Spectrochimica Acta Part B 59 (2004) 755 – 792
www.elsevier.com/locate/sab
Review
Gas chromatography/plasma spectrometry—an important analytical
tool for elemental speciation studies
Jorgelina C.A. Wuilloud a,b, Rodolfo G. Wuilloud a,b, Anne P. Vonderheide a, Joseph A. Caruso a,*
b
a
Department of Chemistry, University of Cincinnati, P.O. Box 0172, Cincinnati, OH 45221-0172, USA
U.S. Food and Drug Administration (FDA), Forensic Chemistry Center, Cincinnati, OH 45237-3097, USA
Received 8 August 2003; accepted 28 March 2004
Abstract
In this review, a full discussion and update of the state-of-the-art of gas chromatography (GC) coupled to all known plasma
spectrometers is presented. A brief introductive discussion of the advantages and disadvantages of GC – plasma interfaces, as well as types
of plasmas and mass spectrometers, is given. The plasma-based techniques covered include inductively coupled plasma mass spectrometry
(ICP-MS) microwave-induced plasma optical emission spectrometry (MIP-OES), and inductively coupled plasma optical emission
spectrometry (ICP-OES). Also, different variants of plasma sources, such as low power plasmas and glow discharge (GD) sources, are
described and compared with respect to their capabilities in elemental speciation. Recent advances and alternative mass analyzers (collision/
reaction cell; time-of-flight; double-focusing sector field) are also mentioned. Different aspects of the GC – plasma coupling are discussed
with particular attention to the applications of these hyphenated techniques to the analysis of elemental species. Additionally, classical and
modern sample preparation methods, including extraction and/or preconcentration and derivatization reactions, are presented and evaluated.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Review; Gas chromatography; Plasma spectrometry; ICP; MIP; Glow discharge; Speciation
1. Introduction
Speciation studies are useful and recognized tools for
environmental, geological, biological and clinical studies.
Because bioavailability, mobility, and ultimately, toxicity,
are strongly dependent upon the physical and chemical form
of an individual element, total elemental concentration may
be uninformative and even misleading regarding any positive or negative effects. The analytical performance of any
speciation method is related to its selectivity and sensitivity.
The use of ‘‘hyphenated’’ techniques for speciation studies
normally describes the coupling of a powerful separation
step, such as liquid chromatography (LC), supercritical fluid
chromatography (SFC), capillary electrophoresis (CE), or
gas chromatography (GC), with a suitable detector using
plasma source atomic spectrometric techniques such as
inductively coupled plasma mass spectrometry (ICP-MS)
* Corresponding author. Tel.: +1-5135569306; fax: +1-5135569239.
E-mail address: [email protected] (J.A. Caruso).
URL: http://www2.uc.edu/plasmachem/default.html.
0584-8547/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2004.03.009
[18,47,78,83,86,125,143,146,152,165,182,185,188], microwave-induced plasma optical emission spectrometry (MIPOES) [10,41,56,75,76,124,130,158], or inductively coupled
plasma optical emission spectrometry (ICP-OES) [2,66,84].
Publications of the last years show that the number of
reports employing the GC – ICP-MS coupling has increased
dramatically, as presented in Fig. 1. The high resolving
capacity of GC and the high sensitivity capability of ICPMS have made the combination most efficient and attractive
for speciation analysis of metallic and non-metallic elements
in environmental, industrial, and biological samples. The
high sensitivity and low detection limits obtained with ICPMS justify the major use of this technique compared to other
plasma-based detectors (Fig. 2). This fact is reflected in the
predominant number of publications using ICP-MS as an
elemental detector for GC, as shown in Fig. 1. Although an
important number of publications involving the use of ICPMS as an elemental detector for GC exist in the literature,
alternative plasma sources have been applied to fulfill the
same purpose (Fig. 1). Therefore, the development and
application of GC coupled to element-specific detection
756
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
Fig. 1. Frequency of reports on gas chromatography – plasma spectrometry
coupling applications.
involving the use of different plasmas sources, fundamentally ICP, MIP and glow discharge (GD), is presented and
discussed in this review.
This paper also reviews the many applications of plasma
source-based spectrometers as GC detectors for speciation
of metallic and non-metallic elements in environmental,
food and biological samples. The scope and limitations of
the different techniques emerging from GC – plasma spectrometry couplings are discussed. Since interfacing of GC to
plasmas is one of the most critical points in the performance
of this hyphenated technique, an analysis and critical discussion is briefly given. Likewise, the sample preparation
steps are crucial in speciation analysis (avoiding the transformation of the original elemental species present in the
sample and the formation of artifacts) in an effort to obtain
accurate and reproducible results. Finally, a summary of the
applications involving the use of GC – plasma spectrometers
published in the last 10 years is shown with particular
emphasis on the most recent research.
because of their efficient pre-concentration of the analyte
[6,7,188]. However, the high temperatures produced in a
high power atmospheric pressure argon ICP do not allow
one to obtain molecular information as atomization and
ionization are predominant in this plasma source. Additionally, due to the low degree of ionization of non-metallic
elements (e.g., carbon, phosphorus, sulfur and halides)
obtained with ICP, its application to biological, geochemical, and environmental studies involving these elements is
limited. Other problems emerge from isobaric interferences
due to the presence of polyatomic ions and chemical and
physical effects, which produce modification of spectral
intensities leading to erroneous measurements.
Consequently, to resolve these issues generated from the
use of ICP sources, other types of plasma sources have been
employed. These sources include MIP and reduced pressure
ICP with the use of helium instead of argon due to the
higher ionization energy of helium (24.6 eV) in comparison
to argon (15.8 eV) and minimal plasma gas based polyatomic interferences [10,18,57,142]. Low-power MIPs are
formed at lower temperatures than argon ICPs and therefore,
liquid samples cannot be introduced as these plasmas are
extinguished by even small amounts of solvent vapor.
However, the coupling of GC to MIP may have advantages
over GC –ICP. The most important is the higher ionization
energy obtained with a helium-MIP, which enables quantification of metals and semi-metals as well as other organic
compounds containing elements with high ionization potentials [69,163,164]. Other advantages of the MIP are the
small dead volume of the discharge tube and the compatibility of the plasma with the low carrier gas flows used in
capillary GC columns, which together make it selective and
often (e.g., for selenium and for most elements with atomic
masses lower than 80) less subject to interference than the
more sensitive ICP-MS system [99,100]. Fig. 2 shows that
limits of detection are at least two orders of magnitude better
for GC – MIP-OES than GC – ICP-OES. There is no doubt
that these properties were responsible for the worldwide
2. Plasma spectrometers for gas chromatographic
detection
Asx may be observed in Fig. 1 and Table 1, the use of
ICP-MS demonstrates extensive growth in the number and
variety of applications for speciation analysis of metallic
and non-metallic compounds in environmental and biological samples. Also, several publications have shown that
using ICP-MS as a detector for capillary GC [130,173] can
yield detection limit improvements in comparison with
MIP-OES (Fig. 2). An additional gain in sensitivity can be
achieved for volatile species-forming elements by using
automated, simple and low cost purge-and-trap injectors
Fig. 2. Range of detection limits for hyphenated gas chromatography –
plasma spectrometry methods.
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
757
Table 1
Summary of GC – plasma spectrometric methods for speciation studies in various samples matrices
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
Anaerobic
environments
AsH3, MeAsH2,
Me2AsH and Me3As
ICP-MS
Non specified
[53]
2000
Waste solids
MeAsH2, Me2AsH
and Me3As
ICP-MS
Non specified
1999
Gaseous
emission
from soil
Arsine and
trimethylarsine
ICP-MS
Non specified
1998
Gas samples
from sewage
treatment
AsH3, MeAsH2,
Me2AsH, Me3As,
MeAs(O)(OH)2,
Me2As(O)(OH) and
Me3As(O)
ICP-MS
Non specified
The effect of CO2 on the ICP-MS
was monitored by the use of indium
as an internal standard. Volatiles of
Sn and Sb also speciated.
HG and low temperature GC used to
investigate soils contaminated with
different types of wastes. Sn, Ge, Sb,
Bi and Se were also speciated.
Soil samples were equilibrated in a
microcosmos experiment and
HR-ICP-MS used to study the arsenic
species in the gaseous emissions.
HG – GC – ICP-MS used to study the
formation of ionic and volatile
arsenic compounds produced in a
batch culture of an anerobic
methanogen.
Waste solids
Me3Bi
ICP-MS
Non specified
Gas samples
from waste
deposits
Me3Bi
ICP-MS
Non specified
Br
2002
Sewage sludge
ICP-MS
2002
Seawater
2000
Synthetic samples
Polybrominated
biphenyl ethers
(BDE-28, BDE-47,
BDE-85, BDE-99,
BDE-100, BDE-128,
BDE-153, BDE-154)
CH3Br; C2H5Br;
2-CH3H7Br;
CH2Br2; CHBrCl2;
CHBr2Cl;
CH2BrI; CHBr3
Bromobenzene;
1-bromoheptane;
benzyl bromide
2000
Synthetic samples
1999
Seawater
1998
Crude oil;
sludge deposit
1997
Polluted
ground water
As
2001
Bi
2000
1994
[81]
[138]
[188]
HG – low temperature GC used to
investigate soils contaminated with
different types of wastes. Sn, Ge, Sb,
Bi and Se were also speciated.
Low temperature GC was used for
separation. Volatiles of Sn, Hg, Ar,
Sb and Te were also speciated.
[81]
1 – 4 pg as Br
Helium was used as an optional gas.
[182]
ECD/ICP-MS
10 pg as Br
Simultaneous ECD/ICP-MS
detection permitted determination of
the association of halogens to organic
matter.
[152]
(LP-RP)ICP-MS
4.2 – 11 pg
[185]
Bromoform;
bromobenzene
ICP-TOF-MS
3 – 9 pg
CH2BrCl; C2H2Br2;
CHBrCl2; C2H4BrCl;
CHBr2Cl;
1,2-C2H4Br2; CHBr3
1,4-dibromobenzene
MIP-OES
0.01 – 0.04 ng
Molecular ions for all three species
were obtained as well as some
characteristic alkyl chain fragments
for 1-bromoheptane.
Use of GC was coupled to a directcurrent GSGD ionization source to
analyze halogenated hydrocarbons by
mass spectrometry.
Volatile halogenated organic
compounds were determined using an
automated purge and trap GC system.
MIP-MS
37 pg as Br
MIP-MS
Non specified
Bromine-containing
contaminants
Use of a microplasma ion source: a
radio-frequency plasma contained
inside the last 4 – 5 cm of a 0.32 mm
i.d. fused silica capillary column.
Interfacing GC directly with a MIP
torch and quadrupole MS provided
information about elemental
compositions.
[46]
[70]
[155]
[20]
[142]
(continued on next page )
758
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
Crude oil;
chimney soot
Polybrominated
biphenyls
(rf)ICP-OES
1 – 5 pg
[9]
1997
Synthetic samples
Dibromobenzene
(LP)ICP-MS
229 pg
1994
Synthetic samples
Dibromobenzene
ICP-OES
0.9 – 3.1 pg
1993
Synthetic samples
1-bromononane
(LP)ICP-MS
Non specified
1990
Motor car
exhaust gases
HBr; CH3Br;
C2H3Br; C2H4Br2
MIP-OES
Non specified
1990
Synthetic
samples
CHBrCl2;
CHBr2Cl;
CHBr3
MIP-OES
4 pg
A GC system with on-column radio
frequency plasma AED was applied
for the determination of PBDEs.
Enhancement of all analyte molecular
and fragment ion signals by adding
isobutene.
The measuring of bromine was
performed using 827.2, 863.9 and
889.8 nm spectral lines.
Generation of a low pressure Ar
ICP-MS without modifying the torch
box of a commercial ICP-MS
instrument.
Separation and determination of the
bromine species within 10 min. The
bromine detection was performed at
470.49 nm.
Coupling of GC system to MIP to
determine traces of nonmetallic
elements that are not traditionally
determined by OES.
Synthetic
samples
Alcohols; aromatic
hydrocarbons
ICP-MS
0.001 – 400
ng s-1
Atomic mass spectra from organic
compounds containing B, Br, Cl, Si,
P, O, I, N and S were obtained. The
compounds’ atomization was nearly
complete and independent of
molecular structure.
[27]
Environmental
gases
Volatile cadmium
ICP-MS
0.27 pg
Calibration using an aqueous solution
for quantitation of volatile element
species. Volatile species of Ge, As,
Se, Cd, Sn, Sb, Te, I, Hg, Pb and Bi
were also speciated.
[47]
Seawater
CH2BrCl; CHBrCl2;
CH2ClI; 1,2-C2H4BrCl;
2,1-C3H6BrCl; CHBr2Cl;
1,3-C3H6BrCl
Endosulfan I; dieldrin;
4,4V-DDE; endrin;
endosulfan II;
4,4V-DDD; 4,4V-DDT
Hexachloroethane
ECD/ICP-MS
50 pg as Cl
[152]
MP-MS
30 – 190 pg
as Cl
MP-MS
0.35 pg
as Cl
GD-ICPTOF-MS
5 – 24 pg
Comparison of different detectors for
the GC separation. The lowest
detection limits were obtained with
ECD detection.
Molecular fragmentation of a mixture
of VOCs was demonstrated by
placing the GC column at the plasma
expansion stage.
The mechanisms of negative ion
formation and breakdown were
discussed.
The elemental ratio (35Cl/12C)
permitted the differentiation of
several chlorinated hydrocarbons.
(HC)GD-OES
3 pg s
MIP-OES
0.03 – 0.12
ng as Cl
Br
1997
C
1987
Cd
1997
Cl
2002
2000
Petroleumcontaminated
reference soil
2000
Synthetic
samples
2000
Synthetic
samples
1999
Synthetic
samples
1999
Seawater
1-chloropentane;
1-chlorohexane;
1-chloroheptane;
1-chlorooctane;
1-chlorononane;
1-chlorodecane; chloroform
1-bromo-3-chloropropano
1-bromo-2-chloroethane and
dichloro-methane
CH2BrCl; 1,2-C2H4Cl2;
C2HCl3; CHBrCl2; C2H4BrCl;
C2Cl4; CHBr2Cl
1
A hollow cathode glow discharge
was used as an ionization source.
Brominated analytes examined as
well.
Determination of coeluting
halogenated alkanes using OES and
ECD.
[119]
[127]
[45]
[12]
[1]
[191]
[19]
[70]
[151]
[155]
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
759
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Cl
1998
Synthetic samples
Carbon tetrachloride;
chlorobenzene and
chloroform
ICP-OES
10 fg s
1998
Synthetic samples
MIP-TOFMS
100 fg
1998
North sea crude
oil; sludge from
Nickel refinery
Polluted ground
water; pesticide
mixture
Chlorobenzene
1-chloropentane and
p-chlorotoluene
1,3,5-trichlorobenzene
MP-MS
9.7 pg as Cl
PCBs; 15 chlorinated
pesticides
MIP-MS
1 ng as Cl
1997
1
Comments
Ref.
A (LP-RP)ICP was used as an
emission source for chlorine to
overcome the large dilution of the GC
effluent with the plasma gas when
utilizing conventional ICP.
Oxygen or helium added to the MIP
at values up to 1% were found to
increase sensitivity for chlorine.
An alternative ionization source to CI
and EI is presented in this work.
[84]
The design and application of the
GC – MIP interface demonstrated to
be comparatively simpler than for
GC – ICP-MS.
The detection was found not to be
structure-dependent. Arochlor 1260
was analyzed in this work.
The addition of nitrogen increased
plasma stability and improved the
detection limits of chlorobenzene.
Seven ‘‘indicator’’ PCBs in biotic
matrices were evaluated. Detection of
chlorine was performed at 479 nm.
A low-pressure helium plasma was
used for the ionization of chlorine due
to the helium’s higher ionization
energy (He: 24.6 eV; Ar: 15.8 eV).
Suppression of peak tailing, high
selectivity as well as repeatability by
doping the (rf)ICP with oxygen.
The systems presented good
sensitivity for the determination of
phosphorus, sulfur, chlorine and
bromine in GC eluates.
[122]
[20]
[142]
1997
Crude oil;
chimney soot
Polychlorinated biphenyls
(rf)ICP-OES
1 – 5 pg as Cl
1997
Synthetic samples
Chlorobenzene
(LP)ICP-MS
100 pg
1995
Freshwater fish;
Cow bioptic fat
MIP-AED
0.54 pg as Cl
1994
SRM 2261
PCB 28; PCB 52; PCB 101;
PCB 118; PCB 153; PCB 138;
PCB 180
Chloroheptane,
chlorobenzene and
chlorinated pesticides
(LP)ICP-MS
10 pg
1994
Synthetic samples
Trichlorobenzene
(rf)ICP-AED
1.1 pg as Cl
1993
Supelco pesticide
mixture
Chlorotoluene;
chloronaphtalene
RP-MIP-MS
2 – 10 pg as Cl
Combustion
effluents
Cu – CuSO4 or CuSO4H2O
ICP-MS
Non specified
The samples were analyzed by low
temperature GC. Volatile species of
Se, Hg and Sn were also determined.
[125]
F
2000
Synthetic samples
1-fluoronaphthalene
MP-MS
12 pg as F
[20]
1998
North sea crude oil
1-fluoronaphthalene
MP-MS
6.1 pg as F
1994
Synthetic samples
Trifluoronitrotoluene
(rf)ICP-AED
13 pg as F
1994
Synthetic samples
Fluoroethers
MIP-AED
0.82 ng as F
1983
Rat blood plasma
Metabolites of
2-(Heptadecafluorooctyl)
ethanol
MIP-OES
Non specified
The interference at m/z 19 (H3O+) in
the positive detection mode was
avoided by working in the negative
mode.
Difficulties in the selective
determination of F were observed
when the m/z 19 isotope was utilized.
A H2 + O2 mixture was found to be
efficient to avoid peak tailing for
fluorine.
Fluorine and oxygen were
simultaneously monitored in the
plasma at 775 nm and 777 nm
emission lines, respectively.
A MIP-OES was interfaced to GC
utilizing a dual column system;
parallel detection using FID or ECD
to MIP-OES detection was employed.
Cu
2002
[9]
[119]
[73]
[25]
[127]
[160]
[20]
[127]
[72]
(continued on next page )
760
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
F
1980
Synthetic samples
Benzene trifluoride and
o-fluorotoluene
ICP-OES
1 Ag
The quantitative fluorine response
was found to be independent of
molecular species, yet proportional to
fluorine content.
[59]
Crude oil,
SRM 1580,
SRM 1582
Fortified water
and harbor
sediment
Alkylphenols derviatized by
ferrocene carboxylic acid
chloride
Ferrocene
ICP-OES
0.05 pg s
[148]
ICP-MS
3.0 pg s
Alkylphenols in nonpolar matrices
were derivatized; each phenol
molecule labeled with one Fe atom.
Volatile organo-metallic compounds
of Sn and Ni also speciated.
Ge
2001
Human urine
GeH4 and MeGeH3
ICP-MS
2 – 12 pg l
[88]
2000
Soils
GeMeH3, GeMe2H2 and
GeMe3H
ICP-MS
Non specified
2000
Natural waters
GeH4, MeGeH3, Me2GeH2,
Me3GeH and Et2GeH2
ICP-MS
100 fg
HG – low temperature GC was
coupled to ICP. Hydrides and
methylated species of As, Se, Sn, Ab
and Hg were also speciated.
A HG – low temperature GC
hyphenated system was used.
Methylated species of Sn, As, Sb, Bi
and Se were also speciated.
Inorganic and methyl germanium
species were detected in all estaurine
waters investigated. Methylated
species of As, Hg and Sn were also
studied.
TORT-1 lobster
hepatopancreas,
DOLT-2 liver,
DORM-2 dogfish
and CRM 463 fish
Tissue fish,
mountain ice,
DORM-2 dogfish
and CRM 464 fish
PACS-1 and
PACS-2 sediment,
DORM-2 dogfish
TORT-1 lobster
hepatopancreas
and SRM 1566b
oyster, SRM 1646a
estuarine sediment,
SRM 1941a marine
sediment, SRM 1941b
marine sediment,
SRM 1944 waterway
sediments, SRM 1946
lake fish, SRM 1974a
mussel, SR 2974
mussel, SRM 2976
mussel, and
SRM 2977 mussel
Synthetic standards
solutions
MePhHg; Ph2Hg
MIP-OES
0.12 – 0.86
Ag l-1
Organo-Hg speciation by acidic MAE
followed by NaBPh4 derivatization
and HS-SPME prior to GC
separation.
[144]
Hg2 +; MeHg
ICP-TOFMS
1.5 – 20 pg
[94]
MeHg
MIP-OES
f 1.5 Ag kg
Monitoring of Hg isotopes (198, 199,
200, 201, 202) as a tracer of
transformation of MeHg. Use of CT
prior to GC.
Use of a MAE digestion followed by
a derivative step with NaBEt4 and
SPME extraction prior to GC
analysis.
Hg2 +
ICP-QMS
ICP-TOFMS
LODQMS are
5- to 10-fold
LODTOF
Fe
2001
1992
Hg
2002
2002
2002
2002
1
1
1
ICP-QMS stands up in a general
comparison for speciation analysis
purposes.
[85]
[81]
[172]
[175]
[129]
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
761
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Water, sediment and
biological tissue
MeHg; Me2Hg; EtHg;
PhHg; Ph2Hg; Hg2 +
MIP-OES
2002
Natural waters
MeHg; Hg2 +
MIP-OES
0.8 – 1.1 ng l
2002
TORT-2 lobster
hepatopancreas
and DORM-2
dogfish
Brackish water
sediments
Me2Hg; EtHgMe;
Et2Hg; MeHg
MIP-OES
Non specified
MeHg; Hg2 +
ICP-MS
2001
Seawater, river
water, snow
MeHg; Hgo; Hg2 +
ICP-MS
Methylation:
0.1 ng l 1; Demethylation:
0.2 ng l 1
Non specified
2000
Estuarine water
MeHg; Hgo
ICP-MS
2 – 50 pg
2000
Fish tissue and
CRM 464 fish and
DORM-2 dogfish
MeHg
MIP-OES
0.01 – 0.06
Ag g-1
2000
Natural gas
condensate
Me2Hg; MeHgCl; HgCl2;
MeHgCl
ICP-MS
FAPI-MS
2000
DOLT-2 liver
MeHg; Hg2 +
ICP-MS
2 – 8 pg
(ICP-MS);
33 pg
(FAPI-MS)
100 – 600 fg
2000
TORT-2 lobster
hepatopancreas,
DOLT-2 liver and
CRM 463 fish
Marine fish, IAEA
142 fish, NIST 8044
fish and DOLT-2 liver
Rainwater
MeHg
MIP-OES
ICP-MS
MeHg
AFS ICP-MS
MeHg; Hg2 +
ICP-MS
Hg
2002
2001
1999
1999
Detection limit
4.4 ng g 1
(MIP-OES);
2.6 ng g 1
(ICP-MS)
0.9 pg (AFS);
0.25 pg
(ICP-MS)
1999
DOLT-2 liver and
DORM-2 fish
MeHg; EtHg and Hg2 +
(rf)GD-OES
0.2 – 0.3 pg
1998
Natural gas
condensate
DMeHg; DbuHg DBuHg
MIP-OES
FAP-OES
1.5 – 4.7 pg
(LOD
comparables)
1998
Natural gas
condensate
Hgo; HgCl2; DMeHg; MeEtHg;
DetHg; MeHgCl; DBuHg;
EtHgCl
ICP-MS
19 – 340 fg
1
Comments
Ref.
Review of GC – spectrometric
methodologies and also derivatization
techniques for the analysis of
organo-Hg, -Pb and -Sn compounds.
Use of HS-SPME after a
derivatization step prior to GC
analysis. Study of auxiliary gases,
H2, O2 and He, on MIP-OES
response.
By using isothermal MC GC, the
separation of mercury species could
be performed within 45 s.
[130]
Evaluation of the transformation of
MeHg and formation of MeHgBr
during environmental speciation
analysis.
Use of an alternative derivatizing
reagent, NaBPr4, to avoid
transformation of organomercurial
species by halide ions.
HG – cryofocusing-GC method for
simultaneous analysis of organo-As, Ge, -Hg and -Sn after derivatization
with NaBEt4.
Use of an optional derivatizing
reagent, NaBPh4, for organo-Hg
compounds to avoid MeHg
formation.
Synthesis of Me2Hg and MeHg with
isotopically enriched mercury
(198Hg and 202Hg). Performance
study of FAPI-MS as GC detector.
Comparison of derivatization
reagents: Grignard, NaBEt4 and
NaBPr4.
Monitoring of 201Hg2 + isotope as a
tracer of MeHg formed during acid
leaching and subsequent
derivatization with NaBEt4.
Comparative study of ICP-MS and
AFS detector for GC in the analysis
of organo-Hg species.
In situ derivatization of Hg species
and use of TT before GC analysis.
Monitoring of 200Hg2 + isotope as a
tracer of MeHg.
Grignard derivatization was applied
to the organo-Hg species before GC
analysis.
Comparison of performance of both
plasma source-GC detectors.
Molecular NO bands increased the
background in both cases.
Use of a DB-1701 column, pretreated
with HBr, to separate organo-mercury
species chromatographically without
derivatization.
[16]
[149]
[91]
[34]
[172]
[124]
[159]
[55]
[173]
[8]
[82]
[178]
[56]
[167]
(continued on next page )
762
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
DOLT-2 liver and
DORM-2 fish
MeHg; EtHg; Hg2 +
(dc)GD-OES
(rf)GD-OES
1998
Estuarine water
Me2Hg; Et2Hg
ICP-MS
1.3 – 3.0 mg l
(LOD
comparables)
f 0.2 pg l 1
1997
MeHg; Hg2 +
ICP-MS
MeHg; Hg2 +
ICP-MS
1997
IAEA 356 sediment,
CRM S19 sediment
and CRM ‘‘A’’
sediment, DOLT-2
liver, DORM-2 fish,
CRM 463 fish,
CRM 464 fish,
IAEA 086 hair,
IAEA 392 algae
IAEA 356
sediment, DORM-2
fish, DOLT-1 liver
and IAEA 086 hair
Marine sediments
MeHg
ICP-MS
1996
Natural gas condensate
Me2Hg; MeHg and Hg2 +
MIP-OES
1996
PACS-1 sediment
MeHg
MIP-OES
0.24 – 0.56
Ag l 1
0.1 ng g 1
1995
Lake sediments and
IAEA 356 sediment
MeHg; MeHgEt; EtHgEt and
Hg2 +
ICP-MS
1 pg
1995
River sediments
MeHg
ICP-MS
500 fg
Drinking water;
river water
2-iodophenol; 4-iodophenol;
2,4,6-triiodophenol
ICP-MS
0.07 – 0.12
ng l 1
2002
Seawater; air
ECD/ICP-MS
0.5 pg
2000
ICP-MS
0.3 pg as I
2000
Soil samples from
municipal waste
deposits
Synthetic samples
CH3I; C2H5I; 2-C3H7I;
1-C3H7I; CH2ClI; 2-C4H9I;
i-C4H9I; 1-C4H9I; CH2I2
CH3I
Iodobutane
GD-TOFMS
4 pg
2000
Synthetic samples
Iodobenzene; Iodoheptane
MP-MS
0.13 pg as I
1999
Seawater
CH3I; C2H5I; CH2ClI; CH2I2
MIP-OES
11 – 257 pg for
compounds
Hg
1998
1997
I
2003
1
MeHg
increment:
0.25% ; MeHg
reduction: 2%
4.3 ng l 1
Comments
Ref.
Grignard derivatization was applied
to the organo-Hg species before GC
analysis.
Multi-elemental PCT method for the
speciation of organo-metallic com
pounds of Se, Hg, Sn and Pb.
Study of ]MeHg formation during
several extractive techniques by
monitoring 199Hg, 200Hg, 202Hg. Use
of TT prior to GC.
[120]
Study of MeHg formation during
several extractive techniques by
monitoring 199Hg, 200Hg, 202Hg. Use
of TT prior to GC.
Comparison of L/L vs. HS-SPME for
simultaneous determination of
organo-Hg, -Sn and -Pb after in situ
derivatization with NaBEt4.
Use of on-line PT to retain organo-Hg
species after their GC separation.
The 199Hg tracer isotope evidenced
the formation of MeHg during SFE.
Co-extraction of sulfur-compounds
associated with MeHg.
Coupling of PT technique to GC to
analyze organo-Hg species. The
isotopes monitored were 199Hg,
200
Hg, 202Hg.
Simultaneous determination of
organo-Hg, -Sn and -Pb. Use of
NaBEt4 as derivatizing reagent prior
to GC analysis.
Optimization of different optional
gases. Extraction and
preconcentration of iodophenol
species by using SPME.
The coupling of GC to ECD and
ICP-MS detectors is initially
developed.
Multielemental speciation was carried
out using hydride generation before
GC analysis.
A controlled discharge was generated
that allowed switching between
atomic and molecular ionization
modes.
The mechanisms of negative ion
formation and breakdown were
discussed.
A purge and trap system was coupled
to GC – MIP-OES to preconcentrate
haloorganic species.
[6]
[80]
[78]
[111]
[158]
[41]
[79]
[83]
[189]
[152]
[67]
[70]
[21]
[155]
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
763
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
Sea crude oil; nickel
refinery deposited
sludge
Iodobenzene
MP-MS
53 pg as I
[20]
1997
Synthetic samples
Iodobenzene
(LP)ICP-MS
140 pg
1994
Synthetic samples
Iodobenzene
(rf)ICP-AED
1.0 – 2.8 pg as I
1993
Synthetic samples
Iodobenzene
MIP-MS
20 – 100 pg
1990
Synthetic samples
Iodobenzene
(LP)MIP-MS
0.1 pg as I
1989
Synthetic samples
Iodobenzene
MIP-MS
0.16 pg
1987
Synthetic samples
Iodopropane
ICP-MS
1 pg as I
1977
Synthetic samples
1-iodopropane; 2-iodopropane
MIP-OES
0.46 – 0.56 ng
A radio frequency plasma contained
inside a silica capillary column was
presented. Oxygen gas was employed
to avoid carbon deposition.
A (LP)ICP source sustained at 6 W
and utilizing 6 ml min -1 He was
investigated as an ionization source
for molecular and atomic MS.
The elimination of the make-up gas
allowed a 350 kHz radio frequency
plasma to be sustained inside the end
of a fused silica GC column.
Use of reduced-pressure water cooled
MIP torch to interface a GC with the
plasma mass spectrometer.
Utilization of GC to quantitatively
introduce halogenated compounds to
evaluate the over-all system
performance.
Significant improvement in detection
limits in comparison with others
works.
Atomization of injected compounds
was nearly complete and independent
of molecular structure.
Initial studies were developed
regarding the GC – MIP coupling.
Characterization of the method in
terms of linear response,
sensitivity, etc.
In
1998
Air above oil
Me2InH and MeInH2
ICP-MS
Non specified
Samples were collected by
cryofocusing and the separation was
performed with low temperature GC.
Volatile species of Pb, Sn, Hg, Se and
P also speciated.
[126]
Mn
1993
Coals and oil shale
Manganese porphyrins
ICP-MS
0.10 ng
High temperature GC was used for
separation. Ni, Fe, Cu, Zn and V
metalloporphyrins were also
speciated.
[137]
Soil samples from
waste deposits
Mo(CO)6
ICP-MS
0.7 pg
[67]
Fermentation gases
from a municipal
sewage treatment
plant
Gases of waste deposits
Mo(CO)6
ICP-MS
Non specified
Mo(CO)6
ICP-MS
Non specified
A cryotrapping – cryofocusing sample
introduction technique was used for
Mo speciation among Ge, As, Se, Sn,
Sb, Te, I, W, Hg, Pb and Bi
compounds.
A cryotrapping – cryofocusing
method was used for analysis of Mo
species among Ni, Fe and W
carboxylic species.
Different types of species (hydrides,
methyl-) of As, Se, Sn, Sb, Te, Hg,
Pb, Bi were analyzed.
I
1998
Mo
2000
1999
1997
[119]
[127]
[160]
[30]
[112]
[28]
[176]
[48]
[49]
(continued on next page )
764
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
N
1987
Synthetic samples
Alcohols; aromatic
hydrocarbons
ICP-MS
200 ng s
1981
Synthetic samples
Ethylamines and pyridine
ICP-OES
Non specified
Fermentation gases
from a sewage
treatment plant
Fortified water and
harbor sediment
Ni(CO)4
ICP-MS
10 pg
Nidt2
ICP-MS
6.5 pg s
O
1987
Synthetic samples
Alcohols; aromatic
hydrocarbons
ICP-MS
400 ng s
1981
Synthetic samples
Oxygen
ICP-OES
625 ng
P
2003
Drinking water
Diazinon; Disulfoton;
Terbufos; Fonofos
ICP-MS
0.5 Ag l
1998
Air above oil
PH3
ICP-MS
Non specified
1993
Synthetic samples
Triethyl phosphate;
malathion and diazinon
MIP-MS
100 – 200 pg
Pb
2002
Synthetic solutions
Me3Pb; Pb2 +
ICP-MS
ICP-TOFMS
LODQMS are 5
to 10-fold
LODTOF
2002
Water, sediment and
biological tissue
Et4Pb; Me4Pb;
MenEt4 nPb
MIP-OES
ICP-MS
2001
Rain water
Me3Pb; Me2Pb;
Et3Pb; Et2Pb
MIP-OES
ICP-TOFMS
2001
BCR 605-CRM road dust
Me3Pb; Me2Pb;
Et3Pb; Et2Pb
ICP-MS
MIP-OES:
1 – 4.15 pg;
ICP-TOFMS:
3 pg
Not specified
2001
NIST SRM 981
PbEt4
ICP-MS
0.3 – 20 pg
Ni
1999
1992
1
1
1
1
Comments
Ref.
A packed column was used to
separate various nitrogen-containing
organic compounds. High RSD
(18%) obtained for N isotope ratio.
Use of ICP as a nitrogen-specific
detector. Organic compounds
containing B, Br, Cl, Si, P, O, I and S
also speciated.
[27]
Packed column GC was used for
separation of the carbonyls of Mo,
W and Fe.
A GC column length of 5 m was
employed; volatile organo-metallic
compounds of Sn and Fe also
speciated.
[48]
[22]
[85]
Oxygen containing organic
compounds were separated with a
packed GC column. Organic
compounds with B, Br, Cl, Si, P, C I,
N and S were also speciated.
An extended torch design was used to
eliminate atmospheric entrainment
and the effects of this on quenching
and contamination are studied.
[27]
Use of optional gas and collision cell
for enhanced sensitivity of the
organophosphorus pesticides by
GC – ICP-MS.
Plasma stability was monitored
throughout analysis by Xe as internal
standard. Volatile species of Pb, Sn,
Hg, Se and In also speciated.
A water-cooled torch was employed
for the reduced-pressure helium MIP.
Compounds containing Cl, S, Br and
I were also speciated.
[181]
ICP-QMS stands up in a general
comparison for speciation analysis
purposes.
Review of GC – spectrometric
methodologies and also derivatization
techniques for the analysis of
organo-Hg, -Pb and -Sn compounds.
Comparison of pre-concentration
efficiency of organo-Pb compounds
on C60 fullerene and RP-C18 sorbents
prior to GC analysis.
Study of interconversions during
ethyl and butyl derivatization prior to
GC analysis.
202
Hg, 203Tl, 204Pb, 205Tl, 206Pb,
207
Pb and 208Pb isotopes were
monitored simultaneously with a
multicollector ICP-MS.
[23]
[126]
[160]
[129]
[130]
[10]
[44]
[90]
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
765
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
Pb
2001
PACS-2-CRM Sediment
Me3Pb; Et3Pb
rf-(HC)GD-OES
0.15 – 0.03
Ag l 1
[121]
2000
Synthetic solutions
Et4Pb
ICP-TOFMS
1999
Snow and BCR
605-CRM road dust
Me3Pb; Me2Pb;
Et3Pb; Et2Pb
MIP-OES
106 fg
(analog mode);
9 (Ion counting
mode)
77 – 102 fg
Organo-Pb species were extracted
with a SPME fiber and desorbed at
250 jC in the GC injector prior their
analysis.
Multi-elemental comparison of
organo-Sn and -Pb transient signals.
[76]
1998
Water, peat and BCR
605-CRM road dust
Me3Pb; Me2Pb;
Et3Pb; Et2Pb
MIP-OES
43 – 83 fg
1998
Natural water
Me4Pb; Et4Pb
ICP-MS
0.08 pg l
1997
Natural waters
Me3Pb; Me2Pb;
Et3Pb; Et2Pb
ICP-MS
10.1 – 16.1 fg
1997
Water
Me3Pb
ICP-MS
0.19 ng l
1997
MeEt3Pb; Me2Et2Pb;
Me3EtPb;
Me4Pb; Et4Pb
Me3EtPb; Et4Pb
MIP-OES
< 1 Ag l
1995
Gasoline and NIST
SRM 2715 Pb
in fuel
Wet sediments
ICP-MS
100 fg
1995
River Elbe sediments
MeEtPb
ICP-MS
100 fg
1992
Fuel
Me4Pb; Me3EtPb;
Me2Et2Pb;
MeEt3Pb*; Et3Pb
ICP-MS
*0.7 pg s
In situ propylation with simultaneous
extraction of the derivatized species
into hexane prior to GC analysis.
In situ butylation with simultaneous
extraction of the derivatized species
into hexane prior to GC analysis
Multi-elemental PCT method for the
organo-metallic compounds of Se,
Hg, Sn and Pb.
Derivatization with Grignard reagent
after extraction of organo-Pb species
as their diethylditiocarbamate
complexes.
Comparison of L/L vs. HS-SPME for
simultaneous determination of
organo-Hg, -Sn and -Pb after in situ
derivatization with NaBEt4.
Five tetraalkyllead species were
isothermally baseline separated and
quantified within 10 s.
Multi-elemental determination (Hg,
Sn and Pb) using a home-made quartz
heated transfer line for coupling GC
to ICP-MS.
Simultaneous determination of
organo-Hg, -Sn and -Pb. Undesired
ethylation of Pb species by NaBEt4
derivatizing reagent.
Successful coupling of MC-GC –
ICP-MS by developing an interface
and modifying the plasma torch.
S
2002
Plants
Volatile sulfur compounds
ICP-MS
30 – 300 ng l
2001
Breath samples
Sulfur gases and volatile
compounds
HR-ICP-MS
ICP-MS
8 – 33 Ag l
1999
Synthetic samples
D- and L- methionine; a
sulfur-containing amino acid
ICP-MS
Not specified
Sb
2001
Landfill gas samples
SbH3; MeSbH2
ICP-TOFMS
Not specified
Filamentous fungus
cultures
Me3Sb
ICP-MS
f 0.15 pg
1999
1
1
1
1
1
1
[92]
[75]
[6]
[77]
[111]
[131]
[136]
[83]
[86]
The carboxen SPME fiber was found
to best extract the sulfur volatiles. Se
compounds were also speciated.
Saliva was incubated in anaerobic
conditions at 37 jC reproducing an
anaerobic microbiota.
A novel interface was employed. Se,
Pb, Hg and Sn were also speciated.
[106]
A comparative study between
ICP-QMS and ICP-TOFMS for the
determination of antimony species.
Identification of the species was
based on retention time. A sample of
Me3Sb was generated by NaBH4
reduction of Me3SbCl2.
[71]
[146]
[117]
[7]
(continued on next page )
766
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
Standing rainwater;
aqueous fungus extract
SbH3; MeSbH2; Me2SbH;
Me3Sb;
ICP-MS AAS
0.1 ng
(ICP-MS);
4 ng (AAS)
[87]
Landfill and sewage
sludge fermentation gases
Me3Sb
ICP-MS
EI-MS-MS
0.3 pg
(ICP-MS);
0.2 ng
(EI-MS(2))
Hydride organo Sb species were
generated before GC analysis.
Pleurotus flabellatus cultures used in
studies.
Complementary use of ICP-MS and
EI-MS-MS to speciate volatile
organo-metallic and metalloid com
pounds after CT-GC separation.
Lupine, yeast, Indian
Mustard and garlic
Me2Se, Et2Se, Me2Se2
MIP-OES
0.19 – 0.57
Ag l 1
2003
Roasted coffee
Et2Se2, Et2Se,
Ethilmethylselenosulfonate,
Ethilmethildiselenide
ICP-MS
Not specified
2002
Water, sediment and air
from European estuaries
Me2Se, Me2SSe, Me2Se2
ICP-MS
1 pg
2002
Brassica juncea, onion
and garlic
Me2Se, Me2S, Me2S2, Et2S2,
Me2Se2, Et2Se2
ICP-MS
1 – 10 ng l
2002
Plants
ICP-MS
7 – 300 pg l
2002
Biological samples
ICP-MS
0.1 Ag
2002
Water
Me2Se, Me2S, Me2S2, Et2S2,
Me2Se2, Et2Se2, Se-cysteine,
Se-methyonine,
Se-methylselenocysteine,
Se-cystathionine,
Se-methylselenomethionine,
dimethylseleniopropionate
Racemic mixtures of
Se-cysteine, Se-methyonine,
Se-methylselenocysteine,
Se-cystathionine,
Se-methylselenomethionine,
dimethylseleniopropionate,
Se-lanthionine, Seadenosilselenohomocysteine
and g-glutamil
Se-methylselenocysteine
Se-methionine, Se-ethionine
and Se-cystine
ICP-MS
14 – 30 ng l
2001
North Atlantic Ocean
Me2Se, Me2SeS, Me2Se2,
Me2S
ICP-MS
0.8 – 1.2 pg
2001
Yeast
Se-methionine, Se-ethioninerf
(rf)GD-MS
100 – 115 pg
1999
Parental Soluition and
selenized yeast
D;L-Se-methionine
ICP-MS
100 ng 1
Sb
1998
1998
Se
2004
1
1
1
1
[51]
Use of SPME as a sample
introduction technique for
multicapillary GC. Se species found
in plants are different from those
released by them.
Use of SPME to sample the head
space of the roasted coffee grain. Use
of collision/reaction cell in ICP-MS
to improve the figures of merit of the
method.
Use of a purge and cryotrap system as
a sample introduction. Volatile
species of iodine were also studied.
Use of SPME technique to sample the
Se-volatile species from the head
space of several plants. Volatile S
compounds also speciated.
Summary of studies about extraction
of Se-species, cleaning procedures,
separation methodologies and mass
spectrometric techniques.
[37]
Reported chiral speciation studies of
Se-aminoacids in real samples were
reviewed. The coupling GC – ICP-MS
reports better detection limits than
LC-ICP-MS, however needs a
derivatization reaction for the
analysis of Se-aminoacids.
[150]
Commercial SPME fibers were not
rugged in the extraction of the
derivatized Se-amino acids. Sol – gel
chemistry was applied in the
preparation of alternate fibers.
Study of the release of Se-compounds
from the ocean. Use of a purge and
trap system for sample introduction.
Study of the cell pressure and power
effects on fragmentation patterns in a
source characterization. The species
were enzymatically extracted with
Proteinase K.
Methods applied to determine the
purity of L-selenomethionine in
commercial samples and enantio
meric ratio of SeMet in
parenteinase K.
[183]
[105]
[169]
[106]
[118]
[5]
[116]
[107]
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
767
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
Se
1998
Air
Me2Se
ICP-MS
2.5 pg
[126]
1998
Natural waters
Dimethyl selenide and
dimethyl diselenide
ICP-MS
10.0 pg l
1996
NIST SRM 1643b,
BCR CRM 602
Selenate and selenite
ICP-MS
0.02 ng ml
1
Use of a purge and cryotrap system as
a sample introduction. Other species
of Pb, Hg, Sn, In, Ga, P and As were
also analyzed.
It was speculated that the presence of
volatile Se compounds is related to
exchanges between environmental
compartments and anthropogenic
inputs. Volatiles of Hg, Sn and Pb
were also speciated.
A diffusion cell was used to
determine the mass discrimination
factor for the isotope ratio
measurement and to specifically
optimize the plasma conditions.
Synthetic simples
Silylated butanol; pentanol;
hexanol; and heptanol
HR-ICP-MS
100 nmol l
1
Gas and liquid taken
from waste sources
Volatile organic silicon species
including trimethyl Silanol
ICP-OES
Non specified
Water, sediment and
biological tissue
Et4Pb; Me4Pb; MenEt4
MIP-OES
ICP-MS
Non specified
2002
Synthetic samples
TMT; TTET; DBT; TTBT;
DOT; TPhT; TTPhT
ICP-MS
68 – 250 fg
2002
Marine sediment
PACS-2
TBT
ICP-MS
0.09 mg kg
2002
PACS-2 and BCR-646
sediments
TBT; DBT; MBT
ICP-MS
Non specified
2002
Coastal sea-water
TBT; DBT; MBT
ICP-MS
0.09 – 0.27
ng l 1
2002
Sea and river water
MBT; DBT; TBT
MIP-OES
0.4 – 0.6
ng l 1
2002
Marine tissue and
sediment
MBT; DBT; TBT
MIP-OES
10 – 100
ng kg 1
2001
PACS-2 sediment
MBT; DBT; TBT
rf-(HC)GD-OES
75 – 21 ng l
Si
2002
1998
Sn
2002
nPb
1
1
1
The authors speculate on the
applicability of the silylation method
to the analysis of other organic
compounds by HR-ICP-MS, such as
alcohols, amines, acids or ketones.
Low temperature GC was used in the
analysis of gaseous and liquid
samples from waste deposit sites,
waste composting tanks and sewage
disposal plants.
Review of GC – spectrometric
methodologies and also derivatization
techniques for the analysis of
organo-Hg, -Pb and -Sn compounds.
Analysis of high boiling analytes at
only 140 jC. The homemade
interface permitted the injection of
large volumes of solvent.
Both 117Sn and 118Sn were
simultaneously monitored. The HSSPME technique was used to extract
and pre-concentrate TBT from the
sample.
Degradation of organo-Sn species by
using high-MW energy. Ultrasonic
and mechanical extractions did not
show this degradation.
Organo-Sn species were derivatized
with NaBEt4 at pH 5.4 prior to GC
analysis. Both 118/119 and 120/119
isotope ratios were quantified.
A PDMS fiber was selected for the
pre-concentration of the organo-Sn
species by the HS-SPME technique.
Derivatization of butyl-Sn species
with NaBEt4 prior to SPME
extraction and GC analysis.
A signal improvement of 200 times
was obtained with SPME compared
to normal injection.
[6]
[60]
[40]
[66]
[130]
[64]
[190]
[43]
[147]
[16]
[175]
[121]
(continued on next page )
768
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
Table 1 (continued )
Year
Sn
2001
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
PACS-2 sediment and
wastewater sample
MBT; DBT; TBT;
MPhT; PDT;
TPhT
MBT; DBT; TBT;
MPhT; PDT; TPhT
ICP-OES
13 – 32 pg
[3]
FPD; PFPD;
MIP-OES;
ICP-MS
Quasi-dry plasma conditions and a
high helium carrier gas flow rate were
required to obtain good sensitivity.
SPME was used in all cases prior to
GC separation and detection by each
technique.
2001
PACS-2 sediment and
NIES-11 fish
2001
Sediment and seawater
MBT; DBT; TBT;
TBMT; MOT; DOT; TOT
ICP-MS
2001
Aqueous standard; harbor
waters; mussels
TBT; TPhT
ICP-MS
6 – 583 (FPD);
1 – 200
(PFPD);
9 – 415(MIPOES); 0.6 – 20
(ICP-MS)
pg l 1
0.019 – 0.85
pg l 1 (Water)
and 0.23 – 0.48
mg kg 1
(Sediment)
10 fg l 1
2001
Landfill gas samples
SnH4; MeSnH3; Me2SnH2;
Me3SnH; and BuSnH3
ICP-TOFMS
Non specified
2000
PACS-2 and CRM-462
sediment
DBT
ICP-MS
Non specified
2000
Synthetic solutions
TET; TMPT; TMT
(LP-RP)
ICP-MS
0.25 – 0.87 pg
2000
PACS-2; NIES No. 12;
Marine sediment
MBT; DBT; TBT;
TPhT; TPeT
ICP-MS
0.23 – 0.48
ng g 1
2000
Mussels; Potatoes
TPET
ICP-MS
125 pg l
2000
Synthetic solutions
Me4T; Et4T
ICP-TOFMS
11 – 81 fg
1999
Open ocean seawater
Sn; MBT; DBT; TBT; MPhT;
TeBT; TPeT; DPhT; tPET
ICP-MS
510 – 3.0 fg
1999
NIES-11 fish
TBuSnCl; TPrSnCl
(LP-RP)
ICP-MS
4 – 11 pg
1998
Synthetic solutions
TET; TMPT; TBT
(LP-RP)
ICP-MS
0.12 – 0.56 pg
1998
Harbour sediment;
sea water
MBT; DBT; TBT
ICP-MS AAS
0.1 ng g-1
1997
Sea water
MBT; DBT; TBT; MPhT; PDT;
TPhT
MIP-OES
17.7 – 33.4
ng l 1
1996
Harbour water samples
MBT; DBT; TBT
ICP-MS
15 – 21 ng l
1
1
[2]
An extraction procedure for organoSn species including 0.1% tropolone
and 1 mol l-1 HCl-methanol solutions
was applied.
[140]
The authors published the lowest
detection limits ever reported for
these types of compounds.
A CT-GC method was used to
analyze organo-Sn species. The best
precision for 118Sn/120Sn isotopic
ratio was attained in analog mode.
Determination was carried out by
using an 118Sn-enriched DBT spike.
The 118/120 isotopic ratio was used
to quantify DBT species.
Different LODs were obtained
depending on the He/Ar ratio. LOD
values were lower for lower Ar
proportions in the gas mixture.
Comparative study of MAE vs.
ultrasonic extraction. No degradation
of organo-Sn species was reported.
A HS-SPME procedure was applied
to extract organo-Sn species prior to
GC analysis.
Transient chromatographic signals
were collected in a very short time.
Increase in sensitivity by using a
shielded torch. No differences were
found by using different
derivatization procedures.
Ethyl recombination products for
TBT were observed in the mass
spectra and similarity with EI-MS
spectra is discussed.
Tunable fragmentation of tin species
was possible by changing the plasma
conditions such as forward power and
plasma gas flow.
A study of the organo-Sn species
distribution between sediment and
marine water of The Netherlands
coasts.
Tin hydride formation as a
consequence of H2 added. Volatile
hydrides are easily excited thus
improving the sensitivity.
The necessity of applying double
internal standardization, with Bu3
PeSn and Xe gas, was shown.
[180]
[71]
[42]
[110]
[141]
[179]
[92]
[168]
[185]
[184]
[143]
[63]
[35]
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
769
Table 1 (continued )
Year
Sample
Species determined
Detection
technique
Detection limit
Comments
Ref.
Sn
1995
Wet sediments samples
ICP-MS
10 – 20 pg
River sediment
MIP-OES
0.8 pg
A quartz heated transfer line was used
to couple GC to ICP-MS.
Study of auxiliary gases, H2, O2, on
MIP-OES response. A sensitive
dependence of the organo-Sn species
was observed.
[136]
1994
Several ethyltin and
propyltin species
MBT; DBT;
TBT; tetraBT
Te
2000
Gases from domestic
waste deposits
(Me3)2Te
ICP-MS
0.6 pg
Volatiles from waste
deposits
(CH3)2Te
ICP-MS
Non specified
Coals and oil shale
Vanadium porphyrins
ICP-MS
Soil samples from
waste deposits
W(CO)6
1999
Fermentation gases
from a municipal sewage
treatment plant
1997
1994
V
1993
W
2000
Zn
1993
[174]
A cryotrapping – cryofocusing
method was coupled to HG – low
temperature GC. The method was
applied to gaseous, liquid and solid
samples.
Low temperature GC was used in the
analysis of gaseous and condensates
samples. Te species were identified
by boiling point calibration. Volatiles
of Sn, Hg, Ar, Sb and Bi also
speciated.
[67]
0.51 ng
High temperatures were used for the
GC separation. Ni, Fe, Cu, Zn and
Mn metalloporphyrins were also
speciated.
[137]
ICP-MS
< 0.7 pg
[67]
Wo(CO)6
ICP-MS
Non specified
Gases of municipal
waste deposits
W(CO)6
ICP-MS
Non specified
A cryotrapping – cryofocusing
method was coupled to low
temperature GC. The method was
applied to gaseous, liquid and solid
samples.
A cryotrapping – cryofocusing
method was used for analysis of Wo
species as well as Ni, Fe and Mo
carboxylic species.
Different types of species (hydrides,
methyl-) of As, Se, Sn, Sb, Te, Hg,
Pb, Bi were also analyzed.
Coals and oil shale
Zinc porphyrins
ICP-MS
0.14 ng
Ni, Fe, Cu, V and Mn
metalloporphyrins were also
speciated. High temperatures were
used in the GC separation due to the
large molecular weights of the
species.
[137]
commercial success of the GC – MIP-OES system at the end
of the 1980s [41,56,124,158,173].
The capability of low power/reduced pressure plasma
sources when coupled with mass spectrometry for providing
low levels of elemental detection, and in some cases,
structural information, has been documented in the literature
[185]. These experimental plasma sources could be a
valuable addition to current elemental speciation methodologies for which the combination of chromatographic information with a destructive detection method, such as the
conventional ICP, is insufficient for the identification of
[46]
[48]
[49]
some chemical species. Conventional plasma source mass
spectrometry, e.g., a high power (1000 – 1600 W) atmospheric-pressure argon plasma (ICP), has provided enhanced sensitivity and selectivity for organometallic
analyses when compared with electrospray ionization mass
spectrometry (ESI-MS); however, the high power sources
provide no molecular information. Many speciation studies
thus require complementary techniques for qualitative and
quantitative determinations.
As the bulk of glow discharge (GD) applications have
so far been addressed to direct solid sample analysis
770
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
[104], this technique has been minimally applied to the
analysis of gases. Recently, GD has been shown to allow
sensitive detection of organic compounds separated by
GC [95,96,102,103,156,157]. Physical features of a lowpressure GD as a spectrochemical source for OES detection makes the investigation of this source for the analysis
of gases very attractive. The potential of a GD as an ion
source for metal and some non-metal speciation has been
successfully demonstrated for the determination of
organo-metallic compounds of Cl, Hg, Pb, Se and Sn,
separated by GC [116,120,121,151,178]. Analytical properties, along with low cost of acquisition and maintenance, point to GD as an alternative promising detector
for GC.
Another recently developed source is furnace atomization plasma emission spectrometry (FAPES). This capacitively coupled radio-frequency plasma is formed between a
graphite tube and a central electrode. It can be sustained at
atmospheric pressure and combines the advantages of the
graphite atomizer with those of the capacitively coupled
plasma [97,162]. High plasma excitation temperatures
(3500 K) give rise to excellent atomic and molecular emission
sensitivities and the source has also been coupled to MS for
evaluation of organospecies detection. Several physical properties of the FAPES have been characterized, wherein it was
concluded that typical temperatures and electron densities in
this helium plasma are similar to those in a helium-MIP [161].
The detection limits achieved with GC –FAP-OES are comparable to those obtained by GC – MIP-OES and GC – GDOES. However, its coupling to GC is not as simple as in the
former cases. This is reflected by the small number of
applications developed with GC –FAP-OES [65,159].
Most mass spectrometers that have been used with
plasma ionization sources for speciation analysis have been
scanning analyzers, such as the quadrupole (Q) mass filter
and the double focusing (DF) sector-field mass spectrometer. The number of applications using sector-field mass
analyzers [89,90,138,146], also with multiple collectors
[89,90], is still scarce. Some of these reports concerned
the precise measurement of isotopic ratios by GC –ICP-MS
with multicollector detection facility [89,90]. Quadrupole
mass filter and sector-field mass analyzers are scanningbased instruments that measure only a single mass-to-charge
ratio at any given time. Hence, truly simultaneous determination of multiple isotopes is not possible without the
introduction of ‘‘spectral skew’’ when fast transient or
time-dependent signals are analyzed. Time-of-flight mass
spectrometry (TOFMS) has been proposed as an alternative
to overcome these limitations [68]. In ICP-TOFMS, all ions
are simultaneously extracted from the plasma so multielemental and multi-isotope analyses of transient signals
are free of spectral skew. As a result, ratioing can be
routinely performed with high precision. All these features
have made ICP-TOFMS adequate to measure fast transient
signals typically produced by some speciation techniques,
such as GC [10,94,123] and CE [15,29], with excellent peak
definition and ultra-trace sensitivity (Fig. 2). However,
TOFMS instruments as detectors for GC present some
problems, such as (1) the number of acquired mass spectra
per second achievable is noteworthy but the large volume of
information collected makes limitations necessary and (2)
the lower sensitivity in the single ion monitoring mode in
comparison with the latest generation of ICP-QMS.
Recently, two new devices, the shielded torch and
collision/reaction cell, have been developed and implemented in ICP-MS instruments which can be utilized to
reduce problems associated with polyatomic species prior to
the mass analyzer [171]. Excellent discussions of plasma
theory, structures, and applications are available in the
literature [113 –115].
3. GC –plasma spectrometry interfaces
The interfacing of GC with plasma sources, and more
specifically with ICP-MS, is quite straightforward [177].
Basically, the effluent from the GC column must be transported to the inlet of the torch. The main requirement of any
GC – plasma interface is that the volatilized analytes remain
in the gas phase during the transport from the GC column to
the plasma. Therefore, any condensation of the analytes
should be avoided to assure not only no loss of analyte but
also the peak sharpness necessary for high sensitivity and
low detection limits. This is normally achieved by heating
the entire transfer line to avoid any cold regions or by using
an aerosol carrier. In the first approach, the conventional
spray chamber is removed and the transfer line inserted into
the central channel of the torch; here a carrier or make-up
gas flow is also introduced (Fig. 3(a)). Depending on the
volatility of the analyte species, the degree of heating is
varied. In a second device, both an aqueous aerosol and the
GC column effluent are mixed prior to their introduction
into the plasma (Fig. 3(b)).
The main advantage of the use of a transfer line is the
absence of aerosol in the plasma, thereby diminishing
energy losses due to desolvation and vaporization and
leading to high sensitivity, low detection limits and minimal
polyatomic interferences. Since the normal flows used in
GC systems are on the order of a few ml min 1, a make-up
carrier gas flow through the central channel of the torch is
required to allow introduction of the analytes into the
plasma. The addition of Xe gas to the make-up carrier gas
is often used for optimizing the plasma conditions. The
main differences between the different interface designs
within this category are the heating device, coupling and
decoupling, flexibility, and the maximum temperatures
obtainable. Basically, three different interface designs exist,
each depending on the extent of heating along the transfer
line (non-heated, partially heated, and fully heated interfaces) [18]. Non-heated interfaces have been employed for
transporting volatile compounds which were previously
retained and preconcentrated by cryotrapping and released
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
771
Fig. 3. Two of the most common GC – ICP-MS interface designs. (a) Schematic diagram of the commercially available interface (Agilent Technologies). Insets
A – D show cross sections of the interface at different locations. Reproduced from Rodriguez et al. [145] by permission of American Chemical Society. (b)
Typical interface using a spray chamber. Reproduced from Krupp et al. [90].
by thermal desorption [61,126,154,172,186,187]. In this
type of interface, the outlet of the GC column is directly
connected to a T-piece device in which the column effluent
is mixed with a proper flow of a make-up carrier gas. The
advantage of this interface is the simplicity of coupling,
however its use is limited to low boiling point ( < 200 jC)
compounds, as peak broadening can be produced by analyte
condensation in cold regions [186,187]. To increase the
transport of less volatile compounds to the plasma, partially
heated interfaces may also be used [8,14,36,39,
85,86,93,136]. This design assumes that the GC effluent is
sufficiently hot and will not condense on the non-heated
regions as it passes through the transfer line. Despite the
simplicity of these interfaces, the materials employed for the
construction and the limited heating along the transfer line
limit the working temperature and generate peak broadening
[14,93]. Consequently, although the partially heated interface design was promising in the beginning of its development, its applicability to high boiling point compounds was
not possible. Furthermore, a common problem of previous
interface designs was that the part of the transfer line
occupying the central channel in the torch could not be
efficiently heated, which thus generated cold regions, leading to peak broadening or even analyte loss by condensation. Therefore, fully heated interfaces allowing the GC
capillary to be as close as possible to the plasma were
proposed [137,141,145,167,168,182,189] (Fig. 3(a)). The
commercial design manufactured by Agilent Technologies
772
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
is based on the use of a 1-m flexible and resistively heated
transfer line housing the capillary. A 10-cm metallic transfer
line replaces the normal position of the central channel
inserted into the torch (Fig. 3(a)). The make-up carrier gas is
previously heated by passing through a 1-m 1/16 in. coil
placed inside the GC oven. Thus, the make-up carrier gas
flows in the space between the GC capillary and the internal
wall of the heated transfer line. This type of interface design
has broadened the applicability of the GC –ICP-MS technique for the determination of many different volatile
compounds due to the possibility of working at temperatures
as high as 325 jC [106,182,189].
Interface designs employing a transfer line connected to
the tip of the central channel force the disassembly and
reassembly of the conventional sample introduction system
for ICP. Additionally, variations in the plasma conditions
can be observed as a result of the chromatographic effluent
composition. This has been alleviated to some extent by
constant monitoring of Xe added to the make-up carrier
gas flow [167,168]. However, continuous introduction of
an internal standard, required frequently for isotope dilution, cannot be performed by using these interfaces.
Therefore, different approaches have been proposed that
circumvent the removal of the spray chamber, allow
constant internal standard introduction and avoid the inconvenience of switching the assembly to analyze liquid or
gaseous flows [17,50,134,135,138]. In most of these publications, an aqueous aerosol, formed in a regular introduction system with a concentric nebulizer and a spray
chamber, is mixed with the GC effluent by means of a Tpiece connection (Fig. 3(b)). Consequently, both the analytes in the gas phase and an internal standard in the
aerosol can be simultaneously mixed and transferred to the
plasma. However, the disadvantage of this device is
the loss of plasma energy due to the desolvation of the
aerosol. This produces higher detection limits as opposed
to utilizing the same GC – ICP-MS technique, but measuring of the analytes in dry plasma conditions.
4.1. Solid-phase micro-extraction (SPME)
Solid phase microextraction (SPME) is an inexpensive
and solvent-free technique that gives a ‘‘quasi on-line’’
process from the sample preparation to the analysis. Since
1992, SPME has been successfully applied to the extraction
of numerous trace pollutants such as organic forms of lead
[111,121], mercury [111,144,175] and tin [111,121,179].
High enrichment factors are obtained, facilitating the analysis of organometallic compounds at trace and ultra-trace
levels, as required in environmental controls [109]. The
SPME technique consists of the sorption of the analytes
originally in solution or a headspace gaseous phase onto the
surface of a microfiber coated with a proper sorbent. This
system is incorporated in a microsyringe or a suitable
holder. After a specific sorption time, the analytes are
desorbed from the microfiber by heating in a GC injection
port. Many applications of SPME for extraction/preconcentration of elemental species in environmental, biological,
and food samples have been published in the literature
[2,32,38,65,105,109,179,183,189,190]. The main advantages of the use of SPME are the small amount of solution
required, low cost, compatibility with on-line analytical
techniques, solvent free, and fast desorption of the analytes.
The most dramatic advantages of SPME exist at the
extremes of sample volumes. Because the set-up is small
and convenient, coated fibers can be used to extract analytes
from very small samples. Since SPME is an equilibrium
technique and therefore does not extract target analytes
exhaustively, its presence in a system does not result in
significant disturbance. Additionally, the technique facilitates speciation in natural systems, since SPME removes
small amounts of analyte and is therefore not likely to
disturb chemical equilibria. The amount of analytes
extracted is very small and therefore its combination with
a very sensitive technique involving GC – plasma spectrometry, and particularly GC – ICP-MS, is quite attractive.
4.2. Stir bar sorptive extraction (SBSE)
4. Sample preparation for GC– plasma spectrometry
The development of sample preparation techniques
allowing extraction, preconcentration, or adaptation of
elemental species for analysis by GC –plasma spectrometry is a critical analytical challenge in striving for reliable
speciation methods. Different techniques for the extraction
of various elements in diverse matrices include the use of
microwave-assisted extraction [62,132,144,166,175], headspace solid-phase microextraction (SPME) [16,109,183,
189], stir bar sorptive extraction (SBSE) [180], and purge
and capillary trapping for analyte retention and preconcentration [6,26,153,187]. Regarding the development of
derivatization procedures, the implementation of sodium
tetra(n-propyl)borate (NaBPr4) reagent represents the most
recent advance in this area [31].
Stir bar sorptive extraction (SBSE) applies stir bars that
vary in length from 1 to 4 cm coated with a relatively thick
layer of PDMS (0.3 – 1 mm), resulting in PDMS volumes
varying from 55 to 220 Al. The stir bar is added to an
aqueous sample for stirring and extraction, and after a
certain stirring time, the bar is removed from the aqueous
sample and the contents thermally desorbed in a gas
chromatograph. Due to the much larger volume of the
PDMS-phase, extraction efficiency is far better than for
SPME [11].
A recent paper by Vercauteren et al. [180] reported the
use of SBSE in combination with GC –ICP-MS for the
speciation of organotin species. The compounds were derivatized in the aqueous sample by use of sodium tetraethylborate and subsequently extracted on to a stir-bar coated
with 55 Al PDMS. The derivatized analytes were released
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
from the bar by thermal desorption, followed by cryofocussing of the compounds on a precolumn at
40 jC and
subsequent release by flash heating onto a GC column. The
applicability of the technique was demonstrated both for
environmental aqueous samples and for speciation of organotin compounds in mussel tissue. Detection limits in the
low pg l 1 range and a relative standard deviation of 10%
were obtained with this method. Tetracyclohexyltin was
used as an internal standard. The performance of the SBSE
technique was considered to be very good for the complex
sample pretreatment procedure and the low concentration
determined.
4.3. Derivatization techniques
Derivatization techniques employed for elemental speciation by GC – plasma spectrometry have generally consisted
of: (a) hydride generation, (b) extraction into an organic
solvent and derivatization with an alkylating agent, and (c)
in situ ethylation with sodium tetraethylborate (NaBEt4)
with posterior head-space analysis. Considerable efforts
have been devoted to this area since the 1970s and encompass the development of derivatization methods utilizing
hydride generation and alkylation with Grignard reagents
for elements such as Sn, Se, As, Bi, Te, Sb, and most of the
light alkylated Pb and Hg species [98]. Alkylation of
organometallic compounds using Grignard reagents can
provide quick derivatization for organotin, mercury, lead
and other elements. Depending on the characteristics of the
target, alkylating reagents with different alkyl-groups, including methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl- and
phenyl-, are available [33]. Compared to hydride generation,
ethylation by NaBEt4 provides more reproducible results
and is not affected by inorganic interferents. In addition, the
detection limits for some organometallic compounds can be
significantly improved by ethylation because it is a foamfree derivatization [33]. In comparison to Grignard reagents,
NaBEt4 is stable in water and consequently, the derivatization can take place in aqueous media. This can be particularly useful for speciation analysis of water samples.
5. The application of GC – plasma spectrometry to
elemental speciation
The analytes studied using GC –plasma spectrometrybased techniques comprise original volatile or thermally
stable species, or those converted to a volatile stable form
after a suitable derivatization procedure. Several different
compounds have been determined by GC with plasma
source detection from highly volatile species with sub-zero
boiling points to relatively high molecular weight compounds such as metalloporphyrins. In this section of the
review, information and discussion concerning the specific
application of GC – plasma spectrometric techniques for
speciation of metallic and non-metallic elements in envi-
773
ronmental, biological, and industrial samples is presented.
The publications related to the application of these techniques are summarized in Table 1. However, the most recent
advances in the speciation of different elements of interest
including, As, Bi, Br, C, Cd, Cl, Cu, F, Fe, Ge, Hg, I, In,
Mn, Mo, N, Ni, O, P, Pb, S, Sb, Se, Si, Sn, Te, V, W, and Zn
are discussed in the following sections.
5.1. Antimony
Antimony is a metalloid with chemical behavior similar
to that of arsenic. Its presence in the environment is
increasing due to the extensive use of antimony compounds
as flame retardants in plastics and textiles, as additives in
metal alloys, as doping agents in semiconductors, and as
antiparasitic drugs. Its species of interest include Sb(III),
Sb(V), monomethylstibonic acid, and dimethylstibonic acid.
Antimony toxicity depends strongly on its chemical form
and concentration, which make speciation analysis necessary to assess its impact on the environment [87]. However,
there are only a few applications of gas chromatography
coupled to plasma detectors for the speciation analysis of
antimony compounds.
The latest advances in antimony speciation are related
to the methylation processes produced as a consequence
of microbial activity. Antimony species have been also
evaluated by isotopic ratio studies. A recent study on the
speciation of antimony was published by Haas et al. [71].
Volatile antimony species, including SbH3 and MeSbH2,
were studied and determined in landfill gas samples.
Cryotrapping GC – ICP-TOFMS methodology was developed to evaluate the capabilities of the TOF mass
spectrometer for multi-elemental speciation analysis and
multi-isotope ratio determinations were performed. The
121
Sb/123Sb isotopic ratio was determined in standard
atmospheres. The detection system, in both pulse counting and analog mode, was examined. The precision for
low concentration (100 pg SbH3 and MeSbH2) was better
using the counting mode than the analog mode. However,
at higher concentrations, the analog signal was more
precise. Whether this precision is sufficient to enable
identification of isotopic fractionation of antimony
through biovolatilization could not be answered.
The GC – ICP-MS technique was utilized to evaluate the
generation of Me 3Sb from a filamentous fungus by
Andrewes et al. [7]. The Me3Sb was purged from Scopulariopsis brevicaulis cultures using a continuous flow of
compressed air and trapped in a U-shaped tube containing
Supelcoport SP 2100 at
78 jC. The trap contents were
determined using GC – ICP-MS. The detection limit was
approximately 0.15 pg. Koch et al. [87] worked with waste
water and aqueous fungus extract and developed two
methods for the speciation of antimony compounds in
these samples. The methods include hydride generation
(HG) followed by GC separation and determination by
ICP-MS and AAS, respectively. In both methods, an
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J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
enhancement of the demethylation of Me3Sb species was
observed as the pH decreased. The authors concluded that
when analyzing a sample for methylated antimony compounds by the HG method, the reaction conditions should
be carefully tested with standard compounds such as
Me3SbCl2. Feldmann et al. [51] studied the possibilities
of ion trap EI-MS-MS and ICP-MS techniques as two
different detectors for a GC system to provide complementary information about volatile organo-metallic species
in landfill and sewage sludge fermentation gases. The
GC – ICP-MS technique with cryotrapping was utilized
for the elemental-identification of the volatile antimony
species. For the first time, parent ions, fragmentation
patterns, isotopic ratios for Sb, and MS-MS data were
used to identify Me3Sb in landfill gas and Me3Sb in
fermentation gas. Using GC – ICP-MS, the LOD for Me3Sb
species was 0.3 pg (as Sb), without an optimized separation technique and without any clean-up techniques.
Many authors included the HG technique in the speciation method of antimony, however only Koch et al. [87]
reported a demethylation phenomenon occurring with the
methylated antimony species when HG was used. These
authors studied the influence of the acid type, concentration
and pH on the demethylation process. They reported that
demethylation of the methylated antimony species was
observed for all HG conditions however, it was most
pronounced at lower pH values, higher acid concentrations
and longer analysis times.
It can be concluded that the number of studies involving
antimony speciation is still scarce considering the environmental and toxicological importance of this element. The
latest developments have demonstrated the use of TOFMS
for mass analysis, however, there are no recent advances in
extraction and/or preconcentration techniques.
Pécheyran et al. [126] developed a qualitative method
for the determination of several metallic and non-metallic
species including arsine and tert-butylarsine. The proposed
methodology consisted of an automated field cryotrapping
device to collect air samples at
175 jC. Samples were
then flashed-desorbed in a cryogenic trapping (CT)-GC –
ICP-MS system for determination of volatile species.
Xenon gas was used as an internal standard and for
optimization of the torch position. Carbon deposition due
to the burning of methanol as organic solvent was observed and oxygen addition was used to avoid this
problem. Although the system presented low detection
limits (fg range) for Pb, Se, Sn, and Hg, quantification
of As species was not accomplished. Additionally, a strong
interference due to the presence of carbon dioxide was
observed. Feldman et al. [53] determined AsH3, MeAsH2,
Me2AsH and Me3As by using capillary GC –ICP-MS. The
authors were interested in the analysis of these arsenic
species in anaerobic environments and therefore used a
NaOH-filled CO2 trap to isolate the analytes from the
major gases that would also be present.
Wickenheiser et al. [188] used GC – ICP-MS for the
analysis of volatile hydride and methylated arsenic species
released from sewage treatment facilities and municipal
landfills. Both hydride generation and purge-and-trap techniques were used to isolate the analytes of interest from the
headspace. In both techniques, the analytes were cryofocused on the GC column, which was initially maintained at
196 jC. Prohaska et al. [138] speciated arsenic in gaseous
soil emissions. A sector field ICP-MS was operated in low
resolution mode (m/Dm = 300) and arsenic was subsequently
monitored at m/z = 75 without any interference from the
typical ArCl+ interference. Arsine and trimethylarsine were
determined to be the main components of the gaseous
emissions.
5.2. Arsenic
5.3. Bismuth
Arsenic speciation is critical in many fields of study due
to the differences in toxicity of its numerous species. The
oxidation state of these species can be changed depending
on the pH conditions and redox potential. Arsine and
arsenite are highly toxic while others, such as arsenobetaine,
are innocuous for some living organisms. Therefore, the
strong dependence of toxicity on the type of species makes
the ability to differentiate the various arsenic species a
necessity.
The volatile species of arsenic commonly analyzed by
GC are AsH3, MeAsH2, Me2AsH, t-BuAs, Me3As, Ph3As
and Et3As. The sampling procedure is carried out by using a
trap such as a liquid-nitrogen-cooled trap or a NaOH-filled
CO2 trap. With regard to the nonvolatile species of arsenic,
most authors propose derivatization of the arsenic species
into the corresponding hydrides by using sodium borohydride in an acidic medium. The implementation of this
derivatization requires the use of a trap to introduce the
arseno-hydride species into the GC.
Bismuth compounds are widely used in alloys, cosmetics
and pharmaceutical products; however, the speciation of this
element in the environment is a field barely explored. GC –
ICP-MS has been successfully applied for the analysis of
volatile species of bismuth; nevertheless, no reliable speciation methods for non-volatile bismuth compounds are
available. Gruter et al. [67] report the use of the hydride
generation technique for the analysis of bismuth compounds, among species of 11 other elements (arsenic,
selenium, mercury, germanium, molybdenum, antimony,
tin, lead, tungsten, molybdenum, tellurium) in solid samples
from a municipal waste deposit. However, Feldmann et al.
[52] reported a possible demethylation phenomenon when
trimethylbismuth (TMB) was derivatized to a hydride for
introduction in a GC – ICP-MS system. These findings
suggest that more studies need to be done to evaluate
hydride generation for bismuth species, and most specifically, for those that are methylated.
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
In early work done by Feldman et al. [46], a volatile
compound of bismuth was determined in domestic waste
deposits. Analysis was conducted by GC –ICP-MS and
209
Bi was monitored. An isolated Bi peak was detected
and tentatively identified as unstable trimethylbismuth. If
water samples were equilibrated with the gaseous phase
containing Bi(CH)3, inorganic Bi would be formed.
Consequently, inorganic bismuth as volatile BiH3 was
detected in condensed water only. The work by Hirner et
al. [81] showed the possibility for biomethylation of
bismuth. In one particular waste contaminated soil, 4
ng kg 1 Bi as BiMe2H and 4 Ag kg 1 Bi in BiMeH2
were found. After passing through a drying tube, the
volatile Bi compounds were cryotrapped and analyzed by
GC –ICP-MS.
5.4. Bromine
Bromine compounds have been studied in different
types of samples, including environmental, food and
pharmaceutical samples. GC coupled to plasma source
detectors has been applied for the analysis of flame
retardant, pesticides and volatile organic hydrocarbons in
environmental samples. However, this coupling has not
been extensively used for the analysis of brominated
compounds in food and pharmaceutical samples. To
explore these fields, liquid chromatography was the separation technique mostly applied with the plasma source
detectors.
A low power/reduced pressure helium ICP ionization
source was used by Waggoner et al. [185] for the determination of the organo-bromine compounds, bromobenzene, 1-bromoheptane and benzyl bromide. Elemental
information was augmented with the capability to take
fragment spectra and therefore provide structural information. The brominated flame retardants have recently come
under scrutiny due to their appearance in various environmental media. Vonderheide et al. [182] developed a
method for the analysis of polybrominated diphenyl ethers
which coupled fast gas chromatography to ICP-MS detection. The authors explored the addition of different gases
to the argon plasma in an effort to improve detection
limits. Detection limits of 0.5 to 2 ng l 1 were achieved
with the addition of approximately 4% nitrogen to the
argon plasma. Schwarz et al. [152] explored the use of the
ICP-MS for the analysis of brominated volatile organic
compounds. They employed a hyphenated GC –ECD/ICPMS system. Interestingly, the coupling of these two detectors was obtained with a flexible transfer line that
connected the ECD vent to the ICP torch.
Other applications to brominated compounds include
GC –MIP-OES [1] and GC – (LP)ICP-MS [45,70,74,185].
Innovations have been directed to the design of new GC –
plasma interfaces, use of low power plasmas to obtain
molecular structural information and the development of
more sensitive and robust analytical methodologies.
775
5.5. Cadmium
Although cadmium is an element of great concern due to
its toxicity, the speciation of volatile species of this element
is a field scarcely explored. Screening for metal and
metalloid compounds in environmental gases requires a
sensitive element specific detection method coupled to a
chromatographic system. Volatile metal(loid) species are
generally not very stable, and therefore their quantification
can be difficult. Additionally no reference materials or
standard gas mixtures are available for determining the
metal content in gases, and the stability of metal-containing
gas mixtures has not yet been investigated. Regarding this
problem, Feldmann et al. [47] developed a calibration
method that allows a semi-quantitative determination of
volatile heavy element species in environmental gases using
GC –ICP-MS. Cadmium was included in this list and was
monitored at m/z = 113. The developed method used an
aqueous element solution for quantitation of the volatile
element species, as gaseous standards were not available.
Rhodium was used as a continuous internal standard and
was introduced into the plasma simultaneously with the gas
sample throughout the entire analysis. The absolute limit of
detection of cadmium was given as 0.27 pg.
Scientific studies have been developed to evaluate
emission of heavy metals during coal combustion processes. However, information about the volatile species of
cadmium released from combustion processes is notoriously limited. Also, there exist other emission sources of
volatile species of cadmium, such as the conversion of
cadmium species by microorganisms, that have narrowly
been explored. The identification and quantification of
individual volatile trace cadmium species in the gas phase
is imperative for addressing questions regarding toxicity,
mobility, and atmospheric fate and transport mechanisms,
since each species possesses distinctive physical and
chemical properties governing their environmental impact.
Furthermore, it is important as an effective emission
control to distinguish between the various gaseous forms
in which metals are released into the atmosphere and the
metals bound to particulate matter.
5.6. Carbon
Due to the high ionization potential of carbon, the
number of applications targeting its determination by
plasma source coupled to GC is sparse. Furthermore,
although carbon can be ionized in an ICP, its ubiquitous
nature results in a large background. Early on in coupling
GC to ICP-MS, Chong and Houk [27] explored the
determination of carbon by this technique. GC calibration
standards for alcohols and aromatic hydrocarbons were
used and the isotope ratio of 12C/13C was calculated. Many
other isotope ratios were investigated in this work, including B, Br, Cl, Si, P, O, I and S. Detection limits were in
the range of 0.001 to 400 ng s 1.
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5.7. Chlorine
Metals are released in the effluents of most combustion
processes and it is important for an effective emission
control to distinguish between the different gaseous forms
that are released into the atmosphere. In the investigation of
the volatile species released in these effluents, Pavageau et
al. [125] discovered the presence of a volatile copper
species. For qualitative analysis, Cu was monitored at m/
z = 63 and 65 and two compounds were proposed, CuO –
CuSO4 and CuSO4H2O, as the possible volatile Cu species.
anthropogenic activities due to its application as refrigerants, propellants, agrochemicals, surfactants and lubricants;
natural organofluorine compounds are rare, even considering that fluorine is the most abundant halogen and the 13th
most abundant element in the Earth’s crust. The increasing
interest in natural organofluorine compounds arises somewhat from fundamental peculiarities in the chemistry of
fluorine. Fluorine has a relatively low bioavailability in
comparison to the other halogens, since it is in a largely
insoluble form. Thus, the concentration of fluoride in
seawater (1.3 ppm) is several orders of magnitude lower
than that of chloride (19,000 ppm). Additionally, due to its
high hydration energy, the fluoride ion is a poor nucleophile
in aqueous solution, limiting its participation in displacement reactions. Finally, fluorine is not incorporated into
organic compounds via the haloperoxidase reaction since
the redox potential required for the oxidation of fluoride is
much greater than that generated by the reduction of
hydrogen peroxide. Consequently, the binding mechanism
of fluorine to carbon in biological system is of considerable
interest. Despite the great interest that fluorine has for
environmental and biological studies, the number of analytical methodologies for fluorine speciation analysis is limited
(Table 1). This is a result of the fact that fluorine, and the
halogens in general, possess a high ionization potential and
therefore ionization efficiency is low even with the high
temperatures that can be reached in plasma sources.
As an example, it is interesting to mention the scientific
report of Fry et al. [58] who utilized optical emission
spectroscopy for the detection of fluorinated organic compounds that were previously separated by gas chromatography. The ICP was used as an excitation source for the
fluorine atoms and the methodology was applied to the
analysis of benzene trifluoride and o-fluorotoluene. Brede et
al. [20] developed a hyphenated technique involving the use
of GC –MIP-MS for the determination of fluorine species
present in crude oil samples. Difficulties in the selective
determination of F were observed when the m/z 19 isotope
was utilized and this was determined to be a result of the
presence of the H3O+ molecular ion generated by the
introduction of hydrogen as an additional gas into the
plasma. Similar interference problems were observed by
introducing a minimal amount of 20 ng of hydrocarbon
compound (n-decane). This was assigned to the generation
of hydrogen which contributes to the occurrence of H3O+ as
discussed above. The background signal was significantly
reduced by increasing the power applied to the plasma. In
spite of these problems, detection limit for fluorine was
found to be 6.1 pg as 1-fluoronaphthalene. Matrix effects in
crude oil samples were studied by fortification with 1fluoronaphthalene species.
5.9. Fluorine
5.10. Germanium
The presence of fluorine in the environment has received
increasing attention in the last decade. It is mostly related to
Germanium speciation has been generally performed
with hydride generation prior to GC – ICP-MS analysis.
Chlorinated compounds have been studied in different
types of samples, including environmental, biological and
food samples. GC coupled to a plasma source detector has
mainly been applied for the analysis of pesticides and
volatile organic hydrocarbons in environmental samples
such as soils, sediments and different types of water. This
gas chromatography coupling was successfully used in
several plasma studies, however, it has not been extensively
used for the analysis of chlorinated compounds in biological
and related samples.
Although chlorine can be measured by ICP-MS, low
sensitivity results due to its high backgrounds. In work
performed by Castillano et al. [25] the promise of using a
low pressure inductively coupled He plasma mass spectrometer for the analysis of halogenated hydrocarbons was
demonstrated. Chlorine was monitored at m/z = 35 and
limits of detection in the low pg range were reported. Pack
et al. [122] coupled gas chromatography to a helium MIP
and TOF mass spectrometer to analyze chlorinated hydrocarbons as well as other halogenated species. Chlorinated
compounds examined included chlorobenzene, 1-chloropentane and p-chlorotoluene and detection limits of approximately 100 fg as chlorine were reported.
A hollow cathode glow discharge was used in the
analysis of chlorinated hydrocarbons after their separation
by GC in work published by Schepers and Broekaert [151].
In general, this type of ionization source offers high sensitivity because of the long residence time of the analyte in the
low pressure plasma. Detection was performed by atomic
emission, and limits of detection obtained with exponential
dilution experiments were 3 pg s 1. Jerrell et al. [84]
utilized a low power ICP source for element selective
atomic emission detection of chlorinated hydrocarbons;
compounds of interest were separated by GC prior to
analysis. Helium was used as the plasma gas and specific
analytes included carbon tetrachloride, chlorobenzene and
chloroform.
5.8. Copper
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Occasionally, a cryofocusing device has been coupled to GC
and ICP-MS to increase the detection power of the technique. Although many germanium species found in soil,
domestic waste and coal samples have been identified,
several still remain as unknown peaks in the chromatograms
presented in scientific reports. It should be mentioned that
contents and potential emissions from industrial or electronic waste have yet to be analyzed for metal(loid)organic
compounds.
Hirner et al. [81] used HG – GC – ICP-MS to separate
methylated germanium species. The method was applied to
the analysis of solid samples, although partly methylated
species of germanium are usually present in aqueous solutions only. The methyl-Ge species present in the solid were
volatilized through reduction with NaBH4 in acidic aqueous
medium and then cryotrapped. The species were separated
and detected by GC –ICP-MS. The low concentrations of
alkylated species in waters generally require large sample
volumes to obtain adequate sensitivity. Tseng et al. [172]
investigated the use of a shipboard hydride generation system
for application in field work. Several germanium species
were considered, including GeH4, MeGeH3, Me2GeH2,
Me3GeH and Et2GeH2 and the detection limit was reported
as 100 fg as germanium. The presence of organo-metallic
germanium species in human urine after fish consumption
was investigated by Kresimon et al. [88]. The 73Ge isotope
was monitored and the authors found two germanium species
present in the urine samples. They identified these species as
GeH4 and (CH3)GeH3 by fortifying the solutions with pure
compounds.
5.11. Indium
A current area of interest concerns industrial hygienerelated aspects, particularly in the semiconductor industry,
where highly toxic gases containing indium are used in the
epitaxial growth of crystals. Pecheyran et al. [126] simultaneously determined several volatile metal species, including
indium, in different atmospheres. Oxygen addition to the
carrier gas was used to reduce interferences originating from
the presence of volatile carbon-containing species in the
sample. An indium-containing peak was tentatively identified as either Me2InH or MeInH2 by calculation of boiling
points.
5.12. Iodine
An environmental application of the GC – plasma source
detector coupling is the speciation of volatile iodine compounds resulting from microbiological degradation of organic matter present in seawater. In this sense, a recent
development in GC coupling to different detectors has been
proposed by Schwarz and Heumann [152]. A GC system
was simultaneously coupled to an ECD detector and then to
ICP-MS for the determination of iodinated volatile organic
compounds resulting from aquatic and air systems. The
777
GC –ECD/ICP-MS system provided high selectivity and
sensitivity for the individual detection of volatile organic
compounds (VOCs) under fast chromatographic conditions.
The two dimensional GC – ECD/ICP-MS instrumentation
was compared with electron impact mass spectrometry
(EI-MS) and MIP-OES. It was concluded that the main
advantage of the GC – ECD/ICP-MS coupling was the
possibility of identifying co-eluting compounds.
More recently, Wuilloud et al. [189] studied the determination of the iodophenols with GC –ICP-MS. The compounds of interest included 2-iodophenol, 4-iodophenol and
2,4,6-triiodophenol; these compounds are classified as disinfection by-products in the use of iodine for recycled water
disinfection. The authors explored the use of optional gases
added to the argon plasma as well as SPME in an effort to
obtain low limits of detection. They observed that the use of
oxygen as an optional gas yielded detection limits of 0.07 ng
l 1 (2-iodophenol), 0.12 ng l 1 (4-iodophenol), and 0.09
ng l 1 (2,4,6,triiodophenol).
5.13. Iron
When ICP-MS is used as detector for GC effluents,
screening iron species at m/z 56 highlights an interference
by 40Ar16O+. Therefore, the identification of the iron containing peaks is performed by monitoring the other masses
of its natural isotopic pattern (m/z 54, 57 and 58). Feldman
[48] coupled a cryotrapping gas chromatographic separation
to ICP-MS for the determination of Ni(CO)6 as well as
Fe(CO)5, Mo(CO)6 and W(CO)6 in sewage gas samples.
The identification of the chromatographic iron peaks was
successfully carried out by analyzing the natural isotopic
pattern of this element. Although the results of the method
obtained with standards were found reliable, iron was not
detected in the sewage sample analyzed. Kim et al. [85] also
used the natural isotopic pattern of iron to monitor the
presence of ferrocene in fortified water samples and in
harbor sediment by GC – ICP-MS. A very low limit of
detection for iron on the order of 3.0 pg s 1 was obtained.
An alternative for the analysis of iron in the GC effluent
is the coupling GC – MIP-OES which results in the advantage of elimination of the argon interference. Alkylphenols
have various anthropogenic and natural sources and therefore occur in many different matrices. Ferrocenecarboxylic
acid chloride was used to derivatize the alkylphenols in nonpolar matrices [148]. Hence, every phenol molecule was
labeled with one iron atom and the resulting compounds
were analyzed by GC – MIP-OES. By optimizing the gas
flow rates of the plasma, limits of detection of about 0.05 pg
s 1 were found for iron and the methodology was applied to
the analysis of crude oil samples.
5.14. Lead
Organo-lead compounds are ubiquitous pollutants in air,
atmospheric aerosols, water and sediments. Tetraalkyllead
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species (TAL), mainly Et4Pb, Me4Pb and MenEt4 nPb, are
still used in some countries as anti-knocking additives in
gasoline [101]. The toxicity of organo-lead compounds
depends on the organic groups bound to the lead atom
(methylated species are less toxic than the corresponding
ethylated compounds, but are more stable and volatile)
[139]. Gas chromatography coupled to element-selective
detection is commonly used for the speciation of lead
compounds. Rodrı́guez Pereiro and Lobinski [131] proposed the use of multicapillary GC for the introduction of
gasoline samples into a MIP-OES for fingerprinting and
speciation analysis of organo-lead additives. The tetraalkyllead species were isothermally baseline separated and quantified within 10 s in comparison with about 10– 20 min
required by conventional GC procedures. Detection limits
were below 1 Ag l 1.
The use of SPME for the determination of organo-lead
species was described by Moens et al. [111]. The organolead species were derivatized in situ with NaBEt4, sorbed
on a PDMS-coated fused silica fiber, and desorbed in the
splitless injection port of the GC. Methyllead was determined by ICP-MS coupled to GC using a transfer line
developed in-house. A more recent study using the headspace SPME technique previous to GC-rf (HC)GD-OES
was developed by Orellana-Velado et al. [121]. Organolead species, including Me3Pb and Et3Pb, were extracted
using a SPME fiber coated with PDMS. A transfer line to
couple the GC system to the GD-OES detector was
designed. Detection limits for Me3Pb and Et3Pb were
0.15 and 0.03 Ag l 1, respectively. These values were
40 –230 times lower than those obtained with conventional
injection.
Heisterkamp et al. [75,76] reported fast and simple
preparation procedures for the speciation of organo-lead
compounds by GC – MIP-OES in two different studies. In
both cases, the method consisted of acid leaching to desorb
the species of interest from the matrix followed by an in situ
derivatization with simultaneous extraction of the derivatized species into hexane. In the first work, tetrabutylammonium tetrabutylborate was used to butylate the organo-lead
species at pH 4 [75]; however, in the second work, sodium
tretrapropylborate was used to propylate at pH 4.5 [76]. The
propylation method was applied for the analysis of Me3Pb,
Me2Pb, Et3Pb and Et2Pb on snow samples and the butylation was used for the analysis of these species in peat and
water samples. Both methods were also applied to road dust
reference material for an accuracy study. Detection limits
were in the range of 43 to 83 and 77 to 102 fg (as Pb) for the
butylation and propylation methods, respectively. RuizEncinar et al. [44] observed that ethylation and butylation
with n-butylmagnesium chloride and sodium tetraethylborate, respectively, did not produce changes in the isotope
ratio of the measured isotopes. The study was developed by
using GC – ICP-OES for the analysis of Me3Pb, Me2Pb,
Et3Pb and Et2Pb species of airborne particulate matter
samples.
Baena et al. [10] used an automatic pre-concentration
unit coupled to a gas chromatograph for the analysis of
organo-lead compounds in the screening of rainwater. A
systematic overview is given of the advantages and disadvantages of several detectors (EI-MS, MIP-OES and
ICP-TOFMS) for the speciation of Me3Pb, Me2Pb, Et3Pb
and Et2Pb on the basis of sensitivity, selectivity and
reliability. C60 fullerene and RP-C18 were used as sorbent
materials for the retention of the sodium diethyldithiocarbamate (NaDDC) chelates formed with the organo-lead
species mentioned above. The primary advantages of the
fullerene sorbent, as compared to the C18 sorbent, were
high sensitivity and selectivity resulting from efficient
adsorption due to large surface area and interstitial volume.
However, environmental compounds, such as MeEt3Pb,
Me4Pb or Et4Pb could not be determined using this
method because tetraalkyllead compounds are not able to
form chelates with NaDDC, and thus are not retained on
the C60 fullerene column. Leach et al. [92] used the
TOFMS as a mass detector for speciation analysis of
Et4Pb. It was noted that for best performance of the
system, ion-counting devices required the detection of
one ion at a time. The detection limit for Et4Pb in the
analog mode was higher than with the ion-counting mode:
106 and 9 fg, respectively. Pelaez et al. [129] studied the
advantages and disadvantages of the use of ICP-QMS and
ICP-TOFMS in the analysis of lead species. Inorganic lead
and Me3Pb were determined using both detectors and
measuring lead at m/z 206 and 208. The authors found
similar precision for up to 25 isotopes for both detectors
when transient signals of about 10 s were measured.
Detection limits obtained using ICP-QMS were 5 to 20
times better when compared with those observed with
TOFMS.
5.15. Manganese
In the petroleum industry, metalated porphyrins can
affect crude oil refining processes by reducing the lifetimes
of catalysts or by catalyzing the formation of unwanted byproducts. Manganese octaethylporphyrin chloride was utilized as a standard in the analysis of metalloporphyrins
conducted by Pretorius et al. [137]. High temperature GC
(410 jC) was employed for separation and detection of
manganese was performed by monitoring m/z = 55 by ICPMS. The detection limit was given as 0.10 ng as Mn on
column.
5.16. Mercury
Mercury represents one of the elements whose speciation
methods have been investigated most intensely from the
environmental and ecotoxicological points of view. Diverse
studies include artificial formation or decomposition of
mercurial species; derivatization reagents; trap systems
coupled to GC prior to separation of mercurial species;
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GC systems and plasma source detectors for GC effluents.
Table 1 shows that the applications have been mainly
focused on environmental samples rather than biological
or pharmaceutical matrices.
Holz et al. [82] used Tenax trap-GC – ICP-MS to corroborate the formation of MeHg from Hg2 + during the derivatization step with NaBEt 4 . Rainwater samples were
fortified with Hg2 + prior analysis. The formation of MeHg
was considered insignificant. Considering this observation,
the authors then applied the method to the analysis of MeHg
species in rainwater that involved an in situ derivatization
with NaBEt4 and enrichment on a Tenax trap before GC –
AFS analysis. Demuth and Heumann [34] studied the
transformation of MeHg into metal mercury (Hgo) by using
NaBEt4 for the volatilization prior to GC –ICP-MS analysis.
From the investigation of synthetic solutions, it was observed that halide ions are responsible for this transformation process. In contrast to ethylation, propylation by
NaBPr4 did not cause any transformation. Garcia Fernandez
et al. [55] published a comparative study encompassing
three derivatization processes: anhydrous butylation using
Grignard reagent, aqueous ethylation by means of NaBEt4,
and aqueous propylation with NaBPr4. They applied these
to mercury speciation analysis in biological tissues of
certified reference materials (DOLT-2 dogfish liver) using
GC –ICP-MS methodology. Lambertsson et al. [91] also
reported the use of an isotope dilution method based on a
NaBEt4 derivatization prior to Tenax trap-GC – ICP-MS
analysis to determine incipient concentrations of MeHg as
well as the degree of methylation of Hg2 + and de-methylation of MeHg in brackish water sediments. Sediment
incubation with 201Hg2 + and Me198Hg showed transformations differing between depths, being higher in the top 3 cm
of the sample. Detection limits for methylation of 201Hg2 +
and de-methylation of Me198Hg were 0.1 and 0.2 ng l 1 as
Hg, respectively. Emteborg et al. [41] reported the development of a method employing supercritical fluid extraction
(SFE) and GC – MIP-OES for the determination of MeHg in
PACS-1 sediment. Using a stable isotope tracer, 199Hg, and
ICP-MS, the authors found evidence of spurious formation
of MeHg during SFE under certain conditions. It was also
proposed that the co-extracted sulfur from the sediment
mediates the transport of MeHg and, to some extent,
Hg2 + from the sediment. The detection limit for MeHg in
sediment was estimated at 0.1 ng g 1 as Hg. Tu et al. [173]
recently published a sample pre-treatment for the determination of MeHg in biological reference materials (TORT-2
lobster hepatopancreas, DOLT-2 dogfish liver and CRM 463
fish). The procedure was based on acid leaching of the
sample followed by simultaneous in situ derivatization in
the presence of NaBEt4, extraction with nonane and analysis
by GC – MIP-OES and GC – ICP-MS. Detection limits were
4.4 and 2.6 ng g 1 as Hg, respectively. Rodil et al. [144]
developed an extractive method to determine MePhHg and
Ph2Hg in biological reference materials (TORT-1 fish,
DOLT-2 liver, DORM-2 fish and CRM 463 fish) by GC –
779
MIP-OES. The procedure involved an acid microwave
extraction followed by aqueous-phase derivatization with
NaBPh4 and head-space-SPME with a silica fiber coated
with polydimethylsiloxane. Detection limits of the organomercury compounds were 0.12 and 0.86 Ag l 1 as Hg,
respectively.
Some authors avoided the species transalkylation and
losses during the NaBEt4 derivatization by focusing their
efforts on gas chromatography. Tao et al. [167] developed a
simple and rapid GC – ICP-MS speciation method for mercury in natural gas condensate, naphtha fraction and crude
oil samples. The authors used a DB-1701 column, pretreated
with HBr, to attain sharp peaks for organo-mercury species
without derivatization. Six organo-mercury species, Me2Hg,
MeEtHg, Et2Hg, MeHgCl, Bu2Hg and EtHgCl, were resolved from Hgo and HgCl2 within 6 min when the pulsed
splitless injection mode was used. Detection limits were in
the range 19 –340 fg as Hg, whereas detection limits for Hgo
and Me2Hg were 34 and 130 fg as Hg, respectively. Rosenkranz and Bettmer [149] presented isothermal multicapillary chromatography as an attractive alternative for fast
separation of mercury species (Me2Hg, EtHgMe, Et2Hg
and MeHg). In comparison with conventional capillary
GC, run time is up to a factor of 10 faster without loss of
resolution. Armstrong et al. [8] developed a comparative
study in which they showed the AFS and ICP as suitable
detection techniques for organomercury speciation in marine tissue reference materials (IAEA 142 fish muscle, NIST
8044 fish muscle and DOLT-2 liver) after separation with
gas chromatography. Detection limits for MeHg were 0.9
and 0.25 pg as Hg, respectively. Orellana-Velado et al.
[120,178] published two comparative studies evaluating
different plasma sources as detectors for GC in the speciation analysis of low levels of organo-mercury compounds
(MeHg, EtHg and Hg2 +) in fish reference materials (DOLT2 liver and DORM-2 fish) after a Grignard derivatization. In
one of the studies, radio-frequency (rf) was compared with
direct current (dc) glow discharge atomic emission spectrometry (GD-AOS) as an element selective detector for GC.
The second work represented the comparison of a hollow
cathode with radio-frequency source (rf-HC) for GD-OES
with rf-GD-OES (flat cathode) and MIP-OES. The figures
of merit obtained in the speciation analysis of mercury were
similar for dc-GD and rf-GD-OES. However, for the hyphenated GC – rf-HC-GD-OES method, detection limits
were up to 5– 10-fold better than those encountered using
flat HC-GD-OES and MIP-OES [24]. The detection limits
were in the range of 1.3 to 3.0 pg for GC-dc-GD-OES and
GC-rf-GD-OES. Vazquez Pelaez et al. [129] reported a
critical comparison of the performance of a sequential
quadrupole mass analyzer (QMS) referenced against an
ICP-TOFMS instrument for ICP-MS multi-elemental analysis of different types of transient signals, including those
obtained by GC. Results demonstrated that only for transient signals faster than 8 s (baseline) and the number of
isotopes to be measured above 15, can the use of a TOF
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mass analyzer be recommended in terms of isotope ratio
precisions attainable. Conversely, the QMS offered precision similar to ICP-TOFMS for transient signals of about
10 s or more, even when 25 isotopes were analyzed.
Frech et al. [56] compared MIP-OES and FAP-OES
sources for the analysis of derivatized mercury species when
coupled with GC for sample introduction. Natural gas
condensate was used as a test material. Comparable detection limits estimated for Me2Hg, MeBuHg and Bu2Hg in
diluted condensate (5%) were in the range of 1.5 and 4.7 pg
as Hg. However, measurement of Me2Hg was not possible
with the MIP-OES since the plasma was extinguished due to
solvent vapor overload. Molecular emission from NO bands
gave rise to background in both sources. In the FAP-OES
source, hydrocarbon effluents reduced the NO concentration, giving rise to background fluctuation, whereas in the
MIP, background fluctuations arose mainly from quenching
of the plasma. Clearly, FAP-OES is a useful source for GC
effluent detection, particularly in view of the additional
flexibility arising from furnace heating.
Leenaers et al. [94] used ICP-TOFMS as a detector for
capillary GC with purge-and-trap injection for the speciation analysis of Hg2 + and MeHg. They observed that not
only is it possible to obtain multi-elemental and multiisotope detection of very fast transient signals (peaks
widths shorter than 1 s) without peak distortion or spectral
skew, but also that metal speciation can be performed at fg
levels. The authors list advantages of this hyphenated
method, such as low sample volume required, in situ
sample derivatization with NaBEt4 and relatively high
throughput, all of which make the hyphenated method
suitable for speciation analysis of organomercury compounds in biological and environmental samples. Rodriguez Pereiro and Diaz [130] published a critical review
concerning advantages and limitations of the GC – MIPOES for mercury, tin and lead speciation in environmental
samples. Since the sample preparation is also a vital step
for the analysis of these compounds, the effect of samplepreparation methods on the accuracy and precision of the
results was also discussed. Tutschku et al. [175] published
an analytical method to determine MeHg and BuSn compounds in sediment and fish tissue reference materials
(PACS-1 and PACS-2 sediment, DORM-2 dogfish muscle
TORT-1 lobster hepatopancreas and SRM 1566b oyster
tissue, SRM 1646a estuarine sediment, SRM 1941a marine
sediment, SRM 1941b marine sediment, SRM 1944 waterway sediments, SRM 1946 lake fish tissue, SRM 1974a
mussel tissue, SR 2974 mussel tissue, SRM 2976 mussel
tissue, and SRM 2977 mussel tissue). Carpinteiro Botana
et al. [16] developed a procedure for the simultaneous and
fast determination of MeHg, Hg2 + and organotin species
(BuSn, Bu2Sn and Bu3Sn) in water samples as ethylated
derivatives using a multicapillary GC column coupled to
MIP-OES. The simultaneous determination of both elements was performed using headspace SPME after a
derivatization step with NaBEt4. The influence of the
auxiliary gas (H2, O2 and He) pressure was also evaluated,
since it affected the MIP-OES response. Detection limits
were 0.8 and 1.1 ng l 1 as Hg for MeHg and Hg2 +,
respectively. Tseng et al. [172] developed two hydride
generation manifold systems utilizing flow injection and
cryotrapping techniques for alkyl-metal speciation analysis
in natural waters. Ultra-trace multi-elemental determination, including mercury, was performed by a cryogenicGC – ICP-MS technique. Routine detection limits of 2 and
50 pg as Hg were achieved for Hgo and MeHg species,
respectively.
5.17. Molybdenum
Molybdenum and tungsten are widely used in hard alloys
for tools or in light bulbs; therefore, municipal waste
contains detectable amounts of these elements. The chemical
synthesis of Mo(CO)6 and W(CO)6 usually requires a source
of the metal and a high pressure of carbon monoxide (>1
bar). Under anaerobic conditions, waste deposits release
mainly gaseous compounds such as methane and carbon
dioxide as well as a small amount of carbon monoxide
(approximately 0.1% (v/v)). The most common soluble form
of molybdenum is the anionic molybdate ion (MoO42 ).
This can react with hydrogen sulfide to form sulfide compounds such as MoS3, MoS2, or MoS42 . It is possible that
these compounds may react directly with carbon monoxide
under landfill conditions to form the hexacarbonyl compound in the absence of oxygen. A cryotrapping –cryofocusing GC – ICP-MS method for the determination of volatile
molybdenum compounds (Mo(CO)6) in fermentation gases
from a municipal sewage treatment plant and gases from
three different municipal waste deposits was applied by
Feldmann and Cullen [49] and Feldman [48], respectively.
The gas samples were cryogenically preconcentrated by
trapping the gases on Chromosorb (10% SP-2100 60/80
mesh, Supelco) at
78 jC (dry ice/acetone slush). In a
cryofocusing step, the species were volatilized by increasing
the temperature of the trap from 78 to 150 jC, and the
released gas was frozen (liquid nitrogen) onto a second Ushaped trap (6 mm o.d., 31 cm length), which was packed
with Chromosorb 10% (SP-2100 45/60 mesh Supelco). The
column was heated from 196 to 150 jC within 3 min, and
the gases were separated by using a He flow of 133 ml
min 1. In addition, an aqueous solution was introduced as a
wet aerosol into the plasma by using a nebulizer. Molybdenum was monitored at m/z = 92, 94, 95, 96, 97 and 98. The
isotopic pattern was considered in the determination of
molybdenum-containing samples. The molybdenum hexacarbonyl was identified by retention time matching and
element-specific detection (ICP-MS).
Gruter et al. [67] applied a HG –LT-GC – ICP-MS method
to analyze metal(loid)organic compounds of 12 elements
simultaneously with LODs in the upper femtogram-level.
Element hydrides, methylated species and compounds containing lower molecular organic groups up to the butyl-level
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
could be identified by boiling-point/retention-time correlation. Standards were used to identify such species as
W(CO)6 and Mo(CO)6, which do not form hydrides, and
their retention times depended mainly on their vapor pressures. The method was applied in the measurement of soil
samples from municipal waste deposits. However, a lot of
structural analytical work remains to be done to identify all
the unknown species of the elements As, Sb, Sn, Se, I, Mo,
W, Te, Pb, Bi and Hg.
5.18. Nickel
Nickel tetracarbonyl is used in the manufacture of
catalysts, in nickel vapor plating, as an intermediate in
nickel refining, and in the manufacture of high purity nickel
powder. Also, there are some reports of the presence of
volatile nickel compounds in cigarette smoke, in carbon
monoxide containing industrial hydrogen or nitrogen gas, in
automobile exhaust, and in urban air [49]. Nickel carbonyl
is liposoluble and volatile (bp 43 jC). It can be inhaled and
absorbed by traversing pulmonary alveolar membranes and
the blood –brain barrier [48]. It exhibits acute toxicity, as
well as carcinogenicity and teratogenicity. In spite of the
great concern presented by these issues, the number of
publications about speciation of volatile nickel compounds
is limited.
A cryotrapping –cryofocusing GC –ICP-MS method was
applied by Feldman [48] in the determination of Ni(CO)4 in
fermentation gases from a municipal sewage treatment plant.
No clean-up procedure or derivatization was performed on
the gas samples in order to avoid a change in the molecular
structure of the volatile metal compounds. The analytical
procedure applied was a combination of thermodesorption
of the cryotrapped sample and separation using a non-polar
chromatographic column. The column was heated exponentially from 196 to 150 jC within 3 min and the gases were
separated using a He carrier flow. Although Ni possesses
molecular interferences when it is measured by ICP-MS, it
could be quantified by a semi-quantitative method using an
aqueous standard. The author confirmed the presence of
nickel carbonyl by retention time matching and elemental
identification by isotopic confirmation.
Kim et al. [85] used GC – ICP-MS to analyze nickel
diethyldithiocarbamate compounds in samples such as fortified waters and harbor sediment. Nickel was monitored at
m/z = 58. Signal to background ratios were found to be
acceptable and a detection limit of 6.5 pg s 1 as Ni was
reported.
5.19. Nitrogen
Nitrogen can be measured by ICP-MS, however, with
low sensitivity due to the high background present. Chong
and Houk [27] monitored nitrogen present in various
volatile organic compounds. Although the isotope ratio
was investigated, they encountered difficulties with the
781
low abundance of 15N. Detection limits were reported on
the order of 200 ng s 1.
5.20. Oxygen
It is very difficult to measure oxygen by ICP-MS because
of the high background; oxygen is quite reactive and it is
nearly impossible to remove all oxides that are formed in the
plasma. Brown and Fry [23] reported two adverse effects in
analyzing oxygen by emission detection after excitation in a
plasma; both were due to the entrained atmospheric gas. The
first entailed quenching effects and the second, contamination. Subsequently, the authors reported a limit of detection
of 625 ng with GC for the analysis of oxygen-containing
compounds. To date, Chong’s work in monitoring oxygen
after separation of O-containing compounds by GC and
detection by ICP-MS remains one of the few attempts to
characterize it [27]. In monitoring 16O, the authors were able
to establish a detection limit of 400 ng s 1 for various
alcohols and ketones.
5.21. Phosphorus
Story and Caruso [160] used a reduced pressure helium
MIP to interface a gas chromatograph with a mass spectrometer. Phosphorus in several compounds, including triethylphosphate, malathion and diazinon, was monitored at
m/z = 31. Limits of detection for these compounds ranged
from 100 to 200 pg. Pecheyran et al. [126] tentatively
identified PH3 in semiconductor factory air. Analysis was
performed by GC – ICP-MS and the species identification
was made after calculation of the boiling point. Vonderheide
et al. [181] used ICP-MS for the detection of several of the
organophosphorus pesticides. The use of nitrogen in the
argon plasma yielded an increase in sensitivity of over one
order of magnitude; however, this also served to exacerbate
the presence of polyatomic interferences, such as 14N16O1H+
and 15N16O+, at m/z = 31. The authors employed a collision
cell using He as collision gas to reduce the background
without affecting the analyte signal. Instrument detection
limits of approximately 200 ng l 1 were reported.
5.22. Selenium
Selenium is known to be an essential micronutrient for
most plants and animals including man, and, as a constituent of selenoproteins, it plays a role against oxidative
stress, in the production of thyroid hormones and in the
functioning of the immune system [5]. Organic selenium
species in biological and environmental matter are likely
to be generated from bioalkylation processes, similar to
those established for Hg, Pb, As and Sn. These transformations are probably caused by bacteria and microorganisms; other sources for organo-selenium species may
be animal exhalation from seleno-protein degradation and
metabolites of inorganic selenium absorbed by plants
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[37]. Among the most abundant organic species in environmental and biological samples are volatile methylselenides (dimethylselenide (DMSe), dimethyldiselenide
(DMDSe)); others frequently found are the trimethylselenonium ion and several seleneoaminoacids (selenomethionine, selenocysteine). Gas chromatography has been
successfully applied as a separative technique for Se
species prior to ICP-MS, rfGD-MS or MIP-OES [6,13,
37,108,126]. Due to the high efficiency of the sample
introduction, GC – ICP-MS coupling seems to be the most
sensitive and selective hyphenated method (among other
couplings such as LC-ICP-MS and CE-ICP-MS) for
speciation analysis of seleno-compounds. Different sample
introduction techniques have been assessed for the study
of selenium species in sediments, air and water samples
as well as plants and yeast. Donard’s group utilized a
purge and cryogenic trapping system previously published
by Pechyran et. al [126], for the analysis of selenospecies (Me2Se, Me2Se2, Me2SeS, Me2S) in ocean, estuary and natural surface water samples [5,6,169,170]. In
general, the desorbed analytes were flushed onto a GC
column, separated and detected by ICP-MS at m/z = 82. In
an alternative sample preparation procedure, SPME was
been used for sample introduction to GC – ICP-MS and
MIP-OES of volatile species of selenium, including
Me2Se, Et2Se, Me2Se2, Me2SeS, Me2S from the headspace of selenium accumulating biological matter, such as
lupine, yeast, Indian Mustard, onion, garlic and roasted
coffee [37,106]. SPME was also applied for sample
introduction of seleno-amino acids (selenomethionine,
selenoethionine and selenocystine) after their derivatization with isobutylchloroformate to acylate the amino
group and esterify the carboxylic group in these compounds [183].
There are many other species of selenium that are not
directly amenable to separation by GC and various authors
have used other means to impart volatility. Gallus and
Heumann [60] applied isotope dilution mass spectrometry
in the analysis of inorganic selenium. Selenite was converted into a volatile piazselenol prior to determination and
selenate was determined after conversion into selenite.
Others derivatization reactions have also been utilized as a
means to analyze the selenoamino acids by GC. MontesBayon et al. [116] used ethanol, pyridine and ethylchloroformate to esterify the carboxylic acid and acylate the
amino group of various selenoamino acids. The volatile
analytes were detected by GD-MS. Detection limits of 100
and 115 pg (as Se) were achieved for Se-methionine and Seethionine, respectively. Vonderheide et al. [183] used the
isobutyl counterparts of the same derivatizing reagents to
increase the absorption of the selenium compounds on the
polydimethylsiloxane coating. Detection was performed by
quadrupole ICP-MS and m/z = 77, 78 and 82 were used to
identify selenium. Detection limits of 16, 14 and 29 ng l 1
were achieved for Se-methionine, Se-ethionine and Secystine, respectively. Pelaez et al. [128] published a com-
parison of two derivatization procedures employed in the
analysis of the selenoamino acids. Results showed that the
procedure accomplished esterification and acylation with
propan-2-ol and an anhydride, respectively, and provided
much cleaner chromatograms and more stable derivatives.
Other researchers have focused on the chiral separation of
the selenoamino acids [150] using GC columns containing
suitable stationary phases for their separation. Mendez et al.
[107] used a fused silica Chirasil-L-Val column to separate a
racemic mixture of derivatized DL-selenomethionine. Utilizing ICP-MS allowed for high specificity and sensitivity in
the detection of selenium and detection limits in the high ng
l 1 range were achieved.
5.23. Silicon
Silicones are a diverse class of materials, which may
take the form of fluids, elastomers, or resins and the most
widely used is polydimethylsiloxane (PDMS). Grumping
et al. [66] utilized ICP-OES for the detection of volatile
organosilicon species. Optical emission spectroscopy was
chosen over mass spectrometry because of the non-spectral
matrix effects and mass interferences present in the low
mass region. Trimethylsilanol was found to be the dominant species in gaseous and liquid samples taken from
waste deposit sites, waste composting tanks and sewagedisposal plants. Edler et al. [40], utilized silicon as a
labeling agent to allow detection of n-alkanols by ICPMS. Silylation of butanol, pentanol, hexanol, and heptanol
was performed with N-methyl-N-trimethylsilyltrifluoracetamide in pyridine. A high resolution sector field ICP-MS
was utilized to avoid the polyatomic ions (12C16O+ and
14 +
N2 ) that would affect the detection of silicon at its most
abundant isotope, m/z = 28.
5.24. Sulfur
Sulfur gases such as hydrogen sulfide (H2S) and
methylmercaptan (CH3SH), together with other volatile
sulfur compounds, such as thiols, organic sulfides and
polysulfides, were separated by GC in a study published
by Rodriguez-Fernandez et al. [146]. The authors utilized
double focusing sector-field ICP-MS as a means of
detection. The high resolving power of this instrument
allowed the specific monitoring of the most abundant
isotope of sulfur at m/z = 32. The method was applied to
the analysis of breath samples and detection limits of
between 8 and 33 ng l 1 were reported. Sulfur and
mixed sulfur –selenium volatile compounds were monitored by Meija et al. [106] in Brassica juncea. Sulfur
species, allyl (2-propenyl) isothiocyanate and 3-butenyl
isothiocyanate, were detected in high abundance and were
further characterized by GC – MS. Gas chromatographic
chiral speciation of D- and L-methionine, a sulfur-containing amino acid, was performed on a chiral column that
utilized L-valine tert-butylamide as the stationary phase
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
(Chirasil-L-Val). In this work, Montes-Bayon et al. [117]
monitored sulfur at m/z = 34 by ICP-MS.
5.25. Tellurium
The volatility of the hydride species of tellurium and its
alkyl-species ((Me3)2Te) allows their analysis by GC. GC –
ICP-MS has been frequently used to monitor Te species in
gaseous samples related with domestic waste deposits.
Gruter et al. [67] combined the advantages of two complementary techniques, hydride generation and cryotrapping,
with the separation capabilities of a home-made low temperature-GC and a multielemental detector such as ICP-MS.
The method was successfully applied for the analysis of
metal(oid) organic compounds of 12 elements, including
tellurium. Element hydrides, methylated species and compounds containing lower molecular organic-groups up to the
butyl-level could be identified by a correlation between their
boiling-point and their retention-time. The method was
applied to the measurement of soil samples from municipal
waste deposits. The (Me3)2Te species was identified in the
samples analyzed, however, two other Te-containing peaks
remained unidentified. Volatile species of tellurium were
also investigated in a work developed by Feldmann et al.
[46]. Samples were taken from the headspace of domestic
waste deposits by collection on a trap that was cooled with
acetone/liquid nitrogen (about 80 jC). Samples were then
analyzed by GC –ICP-MS. The 125Te and 126Te isotopes
were monitored and the boiling point of the main peak
present in these chromatograms was calculated. The tentative identification was (CH3)2Te.
5.26. Tin
Tri-substituted butyl- and phenyltins (TBT and TPhT)
have been extensively used in agrochemical products and
biocides. Mono- and di-substituted butyltin compounds are
also widely employed as PVC stabilizers, catalysts or wood
preservatives [54]. These numerous applications give rise
directly or indirectly to the diffusion of free organo-tins in
the environment. An interference-free analytical method for
the determination of MBT, DBT, TBT, monophenyltin
(MPhT), diphenyltin (DPhT), and triphenyltin (TPhT) in
seawater was developed by Girousi et al. [63]. Complete
resolution of the peaks was obtained in a minimal time of 10
min. An optimization of O2 and H2 as make-up gases
prevented carbon deposition as well as increased sensitivity.
The detection limits for all organo-tin species (measured as
Sn at 303.419 nm) were in the range of 17.7 to 33.4 ng l 1.
Carpinteiro Botana et al. [16] reported a procedure for the
simultaneous determination of MeHg, Hg2 +, MBT, DBT,
and TBT species in water samples. The compounds were
analyzed as ethylated derivatives using a multicapillary GC
column and MIP-OES detector. The combined derivatization/microextraction procedure yielded detection limits in
the range of 0.4 to 0.6 ng l 1 with a separation time of 5
783
min. In a recent paper, Tutschku et al. [175] described a
method for the determination of butyltin compounds, including MBT, DBT, and TBT, in marine sediments and
tissue using microwave-assisted acid digestion and SPME
followed by GC – MIP-OES analysis. A SPME procedure,
utilizing a PDMS fiber coating material was used (as
opposed to the typical hexane extraction) achieving enrichment factors of 50 –100 for the butyltin compounds. In this
study, the authors extracted the butyltin species from the
sediments using a low-power microwave field to avoid a
possible decomposition of the butyltin compounds. Further
investigation of the optimal extraction time using several
samples of PACS-1 showed that quantitative extraction of
the butyltin compounds was attained after 4 min. The
detection limits achieved were in the range of 10 to 100
ng kg 1. The application of the GC – MIP-OES coupling for
the speciation analysis of mercury, tin, and lead in environmental samples, has been recently reviewed by Rodrı́guez
Pereiro et al. [130]. The advantages and disadvantages of
GC –MIP-OES are discussed and the broad application of
this technique is justified considering the possibility of low
detection limits and an extensive linear range of calibration
curves. Regarding the different fields of application, GC –
MIP-OES has been used mainly for the determination of
MBT, DBT, TBT, TPhT and DPhT. In all cases, tin species
were determined primarily in water, sediments and biological tissues. From the present information about speciation
analysis of tin compounds, difficulties still remain and
include contamination of blank solutions, limiting sensitivity, and decomposition or transformation of the tin compounds. Moreover, the most important drawback of the
GC –MIP-OES technique is the spectral interferences from
the presence of organic matter as a consequence of the low
temperature used in the generation of the plasma.
Aguerre et al. [3] developed a methodology for the
determination of organo-tin species by GC –ICP-OES. This
publication was the first one that reported the hyphenated
GC –ICP-OES application for the analysis of trace level
organo-tin compounds. A new interface to connect GC with
the ICP-OES detector was designed with the possibility of
using, simultaneously, a cyclonic spray chamber with a
concentric nebulizer for multi-elemental analysis. SPME
was used for the extraction/pre-concentration of MBT,
DBT, TBT, MPhT, DPhT, and TPhT species prior to
separation and detection. The methodology was applied to
the determination of organo-tin species in a PACS-2 sediment certified reference material and a wastewater sample.
A comparative study of flame photometric detection (FPD),
pulsed flame photometric detection (PFPD), MIP-OES, and
ICP-MS after GC separation was carried out by Aguerre et
al. [2] for organotin species present in environmental
samples. Figures of merit obtained and accuracy in the
determination of MBT, DBT, and TBT in PACS-2 sediment
and NIES-11 fish tissue certified reference materials are
reported in the evaluation. It was also noted that, although
SPME-GC – ICP-MS is the most sensitive technique for the
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determination of organotin species, other detectors, such as
FPD and MIP-OES, present broad application in a number
of laboratories.
A modified interface between GC and a hollow cathode
(HC) radio-frequency (rf) glow discharge (GD) with detection by OES has been investigated by Orellana-Velado et al.
[121]. The SPME technique was used for extraction and
pre-concentration of MBT, DBT, and TBT as the ethylated
derivatives. Detection limits obtained were found in the
range of 75 to 21 ng l 1 for tin species. Finally, the
methodology developed was applied to the determination
of the organo-tin species in PACS-2 sediment certified
reference material.
There are few applications of low power/reduced pressure (LP-RP)-ICP-MS as a GC detector in the determination
of tin species. Waggoner et al. [185] used a (LP-RP)ICP-MS
as a GC detector for the determination of tetraethyltin
(TET), trimethylphenyl tin (TMPT), and TBT. A helium
ICP source was operated at an estimated incident rf power
of 12– 15 W and pressures ranging from 0.37 to 1.2 mbar.
Several organotin fragment ions were identified by using
this device. The potential of the source to provide tunable
fragmentation was also investigated. The detection limits
were found in the range of 4 to 11 ng (as tin) for each tin
species. Quantitative and qualitative mass spectrometric
results have been obtained by Milstein et al. [110] for
TET introduced into a mixed gas He/Ar plasma. Detection
limits were found in the range of 0.25 to 0.87 pg. The
methodology was applied only to synthetic aqueous samples. In a different study, Waggoner et al. [184] applied
GC –(LP-RP)ICP-MS for the separation and determination
of organotin and organobromine compounds. Ethylated
forms of the ionic tri-substituted organotin species, tributyltin chloride (TBuSnCl) and tripropyltin chloride
(TPrSnCl) were determined. Chromatographic retention
time and mass spectral matches with ethylated organotin
standards were obtained for the TBuSnCl component of the
certified reference material NIES-11. In this case, the
detection limits were found in the range of 0.12 to 0.56
pg (as Sn) for all species. Glindemann et al. [64] developed
a homemade multifunction interface to connect a capillary
gas chromatograph and an ICP-MS. They analyzed compounds with boiling points as high as that of C26 n-paraffin
(412 jC) using only a temperature of 140 jC for the transfer
line. The design permitted splitless large volume solvent
injection to analyze very low and high boiling analytes in
one run. Detection limits for 20 Al injections of organo-tin
species (propyl derivatives of all methyl and n-butyl, monoand di-n-octyl, and all phenyltin) ranged from 68 to 250 fg
absolute after extraction of an 80 ml synthetic sample
volume and concentration to 1 ml of cyclopentane.
Different approaches utilizing isotope dilution (ID) with
GC –ICP-MS have been applied in order to increase the
accuracy and precision of the determination of organotin
species. Ruiz Encinar et al. [42] used isotope dilution for the
determination of DBT species in PACS-2 and CRM-462
sediment certified reference material with GC separation
coupled to ICP-MS detection. Although this methodology
yielded good accuracy and precision, high blank signals and
sample inhomogeneity produced a deterioration of the
precision. Also, broadening effects of the DBT and TBT
peaks were found to occur due to organic matter deposition
in the PFA transfer line between the GC and ICP-MS. Yang
et al. [190] developed a methodology for the determination
of butyltin species in marine sediment PACS-2 standard
reference material by using a 117Sn-enriched tributyltin
(TBT) spike. SPME was combined with GC separation
and ICP-MS detection. Butyltin compounds were ethylated
in aqueous solution with sodium tetraethylborate and the
headspace sampled with a polydimethylsiloxane-coated
fused silica SPME fiber. An 18-fold improvement in the
precision of the measured TBT concentration using ID was
obtained. The detection limit obtained for TBT in PACS-2
sediment was 0.09 ng g 1. In a different study, Ruiz
Encinar et al. [43] utilized the ID technique to determine
the performance of several extraction procedures for butyltin species in PACS-2 and BCR-646 sediment certified
reference materials. The leaching extractions were performed with a methanol – acetic acid mixture. 119Snenriched MBT, 118Sn-enriched DBT and 119Sn-enriched
TBT were evaluated in the ID analysis. After derivatization
with sodium tetraethylborate, the organotin species were
determined by GC – ICP-MS analysis. Results confirmed
that no degradation of the organotin species took place
when ultrasonic or mechanical extractions were applied.
However, degradation factors, up to 7% for TBT and DBT
and 16% for DBT and MBT, were obtained for both
reference materials when high-microwave (MW) energy
was applied in the extraction step. More specifically, a
recent review paper [4] as well as other published results
[44,133,141] describe and analyze the influence of highMW energy, ultrasound and mechanical shaking extraction
procedures in the speciation analysis of MBT, DBT, and
TBT from PACS-2, CRM 462, and CRM 646 sediments. In
all cases, the authors emphasize the possible degradation of
the organo-tin species during extraction procedures and
propose correction factors for the transformation of the tin
species. Rodrı́guez-González et al. [147] developed a method for the simultaneous determination of MBT, DBT, and
TBT in coastal seawater samples by GC – ICP-MS. The
method was based on the use of isotope dilution using
119
Sn enriched butyltin species. The detection limits
achieved were in the range of 0.09 to 0.27 ng l 1. A simple
method was developed for the simultaneous extraction of
Sn, MBT, DBT, TBT, TPhT, and tripentyltin (TPeT) from
sediments before GC –ICP-MS determination [141]. The tin
species were quantitatively extracted from sediment by
mechanical shaking into tropolone –toluene and HCl – methanol mixtures. The methodology was applied to the determination of the organo-tin species in PACS-2 and NIES No.
12 sediment certified reference materials, and marine sediment samples. Rajendran et al. [140] determined organo-tin
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
compounds and inorganic tin in seawater and sediments from
two harbors and several locations on the southeast coast of
India. The GC and ICP-MS systems employed were
connected by a laboratory-made transfer line. Different
organo-tin species were determined, including MBT, DBT,
TBT, tributylmonomethyltin (TBMT), monooctyltin (MOT),
dioctyltin (DOT), and trioctyltin (TOT). High concentrations
of inorganic tin in estuarine sediments indicated an elevated
rate of debutylation in the estuarine environment. A significant correlation between total butyltin and organic carbon in
sediment was observed. The extraction and pre-concentration capabilities of a new extraction technique using stir bar
sorptive extraction were combined with GC – ICP-MS by
Vercauteren et al. [180]. Different organo-tin species, including TBT and TPhT, were determined in aqueous standard
solutions, harbor water, and tissue samples. The compounds
were extracted from their aqueous matrix using a 1-cmlength stir bar, coated with PDMS. Organo-tin species
adsorbed on the stir bar coating material and were then
desorbed in a thermal unit at 290 jC for 15 min, coldtrapping the compounds on a precolumn at
40 jC. A
homemade transfer line was used to connect the GC and ICPMS. Detection limits on order of 10 fg l 1 were reported for
the method. These LOD values were the lowest reported to
date and are 2 – 3 orders of magnitude lower than those
obtained by HS-SPME-GC – ICP-MS. Vercauteren et al.
[179] also developed a method to speciate TPhT and the
fentin pesticide by using HS-SPME before separation and
GC – ICP-MS. This pesticide was determined in potato
samples due to its application as a fungicide. An enhancement of 11-fold was obtained when the headspace technique
was applied instead of direct aqueous SPME. A low instrumental detection limit (125 pg l 1) was obtained for fentin in
aqueous solutions.
Time-of-flight mass spectrometry for GC detection has
not been extensively applied for speciation studies of tin.
Leach et al. [92] used ICP-TOFMS as a detector for GC
separation in the speciation analysis of tetramethyltin
(Me4T), tetraethyltin (Et4T), and tetraethyllead. Data acquisition was limited to 78 integrated complete mass spectra
per second. However, collection of data points every 12.75
ms was sufficient for the measurement of the fastest
transient signals. Determination of the organo-tin species
was performed in standard aqueous solutions and the
absolute detection limits were 125 pg l 1. Another application of GC – ICP-TOFMS for the determination of volatile
tin compounds in landfill gas samples has been reported by
Haas et al. [71]. A cryotraping GC – ICP-TOFMS methodology was developed and the suitability of the TOF mass
analyzer for multiple elemental speciation analysis and
multi-isotope ratio determinations was evaluated in terms
of accuracy and precision. The isotopic ratio 118Sn/120Sn
was utilized for different elemental species, including SnH4,
MeSnH3, Me2SnH2, Me3SnH, and BuSnH3. It was observed
that a minimum of f 500 pg of each species was necessary
in order to measure isotopic ratios with good precision.
785
A method for the determination of ultratrace organo-tin
species was described by Tao et al. [168]. The sensitivity of
GC – ICP-MS was increased 100-fold through use of a
shielded torch. The authors suggest that the reason for this
improvement in sensitivity might be a decrease in the
secondary discharge process at the interface region, which
could decrease ion energy dispersion and consequently
increase ion transmission into the mass spectrometer. An
instrumental detection limit of 0.01 pg l 1 was obtained
after extraction with hexane, producing a concentration
factor of 1000. The methodology was applied to the
determination of inorganic Sn, MBT, DBT, TBT, MPhT,
DPhT, and TPhT in open ocean seawater samples.
5.27. Tungsten
Although the information of tungsten-containing
enzymes in the biosphere is limited, it is well known that
these are present in anaerobic and aerobic organisms such as
bacteria, plants, and animals. These organisms are believed
to be involved in the generation of W(CO)6, either producing it themselves or reducing biologically or chemically the
metallic species into a very active form of the element that
reacts with CO to produce the hexacarbonyls. Tungsten as
well as molybdenum are widely used in hard alloys;
therefore, municipal waste is also a possible source of these
elements.
The analysis of volatile species of tungsten (W(CO)6),
among other volatile species of metal and metalloid elements in sewage and waste deposits, has been carried out by
using different cryotrapping methods coupled to a GC –ICPMS system [48,49,67]. In all the cases, the species has been
identified by retention time and by using an elementalspecific detector (ICP-MS).
5.28. Vanadium
Metal associated porphyrins are constituents of many
crude oils, shale oil and sedimentary rocks and they have
been proposed as maturity indicators for such substances. In
the analysis of metalloporphyrins, Pretorius et al. [137]
isolated vanadyl porphyrins by column chromatography to
obtain a standard for analysis. Metalloporphyrins were
separated by GC prior to ICP-MS detection. Due to the
large molecular size, a high temperature aluminum-clad
column was used and the temperature was programmed
from 60 to 410 jC. Vanadium was monitored at m/z = 51
and the limit of detection for vanadyl octaethylporphyrin
was given as 0.51 ng as V on column.
5.29. Zinc
The analysis of metal porphyrins (geoporphyrins) is
important in the petroleum industry. In pursuit of this,
Pretorius et al. [137] used high temperature GC –ICP-MS
for the analysis of zinc octaethylporphyrin; oven temper-
786
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
atures were taken to 410 jC during the course of the run.
The authors utilized a 10-m, aluminum-clad high-temperature column to accomplish the separation of the various
metalloporphyrins of interest. Zinc was monitored at
m/z = 64 and the limit of detection for the zinc porphyrin
was reported at 0.14 ng on column.
[4]
[5]
6. Conclusions
The technique of coupling gas chromatography to plasma
spectrometry has expanded the applicability of each individual technique in the area of speciation studies. Recent
publications have shown comparable figures of merit among
different plasma sources used as detectors for gas chromatography in standard applications such as the analysis of
organo-mercury, organo-lead and organo-tin species. The
coupling of GC to plasma detectors not only yields low
detection limits but represents an efficient way to perform
isotopic studies. Mass spectrometry is an efficient tool,
which when combined with isotope dilution, has been
applied for speciation studies on real samples and also to
evaluate the performance of the derivatization reagents for
organo-mercury, organo-lead and organo-tin species prior to
GC analysis. Some optical spectrometric techniques, such as
MIP-OES, FIP-OES and GD-OES, have been successfully
applied for identification studies of organometallic and also
non-metallic species. Microwave-assisted or supercritical
fluid extractions have been used in the sample preparation
step as an alternative to conventional acidic leaching due to
their high efficiency and minimal decomposition effects.
Other improvements in the sample introduction steps have
been observed with the use of cryogenic traps, solid phase
micro-extraction, cold vapor generation, stir bar sorptive
extraction and pre-concentration on C18 or fullerene resins.
These techniques are useful not only to introduce the analyte
into the gas chromatograph, but also to avoid interferences
by carbon when MIP-OES or FIP-OES are employed as
detectors.
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
Acknowledgments
[16]
We would like to acknowledge NIEHS grant #ES04908
for partial funding of this review.
[17]
References
[1] M.M. Abdillahi, Gas-chromatography microwave-induced plasma
for the determination of halogenated hydrocarbons, J. Chromatogr.
Sci. 28 (1990) 613 – 616.
[2] S. Aguerre, G. Lespes, V. Desauziers, M. Potin-Gautier, Speciation
of organotins in environmental samples by SPME-GC: comparison
of four specific detectors: FPD, PFPD, MIP-AES and ICP-MS, J.
Anal. At. Spectrom. 16 (2001) 263 – 269.
[3] S. Aguerre, C. Pecheyran, G. Lespes, E. Krupp, O.F.X. Donard, M.
[18]
[19]
Potin-Gautier, Optimisation of the hyphenation between solid-phase
microextraction, capillary gas chromatography and inductively coupled plasma atomic emission spectrometry for the routine speciation
of organotin compounds in the environment, J. Anal. At. Spectrom.
16 (2001) 1429 – 1433.
J.I.G. Alonso, J.R. Encinar, P.R. Gonzalez, A. Sanz-Medel, Determination of butyltin compounds in environmental samples by isotope-dilution GC – ICP-MS, Anal. Bioanal. Chem. 373 (2002)
432 – 440.
D. Amouroux, P.S. Liss, E. Tessier, M. Hamren-Larsson, O.F.X.
Donard, Role of oceans as biogenic sources of selenium, Earth
Planet. Sci. Lett. 189 (2001) 277 – 283.
D. Amouroux, E. Tessier, C. Pecheyran, O.F.X. Donard, Sampling
and probing volatile metal(loid) species in natural waters by in-situ
purge and cryogenic trapping followed by gas chromatography and
inductively coupled plasma mass spectrometry (P-CT-GC – ICP/
MS), Anal. Chim. Acta 377 (1998) 241 – 254.
P. Andrewes, W.R. Cullen, E. Polishchuk, Confirmation of the aerobic production of trimethylstibine by Scopulariopsis brevicaulis,
Appl. Organomet. Chem. 13 (1999) 659 – 664.
H.L. Armstrong, W.T. Corns, P.B. Stockwell, G. O’Connor, L. Ebdon,
E.H. Evans, Comparison of AFS and ICP-MS detection coupled with
gas chromatography for the determination of methylmercury in marine samples, Anal. Chim. Acta 390 (1999) 245 – 253.
T.N. Asp, S. Pedersen-Bjergaard, T. Greibrokk, Determination of
chlorinated and brominated micropollutants by capillary gas chromatography coupled with on-column radio frequency plasma atomic
emission detection, HRC-J, High Resolut. Chromatogr. 20 (1997)
201 – 207.
J.R. Baena, M. Gallego, M. Valcarcel, J. Leenaers, F.C. Adams,
Comparison of three coupled gas chromatographic detectors (MS,
MIP-AES, ICP-TOFMS) for organolead speciation analysis, Anal.
Chem. 73 (2001) 3927 – 3934.
E. Baltussen, C.A. Cramers, P.J.F. Sandra, Sorptive sample preparation—a review, Anal. Bioanal. Chem. 373 (2002) 3 – 22.
H. Baumann, K.G. Heumann, Analysis of organobromine compounds and Hbr in motor car exhaust-gases with a Gc microwave
plasma system, Fresenius Zeitschrift fur Analytische Chemie, 327
(1987) 186 – 192.
M.M. Bayon, C. B’Hymer, C.A.P. de Leon, J.A. Caruso, The use
of radiofrequency glow discharge-mass spectrometry (rf-GD-MS)
coupled to gas chromatography for the determination of selenoaminoacids in biological samples, J. Anal. At. Spectrom. 16 (2001)
492 – 497.
M.M. Bayon, M.G. Camblor, J.I.G. Alonso, A. Sanz-Medel, An
alternative GC – ICP-MS interface design for trace element speciation, J. Anal. At. Spectrom. 14 (1999) 1317 – 1322.
N.H. Bings, J.M. Costa-Fernandez, J.P. Guzowski, A.M. Leach,
G.M. Hieftje, Time-of-flight mass spectrometry as a tool for speciation analysis, Spectrochim. Acta Part B. 55 (2000) 767 – 778.
J.C. Botana, R.R. Rodriguez, A.M.C. Diaz, R.A.L. Ferreira, R.C.
Torrijos, I.R. Pereiro, Fast and simultaneous determination of tin
and mercury species using SPME, multicapillary gas chromatography and MIP-AES detection, J. Anal. At. Spectrom. 17 (2002)
904 – 907.
B. Bouyssiere, F. Baco, L. Savary, R. Lobinski, Speciation analysis for mercury in gas condensates by capillary gas chromatography with inductively coupled plasma mass spectrometric detection,
J. Chromatogr., A 976 (2002) 431 – 439.
B. Bouyssiere, J. Szpunar, R. Lobinski, Gas chromatography with
inductively coupled plasma mass spectrometric detection in speciation analysis, Spectrochim. Acta Part B. 57 (2002) 805 – 828.
C. Brede, E. Lundanes, T. Greibrokk, S. Pedersen-Bjergaard, Capillary gas chromatography coupled with microplasma mass spectrometry—improved ion source design compatible with bench-top
mass spectrometric instrumentation, HRC-J, High Resolut. Chromatogr. 21 (1998) 282 – 286.
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
[20] C. Brede, E. Lundanes, Y. Greibrokk, S. Pedersen-Bjergaard, Simultaneous element-selective detection of C, F, Cl, Br, and I by capillary
gas chromatography coupled with microplasma mass spectrometry,
HRC-J, High Resolut. Chromatogr. 21 (1998) 633 – 639.
[21] C. Brede, S. Pedersen-Bjergaard, E. Lundanes, T. Greibrokk, Capillary gas chromatography coupled with negative ionization microplasma mass spectrometry for halogen-selective detection, J. Anal.
At. Spectrom. 15 (2000) 55 – 60.
[22] J.R.M. Brown, S.J. Northway, R.C. Fry, Inductively coupled plasma
as a selective gas chromatographic detector for nitrogen-containing
compounds, Anal. Chem. 53 (1981) 934 – 936.
[23] J.R.M. Brown, R.C. Fry, Near-infrared atomic oxygen emissions in
the inductively coupled plasma and oxygen-selective gas – liquid
chromatography, Anal. Chem. 53 (1981) 532 – 538.
[24] E. Bulska, D.C. Baxter, W. Frech, Capillary column gas-chromatography for mercury speciation, Anal. Chim. Acta 249 (1991)
545 – 554.
[25] T.M. Castillano, J.J. Giglio, E.H. Evans, J.A. Caruso, Evaluation of
low-pressure inductively-coupled plasma-mass spectrometry for the
analysis of gaseous samples, J. Anal. At. Spectrom. 9 (1994)
1335 – 1340.
[26] M. Ceulemans, F.C. Adams, Integrated sample preparation and
speciation analysis for the simultaneous determination of methylated species of tin, lead and mercury in water by purge-and-trap
injection-capillary gas chromatography atomic emission spectrometry, J. Anal. At. Spectrom. 11 (1996) 201 – 206.
[27] N.S. Chong, R.S. Houk, Inductively coupled plasma-mass spectrometry for elemental analysis and isotope ratio determinations in individual organic compounds separated by gas chromatography, Appl.
Spectrosc. 41 (1987) 66 – 74.
[28] N.S. Chong, R.S. Houk, Inductively coupled plasma-mass spectrometry for elemental analysis and isotope ratio determinations in individual organic-compounds separated by gas-chromatography, Appl.
Spectrosc. 41 (1987) 66 – 74.
[29] J.M. Costa-Fernandez, N.H. Bings, A.M. Leach, G.M. Hieftje, Rapid simultaneous multielemental speciation by capillary electrophoresis coupled to inductively coupled plasma time-of-flight mass
spectrometry, J. Anal. At. Spectrom. 15 (2000) 1063 – 1067.
[30] J.T. Creed, T.M. Davidson, W.L. Shen, J.A. Caruso, Low-pressure
helium microwave-induced plasma mass-spectrometry for the detection of halogenated gas-chromatographic effluents, J. Anal. At.
Spectrom. 5 (1990) 109 – 113.
[31] T. De Smaele, L. Moens, R. Dams, P. Sandra, J. Van der Eycken, J.
Vandyck, Sodium tetra(n-propyl)borate: a novel aqueous in situ derivatization reagent for the simultaneous determination of organomercury, -lead and -tin compounds with capillary gas chromatography
inductively coupled plasma mass spectrometry, J. Chromatogr., A
793 (1998) 99 – 106.
[32] T. De Smaele, L. Moens, P. Sandra, R. Dams, Determination of
organometallic compounds in surface water and sediment samples
with SPME-CGC – ICP-MS, Mikrochim. Acta 130 (1999) 241 – 251.
[33] M.B. delaCalleGuntinas, R. Scerbo, S. Chiavarini, P. Quevauviller,
R. Morabito, Comparison of derivatization methods for the determination of butyl- and phenyl-tin compounds in mussels by gas chromatography, Appl. Organomet. Chem. 11 (1997) 693 – 702.
[34] N. Demuth, K.G. Heumann, Validation of methylmercury determinations in aquatic systems by alkyl derivatization methods for GC
analysis using ICP-IDMS, Anal. Chem. 73 (2001) 4020 – 4027.
[35] T. De Smaele, L. Moens, R. Dams, P. Sandra, Capillary gas chromatography ICP mass spectrometry: a powerful hyphenated technique for the determination of organometallic compounds,
Fresenius’ J. Anal. Chem. 355 (1996) 778 – 782.
[36] T. De Smaele, P. Verrept, L. Moens, R. Dams, A flexible interface
for the coupling of capillary gas chromatography with inductively
coupled plasma mass spectrometry, Spectrochim. Acta Part B. 50
(1995) 1409 – 1416.
[37] C. Dietz, J.S. Landaluze, P. Ximenez-Embun, Y. Madrid-Albarran,
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
787
C. Camara, Volatile organo-selenium speciation in biological matter
by solid phase microextraction-moderate temperature multicapillary
gas chromatography with microwave induced plasma atomic emission spectrometry detection, Anal. Chim. Acta 501 (2004) 157 – 167.
L. Dunemann, H. Hajimiragha, J. Begerow, Simultaneous determination of Hg(II) and alkylated Hg, Pb, and Sn species in human body
fluids using SPME-GC/MS-MS, Fresenius’ J. Anal. Chem. 363
(1999) 466 – 468.
L. Ebdon, E.H. Evans, W.G. Pretorius, S.J. Rowland, Analysis of
geoporphyrins by high-temperature gas-chromatography inductively-coupled plasma-mass spectrometry and high-performance liquidchromatography inductively-coupled plasma-mass spectrometry, J.
Anal. At. Spectrom. 9 (1994) 939 – 943.
M. Edler, D. Metze, N. Jakubowski, M. Linscheid, Quantification of
silylated organic compounds using gas chromatography coupled to
ICP-MS, J. Anal. At. Spectrom. 17 (2002) 1209 – 1212.
H. Emteborg, E. Bjorklund, F. Odman, L. Karlsson, L. Mathiasson,
W. Frech, D.C. Baxter, Determination of methylmercury in sediments using supercritical fluid extraction and gas chromatography
coupled with microwave-induced plasma atomic emission spectrometry, Analyst 121 (1996) 19 – 29.
J.R. Encinar, J. Alonso, A. Sanz-Medel, Synthesis and application
of isotopically labelled dibutyltin for isotope dilution analysis using
gas chromatography – ICP-MS, J. Anal. At. Spectrom. 15 (2000)
1233 – 1239.
J.R. Encinar, P.R. Gonzalez, J.I.G. Alonso, A. Sanz-Medel, Evaluation of extraction techniques for the determination of butyltin compounds in sediments using isotope dilution-GC/ICP-MS with Sn-118
and Sn-119-enriched species, Anal. Chem. 74 (2002) 270 – 281.
J.R. Encinar, I.L. Granadillo, J.I.G. Alonso, A. Sanz-Medel, Isotope
ratio measurements using gas chromatography inductively coupled
plasma mass spectrometry for the assessment of organolead sources,
J. Anal. At. Spectrom. 16 (2001) 475 – 480.
E.H. Evans, J.A. Caruso, Low-pressure inductively-coupled plasma
source for mass-spectrometry, J. Anal. At. Spectrom. 8 (1993)
427 – 431.
J. Feldman, R. Grumping, A.V. Hirner, Determination of volatile
metal and metalloid compounds in gases from domestic waste
deposits with GC/ICP-MS, Fresenius’ J. Anal. Chem. 350 (1994)
228 – 234.
J. Feldmann, Summary of a calibration method for the determination
of volatile metal(loid) compounds in environmental gas samples by
using gas chromatography inductively coupled plasma mass spectrometry, J. Anal. At. Spectrom. 12 (1997) 1069 – 1076.
J. Feldmann, Determination of Ni(CO)(4), Fe(CO)(5), Mo(CO)(6),
and W(CO)(6) in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry, J. Environ.
Monit. 1 (1999) 33 – 37.
J. Feldmann, W.R. Cullen, Occurrence of volatile transition metal
compounds in landfill gas: synthesis of molybdenum and Tungsten
carbonyls in the environment, Environ. Sci. Technol. 31 (1997)
2125 – 2129.
J. Feldmann, R. Grumping, A.V. Hirner, Determination of volatile
metal and metalloid compounds in gases from domestic waste
deposits with GC ICP-MS, Fresenius’ J. Anal. Chem. 350 (1994)
228 – 234.
J. Feldmann, I. Koch, W.R. Cullen, Complementary use of capillary
gas chromatography mass spectrometry (ion trap) and gas chromatography inductively coupled plasma mass spectrometry for the speciation of volatile antimony, tin and bismuth compounds in landfill
and fermentation gases, Analyst 123 (1998) 815 – 820.
J. Feldmann, E.M. Krupp, D. Glindemann, A.V. Hirner, W.R. Cullen,
Methylated bismuth in the environment, Appl. Organomet. Chem. 13
(1999) 739 – 748.
J. Feldmann, L. Naels, K. Haas, Cryotrapping of CO2-rich atmospheres for the analysis of volatile metal compounds using capillary
GC – ICP-MS, J. Anal. At. Spectrom. 16 (2001) 1040 – 1043.
788
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
[54] K. Fent, Organotin compounds in municipal wastewater and sewage
sludge: contamination, fate in treatment process and ecotoxicological consequences, Sci. Total Environ. 185 (1996) 151 – 159.
[55] R.G. Fernandez, M.M. Bayon, J.I.G. Alonso, A. Sanz-Medel, Comparison of different derivatization approaches for mercury speciation
in biological tissues by gas chromatography/inductively coupled
plasma mass spectrometry, J. Mass Spectrom. 35 (2000) 639 – 646.
[56] W. Frech, J.P. Snell, R.E. Sturgeon, Performance comparison between furnace atomisation plasma emission spectrometry and microwave induced plasma-atomic emission spectrometry for the
determination of mercury species in gas chromatography effluents,
J. Anal. At. Spectrom. 13 (1998) 1347 – 1353.
[57] H. Frischenschlager, C. Mittermayr, M. Peck, E. Rosenberg, M.
Grasserbauer, The potential of gas chromatography with microwave-induced plasma atomic emission detection (GC – MIP-AED)
as a complementary analytical technique in environmental screening analysis of aqueous samples, Fresenius’ J. Anal. Chem. 359
(1997) 213 – 221.
[58] R.C. Fry, S.J. Northway, R.M. Brown, S.K. Hughes, Atomic fluorine
spectra in the argon inductively coupled plasma, Anal. Chem. 52
(1980) 1716 – 1722.
[59] R.C. Fry, S.J. Northway, R.M. Brown, S.K. Hughes, Atomic fluorine
spectra in the argon inductively coupled plasma, Anal. Chem. 52
(1980) 1716 – 1722.
[60] S.M. Gallus, K.G. Heumann, Development of a gas chromatography
inductively coupled plasma isotope dilution mass spectrometry system for accurate determination of volatile element species. 1 Selenium speciation, J. Anal. At. Spectrom. 11 (1996) 887 – 892.
[61] E.S. Garcia, J.I.G. Alonso, A. Sanz-Medel, Determination of butyltin compounds in sediments by means of hydride generation cold
trapping gas chromatography coupled to inductively coupled plasma mass spectrometric detection, J. Mass Spectrom. 32 (1997)
542 – 549.
[62] C. Gerbersmann, M. Heisterkamp, F.C. Adams, J.A.C. Broekaert,
Two methods for the speciation analysis of mercury in fish involving
microwave-assisted digestion and gas chromatography atomic emission spectrometry, Anal. Chim. Acta 350 (1997) 273 – 285.
[63] S. Girousi, E. Rosenberg, A. Voulgaropoulos, M. Grasserbauer, Speciation analysis of organotin compounds in Thermaikos Gulf by
GC – MIP-AED, Fresenius’ J. Anal. Chem. 358 (1997) 828 – 832.
[64] D. Glindemann, G. Ilgen, R. Herrmann, T. Gollan, Advanced GC/
ICP-MS design for high-boiling analyte speciation and large volume
solvent injection, J. Anal. At. Spectrom. 17 (2002) 1386 – 1389.
[65] P. Grinberg, R.C. Campos, Z. Mester, R.E. Sturgeon, A comparison
of alkyl derivatization methods for speciation of mercury based on
solid phase microextraction gas chromatography with furnace atomization plasma emission spectrometry detection, J. Anal. At. Spectrom. 18 (2003) 902 – 909.
[66] R. Grumping, D. Mikolajczak, A.V. Hirner, Determination of trimethylsilanol in the environment by LT-GC/ICP-OES and GC – MS,
Fresenius’ J. Anal. Chem. 361 (1998) 133 – 139.
[67] U.M. Gruter, J. Kresimon, A.V. Hirner, A new HG/LT-GC/ICP-MS
multi-element speciation technique for real samples in different matrices, Fresenius’ J. Anal. Chem. 368 (2000) 67 – 72.
[68] M. Guilhaus, Essential elements of time-of-flight mass spectrometry
in combination with the inductively coupled plasma ion source,
Spectrochim. Acta Part B. 55 (2000) 1511 – 1525.
[69] D.F. Gurka, S. Pyle, R. Titus, Environmental applications of gas chromatography atomic emission detection, Anal. Chem. 69 (1997)
2411 – 2417.
[70] J.P. Guzowski, G.M. Hieftje, Gas sampling glow discharge: a versatile ionization source for gas chromatography time-of-flight mass
spectrometry, Anal. Chem. 72 (2000) 3812 – 3820.
[71] K. Haas, J. Feldmann, R. Wennrich, H.J. Stark, Species-specific
isotope-ratio measurements of volatile tin and antimony compounds
using capillary GC – ICP-time-of-flight MS, Fresenius’ J. Anal.
Chem. 370 (2001) 587 – 596.
[72] D.F. Hagen, J. Belisle, J.S. Marhevka, Capillary-Gc Helium Microwave Emission Detector Characterization of Fluorine Containing
Metabolites in Blood-Plasma, Spectrochim. Acta Part B. 38 (1983)
377 – 385.
[73] J. Hajslova, P. Cuhra, M. Kempny, J. Poustka, K. Holadova, V.
Kocourek, Determination of polychlorinated-biphenyls in biotic matrices using gas-chromatography microwave-induced plasma-atomic
emission-spectrometry, J. Chromatogr., A 699 (1995) 231 – 239.
[74] M.L. Hardy, The toxicology of the three commercial polybrominated
diphenyl oxide (ether) flame retardants, Chemosphere 46 (2002)
757 – 777.
[75] M. Heisterkamp, F.C. Adams, Simplified derivatization method for
the speciation analysis of organolead compounds in water and peat
samples using in-situ butylation with tetrabutylammonium tetrabutylborate and GC – MIP AES, Fresenius’ J. Anal. Chem. 362 (1998)
489 – 493.
[76] M. Heisterkamp, F.C. Adams, In situ propylation using sodium tetrapropylborate as a fast and simplified sample preparation for the
speciation analysis of organolead compounds using GC – MIP-AES,
J. Anal. At. Spectrom. 14 (1999) 1307 – 1311.
[77] M. Heisterkamp, T. De Smaele, J.P. Candelone, L. Moens, R. Dams,
F.C. Adams, Inductively coupled plasma mass spectrometry hyphenated to capillary gas chromatography as a detection system for the
speciation analysis of organolead compounds in environmental
waters, J. Anal. At. Spectrom. 12 (1997) 1077 – 1081.
[78] H. Hintelmann, R.D. Evans, Application of stable isotopes in environmental tracer studies—measurement of monomethylmercury
(CH3Hg+) by isotope dilution ICP-MS and detection of species
transformation, Fresenius’ J. Anal. Chem. 358 (1997) 378 – 385.
[79] H. Hintelmann, R.D. Evans, J.Y. Villeneuve, Measurement of mercury methylation in sediments by using enriched stable mercury
isotopes combined with methylmercury determination by gas-chromatography inductively-coupled plasma-mass spectrometry, J. Anal.
At. Spectrom. 10 (1995) 619 – 624.
[80] H. Hintelmann, R. Falter, G. Ilgen, R.D. Evans, Determination of
artifactual formation of monomethylmercury (CH3Hg+) in environmental samples using stable Hg2+ isotopes with ICP-MS detection:
calculation of contents applying species specific isotope addition,
Fresenius’ J. Anal. Chem. 358 (1997) 363 – 370.
[81] A.V. Hirner, U.M. Gruter, J. Kresimon, Metal(loid)organic compounds in contaminated soil, Fresenius’ J. Anal. Chem. 368
(2000) 263 – 267.
[82] J. Holz, J. Kreutzmann, R.D. Wilken, R. Falter, Methylmercury
monitoring in rainwater samples using in situ ethylation in combination with GC – AFS and GC – ICP-MS techniques, Appl. Organomet. Chem. 13 (1999) 789 – 794.
[83] E. Jantzen, A. Prange, Organometallic species of the elements tin,
mercury and lead in sediments of the longitudinal profile of the
River Elbe, Fresenius’ J. Anal. Chem. 353 (1995) 28 – 33.
[84] L.J. Jerrell, M.R. Dunn, J.E. Anderson, H.B. Fannin, Low-power
inductively coupled plasma source for element-selective atomic
emission detection in gas chromatography, Appl. Spectrosc. 53
(1999) 245 – 248.
[85] A. Kim, S. Hill, L. Ebdon, S. Rowland, Determination of organometallic compounds by capillary gas-chromatography – inductively
coupled plasma mass-spectrometry, HRC-J, High Resolut. Chromatogr. 15 (1992) 665 – 668.
[86] A.W. Kim, M.E. Foulkes, L. Ebdon, S.J. Hill, R.L. Patience, A.G.
Barwise, S.J. Rowland, Construction of a capillary gas-chromatography inductively coupled plasma mass-spectrometry transfer line
and application of the technique to the analysis of alkyllead species
in fuel, J. Anal. At. Spectrom. 7 (1992) 1147 – 1149.
[87] I. Koch, J. Feldmann, J. Lintschinger, S.V. Serves, W.R. Cullen, K.J.
Reimer, Demethylation of trimethylantimony species in aqueous
solution during analysis by hydride generation gas chromatography
with AAS and ICP MS detection, Appl. Organomet. Chem. 12
(1998) 129 – 136.
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
[88] J. Kresimon, U.M. Gruter, A.V. Hirner, HG/LT-GC/ICP-MS coupling for identification of metal(loid) species in human urine after
fish consumption, Fresenius’ J. Anal. Chem. 371 (2001) 586 – 590.
[89] E.M. Krupp, C. Pecheyran, S. Meffan-Main, O.F.X. Donard, Precise
isotope-ratio measurements of lead species by capillary gas chromatography hyphenated to hexapole Multicollector ICP-MS, Fresenius’
J. Anal. Chem. 370 (2001) 573 – 580.
[90] E.M. Krupp, C. Pecheyran, H. Pinaly, M. Motelica-Heino, D. Koller,
S.M.M. Young, I.B. Brenner, O.F.X. Donard, Isotopic precision for
a lead species (PbEt4) using capillary gas chromatography coupled to inductively coupled plasma-multicollector mass spectrometry, Spectrochim. Acta Part B. 56 (2001) 1233 – 1240.
[91] L. Lambertsson, E. Lundberg, M. Nilsson, W. Frech, Applications of
enriched stable isotope tracers in combination with isotope dilution
GC – ICP-MS to study mercury species transformation in sea sediments during in situ ethylation and determination, J. Anal. At. Spectrom. 16 (2001) 1296 – 1301.
[92] A.M. Leach, M. Heisterkamp, F.C. Adams, G.M. Hieftje, Gas chromatography – inductively coupled plasma time-of-flight mass spectrometry for the speciation analysis of organometallic compounds,
J. Anal. At. Spectrom. 15 (2000) 151 – 155.
[93] I.A. Leal-Granadillo, J.I.G. Alonso, A. Sanz-Medel, Determination
of the speciation of organolead compounds in airborne particulate
matter by gas chromatography – inductively coupled plasma mass
spectrometry, Anal. Chim. Acta 423 (2000) 21 – 29.
[94] J. Leenaers, W. Van Mol, H.G. Infante, F.C. Adams, Gas chromatography – inductively coupled plasma-time-of-flight mass spectrometry as a tool for speciation analysis of organomercury compounds in
environmental and biological samples, J. Anal. At. Spectrom. 17
(2002) 1492 – 1497.
[95] C.L. Lewis, M.A. Moser, D.E. Dale, W. Hang, C. Hassell, F.L. King,
V. Majidi, Time-gated pulsed glow discharge: real-time chemical
speciation at the elemental, structural, and molecular level for gas
chromatography time-of-flight mass spectrometry, Anal. Chem. 75
(2003) 1983 – 1996.
[96] C.L. Lewis, M.A. Moser, W. Hang, D.E. Dale, D.C. Hassell, V.
Majidi, Influence of discharge parameters on real-time chemical
speciation for gas chromatography pulsed glow discharge plasma
time-of-flight mass spectrometry, J. Anal. At. Spectrom. 18 (2003)
629 – 636.
[97] D.C. Liang, M.W. Blades, An atmospheric-pressure capacitively
coupled plasma formed inside a graphite-furnace as a source for
atomic emission-spectroscopy, Spectrochim. Acta Part B. 44
(1989) 1059 – 1063.
[98] W.P. Liu, K. Lee, Chemical modification of analytes in speciation
analysis by capillary electrophoresis, liquid chromatography and gas
chromatography, J. Chromatogr., A 834 (1999) 45 – 63.
[99] R. Lobinski, Speciation-targets, analytical solutions and markets,
Spectrochim. Acta, Part B: Atom. Spectrosc. 53 (1998) 177 – 185.
[100] R. Lobinski, F.C. Adams, Speciation analysis by gas chromatography with plasma source spectrometric detection, Spectrochim. Acta
Part B. 52 (1997) 1865 – 1903.
[101] R. Lobinski, W.M.R. Dirkx, J. Szpunarlobinska, F.C. Adams, Speciation analysis of organolead compounds by gas-chromatography
with atomic spectrometric detection, Anal. Chim. Acta 286 (1994)
381 – 390.
[102] D.Y. Maeng, S.Y. You, B.C. Cha, H. Kim, H.J. Kim, Fundamental
study and development of oscillating plasma glow discharge GC
detectors, Microchem. J. 55 (1997) 88 – 98.
[103] D.Y. Maeng, S.Y. You, B.C. Cha, H. Kim, G.H. Lee, H.J. Kim,
Analytical characteristics of organic compounds using an oscillating
plasma glow discharge detector for gas chromatography, Microchem. J. 55 (1997) 99 – 109.
[104] R.K. Marcus, T.R. Harville, Y. Mei, C.R. Shick, Rf-powered glowdischarges-elemental analysis across the solids spectrum, Anal.
Chem. 66 (1994) A902 – A911.
[105] J. Meija, J.M. Bryson, A.P. Vonderheide, M. Montes-Bayon, J.A.
[106]
[107]
[108]
[109]
[110]
[111]
[112]
[113]
[114]
[115]
[116]
[117]
[118]
[119]
[120]
[121]
[122]
789
Caruso, Studies of selenium-containing volatiles in roasted coffee,
J. Agric. Food Chem. 51 (2003) 5116 – 5122.
J. Meija, M. Montes-Bayon, D.L. Le Duc, N. Terry, J.A. Caruso,
Simultaneous monitoring of volatile selenium and sulfur species
from se accumulating plants (wild type and genetically modified)
by GC/MS and GC/ICPMS using solid-phase microextraction for
sample introduction, Anal. Chem. 74 (2002) 5837 – 5844.
S.P. Mendez, M.M. Bayon, E.B. Gonzalez, A. Sanz-Medel, Selenomethionine chiral speciation in yeast and parenteral solutions by
chiral phase capillary gas chromatography – ICP-MS, J. Anal. At.
Spectrom. 14 (1999) 1333 – 1337.
S.P. Mendez, E.B. Gonzalez, A. Sanz-Medel, Hybridation of different chiral separation techniques with ICP-MS detection for the
separation and determination of selenomethionine enantiomers: chiral speciation of selenized yeast, Biomed. Chromatogr. 15 (2001)
181 – 188.
Z. Mester, R. Sturgeon, J. Pawliszyn, Solid phase microextraction as
a tool for trace element speciation, Spectrochim. Acta Part B. 56
(2001) 233 – 260.
L.S. Milstein, J.W. Waggoner, K.L. Sutton, J.A. Caruso, Mixed gas
helium/argon low-power/reduced-pressure ICP as a tunable ionization source for the mass spectrometric detection of organotin compounds, Appl. Spectrosc. 54 (2000) 1286 – 1290.
L. Moens, T. De Smaele, R. Dams, P. Vanden Broeck, P. Sandra,
Sensitive, simultaneous determination of organomercury, -lead, and tin compounds with headspace solid phase microextraction capillary
gas chromatography combined with inductively coupled plasma
mass spectrometry, Anal. Chem. 69 (1997) 1604 – 1611.
A.H. Mohamad, J.T. Creed, T.M. Davidson, J.A. Caruso, Detection
of halogenated compounds by capillary gas-chromatography with
helium plasma mass-spectrometry detection, Appl. Spectrosc. 43
(1989) 1127 – 1131.
A. Montaser, D.W. Golightly, Inductively Coupled Plasmas in Analytical Atomic Spectrometry, Wiley, New York, 1992.
A. Montaser, J.A. Mc Lean, H. Liu, J.-M. Mermet, An introduction
to ICP spectrometries for elemental analysis, in: A. Montaser (Ed.),
Inductively Coupled Plasma Mass Spectrometry, WILEY, New
york, 1998.
A. Montaser, M.G. Minnich, H. Liu, A.G.T. Gustavsson, R.F.
Browner, Fundamental aspects of sample introduction in ICP
spectrometry, in: A. Montaser (Ed.), Inductively Coupled Plasma Mass Spectrometry, WILEY, New york, 1998.
M. Montes-Bayon, C. B’Hymer, C.A.P. de Leon, J.A. Caruso, The
use of radiofrequency glow discharge-mass spectrometry (rf-GDMS) coupled to gas chromatography for the determination of selenoaminoacids in biological samples, J. Anal. At. Spectrom. 16
(2001) 492 – 497.
M. Montes-Bayon, M.G. Camblor, J.I.G. Alonso, A. Sanz-Medel,
An alternative GC – ICP-MS interface design for trace element speciation, J. Anal. At. Spectrom. 14 (1999) 1317 – 1322.
M. Montes-Bayon, T.D. Grant, J. Meija, J.A. Caruso, Selenium in
plants by mass spectrometric techniques: developments in bio-analytical methods—Plenary Lecture, J. Anal. At. Spectrom. 17 (2002)
1015 – 1023.
G. Oconnor, L. Ebdon, E.H. Evans, Low pressure inductively coupled plasma ion source for molecular and atomic mass spectrometry: the effect of reagent gases, J. Anal. At. Spectrom. 12 (1997)
1263 – 1269.
N.G. Orellana-Velado, R. Pereiro, A. Sanz-Medel, Glow discharge
atomic emission spectrometry as a detector in gas chromatography
for mercury speciation, J. Anal. At. Spectrom. 13 (1998) 905 – 909.
N.G. Orellana-Velado, R. Pereiro, A. Sanz-Medel, Solid phase
microextraction gas chromatography – glow discharge-optical emission detection for tin and lead speciation, J. Anal. At. Spectrom. 16
(2001) 376 – 381.
B.W. Pack, J.A.C. Broekaert, J.P. Guzowski, J. Poehlman, G.M.
Hieftje, Determination of halogenated hydrocarbons by helium mi-
790
[123]
[124]
[125]
[126]
[127]
[128]
[129]
[130]
[131]
[132]
[133]
[134]
[135]
[136]
[137]
[138]
[139]
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
crowave plasma torch time-of-flight mass spectrometry coupled to
gas chromatography, Anal. Chem. 70 (1998) 3957 – 3963.
B.W. Pack, G.M. Hieftje, An improved microwave plasma torch
for atomic spectrometry, Spectrochim. Acta Part B. 52 (1997)
2163 – 2168.
H.E.L. Palmieri, L.V. Leonel, Determination of methylmercury in
fish tissue by gas chromatography with microwave-induced plasma
atomic emission spectrometry after derivatization with sodium tetraphenylborate, Fresenius’ J. Anal. Chem. 366 (2000) 466 – 469.
M.P. Pavageau, C. Pecheyran, E.M. Krupp, A. Morin, O.F.X. Donard,
Volatile metal species in coal combustion flue gas, Environ. Sci.
Technol. 36 (2002) 1561 – 1573.
C. Pecheyran, C.R. Quetel, F.M.M. Lecuyer, O.F.X. Donard, Simultaneous determination of volatile metal (Pb, No, Sn, In, Ga)
and nonmetal species (Se, P, As) in different atmospheres by
cryofocusing and detection by ICPMS, Anal. Chem. 70 (1998)
2639 – 2645.
S. Pedersenbjergaard, T. Greibrokk, On-column atomic-emission detection in capillary gas-chromatography using a radio-frequency
plasma, J. Microcolumn Sep. 6 (1994) 11 – 18.
M.V. Pelaez, M.M. Bayon, J. Alonso, A. Sanz-Medel, A comparison
of different derivatisation approaches for the determination of selenomethionine by GC – ICP-MS, J. Anal. At. Spectrom. 15 (2000)
1217 – 1222.
M.V. Pelaez, J.M. Costa-Fernandez, A. Sanz-Medel, Critical comparison between quadrupole and time-of-flight inductively coupled
plasma mass spectrometers for isotope ratio measurements in elemental speciation, J. Anal. At. Spectrom. 17 (2002) 950 – 957.
I.R. Pereiro, A.C. Diaz, Speciation of mercury, tin, and lead compounds by gas chromatography with microwave-induced plasma and
atomic-emission detection (GC – MIP-AED), Anal. Bioanal. Chem.
372 (2002) 74 – 90.
I.R. Pereiro, R. Lobinski, Fast species-selective screening for organolead compounds in gasoline by multicapillary gas chromatography
with microwave-induced plasma atomic emission detection, J. Anal.
At. Spectrom. 12 (1997) 1381 – 1385.
I.R. Pereiro, A. Wasik, R. Lobinski, Determination of mercury species in fish reference materials by isothermal multicapillary gas
chromatography with atomic emission detection after microwaveassisted solubilization and solvent extraction, J. Anal. At. Spectrom.
13 (1998) 743 – 747.
I.R. Pereiro, A. Wasik, R. Lobinski, Speciation of organotin in
sediments by multicapillary gas chromatography with atomic
emission detection after microwave-assisted leaching and solvent
extraction – derivatization, Fresenius’ J. Anal. Chem. 363 (1999)
460 – 465.
G.R. Peters, D. Beauchemin, Versatile interface for gas-chromatographic detection or solution nebulization analysis by inductively
coupled plasma mass-spectrometry-preliminary-results, J. Anal. At.
Spectrom. 7 (1992) 965 – 969.
G.R. Peters, D. Beauchemin, Characterization of an interface allowing either nebulization or gas-chromatography as the sample introduction system in ICPMS, Anal. Chem. 65 (1993) 97 – 103.
A. Prange, E. Jantzen, Determination of organometallic species by
gas-chromatography inductively-coupled plasma-mass spectrometry,
J. Anal. At. Spectrom. 10 (1995) 105 – 109.
W.G. Pretorius, L. Ebdon, S.J. Rowland, Development of a hightemperature gas-chromatography inductively-coupled plasma-mass
spectrometry interface for the determination of metalloporphyrins,
J. Chromatogr. 646 (1993) 369 – 375.
T. Prohaska, M. Pfeffer, M. Tulipan, G. Stingeder, A. Mentler, W.W.
Wenzel, Speciation of arsenic of liquid and gaseous emissions from
soil in a microcosmos experiment by liquid and gas chromatography
with inductively coupled plasma mass spectrometer (ICP-MS) detection, Fresenius’ J. Anal. Chem. 364 (1999) 467 – 470.
K. Pyrzynska, Organolead speciation in environmental samples: a
review, Mikrochim. Acta 122 (1996) 279 – 293.
[140] R.B. Rajendran, H. Tao, A. Miyazaki, R. Ramesh, S. Ramachandran,
Determination of butyl-, phenyl-, octyl- and tributylmonomethyltin
compounds in a marine environment (Bay of Bengal, India) using
gas chromatography – inductively coupled plasma mass spectrometry, J. Environ. Monit. 3 (2001) 627 – 634.
[141] R.B. Rajendran, H. Tao, T. Nakazato, A. Miyazaki, A quantitative
extraction method for the determination of trace amounts of both
butyl- and phenyltin compounds in sediments by gas chromatography – inductively coupled plasma mass spectrometry, Analyst 125
(2000) 1757 – 1763.
[142] P. Read, H. Beere, L. Ebdon, M. Leizers, M. Hetheridge, S. Rowland, Gas chromatography microwave-induced plasma mass spectrometry (GC – MIP-MS): a multi-element analytical tool for organic
geochemistry, Org. Geochem. 26 (1997) 11 – 17.
[143] R. Ritsema, T. de Smaele, L. Moens, A.S. de Jong, O.F.X. Donard,
Determination of butyltins in harbour sediment and water by aqueous phase ethylation GC – ICP-MS and hydride generation GC –
AAS, Environ. Pollut. 99 (1998) 271 – 277.
[144] R. Rodil, A.M. Carro, R.A. Lorenzo, M. Abuin, R. Cela, Methylmercury determination in biological samples by derivatization, solidphase microextraction and gas chromatography with microwave-induced plasma atomic emission spectrometry, J. Chromatogr., A 963
(2002) 313 – 323.
[145] I.Rodriguez,S.Mounicou,R.Lobinski,V.Sidelnikov,Y.Patrushev,Yamanaka,
Yamanaka, M. Yamanaka, Species selective analysis by microcolumn multicapillary gas chromatography with inductively coupled plasma mass spectrometric detection, Anal. Chem. 71
(1999) 4534 – 4543.
[146] J. Rodriguez-Fernandez, M. Montes-Bayon, R. Pereiro, A. SanzMedel, Gas chromatography double focusing sector-field ICP-MS
as an innovative tool for bad breath research, J. Anal. At. Spectrom.
16 (2001) 1051 – 1056.
[147] P. Rodriguez-Gonzalez, J.R. Encinar, J.I.G. Alonso, A. Sanz-Medel,
Determination of butyltin compounds in coastal sea-water samples
using isotope dilution GC – ICP-MS, J. Anal. At. Spectrom. 17
(2002) 824 – 830.
[148] J. Rolfes, J.T. Andersson, Determination of alkylphenols after
derivatization to ferrocenecarboxylic acid esters with gas chromatography – atomic emission detection, Anal. Chem. 73 (2001)
3073 – 3082.
[149] B. Rosenkranz, J. Bettmer, Rapid separation of elemental species by
multicapillary GC, Anal. Bioanal. Chem. 373 (2002) 461 – 465.
[150] A. Sanz-Medel, E. Blanco-Gonzalez, Chiral trace-element speciation
in biological samples: present importance and application to speciation for seleno-amino acids, TrAC, Trends Anal. Chem. 21 (2002)
709 – 716.
[151] C. Schepers, J.A.C. Broekaert, The use of a hollow cathode glow
discharge (HCGD) as an atomic emission spectrometric element
specific detector for chlorine and bromine in gas chromatography,
J. Anal. At. Spectrom. 15 (1999) 61 – 65.
[152] A. Schwarz, K.G. Heumann, Two-dimensional on-line detection of
brominated and iodinated volatile organic compounds by ECD and
ICP-MS after GC separation, Anal. Bioanal. Chem. 374 (2002)
212 – 219.
[153] I. Silgoner, E. Rosenberg, M. Grasserbauer, Determination of volatile organic compounds in water by purge- and-trap gas chromatography coupled to atomic emission detection, J. Chromatogr., A 768
(1997) 259 – 270.
[154] S. Slaets, F. Adams, I.R. Pereiro, R. Lobinski, Optimization of the
coupling of multicapillary GC with ICP-MS for mercury speciation
analysis in biological materials, J. Anal. At. Spectrom. 14 (1999)
851 – 857.
[155] S. Slaets, F. Laturnus, F.C. Adams, Microwave induced plasma
atomic emission spectrometry: a suitable detection system for the
determination of volatile halocarbons, Fresenius’ J. Anal. Chem. 364
(1999) 133 – 140.
[156] D.L. Smith, E.H. Piepmeier, Fingerprint identification of organic-
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
[157]
[158]
[159]
[160]
[161]
[162]
[163]
[164]
[165]
[166]
[167]
[168]
[169]
[170]
[171]
[172]
[173]
[174]
compounds using an oscillating plasma glow-discharge detector for
gas-chromatography, Anal. Chem. 66 (1994) 1323 – 1329.
D.L. Smith, E.H. Piepmeier, Multivariate approach to fingerprint
identification of organic-compounds using an oscillating glow-discharge detector for gas-chromatography, Anal. Chem. 67 (1995)
1084 – 1091.
J.P. Snell, W. Frech, Y. Thomassen, Performance improvements in
the determination of mercury species in natural gas condensate using
an on-line amalgamation trap or solid-phase micro-extraction with
capillary gas chromatography – microwave-induced plasma atomic
emission spectrometry, Analyst 121 (1996) 1055 – 1060.
J.P. Snell, I.I. Stewart, R.E. Sturgeon, W. Frech, Species specific
isotope dilution calibration for determination of mercury species
by gas chromatography coupled to inductively coupled plasma- or
furnace atomisation plasma ionisation-mass spectrometry, J. Anal.
At. Spectrom. 15 (2000) 1540 – 1545.
W.C. Story, J.A. Caruso, Gas-chromatographic determination of
phosphorus, sulfur and halogens using a water-cooled torch with
reduced-pressure helium microwave-induced plasma-mass spectrometry, J. Anal. At. Spectrom. 8 (1993) 571 – 575.
R.E. Sturgeon, V.T. Luong, S.N. Willie, R.K. Marcus, Impact of bias
voltage on furnace atomization plasma emission-spectrometry performance, Spectrochim. Acta Part B. 48 (1993) 893 – 908.
R.E. Sturgeon, S.N. Willie, V. Luong, S.S. Berman, J.G. Dunn,
Furnace atomization plasma emission-spectrometry (FAPES), J.
Anal. At. Spectrom. 4 (1989) 669 – 672.
J.J. Sullivan, Screening in gas-chromatography with atomic emission
detection, Trac, Trends Anal. Chem. 10 (1991) 23 – 26.
J.J. Sullivan, B.D. Quimby, Characterization of interferences affecting selectivity in gas-chromatography atomic emission-spectrometry,
Acs Symp. Ser. 479 (1992) 62 – 89.
K. Sutton, R.M.C. Sutton, J.A. Caruso, Inductively coupled plasma
mass spectrometric detection for chromatography and capillary electrophoresis, J. Chromatogr., A 789 (1997) 85 – 126.
J. Szpunar, V.O. Schmitt, R. Lobinski, J.L. Monod, Rapid speciation
of butyltin compounds in sediments and biomaterials by capillary
gas chromatography – microwave-induced plasma atomic emission
spectrometry after microwave-assisted leaching digestion, J. Anal.
At. Spectrom. 11 (1996) 193 – 199.
H. Tao, T. Murakami, M. Tominaga, A. Miyazaki, Mercury speciation in natural gas condensate by gas chromatography inductively
coupled plasma mass spectrometry, J. Anal. At. Spectrom. 13 (1998)
1085 – 1093.
H. Tao, R.B. Rajendran, C.R. Quetel, T. Nakazeto, M. Tominaga, A.
Miyazaki, Tin speciation in the femtogram range in open ocean
seawater by gas chromatography/inductively coupled plasma mass
spectrometry using a shield torch at normal plasma conditions, Anal.
Chem. 71 (1999) 4208 – 4215.
E. Tessier, D. Amouroux, G. Abril, E. Lemaire, O.F.X. Donard,
Formation and volatilisation of alkyl-iodides and -selenides in macrotidal estuaries, Biogeochemistry 59 (2002) 183 – 206.
E. Tessier, D. Amouroux, O.F.X. Donard, Biogenic volatilization of
trace elements from European estuaries, Biogeochem. Environ. Important Trace Elem. 835 (2003) 151 – 165.
R. Thomas, A beginner’s guide to ICP-MS, Part IX—Mass analyzers: collision/reaction cell technology, Spectroscopy 17 (2002)
42 – 48.
C.M. Tseng, D. Amouroux, I.D. Brindle, O.F.X. Donard, Field
cryofocussing hydride generation applied to the simultaneous
multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection, J. Environ. Monit. 2 (2000)
603 – 612.
Q. Tu, J. Qian, W. Frech, Rapid determination of methylmercury in
biological materials by GC – MIP-AES or GC – ICP-MS following
simultaneous ultrasonic-assisted in situ ethylation and solvent extraction, J. Anal. At. Spectrom. 15 (2000) 1583 – 1588.
S. Tutschku, S. Mothes, K. Dittrich, Determination and speciation of
[175]
[176]
[177]
[178]
[179]
[180]
[181]
[182]
[183]
[184]
[185]
[186]
[187]
[188]
[189]
791
organotin compounds by gas-chromatography microwave-induced
plasma-atomic emission-spectrometry, J. Chromatogr., A 683
(1994) 269 – 276.
S. Tutschku, M.M. Schantz, S.A. Wise, Determination of methylmercury and butyltin compounds in marine biota and sediments
using microwave-assisted acid extraction, solid-phase microextraction, and gas chromatography with microwave-induced plasma
atomic emission spectrometric detection, Anal. Chem. 74 (2002)
4694 – 4701.
J.P.J. van Dalen, P.A. de Lezenne Coulander, L. de Galan, Optimization of the microwave-induced plasma as an element-selective
detector for non-metals, Anal. Chim. Acta 94 (1977) 1 – 19.
J.C. Van Loon, Inductively coupled plasma-source mass spectrometry: new element/isotope-specific mass spectrometry detector for
chromatography, Spectrosc. Lett. 19 (1986) 1125 – 1135.
N.G.O. Velado, R. Pereiro, A. Sanz-Medel, Mercury speciation by
capillary gas chromatography with radiofrequency hollow cathode
glow discharge atomic emission detection, J. Anal. At. Spectrom. 15
(1999) 49 – 53.
J. Vercauteren, A. De Meester, T. De Smaele, F. Vanhaecke, L. Moens,
R. Dams, P. Sandra, Headspace solid-phase microextraction-capillary
gas chromatography – ICP mass spectrometry for the determination of
the organotin pesticide fentin in environmental samples, J. Anal. At.
Spectrom. 15 (2000) 651 – 656.
J. Vercauteren, C. Peres, C. Devos, P. Sandra, F. Vanhaecke, L.
Moens, Stir bar sorptive extraction for the determination of ppqlevel traces of organotin compounds in environmental samples with
thermal desorption-capillary gas chromatography – ICP mass spectrometry, Anal. Chem. 73 (2001) 1509 – 1514.
A.P. Vonderheide, J. Meija, M. Montes-Bayon, J.A. Caruso, Use of
optional gas and collision cell for enhanced sensitivity of the organophosphorus pesticides by GC – ICP-MS, J. Anal. At. Spectrom. 18
(2003) 1097 – 1102.
A.P. Vonderheide, M. Montes-Bayon, J.A. Caruso, Development and
application of a method for the analysis of brominated flame retardants by fast gas chromatography with inductively coupled plasma
mass spectrometric detection, J. Anal. At. Spectrom. 17 (2002)
1480 – 1485.
A.P. Vonderheide, M. Montes-Bayon, J.A. Caruso, Solid-phase
microextraction as a sample preparation strategy for the analysis
of seleno amino acids by gas chromatography – inductively coupled
plasma mass spectrometry, Analyst 127 (2002) 49 – 53.
J.W. Waggoner, M. Belkin, K.L. Sutton, J.A. Caruso, H.B. Fannin,
Novel low power reduced pressure inductively coupled plasma ionization source for mass spectrometric detection of organotin species,
J. Anal. At. Spectrom. 13 (1998) 879 – 883.
J.W. Waggoner, L.S. Milstein, M. Belkin, K.L. Sutton, J.A. Caruso,
H.B. Fannin, Application of a low power/reduced pressure helium
ICP ionization source for mass spectrometric detection of organobromine compounds and derivatized organotin compounds, J. Anal.
At. Spectrom. 15 (1999) 13 – 18.
A. Wasik, I.R. Pereiro, C. Dietz, J. Szpunar, R. Lobinski, Speciation
of mercury by ICP-MS after on-line capillary cryofocussing and
ambient temperature multicapillary gas chromatography, Anal. Commun. 35 (1998) 331 – 335.
A. Wasik, I.R. Pereiro, R. Lobinski, Interface for time-resolved
introduction of gaseous analytes for atomic spectrometry by
purge-and-trap multicapillary gas chromatography (PTMGC),
Spectrochim. Acta Part B. 53 (1998) 867 – 879.
E.B. Wickenheiser, K. Michalke, C. Drescher, A.V. Hirner, R. Hensel,
Development and application of liquid and gas-chromatographic speciation techniques with element specific (ICP-MS) detection to the
study of anaerobic arsenic metabolism, Fresenius’ J. Anal. Chem. 362
(1998) 498 – 501.
R.G. Wuilloud, J.C.A. de Wuilloud, A.P. Vonderheide, J.A. Caruso,
Determination of iodinated phenol species at parts-per-trillion concentration levels in different water samples by solid-phase micro-
792
J.C.A. Wuilloud et al. / Spectrochimica Acta Part B 59 (2004) 755–792
extraction/offline GC – ICP-MS, J. Anal. At. Spectrom. 18 (2003)
1119 – 1124.
[190] L. Yang, Z. Mester, R.E. Sturgeon, Improvement in measurement
precision with SPME by use of isotope dilution mass spectrometry
and its application to the determination of tributyltin in sediment
using SPME GC – ICP-MS, J. Anal. At. Spectrom. 17 (2002)
944 – 949.
[191] A.M. Zapata, A. Robbat, Performance enhanced ‘‘tunable’’ capillary
microwave-induced plasma mass spectrometer for gas chromatography detection, Anal. Chem. 72 (2000) 3102 – 3108.