Anal Bioanal Chem (2002) 373 : 323–324
DOI 10.1007/s00216-002-1359-y
E D I TO R I A L
Klaus G. Heumann
Hyphenated techniques – the most commonly used method
for trace elemental speciation analysis
Published online: 20 June 2002
© Springer-Verlag 2002
In elemental trace analysis hyphenated techniques play an
important role for online chromatographic separation or
enrichment of elements prior to their sensitive detection
usually by atom spectrometric methods. But the most fa-
vorable field where hyphenated techniques are applied is
the determination of elemental species at trace levels. An-
alytical online systems coupling separation with detection
methods have, in principle, essential advantages compared
with offline techniques. They result in much better repeata-
bility of analytical results, contamination is minimized,
and they can automatically be run. However, the best sys-
tems are those where the experimental conditions of the
separation and detection technique fit one the other.
The most frequently applied hyphenated systems for
elemental speciation are coupling of HPLC or GC with an
atom spectrometric method but capillary electrophoresis
(CE) becomes more and more popular as an online sepa-
ration technique as well. For element-selective detection
inductively coupled plasma atomic emission spectrometry
(ICPAES) and inductively coupled plasma mass spec-
trometry (ICPMS) are of special interest because of their
multi-element capability. This is one reason they have often
been used more than ten years [1, 2]. Whereas ICPAES
usually allows element detection down to the ng mL–1
range the pg mL–1 level can be reached for many elements
by ICPMS. Both atom spectrometric methods have the
advantage that HPLC as well as GC can be directly cou-
pled without changing the liquid and gas flow, respec-
tively, of the corresponding separation systems. The flow
rate of an HPLC of a few mL min–1 is exactly what usu-
ally is used for introduction systems of an ICPAES or
ICPMS. On the other hand, the argon plasma of the ICP
source, where 15–20 L min–1 argon must be applied for
stable plasma conditions, is normally not disturbed by a
few mL min–1 of the GC carrier gas. Thus, direct intro-
K.G. Heumann
Institute of Inorganic Chemistry and Analytical Chemistry,
Johannes Gutenberg-University Mainz,
Duesbergweg 10–14, 55099 Mainz, Germany
e-mail: heumann@mail.uni-mainz.de
duction of the GC carrier gas flow into the plasma torch of
an ICPAES or ICPMS has the additional advantage that in
contrast to HPLC-ICPAES/ICPMS coupling, where most
of the analyte gets lost in the nebulizer system, 100% of
the analyte reaches the plasma. This results in especially
low detection limits for GC-ICPAES/ICPMS coupling
systems. The interfaces for coupling of HPLC or GC with
the mentioned detection methods are relatively simple con-
structions and many different versions have been described
in the literature, e.g. in [3, 4]. CE coupling with atom
spectrometric methods is not so easy but good solutions
have recently also been developed [5].
The most strongly growing application of hyphenated
techniques in elemental analysis is speciation, which be-
came increasingly important in all disciplines of natural and
environmental sciences, clinical chemistry, toxicology, and
nutrition. It has become clear that the mobility of elements
in the environment, their bioavailability and their toxicity
strongly depend on the chemical form in which they exist.
For example, the alkylated forms of mercury and tin are
highly toxic whereas the inorganic forms of these ele-
ments are much less toxic or do not show toxic properties.
On the other hand, organoarsenic compounds are less
toxic than inorganic ones. The toxicity of individual ele-
mental species is the reason why also legislative bodies
started to notice that it is not always acceptable to only fix
limiting values for the total content of an element. In many
cases it is necessary to differentiate between the various
elemental species. Thus, the application of hyphenated
techniques to control limit values, which are fixed by leg-
islation, will become increasing importance.
This increasing importance of elemental speciation
analysis explains why different textbooks on this topic were
published during the last few years [6, 7, 8, 9] and that a
handbook of elemental speciation is just in preparation
[10]. Critical reviews on the potential of different hyphen-
ated techniques, which are often used for elemental speci-
ation, are given in this issue, for example, by Andersson,
Diehl and Karst as well as by Rosenkranz and Bettmer.
The contributions of Alonso et al. and those of Uden and
of the group of Caruso deal with the determination of two
324

of the most important elements in speciation, tin and sele- sue for their excellent contributions to Analytical and Bio-
nium. The butyltin compounds are well known as a great analytical Chemistry.
problem in environmental chemistry and the selenium spe-
cies play an important role in clinical chemistry and nutri-
tion. Hyphenated techniques were already started to be used References
for the determination of metal species of biomolecules.
Some of the first results in this tremendously important 1. Schöppenthau J, Dunemann L (1994) Fresenius J Anal Chem
349:794
field of investigation for the future are reported by Prange 2. Al-Rashdan A, Heitkemper D, Caruso J (1991) J Chromatogr
and Schaumlöffel, Szpunar and Lobinski as well as by the Sci 29:98
group of Sanz-Medel. 3. Rottmann L, Heumann KG (1994) Fresenius J Anal Chem 350:
Elemental speciation analysis has not become a routine 221
4. Gallus SM, Heumann KG (1996) J Anal At Spectrom 11:887
method up to now. Even if these coupling systems use 5. Schaumlöffel D, Prange A (1999) Fresenius J Anal Chem 364:
methods with selective separation and sensitive detection, 452
there is no guarantee that transformation of elemental spe- 6. Ure AM, Davidson CM (1995) Chemical Speciation in the En-
cies during the whole analytical procedure does not take vironment, Blackie, London, UK
7. Dunemann L, Begerow J (1995) Kopplungstechniken zur Ele-
place. An intensive discussion in Analytical Chemistry on mentspeziesanalytik, VCH, Weinheim, Germany
possible transformations during the analysis of mercury 8. Quevauviller P. (1998) Method Performance Studies for Speci-
species has clearly shown this problem [11, 12]. The use ation Analysis, The Royal Society of Chemistry, Cambridge, UK
of isotopically labeled elemental species in combination 9. Ebdon L, Pitts L, Cornelis R, Crews H, Donard OXF, Que-
with a separation system coupled with a mass spectrometer vauviller P (2001) Trace Element Speciation for Environment,
Food and Health, The Royal Society of Chemistry, Cambridge,
is an elegant method to demonstrate such species transfor- UK
mations, as was shown by a GC-ICPMS system for methyl 10. Cornelis R, Caruso J, Crews H, Heumann KG (2002) Hand-
mercury transformation during the analytical procedure book of Elemental Speciation, vol 1, Wiley, Chichester, UK, in
[13]. Thus, the use of isotopically enriched species will press
11. Quevauviller P, Horvat M (1999) Anal Chem 71 :155A
become an important tool for validation of hyphenated 12. Bloom NS, Evans RD, Hintelmann H, Wilken RD (1999) Anal
techniques used for elemental speciation. On the other Chem 71:575A
hand, isotopically labeled species can also be applied for 13. Demuth N, Heumann KG (2001) Anal Chem 73:4020
isotope dilution mass spectrometry (IDMS) of species. Hy- 14. Brown AA, Ebdon L, Hill SJ (1994) Anal Chim Acta 286:391
phenated techniques using IDMS were started in 1994 by
the groups of Ebdon and Heumann [3, 14] and an excellent
example is also given in this issue for the determination of Klaus Gustav Heumann
butyltin compounds by Alonso et al. using GC-ICPIDMS. is Professor of Analytical
Hyphenated techniques produce transient signals which Chemistry at the Johannes
Gutenberg-University Mainz,
cannot easily be transformed into a quantitative result. Germany. His research inter-
IDMS in connection with hyphenated techniques is the ests lie in the development
only method, up to now, where matrix independent real and application of analytical
time concentrations are received. methods for the determina-
tion of trace elements and
There is no great difference in the principles of hy- trace amounts of elemental
phenated techniques when applying them for the determi- species, using ICP-MS, TIMS,
nation of elemental species or biological and organic mol- different types of optical
ecules. The responsible editors of this issue therefore atomic spectrometry, and elec-
hope that the research work discussed in this issue, which troanalysis as detection meth-
ods, and HPLC or capillary
cover both areas, will stimulate researchers and users of GC as separation methods.
both fields and may initiate adaptation of good ideas from
the other field. We also want to thank all authors of this is-