?, K? partially coeluted). Transition metal

temperature. Optimum temperature: 1 °C; separation within

ions can also be simultaneously eluted because of chelation

determined by atomic emission spectrometry) also included.

Inorganic Cations and Ammonia

100 lL injection loop. Run analysis dependent on column

(K?). Separation in 25 min, with Sr2? and Ba2? (usually

[20] Detection limits between 0.2 lg L-1 (Li?) and 5.4 lg L-1
Non-suppressed [19] Detection limits between 0.25 ng (Li?) and 50 ng (Cs?),

with IDA groups. Separation with 200:1 sodium-to-

Nowadays, ion chromatography is a widely used approach
for the analysis of common inorganic anions (e.g. fluoride,

Separation with 7,000:1 calcium-to-ammonium

chloride, nitrite, bromide, nitrate, phosphate, sulfate).
Conversely, most inorganic cations are usually analyzed by

ammonium concentration ratio is shown

use of spectroscopic methods, for example atomic
absorption (AAS), inductively coupled atomic emission

concentration ratio is possible

(ICP–AES), or inductively coupled atomic emission mass
spectrometry (ICP–MS) which are considered the preferred
choices in routine analysis. This is in facts true for the
listed primary contaminants of drinking water which are
basically transition metal ions. However, some regulated
methods (ASTM US-EPA) use IC for the analysis of
Ref. Comments

inorganic cations (sodium, potassium, calcium, and mag-

nesium) and ammonium in rain water, wet precipitation,
and wastewater [1, 2], because IC is a straightforward,
simple, and selective method for the simultaneous analysis
of these cations [3].
(indirect mode)

external water
Conductometric
conductivity

In the last decade, it has become increasingly clear that

with CSRS

samples characterized by diverse concentration ratios of

Detection

mode

adjacent peaks are of common occurrence, mainly among

environmental matrices. A typical case is given, for
example, by sub-surface brines [4], seawater [5], waters
intended for human consumption, treated or from wells,
where, for instance, low amounts of NH4? ion and high
Ions studied (injection volume)

Mg2?, Ba2?, Sr2? (10 lL)

concentrations of Na? can be present. Because traditional

Li?, Na?, NH4?, K?, Ca2?,
Li?, Na?, NH4?, K?, Rb?,

cation exchangers (sulfonic [6], carboxylic [7–10] or

Cs? (20 or 100 lL)

silica-gel [11]) have similar selectivity for Na? and

NH4?, sufficient resolution is not achieved during anal-
ysis if the concentrations of these ions are too different
and if alkaline earths should also be monitored within the
same run.
Zr-based silica columns, although proved to be suitable
(mL min-1)

for the simultaneous separation of alkali metal cations and

Flow rate

ammonium ion (tartaric acid as eluent) in river and rain

water samples [12] (sodium to ammonium ratio about 30),
0.7
1

have the disadvantage that selectivity problems are

encountered when matrices containing ions at higher
26 mM MSA with step

Na?:NH4? concentration ratios have to be analyzed.

pH 2.75 with HNO3

0.5 mM 18-crown-6,

change at 9 min to
10 mM 18-crown-6,

Significantly better results were obtained by Kadnar

gradient from

60 mM MSA

[13], who achieved analysis of a waste water sample

containing 600 mg L-1 Na? and 0.28 mg L-1 ammonium,
with excellent resolution, by use of a sulfonic-based col-
Eluent

umn (IonPac CS10) (Fig. 1), although alkaline earths

cannot be eluted within the same run.
The problem posed by analysis of small amounts of
Silica-based derivatized

ammonium in the presence of excess of sodium ions, and

IonPac CS12A 5 lm

Ion-exchange group:
with iminodiacetic
Table 1 continued

functional groups
(250 9 4.6 mm)

phosphonic acid

vice versa as typically found in power-industry samples,

carboxylic and
(150 9 3 mm)

was generally faced by acting on the characteristics of

stationary phases which control the selectivity of the sep-
Column

arations. This in turn gave an appropriate boost to evolu-

tion of the technology of chromatographic packing

123
 Table 2 Chromatographic approaches for analysis of PGEs
Chromatographic
support details
123
AG50 W-X8, BIO-RAD, 200–400
mesh (18 9 1.5 cm)
AG1-X8, BIO-RAD, 100-200 (1 ml)
PC88A (2-ethylhexylphosphonic acid
mono-2-ethylhexyl ester)
IonPac AG11 (50 mm 9 4 mm)
IonPac AG11 (50 mm 9 4 mm)
S18
Separation Type of Elements Detection Interferents evaluated Ref. Comments
mechanism coupling studied
Cation Off-line Ru, Pd, Re, ICP–MS Zr, Mo, Hf, W [33] Spectral interferences retained even after ion
exchange Ir, Pt, Os chromatography are reduced by solvent extraction
with N-benzoyl-N-phenylhydroxylamine (BPHA)
in chloroform. Analysis of PGEs and Re in some
geochemical reference materials are shown
Anion Off-line Re, Os, Pt, ICP–MS Zr, Hf [34] Geological samples digested in Carius tubes. Os is
exchange Pd, Ir, Ru separated by extraction in CHCl3 from inverse
aqua regia (5 HNO3: 2 HCl). Acidic solution is
loaded into the anion-exchanger. Zr and Hf are
removed by elution with 0.8 M HNO3 and
1 M HF-HCl. Ir is reduced to ?3 oxidation state
by 0.1 M H2SO3 and then eluted by 2 M HCl. Pt is
eluted by 6 M HCl. Ru and Re are eluted by
4 M HNO3 and Pd by 12 M HNO3
Complexation Off-line Pt(IV), Fe, Al ICP–OES – [43] Metals in HCl solutions are loaded into the resin.
The effect of HCl concentration on the recovery of
metal ions is studied. Differently from Fe and Al,
Pt does not exhibit adsorption
Anion On-line Pt(II), Pt(IV) ICP–MS Hf, Fe, Cu, Zn, Pb [36] Eluent: 75 mM NaClO4, pH 1.4 by HCl. Flow rate:
exchange 0.5 mL min-1. Post column dilution by HNO3 is
required before ICP–MS analysis. The feasibility
of Pt speciation is shown for extracts of road dust
samples. Easily extractable metals from road dust
(Fe, Cu, Zn) elute as a single peak (void volume).
Hf elutes with the void and does not interfere with
the determination of the separated Pt species. A
mathematical HfO-correction is necessary for
determination of total Pt in the extracts. Detection
limits: 0.4 and 1.0 lg L-1 for Pt(II) and Pt(IV),
respectively, (40 ll injection loop)
Anion On-line Pt, Pd ICP–MS Y, Cu, Zr, Zn, Hf, Gd, [37] Gradient elution: 0–3 min 0.14 M HNO3,
exchange Tb, Ga, Sr, Mo 18 mM H2C2O4; 3–4 min to 1.5 M HNO3; from 4
to 9 min 1.5 M HNO3. Flow rate: 1 mL min-1.
Limits of quantification: 425 ng L-1 (Pd) and
9 ng L-1 (Pt), 250 lL injection loop. Analysis of
Pd and Pt in PM10 samples are shown. Spectral
interferences are resolved by chromatographic
separation
M. C. Bruzzoniti et al.
 Table 2 continued
Chromatographic Separation Type of Elements Detection Interferents evaluated Ref. Comments
support details mechanism coupling studied

Acclaim 120, 5 lm, Reversed On-line Co, Ni, Pd UV–Vis Mo, V, Ag, Sn(IV), Cd, Zn, [38] HPLC is hyphenated to SPME by a specially
(25 9 4.6 mm) phase (310 nm) Cr(III), Pb(II), Cu(II) designed interface with an injection loop of 50 lL.
Metal ions are extracted with 0.5 ml 0.02%
morpholine-4-carbodithioate, 30% NaCl, on a non-
bonded PDMS fibre (100 lm film thickness) for
30 min. After 15 min desorption, analytes are
directly injected. Eluent: acetonitrile–water
(60:40). Flow rate: 0.8 mL min-1. Pd detection
limit: 60 ng L-1.
Acclaim 120, 5 lm, Reversed On-line Cu, Co, Ni, UV–Vis Mo, V, Ag, Sn(IV), Cd, Zn, [39] HPLC is hyphenated to SPME as reported in Ref.
(25 9 4.6 mm) phase Pd (390 nm) Cr(III), Cr(VI), Pb(II) [38]. Metal ions are extracted with 0.5 mL 0.1%
2-thiophenaldehyde-3-thiosemicarbazone (pH 8)
prepared in methanol on a non-bonded PDMS fibre
(100 lm film thickness) for 35 min. After 15 min
desorption, analytes are directly injected. Eluent:
acetonitrile–water (65:35). Flow rate:
0.8 mL min-1. Pd detection limit: 7 ng L-1
IonPac AS4 (250 mm 9 4 mm) Anion On-line Pd UV–Vis Pt, Rh, Ir, Ru, Cu, Mn, Zn, Ni, [40] A post column reagent (50 mM KI,
exchange (407 nm) Fe, Pb 1.6 mM Na2SO3, 10 mM HCl) is used. Coupling a
The Challenging Role of Chromatography in Environmental Problems

preconcentration step by anion-exchange (AS11),

detection limits of 300 ng L-1 are achieved. High
concentrations (removable with 0.6 M H3PO4) of
Fe interfere
TSKgel G2500 PWXL, Size- On-line Pt, Pd, Rh ICP–SF- Sr, Rb, Cu, Pb [41] Eluent: 10 mM NaCl. Flow rate: 0.75 mL min-1
300 9 7.8 mm exclusion MS Detection limits: 1.3 pg mL-1, 1.9 pg mL-1,
0.8 pg mL-1 for Pt, Pd, Rh, respectively (50 lL
sample loop). Bioaccumulation of PGEs in grass is
shown
XK 16/70 column packed with Size- On-line Pt ICP–MS – [42] Eluent: phosphate buffer. Flow rate: 1 mL min-1.
Superdex 200 exclusion Detection limit: 15 ng g-1 (in 0.2 g of animal
tissue). A study on the bioavailability of Pd
particles is shown
ICP–OES, inductively coupled plasma optical emission spectrometry; ICP-SF–MS, inductively coupled plasma sector field mass spectrometry
S19

123
 Table 3 Main chromatographic approaches for analysis of HAAs
S20

Column Eluent Flow rate Analytes studied Detection Ref. Comments

(mL min-1) (injection volume)

123
BetaMax Acid (A) 3.5 mM CH3COOH– 0.2 MCA, MBA, MIA, DCA, TCA, ESI–MS (MRM) [47] T = 40 °C. Separation within 12 min (k = 2.9–7.9). Limits
(250 9 2.1 mm) 20 mM CH3COONH4, pH 5.3 DBA, BCA, BDCA, CDBA, of quantification between 1.0 (BCA) and 222 lg L-1
(C12 with polar TBA (50 lL) (MCA)
embedded groups) (B) CH CN Acidification increases k, but suppresses the signal. Higher
3

Gradient from 10% to 73% B over 7 min, CH3CN increases the signal but CDBA and TBA coelute.
kept constant for 5 min, and then This is a problem not resolved by MS. In fact, their
increased to 100%B over 1 min, and kept precursor ions [CDBA-H]- and [TBA-COOH]- both have
constant for 0.5 min. m/z 251 and both can produce Br as product ion. CDBA
interferes with TBA determination. Matrix effect observed
(ion suppression) if tap water is concentrated
UPLC bridged ethyl (A) 5 mM HCOOH–10 mM HCOONH4, 0.5 MCA, MBA, MIA, DCA, TCA, ESI–MS–MS [47] T = 25 °C. Separation within 2 min (k = 1.3–4.3). Limits
hybrid HILIC pH 4.1 DBA, BCA, BDCA, CDBA, (MRM) of quantification between 0.4 (DCA) and 10 lg L-1
column TBA (30 lL) (MCA)
(2.1 9 100 mm), (B) CH CN
3 Sample must be diluted in 90% CH3CN. Direct water
1.7 lm injection worsens peak shape. The beneficial effect of
Gradient from 90% to 80% B in 2 min.
CH3CN in improving the signal is reduced by the need for
dilution. Several peaks coelute. Same interference problem
in TBA determination because of CDBA, as with the C12
column. Matrix effect (ion suppression) observed if tap
water is concentrated
IonPac Cryptand A1 Gradient elution: -8 to 3 min 0.5 MCA, MBA, DCA, TCA, DBA, Conductometric [49] Separation in 25 min. After 25-fold preconcentration,
(150 9 5 mm), 10 mM NaOH; t = 3 min 10 mM LiOH BCA, BDCA, CDBA, TBA, F-, with ASRS- quantitation limits for HAA5 are between 1.5 (MBA) and
5 lm Cl-, Br-, NO2-, NO3-, SO42-, Ultra (external 10 lg L-1 (DCA)
3-
Functional group: PO4 (25 lL) water mode)
cryptand 2.2.2.
IonPac AS24 Gradient elution: -7 to 18 min 0.3 MCA, MBA, DCA, TCA, DBA, ESI–MS–MS [50] Post-column solvent: 100% acetonitrile at 0.3 mL min-1;
(250 9 2 mm) 7 mM KOH; 18–36.5 min 18 mM KOH; BCA, BDCA, CDBA, TBA (100 (MRM) eluent suppression required (ASRS 300, 2 mm, external
Ion exchange group: t = 36.6 min 60 mM KOH lL) water mode); matrix diversion to the waste (min): 17–22
alkanol quaternary (for Cl- removal) and 33–41 (for Br-, NO3-,CO32-,
ammonium ion SO42- removal). Column temperature:15 °C; autosampler
temperature: 8 °C; Separation in 55 min. Minimum
detection limits were 0.1–1.0 lg L-1 for the HAA9 in a
-1
250 mg L-1 Cl-, 250 mg L-1 SO2- 4 , 150 mg L
HCO3-, 30 mg L-1 NO3-, matrix. DCA showed the best
sensitivity and DCBA and CDBA showed the least
sensitivity
IonPac AS11-HC 100 mM ammonium nitrate 1 BrO3-MBA, DBA, BCA, BDCA, ICP–MS [51] Separation within 50 min. Detection limits were 0.16
(250 9 4 mm) CDBA, TBA (500 lL) (m/z) = 79 (MBA)–0.36 (TBA) mg L-1. The effect of Br- ion on the
Ion-exchange group: response of BCA was studied. At 75 mg L-1 Br-, a
alkanol quaternary pretreatment with OnGuard-Ag and OnGuard-H cartridge
ammonium ion is required. Br- concentration decreases up to 55 lg L-1
and does not interfere with BCA determination
M. C. Bruzzoniti et al.
The Challenging Role of Chromatography in Environmental Problems S21

Missouri river water) range between 0.40 (MIA) and 3.28

Na? background noise. Separation in 15 min. Detection of

before analysis. Mono, di, and tri-chloroacetic acids cannot

materials. As an example, advances in column design led to

Detection limits included within 0.3 (BCA and DBA)–24

ASRS (autosuppression external water mode) to reduce
the marketing of dedicated columns, namely IonPac CS12,

chlorinated and brominated HAAs as 35ClO and 79Br.

[53] Separation in 43 min. Only sample filtration is required

[52] Before ICP–MS, eluent is driven into one or better two

be detected. For HAAs, detection limits (evaluated in

CS15 [14], and CS16 [15], of high capacity (2.8 meq for
4 mm 9 250 mm CS12 and CS15 columns and 8.4 meq
for 5 mm 9 250 mm CS16 column) and incorporating
carboxyl groups as cation-exchange sites. Among the col-
umns listed above, IonPac CS15, besides carboxylic
functionality contains phosphonic and crown ether groups
that enhance selectivity among adjacent peaks [16],
through the complexation of cations, with complexation
being largely dependent on the size of the hydrophilic
(BDCA) lg L-1 cavity of the crown ether in relation to the ionic radius of
(TCA) lg L-1

the analytes.
Ref. Comments

Saari-Nordhaus and Anderson [17] showed that by use

of two different columns connected in series (Fig. 2a), one
carrying a conventional carboxylate cation exchanger and
the other carrying a crown ether (18-crown-6), the resolu-
tion between sodium and ammonium and between ammo-
nium and potassium can be increased substantially
compared with each single column (Fig. 2b, c). In fact, in
Detection

the crown ether column, coelution of Li?, Mg2? and Ca2?

MCA, MBA, DCA, BCA, DBA, ICP–MS

ICP–MS

(not complexed by the crown ether) is observed, whereas

the conventional cation-exchange column is suitable only
CIA, BIA, BCA, BDCA, DBCA,
TCA, MBDCA, MCDBA, TBA,

BrO3-, IO3-, Br-, I- (100 lL)

for cation separation when they are present at approxi-

MCA, DIA, MBA, DBA, TBA,

mately the same concentration. The improvement obtained

by the use of the two columns is due to the exploiting of
two different retention mechanisms, cation exchange
(mL min-1) (injection volume)

and complexation that increases the retention of sodium,

Analytes studied

Cl- (150 lL)

potassium, and ammonium, thus increasing resolution. In

the same run, ethanolamine and triethanolamine can be
also separated. Nevertheless, negative system peaks asso-
ciated with Na?, K?, and NH4? are observed. The two
stationary phases may also be mixed and packed into a
Flow rate

single column and the selectivity of the cations can be

adjusted by changing the ratio of the carboxylate cation
1

exchanger to the crown ether packing. In such a case, the

Ion-exchange group: 15% B for 3 min; up to 50% B over 5 min;
for 9 min followed by a linear gradient to

up to 100% B over 18 min; 100% B for

20–100 mM in 0.1 min, 100 mM KOH

system peaks are not observed. When placing the crown

ether column before the cation-exchange column, separa-
Gradient elution: 20 mM for 3 min,

tion for a sodium-to-ammonium ratio equal to 5,000 can be

(A) H2O; (B) 200 mM NH4NO3

obtained.
Another effective way of improving resolution between
sodium and ammonium is to alter the selectivity through
20 mM in 5 min

secondary equilibria in the mobile phase. This is usually

achieved by adding an appropriate reagent in the eluent
(usually a crown ether). Significant studies were conducted
10 min
Eluent

by Richens et al. [18]) using a CS15 column and 18-crown-

6 ether in eluent containing 10.8 mM H2SO4. The authors
found that the presence of 18-crown-6 in the mobile phase
alkanol quaternary
Table 3 continued

IonPac AS11-HC

significantly modifies the retention times of cations that are

ammonium ion

ammonium ion
(250 9 4 mm)

(250 9 4 mm)
group: alkanol

complexed with this ligand in water (K?, Sr2?, NH4?). In

Ion-Exchange
IonPac AG16

quaternary

particular, the retention of Sr2? is reduced when the con-

Column

centration of 18-crown-6 ether is increased. Several

mechanisms affecting the retention times of the cations on

123
S22
Fig. 1 Separation of ethanolamines by use of a sulfonic-based
cation-exchanger (IonPac CS10). Solution 1 1 mg L-1 monoethanol-
amine (MEA), 10 mg L-1 K?, 2 mg L-1 diethanolamine (DEA).
Solution 2 1 mg L-1 Li?, 5 mg L-1 NH4?, 1 mg L-1 Rb?,
5 mg L-1 monomethylethanolamine (MMEA), 50 mg L-1 methyld-
iethanolamine (MDEA). Wastewater 5 lg L-1 Li?, 600 mg L-1
Na?, 0.04 mg L-1 MEA, 2.7 mg L-1 K?, 2.5 mg L-1 DEA,
0.28 mg L-1 NH4?, 2.2 mg L-1 MMEA, 88 mg L-1 MDEA and
alkaline ions (not eluted). Reprinted from Ref. [13]
Fig. 2 Adjustment of selectivity among cations by use of crown ethers
in the stationary phase. Eluent: 3 mM methanesulfonic acid. Flow rate:
1 mL min-1. Column: a experimental crown ether, 250 mm 9
4.6 mm, and Alltech Universal Cation, 100 mm 9 4.6 mm connected
in series; peaks: (1) Li?, (2) Na?, (3) NH4?, (4) Mg2?, (5) Ca2?, (6) K?,
123
M. C. Bruzzoniti et al.
the columns are elucidated and the retention behaviour of
the analytes is explained accordingly.
Because the ammonium ion was retained for longer and
the sodium ion peak remained virtually unchanged, the
separation of Na? and NH4? at concentration ratios as high
as 60,000:1 was possible in the presence of 10 mM
18-crown-6 ether. At high sodium content (600 mg L-1),
the detection limit for ammonium is 0.0023 mmol L-1.
A silica-based column functionalized with iminiodi-
acetic acid, characterized by ion-exchange properties and
strong chelating abilities, was used by Haidekker and
Huber [19] with a mobile phase containing 10 mM
18-crown-6 ether, and HNO3 (pH 2.75). Under these
conditions, the separation of 0.5 mg L-1 NH4? in the
presence of 100 mg L-1 Na? and K? (T = 1 °C) was
achieved. Exploiting the chelation ability of the IDA
column, besides the cation-exchange mechanism provided
by the carboxyl functionality, and the complexation of
18-crown-6 ether, the separation of alkali and transition
metal ions can be achieved if 1.5 mM dipicolinic acid is
added to the eluent.
By using a concentration of 18-crown-6 ether as low as
0.5 mM with a methanesulfonic acid-based eluent, Bruz-
zoniti et al. [20] recently achieved the separation of Li?,
Na?, K?, Ca2?, Mg2?, Ba2?, Sr2?, and ammonium ion by
gradient elution on a CS12A column. The use of this car-
boxylate-functionalized cation-exchange column enabled
inclusion of the determination of barium and strontium in
the same run. These two cations are generally determined
by means of ICP techniques by laboratories in charge of the
control of water quality. In a comparison between the
(7) Na? system peak, (8) NH4? system peak and (9) K? system peak.
b Alltech Universal Cation, 100 mm 9 4.6 mm; peaks as for
a. c Experimental crown ether, 250 mm 9 4.6 mm, peaks: (1) Li?,
Mg2?, Ca2?, (2) Na?, (3) NH4?, (4) K?. Reprinted from Ref. [17]
The Challenging Role of Chromatography in Environmental Problems
Fig. 3 Analysis of NH4? by purge-and-trap ion chromatography.
a Configuration of the purge-and-trap system. NPG N2 pressure
gauge, FRG flow rate gauge, NP N2 purifier, RB recirculation bath, AS
sample, PV purge vessel, TV trap vessel. b Analysis of seawater
samples by coastal sites of Taiwan (Kengting, Hsinchu, Hwalien).
Reprinted from Ref. [2]
performance of the traditional cation-exchange approach
(without any secondary equilibria involved) and the pro-
posed one, for quantification of ammonium in different
water samples (well, tanks, water systems), the authors
show how the traditional method fails to determine
ammonium in some of the samples considered. Because the
selectivity of the column is altered by the presence of the
crown ether in the eluent, NH4? ion elutes after Ca2?.
Separation with 7,000:1 calcium-to-ammonium concen-
tration ratio is possible.
It is well known that, among environmental matrices,
analysis of brines by IC is complicated by the high ionic
strength of the sample and by the presence of the large
amount of sodium chloride in the sample, which hampers
the quantification of minor constituents. Schijf [21]
observed that the high Na? content may reduce the accu-
racy of determination of K? in brine samples. Recently
Wang et al. [22] presented an elegant alternative approach
for the analysis of NH4? in high-salinity samples using a
purge-and-trap device. Ammonium concentrations as low
as 1.3 lg L-1 can be detected, completely avoiding the
interference of Na? ion. In detail, the sample solution is
S23
added to an acceptor solution (10 M NaOH). A purified
flow of N2 is used to purge the ammonia formed which is
trapped in a 1.5 mL trap vessel containing a pre-selected
volume of doubly de-ionized water (Fig. 3a). Subse-
quently, 0.5 mL doubly de-ionized water in the trap vessel
is withdrawn with a syringe and immediately injected into
the ion chromatography system (column: IonPac CS16,
250 9 5 mm, eluent 45 mM methanesulfonic acid, flow
rate 1 mL min-1, detection suppressed conductivity with
CSRS in the recycling mode). Analysis of NH4? in dif-
ferent seawater samples performed by this method are
shown in Fig. 3b.
Table 1 summarizes the characteristics of the methods
discussed above.
Pt Group Elements (PGEs)
Interest in the elements of the Pt group is because of their
extensive use in several applications, e.g. drugs, food
production, and, to a large extent, in automotive catalytic
converters. Consequently, an increase in their concentra-
tion in the environment, mainly water and air, is expected
[23]. Recent studies on PGE toxicity, environmental bio-
availability and concentrations in biologically relevant
media indicate that environmental exposure to these metals
may pose a health risk, especially at a chronic, subclinical
level [24]. Interest in monitoring PGEs at low levels has,
therefore, recently grown, and, at the same time, since the
development of sensitive techniques, for example induc-
tively coupled plasma mass spectrometry (ICP–MS),
determination of ultratrace amounts of PGEs has particu-
larly increased in environmental analysis. Cathodic strip-
ping voltammetry for Pt and Rh and ICP–MS for Pt, Pd and
Rh are practically the only techniques capable of achieving
the necessary detection limits in matrices such as road dust,
plants, tree bark, aquatic microorganisms, and airborne
particles [25, 26].
Concerning air particulate matter, it is widely agreed
that difficulties in determination of PGEs come from the
heterogeneous composition of samples and from the low
concentrations to be detected. Nevertheless, interesting
speculation can be made according to PGEs or other metal
ions content. For example, a Pt/Rh ratio of approximately
4.0 agrees with that of the more commonly used gasoline
car catalyst, whereas a high Pt content in airborne samples
is usually encountered when the Pb, Ce, Zr, and Hf content
is also high; in such a case, traffic has been identified as the
common source of these pollutants [25].
Determination of PGEs by ICP–MS is hampered by
spectral interferences from various elements. For example
179
Hf16O? is an interfering species in 195Pt determination,
and Pd determination is plagued by substantial molecular
123
S24 M. C. Bruzzoniti et al.

required, because of the several steps involved that rarely

attain 100% yields, isotope dilution analyses of the ele-
ments to be analysed must be considered essential.
Starting from a study by Nachtigall et al. [34], who
developed a separation method by LC–UV for the deter-
mination of Pt(II) and Pt(IV) chloro complexes, Nischwitz
et al. [35] modified the original method to achieve on-line
coupling to ICP–MS for Pt speciation in road dust by use of
an anion-exchange column (IonPac AG11 column), a
Fig. 4 Speciation of Pt by IC-ICP–MS. Analysis of a road dust
extract spiked with 25 lg L-1 Pt(II) and 25 lg L-1 Pt(IV). For
75 mM NaClO4 eluent (pH 1.4 by HCl, flow rate
elution conditions see text. Reprinted from Ref. [35] 0.5 mL min-1), and post-column dilution with HNO3.
Although interference by HfO? does not affect quantifi-
interferences arising because of the presence of Cu, Y, Zn, cation of Pt species, because Hf elutes at the void volume
Cd, Mo, Zr, Sr, and Pb. (Fig. 4), a mathematical HfO-correction was shown to be
When using quadrupole-ICP–MS (Q-ICP–MS) the res- required for determination of total Pt in the extracts of road
olution of the technique is, often, not sufficient for dis- dust. Detection limits of 0.4 and 1.0 lg L-1 can be
crimination between PGEs and their interferences. obtained for Pt(II) and Pt(IV), respectively. Other easily
Typically, mass interferences are corrected with a mathe- extractable metals from the road dust (i.e. Fe, Cu, Zn) elute
matical model [27, 28], on a daily basis [29] for each kind as a single peak close to the void volume, and the huge
of sample but this model does not provide satisfactory broad peak obtained for Pb is ascribed to the formation of
results for all masses and kinds of samples. Alternatively, PbCl3- or PbCl42- species in the eluent.
instruments such as high-resolution magnetic sector-field In the same year, Bruzzoniti et al. [36] developed an
ICP–MS (HR-ICP–MS) are used. Here, polyatomic inter- IC-ICP–MS method to determine Pt and Pd content in
ferences are reduced by working with high mass resolution PM10 particulate matter. They first evaluated the perfor-
(m/Dm = 3,000 or 7,500), this is not possible with Q-ICP– mance of five anion exchangers (IonPac AG4A-SC, AG10,
MS [30], but even this technique might not provide satis- AG11, AG15, AG16) in the separation of Pt and Pd species
factory results. in the presence of their common interferents found in
For these reasons, alternative or, at least, additional particulate material from brakes, silencers, and catalytic
approaches are required for removal of isobaric inter-
ferences.
An interesting but time-consuming approach has been
presented by Alsenz et al. [31] who used a reductive co-
precipitation step of Pd by Hg in combination with a col-
lision gas technique in ICP–MS to minimize interferences
in the determination of Pd in particulate matter, with a
calculated limit of determination of 0.05 pg Pd m-3
Chromatographic equilibria, either before or in-line with
the ICP–MS analysis is a reliable way of overcoming
spectral interferences.
Because the affinity of PGEs for cation exchangers is
low for samples solubilized with acids (HCl, HNO3), cat-
ion-exchange purification can be used to remove major
metal ions before ICP–MS analysis. It has been shown [32]
that a further purification step by solvent extraction using
N-benzoyl-N-phenylhydroxylamine in chloroform limits
interference from Zr, Mo, Hf, and W in the subsequent
ICP–MS analysis. Conversely, if an acidic solution (aqua
regia) of PGEs is loaded on to an anion-exchanger [33],
appropriate eluents can be used to fractionate elements, Fig. 5 Analysis of Pd in a simulated digested BCR sample (estuarine
removing Hf and Zr and selectively eluting Pt, Ru, Re, and sediment) by IC. Column: IonPac AS4. Eluent: 1.1 M HCl,
0.1 M HClO4. Flow rate: 1.3 mL min-1. The efficacy of the addition
Pd. Ir is most effectively eluted from the anion-exchange
of H3PO4 in reducing Fe interference is shown (a). The interference is
column if it is reduced to the ?3 oxidation state with removed by washing the preconcentrator (IonPac AG11) with 1 mL
0.1 M sulfurous acid. When a separation procedure is 0.6 M H3PO4 (b)

123
The Challenging Role of Chromatography in Environmental Problems
converters (for 105Pd: 89Y16O?, 40Ar65Cu?, 91Zr14N?,
68
Zn37Cl?; for 195Pt: 179Hf16O?, 40Ar155Gd?, 36Ar159Tb?).
The optimized method (low-capacity AG11 column and
gradient elution from HNO3–oxalic acid to HNO3) enabled
quantification of Pd and Pt at 425 and 9 ng L-1 respec-
tively, in digested atmospheric particulate samples (approx.
140 lg m-3 PM10). This gradient has been programmed to
switch from a complexing eluent to an acidic one that
ensure complete elution of metal ions from the column.
Worthy of mention is the approach of Kaur et al. [37],
who proposed the sorption of metal complexes of Co(II),
Ni(II), and Pd(II) with morpholine-4-carbodithioate on
polydimethylsiloxane (PDMS) fibre from aqueous solution
followed by desorption in the desorption chamber of solid
phase microextraction–high-performance liquid chromatog-
raphy (SPME–LC–UV) interface. Reversed-phase high-
performance liquid chromatography using acetonitrile–water
(40:60) as eluent on a C18 column has been used to achieve the
separation; a detection limit of 60 ng L-1 was achieved for
Pd(II). A detection limit of approximately one order of
magnitude lower (7 ng L-1 Pd) was achieved by the same
authors using the same approach [38] but a different ligand
(2-thiophenaldehyde-3-thiosemicarbazone).
One of the very first approaches for on-line preconcen-
tration and analysis of Pd was presented by Bruzzoniti et al.
[39]. The method proposed is characterized by its simplicity
in the instrumental design required. In fact, post-column
derivatization with KI is coupled before spectrophotometric
detection (k = 407 nm) after the IC separation which is
accomplished by anion-exchange (1.1 M HCl, 0.1 M HClO4
eluent, flow rate 1.3 mL min-1) Among the interferences
evaluated (Pt, Rh, Ir, Ru, Cu, Mn, Zn, Ni, Fe, Pb), Fe, Ru, and
Pt have appreciable absorbance at 407 nm, but only Fe can
be eluted as a chromatographic peak under the optimized
separation conditions. Fe is a problem in Pd determination if
it is present at unbalanced concentration ratios. The method
proposed was tested on a BCR reference material of estua-
rine sediment containing 46.3 mg g-1 Fe and 0.5 lg g-1
Pd. Working on a synthetic solution of the same composition
as the digested BCR sample a procedure was optimized to
remove interference from Fe; in particular, 0.6 M H3PO4
was added (Fig. 5a) and washing of the preconcentrated
substrate with 1 mL phosphoric acid solution (Fig. 5b) was
performed after the loading of the sample on to the precon-
centrator. Application of the optimized procedure to analysis
of the digested BCR sample provided a Pd content of
0.47 lg g-1 (RSD 5.6%), in good agreement with the cer-
tified value.
The power of chromatography in conjunction with the
high detection capabilities of sector-field ICP–MS was used
by Lesniewska et al. [40] who exploited size-exclusion-
equilibria (TSKgel G2500 PWXL, eluent: 10 mM NaCl, flow
rate 0.75 mL min-1) to identify the presence of PGEs
S25
species with different molecular masses in leaf and root
extracts of a forage plant (Lolium multiflorum), by a direct
coupling wih ICP–MS.
Still focussing our attention on the coupling of size-
exclusion chromatography and ICP–MS, Artelt et al. [41],
after growing ultra-fine Pt particles (approx. 4 nm), studied
their bioavailability showing that C90% of the bioavailable
platinum was bound to high-molecular-weight compounds
(80–800 kDa), probably proteins; samples such as rat
plasma, and cells from bronchoalveolar lavage were con-
sidered. Separation was achieved with a phosphate buffer as
eluent (flow rate 1 ml min-1) on a Superdex 200 column.
An interesting application recently appeared for the
selective removal of Al(III) and Fe(III) interferences by a
resin containing 2-ethylhexylphosphonic acid mono-2-
ethylhexyl ester with low affinity for Pt(IV) [42].
Table 2 summarizes the characteristics of the methods
discussed above.
Organic Anions: Haloacetic Acids
Haloacetic acids, halogenated derivatives of acetic acid,
can be found in water intended for human consumption as a
result of the reaction between organic material naturally
occurring in raw waters (humic, fulvic acid) and chlorine
during the disinfection process [43] in potabilization plants.
The haloacetic acids are the second largest group of dis-
infection by-products (DBPs) generated during water dis-
infection and their presence has been linked to possible
threats to human health.
When bromide ions are present in water, bromoacetic
acids and mixed chloro and bromoacetic acids can also be
found. In addition, when iodide ions are naturally present
in source water, iodo-acids (which are now listed within the
emerging DBPs) are formed.
Most of the analytical methods available include the nine
Cl and Br cogeners (the so-called HAA9): monochloroace-
tic, monobromoacetic, dichloroacetic, trichloroacetic,
dibromoacetic chlorobromoacetic, chlorodibromoacetic,
dichlorobromoacetic, and tribromoacetic acids, even if only
the first five haloacetic acids listed above are currently reg-
ulated (and are known under the acronym HAA5). The
maximum contaminant level for HAA5 is set at
0.060 mg L-1 by the Stage 2 Disinfection Byproducts Rule
(71 FR 388, January 4, 2006).
Analytical methods 552 and 552.2 approved by the EPA
are based on liquid–liquid extraction of the analytes by
tert-butyl methyl ether from the acidified sample and on
gas chromatographic separation with electron-capture
detection (GC–ECD). Acidification of the sample is
required to protonate the haloacetate ions (e.g. the pKa of
mono, di, and trichloroacetic acids are 2.86, 1.3, and 0.66,
123
S26
respectively) and to enhance extraction recoveries. An
additional derivatization step is necessary before GC
analysis because HAAs are highly polar and of low vola-
tility. HAAs are usually converted into short-chain esters
using different reagents, for example diazomethane, acid–
alcohol, or BF3–methanol. The basic methods have been
fine-tuned by several researchers [44, 45].
In the last decade, liquid chromatography (LC) has
emerged as a promising alternative technique for HAAs
determination, as an answer to the cumbersome procedure
required by the GC analysis.
Chen et al. [46] recently compared two LC separation
methods coupled with tandem mass spectrometric detec-
tion for analysis of the HAA9 and the emerging HAA
monoiodoacetic acid. The methods discussed are based on
reversed-phase or hydrophilic interaction liquid chroma-
tography (HILIC) mechanisms. In the reversed phase
approach, a C12 column with embedded polar groups
(BetaMax Acid) was used with gradient elution (eluent A:
3.5 mM CH3COOH–20 mM CH3COONH4, pH 5.3; eluent
B: CH3CN; gradient from 10 to 73% B over 7 min, kept
constant for 5 min, and then increased to 100% B over
1 min, and kept constant for 0.5 min). Interference of
chlorodibromoacetic acid (CDBA) with the analysis of
tribromoacetic acid (TBA) cannot be resolved by MS. In
fact, their precursor ions [CDBA-H]- and [TBA-COOH]-
both have m/z 251 and both can produce Br as product ion.
A matrix effect (ion suppression) has been observed if tap
water is concentrated. The same interference problem and
matrix effect has been also observed when the HILIC
mechanism was used. In such work, the column (Acquity
UPLC BEH HILIC) had 1.7 lm bridged ethyl hybrid
(BEH) particles and 1.8 lm high-strength silica (HSS)
particles and a gradient elution was programmed (eluent A:
5 mM HCOOH–10 mM HCOONH4, pH 4.1; eluent B:
CH3CN gradient from 90 to 80% B in 2 min).
Fig. 6 Determination of haloacetic acids in tap water by IC after
preconcentration. Column: Cryptand A1. Eluent: -8 to 3 min
10 mM NaOH; t = 3.1 min 10 mM LiOH. a Tap water, b tap water
spiked with haloacetic acids. A pictorial schematic diagram of eluent
sites versus time is also given
123
M. C. Bruzzoniti et al.
Fig. 7 Diagram of divert valve placement in the sample path in the
instrumental set-up for analysis of HAAs by IC–ESI–MS–MS
Despite the better performance of HILIC in terms of
detection limits (0.08–2.73 lg L-1) in comparison with the
reversed-phase approach (0.18–71.5 lg L-1), analysis by
the HILIC mechanism requires dissolution of the water
samples in 90% acetonitrile before injection, resulting in
sample dilution.
Among liquid chromatography-based methods, those
relying on IC mechanisms are almost the majority and
are the most promising, with the result that EPA recently
adopted IC for Method 557 [47]. The detection limits
that can be achieved are mainly dependent upon the
detection technique coupled to IC. Suppressed conduc-
tivity, electrospray ionization mass spectrometry (ESI–
MS), MS–MS, and ICP–MS are the detection techniques
usually used.
The most significant improvements achieved by IC in
the determination of HAA5 and HAA9 were recently col-
lected and compared by Bruzzoniti et al. [48]. In the same
paper these authors studied, for the first time, the separation
of HAA9 in the presence of drinking water interferents
(F-, Cl-, Br-, NO3-, NO2-, SO42-, PO43-), by use of a
macrocycle-based column containing cryptand 2.2.2 mol-
ecules. Cryptand 2.2.2 molecules host and strongly bind
those cations whose diameter is compatible with their inner
diameter; in this way an anion exchanger is obtained.
Differently from a traditional anion-exchange column, the
capacity of a cryptand column can be modulated simply by
changing the type of cation (or its concentration) inside the
macrocycle, just acting on the eluent composition. Typical
eluents that can be used with this column are LiOH, NaOH,
and KOH, because the alkali metals have different com-
plexation constants with the cryptand 2.2.2. molecules. The
advantage of such an approach is that reduced analysis time
can be achieved. By coupling preconcentration of the
acidified sample by solid-phase extraction on a reversed
phase support (LiChrolut EN), quantitation limits of
The Challenging Role of Chromatography in Environmental Problems
1.5–10 lg L-1 can be achieved using the most conven-
tional, and inexpensive, detection approach, i.e. suppressed
conductivity. Elution is accomplished by use of the
gradient -8 to 3 min 10 mM NaOH; t = 3 min 10 mM
LiOH. Analysis of a tap water sample by this method is
shown in Fig. 6; the type of alkali–cryptate complex
formed inside the stationary phase during the chromato-
graphic run, reflecting the capacity of the column, is also
depicted.
A high-capacity anion-exchange column (IonPac AS24,
250 9 2 mm, 140 leq column-1) to be used with MS or
MS–MS detection [49], was specifically designed by Dio-
nex (USA) for analysis of HAA9. The IonPac AS24 col-
umn proved suitable for analysis of HAAs in the presence
of high matrix content (250 mg L-1 Cl-, 250 mg L-1
SO2-
4 , 150 mg L
-1
HCO3-, 30 mg L-1 NO3-) and for
analysis of bromate and of the organochlorine herbicide
Dalapon, with the gradient composition -7 to 18 min
7 mM KOH; 18–36.5 min 18 mM KOH; t = 36.6 min
60 mM KOH. The instrumental configuration, shown in
Fig. 7, requires a three-way valve, positioned after the
separation column, for diversion of the matrix ions (Cl-,
SO2- - -
4 , HCO3 and NO3 ) to avoid their inlet into the MS
system (ESI–MS–MS, negative polarity, in multiple reac-
tion monitoring (MRM) mode) and a secondary pump to
deliver acetonitrile after the IC suppressor and before the
ESI inlet. It has been shown that addition of CH3CN
improves sensitivity from three to tenfold depending on the
analyte. Detection limits ranging from 0.1 to 0.7 lg L-1
can be achieved. This approach is the basis of US EPA
Method 557.
IC coupled with inductively coupled plasma-mass
spectrometry (IC–ICP–MS) has been used for HAAs
determination [50, 51] at tenth of lg L-1 levels. The recent
interest in the emerging DBPs led researcher interest
toward the development of methods capable of discerning
new analytes in treated waters. In this regard, Shi and
Adams [52] recently proposed a fast, sensitive method for
simultaneous detection of iodoacetic and bromoacetic
acids. By coupling IC with ICP–MS, the authors consid-
ered monochloroacetic, diiodoacetic, monobromoacetic,
dibromoacetic, tribromoacetic, chloroiodoacetic, bromoi-
odoacetic, bromochloroacetic, bromodichloroacetic, and
dibromochloroacetic acids, including also inorganic anions
(bromate, iodate, bromide, and iodide). The advantages of
the method are that no complex sample preparation is
required, except sample filtration, and that detection limits
for natural water range from 0.33 to 0.72 lg L-1 for iodine
species and from 1.36 to 3.28 lg L-1 for bromine species.
One limitation is that mono, di, and trichloroacetic acids
cannot be detected.
The potential of chromatographic techniques has also
been exploited by Wang and Zhu [53] in environmental
S27
chemistry to elucidate the fate of HAAs when drinking
water is delivered through galvanized pipes. The authors
show that in the presence of Zn, sequential dehalogenation
of HAAs is induced, and all the brominated acetic acids are
transformed into acetate ion, and that monochloroacetic
acid is the final product for the dehalogenation of trichlo-
roacetic and dichloroacetic acids.
Table 3 summarizes the characteristics of the methods
discussed above.
Conclusion
This paper shows how powerful ion chromatography is as a
tool for the analysis of cations in complex matrices, and
how it is increasingly evolving as an alternative or at least
as a complementary tool to other approaches, for example
AAS, ICP–AES and ICP–MS, which have long been
regarded as the analytical techniques of choice.
The basic application of IC to the analysis of inorganic
anions has gradually progressed to organic anionic species
also, not only to comply with regulation requirements in
environmental protection and control, but also to enable
comprehension of the source, reactions, and fate of pollu-
tants in our environment.
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