Spectrochimica Acta Part B 55 Ž2000.

917᎐933

Vapor generation or electrothermal atomic absorption

spectrometry? ᎏ Both! 夽

Dimiter L. Tsalev U
Faculty of Chemistry, Uni¨ ersity of Sofia, 1 James Bourchier Bl¨ d., Sofia 1126, Bulgaria

Received 13 December 1999; accepted 27 February 2000

Abstract

Whereas flame atomic absorption spectrometry ŽAAS. lacks sensitivity at analyte concentrations below 0.1 and 10
␮g gy1 in analyses of liquid and solid samples, respectively, two modern AAS techniques with better detection power
for quantitation at nanogram and picogram levels are employed: electrothermal AAS ŽETAAS. and vapor generation
AAS ŽVGAAS., viz. hydride generation AAS ŽHGAAS. or cold vapor technique for mercury ŽCVAAS.. In this
overview are discussed and illustrated the scope, merits, sample pretreatment requirements, methodological con-
siderations and limitations of ETAAS, VGAAS and their recent hyphenations with each other Že.g. the VG᎐ETAAS
coupling with in-atomizer trapping of hydrides and vapors. and with other separationrenrichment analytical
techniques, aimed at solving important analytical problems of elemental trace analysis, microanalysis, speciation, etc.
Optimum application fields are defined and examples from the author’s recent research with biological and
environmental matrices are given. 䊚 2000 Elsevier Science B.V. All rights reserved.

Keywords: Electrothermal atomic absorption spectrometry; Vapour generation AAS; Hydride generation AAS;
In-atomiser trapping; Flow injection

夽
This paper was presented as an Invited Lecture at Colloquium Spectroscopicum Internationale XXXI, held in Ankara, Turkey,
September 1999, and is published in the Special Issue of Spectrochimica Acta Part B, dedicated to that conference.
U
Tel.: q359-2-6256-318; fax: q359-2-96-25-438.
E-mail address: tsalev@chem.uni-sofia.bg ŽD.L. Tsalev..

0584-8547r00r$ - see front matter 䊚 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 5 8 4 - 8 5 4 7 Ž 0 0 . 0 0 2 0 2 - 0
918 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933

1. Introduction Table 1
Classification of AAS techniques

The aim of this overview is to discuss and AAS techniques Selected recent
compare two sensitive atomic absorption spectro- monographs
and reviews
metric techniques and their modern hyphenation
with each other, with a view to defining their Flame AAS ŽFAAS. w1᎐6x
optimal application fields, merits and limitations.
Atomic absorption spectrometry ŽAAS. is Electrothermal AAS ŽETAAS. w1᎐4,6᎐14x
nowadays an essential, very well established
method for trace element analysis. Several AAS Vapour generation AAS ŽVGAAS.
Hydride generation AAS ŽHGAAS. w1᎐4,6,15᎐21x
techniques with different analytical scope, hard- Cold vapor AAS ŽCVAAS. w2,3,6,22᎐24x
ware sophistication, performance characteristics,
sample pretreatment requirements, throughput Hyphenated AAS techniques w6,15,19,21᎐53x
rates, economic parameters and other specific such as HG᎐ETAAS, CV᎐ETAAS,
features can be distinguished ŽTable 1.: FAAS, HPLC᎐HGAAS, VG᎐cryotrapping᎐
ETAAS, VGAAS ŽHGAAS and CVAAS., and GC᎐AAS
hyphenated AAS. Selected references to recent
monographs, book chapters and reviews pertinent guide to the vast literature comprising over
to these techniques are given in Table 1 as a 2 = 10 4 relevant AAS publications. Having

Table 2
General assessment and ranking of AAS techniques a

Metrological and technical characteristics FAAS ␮-FAASb ETAAS HGAAS CVAAS VG᎐ETAAS

Selectivityrinterference control qqq qqq qq q qq qq

Sensitivity
Absolute q qq qqq qq qq qqq
Relative q q qq qqq qqq qqq
Limits of detection ŽLODs, relative.
Instrumental LODs q q qqq qqq qqq qqq
Procedural LODs q q qq qq qq qq
Precision qqq qq qq qq qq q
Sample throughput rates qqq qqq q qq qq qry
Analyte elements coverage qqq qqq qq q yyy q
Microsamplingrscaling down q qq qqq qq qq q
Automation qqq qqq qqq qqq qqq qqq
Sample pretreatment requirements qq qq qqq qry q qry
Calibration Žlinearity, standard additions. qq q qry qry qry qry
Multi-element capabilities
Sequential q q q y yyy qry
Simultaneous y y qry yy yyy qry
Speciation potentialities yyy yyy yy q qry q
Suitability as a chromatographic detector q qry yy qq qqq yyy
Robustness qqq qqq qq q qqq qq
Qualifications of laboratory personnel qqq qqq qq q qq q
Expenses on instrumentation qqq qqq q qq qq qry
Running costs qqq qqq qry q qq qry
General score of technique qqq qqq qq qq qqq qqq
a
Estimated scores of techniques: Žqqq . excellent; Žqq . good; Žq. moderate; Žy. problematic; Žyy . poor; Žyyy . very
poor.
b
Flame microsampling techniques such as pulse nebulization or flow injection.
 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933 919

worked with these techniques during the last three

decades, the author naturally likes and lo¨ es them
all and repeatedly attempts answering the ques-
tion: Quo ¨ adis, AAS? w3,12,13,21,54᎐58x.
General assessment of AAS techniques is given
in Table 2, considering various aspects of individ-
Fig. 1. Elemental coverage by the HGAAS and CVAAS Žfor
ual techniques ranking from ‘excellent’ to ‘very Hg., with representative ranges of characteristic concentra-
poor’. More detailed comparisons will necessarily tions Ž Co . in ␮g ly1 , in continuous flow ŽCF. mode. Symbols
involve individual analyte elements and matrices in bold indicate good, competitive performance characteris-
Žsee Section 5.. tics. Based on data compiled by Dedina and Tsalev w15x.
Electronegativity Ž ␧ . w66x given in parentheses Žsee text..
The title question of this lecture is deliberately
posed in a somewhat provocative and didactic
manner; thus all four possible answers would ing its importance as a simple, widespread, cost-
appear reasonable and could be considered Žin an effective, robust and reliable analytical tool.
increasing order of their probability.: neither;
VGAAS; ETAAS; or both!
3. VG or ETAAS? — VGAAS!

2. VG or ETAAS? — Neither! The CVAAS for Hg and HGAAS for As are

both well established, highly competitive tech-
Whenever possible, the flame AAS serves as a niques for these two difficult analytes. Several
common, preferred routine technique in thou- more hydride forming elements ŽHFEs. with envi-
sands of analytical laboratories, owing to its ronmental and toxicological importance are within
unique combination of numerous positive assets: the application scope of this technique ᎏ up to
remarkable selectivity and reliable interference 11 analytes altogether Žsee Figs. 1 and 2. w15x.
control; large elemental coverage; relatively sim- Vapour generation accessories are relatively
ple sample pre-treatment; very good precision; inexpensive and offer high relative sensitivity, low
well established methodology and profound docu- LODs Ž0.02᎐0.3 ng absolute or 0.1᎐0.3 ␮g ly1
mentation; moderate, affordable price and low relative., automation Žin continuous flow ŽCF.
running costs; simple operation and easy mainte- and flow injection ŽFI. modes., good sampling
nance; relatively fast and simple optimization, frequencies Že.g. 40᎐60 hy1 ., and certain specia-
development and adaptation of analytical proce- tion potentialities Žsee Table 3.. Mercuryrhydride
dures; high sample throughput rates; automation.
Multi-element determinations are straightforward
in a fast, automated yet sequential mode. Unfor-
tunately, FAAS often lacks sensitivity at analyte
levels below 0.1 and 10 ␮g gy1 in analyses of
liquid and solid samples, respectively. Various
techniques for off-line and on-line preconcentra-
tion of trace elements Ženrichment factors 10᎐100
= . have been elaborated w3,6,30x. Attractive flow
injection ŽFI. ᎐FAAS procedures based on auto-
mated, on-line ion exchange, solid phase extrac-
tion, co-precipitation, etc., are expanding poten-
tialities of FAAS down to ng gy1 analyte levels
Fig. 2. Distribution of approximately 3000 publications on
w6,29᎐32,46,59x. In simultaneous multi-element
hydride generation techniques Ž1973᎐1995. between analyte
determinations, the FAAS is facing a serious chal- elements. Adapted from recent bibliographic compilations
lenge by ICP-AES and ICP-MS, while still keep- w3,15,20x.
920 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933

Table 3
HGAAS ᎏ speciation potentialities Žwith selected references .

Species determined Differentiation from: Principle

(a) Direct, non-chromatographic redox speciation w15x

i-SeŽIV. w40᎐43x i-ŽSeŽVI. Reaction kinetics
i-TeŽIV. w43x i-TeŽVI. Reaction kinetics
i-AsŽIII. w36᎐38x i-AsŽV., MMA, DMA pH effect; NaBH4 concentration
i-AsŽIII. q DMA w60x i-AsŽV., MMA pH effect
i-AsŽIII. q i-AsŽV. q ‘Fish arsenic’ ŽAsBet, Me4 Asq, Reaction kinetics
MMAq DMA w61,62x arsenosugars, etc..

(b) Other approaches: coupling with

cryogenic trapping, e.g. alkylated species of As, Sb, Hg, Ge w15,19,21x;
ion exchange, e.g. AsŽIII. w38,51x, SbŽIII. w39x;
on line ‘onroff’ pre-reduction, e.g. As and Se w21,29x; and
on line ‘onroff’ decomposition ŽUV, microwave., e.g. As and Se w19,21,37,38,63᎐65x.

vapor generators can be also coupled with other
atomic spectrometric techniques such as atomic
fluorescence spectrometry ŽAFS., ICP-AES, ICP-
MS w15x as well as with chromatographic w21,26,35x,
cryogenic w19,21,34x and other separations
w15,21,53x. So far approximately one-third of
applications ŽFig. 2. are non-AAS techniques
w15,18,20,29x, some of them exhibiting much bet-
ter LODs Že.g. G 10 = with HGAFS, CVAFS,
HG᎐ICP-MS.. In Fig. 1 are compiled representa-
tive figures of characteristic masses Ž Co . for
HGAAS. Electronegativity Ž ␧ . w66x for each ele-
ment ŽE. is given in parentheses which, as com-
pared with the ␧ figure for the hydrogen atom
Ž ␧ s 2.2., represents an estimate of the covalent
character of the E᎐H bond in the molecule of
hydride produced. Generally, the elements in the
upper right side of the Periodic Table yield
hydrides with a more pronounced covalent char-
acter and relevant stability; they are generated
and transported to the atomization cell with high
efficiency ŽAs, Se, Sb.. On the contrary, the ele-
ments situated downwards ŽSn, Bi, Pb. and partic-
ularly in the bottom left corner: In, Tl, Cd Ž ␧ s
1.5. are more problematic ᎏ see Fig. 2. Accord-
ingly, equilibrium diagrams for the generation of

Fig. 3. Redox potential vs. wHqx rpH equilibrium diagram for hydride-forming elements in aqueous solutions. Adapted from data
compiled by Pourbaix w67x.
 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933 921

Table 4
HGAAS ᎏ limited capabilities for multi-element and multi-species determination Žwith selected references .

Analytes Reaction medium w15x

AsŽIII q V.; SbŽIII q V. KI᎐HCl; KI᎐ascorbic acid᎐HCl;

L-Cysteine᎐dilute
acid; dilute HCl

AsŽIII q V.; SbŽIII q V.; BiŽIII.; L-Cysteine᎐dilute acid w61,62,70᎐72x

SnŽIIrIV.; AsŽIII q Vq MMAq DMA.

SnŽIIrIV.; GeŽIV.; BiŽIII. Dilute acid

SeŽIV q VI.; TeŽIV q VI.; BiŽIII.; From 5᎐6 mol ly1 HCl to dilute HCl
AsŽIII q V.; SbŽIII q V.

PbŽII ª IV.; SnŽIIrIV.; BiŽIII.; K2 S2 O8 ᎐dilute acid w73᎐75x

i-As q org-Asª AsŽV.

BiŽIII.; Hg ŽirMerEt.; SeŽVI ª IV.; BrO3 y᎐Bry᎐dilute acid w73᎐76x

SnŽIIrIV.

hydrides Žas well as H 2 and Hg o vapors. in aque-
ous solutions ŽFig. 3. demonstrate increasing dif-
ficulties in attaining low redox potentials in the
series from Hg, H 2 , Se, Sb and As towards the
difficult HFEs: Pb, Tl, In, Tl. The latter group of
elements would generally require higher NaBH 4
concentrations w15x; hydride generation from
non-aqueous media is expected to be promising.
Alternative chemical systems for vapor genera-
tion other than hydridization with NaBH 4 ᎐dilute
HCl w15x have been described in the literature but
have not reached routine applicability and
commercialization, such as ethylation with sodium
tetraethylborate, NaBŽC 2 H 5 .4 , for Hg, Pb, Se, Sn,
etc. Žreview w49x., carbonyl generation Žfor Ni.,
butylation, etc. w21x.
Several intrinsic limitations and drawbacks of
HGAAS are worth bearing in mind Žsee Table 1..
The chemical vapor generation is essentially a
chemical separation of the analyte element Žor

Fig. 4. Elemental coverage by the ETAAS technique, with representative ranges of characteristic masses Ž m o . in pg. Symbols in
bold indicate straightforward performance for approximately 30 analytes. Based on data compiled by Tsalev w3,13x.
922 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933
species. from the samplermatrix solution, which
is performed in situ and instantaneously; hence
rather complex, on-line chemistry is involved; high
and consistent chemical yields of reaction
products are required; specific chemical pre-treat-
ment is needed so as to reliably transform the
analyte element into a definite, reactive chemical
form and oxidation state. Thus selenium and tel-
lurium analytes have to be pre-reduced to their
hydride-forming oxidation states, SeŽIV. and
TeŽIV.; lead should be pre-oxidized to its
metastable PbŽIV. form; while arsenic and anti-
mony exhibit much better sensitivity as their inor-
ganic AsŽIII. and SbŽIII. oxidation states and
typically call for a pre-reduction step w15x. Hence
reagent blanks and chemical interferences in
aqueous and gaseous phase are involved. Because
of specific hydride generation conditions for indi-
vidual elements Žand species. w15x, the multi-
element capabilities of the HGAAS technique are
rather limited w61,62,68᎐70x ᎏ see Table 4.
4. VG or ETAAS? — ETAAS!
Applications of ETAAS to over 60 analytes
have been documented ᎏ see Fig. 4 for repre-
sentative ranges of characteristic masses Ž m o .;
this technique is straightforward for less than
one-half of these elements for which symbols are
depicted in bold w3,12,13x.
Attractive features of ETAAS are: excellent
absolute and Žless so. relative LODs in the pg and
␮g ly1 range, respectively; microsampling Ž5᎐50
␮l injections.; relatively simple pre-instrumental
treatment of samples, hence better contamina-
tionrblank control; analysis of intact w3,7x, slur-
ried w8,10,77x, solid Žsub-mg. w8,77x, emulsified and
solubilized samples w3,78x, eventually with in situ
chemical treatment by means of versatile chemi-
cal modification w3,6᎐10,54᎐58,79x; automation of
measurements Ž20᎐40 hy1 .; automated FI enrich-
ment capabilities down to ng ly1 levels by VG
w15,21,53x, ion exchange, co-precipitation, etc.
w6,30᎐33,53,80x. ETAAS instrumentation and
methodology is approaching a state of maturity
and widespread, routine applicability, particularly
in the field of biological and environmental con-
trol w13x, being the technique-of-choice for several
of the HFEs: Cd, Cu, Pb, In, Tl, Sn and Žalterna-
tively. for Se. This progress is due to several
important instrumental and methodological de-
velopments in ETAAS which have been discussed
in much detail elsewhere w6᎐14x: the stabilized
temperature platform furnace ŽSTPF. concept
w81x; successful commercialization of more effi-
cient and reliable Zeeman-effect background cor-
rectors w6,7x, simultaneous multi-element facilities
w82,83x, versatile autosamplers for liquids, slurries
and solids w8,77x, and hyphenation with flow and
flow-injection techniques for on-line separation,
enrichment and speciation w6,9,21,29᎐33x; better
understanding and control of matrix effects
w3,6,9,10,84x by means of versatile temperature
programming, alternate gases and more efficient
chemical modifiers w3,6,9,54᎐58,84᎐90x; ‘hot injec-
tions’ w91x and ‘fast’ temperature programs
ŽF 1 min. w91x, etc.
Admittedly, the economic parameters of
ETAAS analyses are less favourable vs. other
AAS techniques, because of higher expenses on
instrumentation ŽG 2᎐3 = . and consumables
ŽG 10 = .; slower sample throughput rates, longer
optimizationrdevelopment times and more fre-
quent QC operations, higher qualification of per-
sonnel.
Among other limitations and drawbacks of
ETAAS technique are worth mentioning its rather
poor speciation capabilities; e.g. some rare exam-
ples being performing in situ chemical reactions
for fractional volatilization of AsŽIII. as AsCl 3
w92x or SeŽIV. as piazselenol w93x and Žmuch bet-
ter. by coupling with FI separations w21,29᎐33,94x.
ETAAS is not a suitable chromatographic detec-
tor because of its discontinuous mode of opera-
tion.
Background correction problems still persist
with high-salt matrices such as seawater, urine,
inorganic slurries. The efficiency of chemical
modification is often impaired in the presence of
complex real matrices Žhalides, HClO4 and H 2 SO4
digests. and with different organoelement species
of analytes ᎏ for example, poor thermal
stabilization and ‘isoformation’ for arsenocholine
w95x, trimethylselenium w96x, some alkyltin com-
pounds w71,97x.
 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933 923

Table 5
Comparative evaluation of the VGAAS and ETAAS techniques for 13 analyte elements, with some specific comments, scores and
selected references a

Analyte VGAASb ETAASc

As Score: Žqqq .; essential routine technique; sample treatment Score: Žqq .; some organoarsenic
critical; blank problems; broad interval of sample acidity for species may not be efficiently
arsenite; pH critical in the presence of L-cysteine; different stabilizedrisoformed w95x
sensitivity for i-AsŽIII., i-AsŽV., MMA and DMA; no background problems frequent;
response from AsBet and AsChol; poor sensitivity for Zeeman effect correction
arsenate; cryotrapping straightforward; speciation potentialities preferable w3,6,7x
w3,6,15,21,36᎐38x

Bi Score: Žqq .; HG tolerant to oxidants; BiH3 thermally unstable; Score: Žqq .; noble metal
broad interval of sample acidity; compatibility with L-cysteine modifiers; enrichment often
w72x; cryotrapping inappropriate required

Cd Score: Žyy .; very unstable hydride; poor efficiency of VG; Score: Žqqq .; essential routine
critical VG conditions such as high NaBH4 concentration, technique; very good sensitivity;
narrow wHClx interval, high Ar flow-rates; aerosol generation; fast signal processing and fast
foaming; strong interferences ŽCu, etc..; rapid recent progress background correction required;
with this analyte but still far from being competitive technique limited linear range; reagent blanks;
w98᎐100x chemical modifiers not particularly
efficient as thermal stabilizers

Cu Score: Žyyy .; VG possible under relatively mild conditions Score: Žqqq .; straightforward
w101x; very high reagent blanks; QTA inadequate technique; reagent blanks; slurry
sampling appropriate w77x;
solid sampling for microanalysis w77x

Ge Score: Žq.; very poor atomization efficiency in QTA, resulting Score: Žqq .; mixed modifiers best;
in inadequate sensitivity; alternative atomization means required enrichment often required w103x
ŽHG᎐FAAS; HG᎐ETAAS w102x.; adsorption losses of
GeH4 ; cryotrapping possible

Hg Score: Žqqq .; CVAAS best routine technique; sample Score: Žq.; poor sensitivity; poor
treatment critical Žvolatilization losses.; stabilization of liquid thermal stabilization by modifiers
samplesrdigests essential in order to avoid adsorption Žnoble metals best.; solidrslurry
lossesrretention losses; good tolerance to oxidants; sampling possible with Zeeman
amalgamation accessories available for on-line enrichment; correction w3,6᎐8x
speciation possibilities w22᎐24x

In Score: Žyyy .; unreliable technique; very low chemical yield of Score: Žqq .; halides depressive
hydride; poor kinetics; inadequate sensitivity w104x

Pb Score: Žq.; good tolerance to oxidants; pre-oxidation to Score: Žqqq .; ETAAS best routine
PbŽIV. essential; relatively narrow pH interval and high NaBH4 technique; reagent blanks; slurry
concentrations required; vigorous reactions Žaerosol and foam sampling possible
formation.; high reagent blanks; good speciation possibilities
for alkylleads; ethylation with NaBŽC2 H5 .4 promising
alternative w105,106x
924 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933

Table 5 Ž Continued.

Analyte VGAASb ETAASc

Sb Score: Žqqq .; good routine technique; blank contributions; Score: Žqq .; noble metal or mixed
relatively broad interval of sample acidity for i-SbŽIII.; poor modifiers w54᎐56x
sensitivity for i-SbŽV.; pre-reduction to SbŽIII. advisable; pre-
reduction conditions with KI, KI᎐ascorbic acid and L-cysteine
less critical as compared with arsenic; different sensitivity for
i-SbŽIII., i-SbŽV., MMS and DMS; cryotrapping
straightforward; speciation potentialities w19,39x

Se Score: Žqqq .; good routine technique; sample pretreatment Score: Žqq .; structured background
critical and prone to volatilization losses; pre-reduction to from Fe and phosphates; Zeeman
SeŽIV. essential Žbromide very promising.; reductants STPF conditions recommended;
depressive in batch mode Žiodide, L-cysteine. w40᎐43x efficient metal modifiers ŽCu, Pd, Ni
etc.. or mixed modifiers essential
w54᎐56x; some organoselenium
species may not be efficiently
stabilizedrisoformed w71,96x

Sn Score: Žqq .; retention and volatilization losses during sample Score: Žqq .; a difficult analyte; noble
treatment; good tolerance to oxidants; no effect of the metals and mixed modifiers required
oxidation state, SnŽII. or SnŽIV.; relatively narrow pH interval w56x; carbide-treated platforms
and high NaBH4 concentrations required; compatibility with advantageous w86᎐88x; some
L-cysteine w72x; high reagent blanks; QTA not organotins may not be efficiently
satisfactory, ‘flame-in-tube’ conditions favourable; stabilizedrisoformed w71,97x
cryotrapping suitable for alkyltin hydrides; speciation
possibilities; poor recoveries of butyltins w44,45,96x

Te Score: Žqq .; pre-reduction of any TeŽVI. to TeŽIV. essential Score: Žqq .; noble metals or mixed
wconditions less critical than for SeŽVI. ª SeŽIV.x; liquid-phase modifiers; enrichment often required
interferences; reductants depressive in batch mode Žiodide,
L-cysteine . w43x

Tl Score: Žyyy .; unreliable technique; very low chemical yield of Score: Žq.; halides strongly
TlH; thermally unstable hydride; inadequate sensitivity depressive; mixed modifiers
w107x; interferences containing noble metal w3,56x
a
Techniques scored within the range of ‘very good, routine applicability’ Žqqq . and ‘poor, unreliable performance’ Žyyy ..
See also the monograph w15x and recent reviews on HGAAS w17᎐21x and CVAAS w22᎐24x.
b
c
STPF conditions w81x, reliable background correction and efficient chemical modification w54᎐56,79x essential for all volatile
analytes; see also recent monographs w2᎐4,6᎐10,14x and reviews w12,77,84x.

5. VG or ETAAS? — Both! 5.1. Comparati¨ e e¨ aluation of VGAAS and ETAAS

In the context of this lecture, the meaning of
the title answer is dual: Ži. both VGAAS and
ETAAS modes are worth recommending as ana-
lytical tools in a trace element laboratory; and Žii.
the usefulness of the VG᎐ETAAS coupling, with
in-atomiser trapping of hydrides or vapors for
automated trace element determination and spe-
ciation is advocated and highly ranked.
The generalized assessment of AAS tech-
niques, given in Table 2, ranks the FAAS, CVAAS
and VG᎐ETAAS as ‘excellent’ and the ETAAS
and HGAAS as ‘good’ analytical methods. Fur-
ther evaluation of the VGAASrETAAS alterna-
tive should involve comparisons made analyte by
analyte ŽTable 5. and matrix by matrix ŽTable 6..
Apparently, each technique exhibits its optimal
Table 6
Comparative evaluation of the application scope of VGAAS and ETAAS techniques a

Sample matrix VGAAS ETAAS

En¨ ironmental
U U U U U
Air particulates Ždigests. As, Bi , Cd, Ge , Pb, Sb , Se , Sn, Te As, Bi, Cd, Cu, Ge, In, Pb, Sb, Se, Sn , Te, Tl
U U U U U U
Air Žvapors. As, Hg, Pb, Sb, Se , Sn , Te As, Cd, Hg, Pb, Sb, Se , Sn, Te , Tl
U
Fly ash As, Bi, Cd, Ge, Hg, Pb, Sb, Se, Sn, Te, Tl As, Bi, Cd, Cu, Ge, Hg, In, Pb, Sb, Se, Sn, Te, Tl

D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933

U U U U
Sediments, sludges As, Bi, Cd, Ge, Hg, Pb, Sb, Se, Sn, Te As, Bi , Cd, Cu, Ge, Hg, Pb, Sb, Se , Sn, Te , Tl
U
Soil As, Bi, Cd, Ge , Hg, Pb, Sb, Se, Sn, Te As, Bi, Cd, Cu, Ge, Hg, Pb, Sb, Se, Sn, Te, Tl
U U U U
Water Žwith low TDS. As, Bi, Cd, Ge , Hg, Pb, Sb, Se , Sn, Te As, Bi, Cd, Cu, Ge, Hg, In, Pb, Sb, Se, Sn, Te, Tl
U U U U
Water Žwith high TDSb . As, Bi, Cd, Ge , Hg, Pb, Sb, Se , Sn, Te As, Bi, Cd, Cu, Ge, Hg, In, Pb , Sb , Se, Sn, Te, Tl

Biological fluids
U U
Blood Žwhole. As, Bi , Cd, Hg, Pb, Sb, Se, Sn, Te As , Bi, Cd, Cu, Hg, Pb, Sb, Se, Sn, Te, Tl
U U U U
Blood plasma or serum As, Bi , Cd, Hg, Pb , Sb, Se, Sn, Te As, Bi, Cd, Cu, Hg, Pb , Sb, Se, Sn, Te, Tl
U U U U U U
Urine As, Bi, Cd, Hg, Pb, Sb, Se, Sn, Te As, Bi , Cd, Cu, Ge, Hg, In, Pb, Sb , Se, Sn , Te , Tl

Biological tissues
Bone, tooth As, Hg, Pb, Sb, Se Cd, Cu, Hg, Pb
U U U U
Hair, nail As, Bi , Cd, Hg, Pb, Sb, Se, Sn As, Bi , Cd, Cu, Hg, In, Pb, Sb, Se, Sn, Te , Tl
U U U U U U
Soft tissues Ždigests. As, Bi, Cd, Hg, Pb, Sb, Se, Sn, Te As, Bi , Cd, Cu, Ge, Hg, In, Pb, Sb, Se , Sn , Te , Tl
U U U U U
Soft tissues Žslurries . Hg, Pb As, Bi , Cd, Cu, Hg , Pb , Sb, Se, Sn , Tl
U U U
Plant tissues Ždigests. As, Bi, Cd, Hg , Pb, Sb, Se, Sn, Te As, Bi, Cd , Cu, Ge, Hg, Pb , Sb, Se, Sn, Te, Tl
U U U U U
Plant tissues Žslurries . Hg , Pb As, Cd , Cu, Hg, Pb , Sb, Se, Sn

Food
U U U
Food Ždigests. As, Bi , Cd, Hg, Pb, Sb, Se, Sn As, Bi, Cd, Cu, Hg, Pb , Sb, Se, Sn
U U U
Food Žslurries . Hg, Pb As, Cd, Cu, Hg, Pb , Sb, Se , Sn
U
Marine tissues Ždigests. As, Cd, Hg, Pb, Sb, Se, Sn As, Bi, Cd, Cu, Hg, Pb, Sb, Se, Sn , Te, Tl
U
Marine tissues Žslurries . Hg, Pb As , Cd, Cu, Hg, Pb, Sb, Se, Sn

Geochemical
Minerals and ores As, Bi, Cd, Ge, Hg, Pb, Sb, Se, Sn, Te As, Bi, Cd, Cu, Ge, Hg, In, Pb, Sb, Se, Sn, Te, Tl
U
Silicate rocks As, Bi, Cd, Ge, Hg, Pb, Sb, Se, Sn, Te As, Bi, Cd, Cu, Ge, Hg, In, Pb, Sb, Se , Sn, Te, Tl

Metallurgical
U
Ferrous alloys As, Bi, Cd, Pb, Sb, Se, Sn, Te As, Bi , Cd, Cu, Ge, Hg, Pb, Sb, Sn
Non-ferrous alloys As, Bi, Cd, Ge, Hg, Pb, Sb, Se, Sn, Te As, Bi, Cd, Cu, Hg, Pb, Sb, Se, Sn, Te
a
For references and analytical procedures, see refs. w1᎐4,6᎐10,15,56x. Legend: Bold symbols: straightforward application at normal analyte levels; asterisk:
straightforward application at elevated analyte levels Žsuch as environmental pollution, biological exposure, therapeutic levels, doped materials, etc..; italic symbols:
enrichment often required; and underlined symbols: indicate strong preference for this analyte over the alternative AAS technique.
b
TDS, total dissolved solids, e.g. in seawater, some mineral waters, brines, etc.

925
926 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933

application field and its specific limitations. For
example, copper and nickel are strongly depres-
sive matrices in HGAAS yet rather beneficial
Žmodifiers. in ETAAS; on the contrary, environ-
mental waters with high total dissolved solids
ŽTDS. content as well as plant digests and ferrous
alloys are troublesome matrices in ETAAS but
very well tolerated in HGAAS. For numerous
reasons, analysis of slurried solids is an attractive
approach; thus slurry sampling is expedited by
ETAAS w6᎐10,77x but is still underdeveloped and
inherently problematic with HGAAS w108᎐112x
and Žless so. with CVAAS w113x. Elaborate wet
chemical digestions and treatments prior to
HGAAS do not appear welcome in clinical and
biochemical laboratories.
As far as the modern, rapidly expanding field of
speciation analysis is concerned w21᎐30,114,115x,
the vapor generation techniques are much better
suited as chromatographic detectors ᎏ see re-
cent reviews w21,34 ᎐ 45 x and monographs
w15,25᎐29x.
Therefore, the choice between analytical tech-
niques would be guided by a whole set of consider-
ations ᎏ up to 20 items ŽTable 2. which are not
necessarily only metrological Žsensitivity, LOD,
expected analyte levels, selectivity and interfer-
ence control. and methodological Žsample treat-
ment, control of contamination and losses,
robustness, QC. but also technical and economic
Žfacilities available, experience, sample turnover,
variety of analytical tasks, etc... The author
strongly believes that these AAS techniques are
supplemental rather than being a dilemma to
each other, thus providing options for better in-
tra-laboratory QC and offering alternate solu-
tions within the general range of a ‘more instru-
mental’ ŽETAAS. and a ‘more chemical’ approach
ŽHGAAS. w12,13x. And this is not surprising since
the whole history of the AAS method demon-
strates a clear tendency of fruitful swinging
between these two tendencies: involving more
chemistry in the ‘instrumental’ ETAAS approach,
such as FI separationsrenrichment and in situ
treatment of analytermatrix by chemical modifi-
cation, and vice versa: successful instrumentaliza-

Table 7
Summary of advantages and problems of VG᎐ETAAS

High absolute sensitivity ᎏ mo in the pg range, owing to the electrothermal atomization mode

High relative sensitivity ᎏ Co in the low ng ly1 range, due to enrichment from large samples Ž0.5᎐10 ml.

Better interference control Žrelease kinetics interferences, interferences in the atomiser w119x., owing to
higher dilution factors, higher Tat and Aint measurement mode

Commercially available instrumentation in both FI and CF mode w80x but also easy modification of
other AAS systems

Automation Ž20᎐90 hy1 .

Very promising performance for Ge w102x Žalso Sn, Pb.

Applicability to chemical systems other than HG such as Hgo , Cd ŽCdo or hydride?. w100x, PbEt4 w105x,
SeEt2 w120x, NiŽCO.4 , CrŽIII. ᎐␤-diketonate, etc.

Potential for speciation, e.g. for Me2 Se, Et2 Se, i-SeŽIV., i-TeŽIV., Bu3 Snq w121x, organoarsenicals w122x,
i-AsŽIII q V. q MMAq DMA w63,71,72x

Other prospects: simultaneous multi-element determinations w68᎐70x Žsee Table 4.;

adaptation of methodology to other multielement techniques such as HG᎐ICP-AES and HG᎐ICP-MS

Problems: blanks ŽAs, Cd, Pb, Sn.; carryover ŽSe.; incomplete isoformation of some alkyltin species w71,72,97x;
double peaks w71,123,124x; interelement interferences w125x; residue accumulation
on quartz capillary tip w71x; expensive.
 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933 927

tion and automation of the ‘more chemical’
VGAAS technique by integrating on-line chemi-
cal treatments prior to vapor generation, such as
UV- or microwave-assisted digestions of different
organoelement species of the analyte, on-line
pre-reduction or pre-oxidation, on-line enrich-
ment and speciation. For recent reviews, see refs.
w21,31᎐33,46,52᎐56,116᎐118x.
5.2. VG᎐ETAAS
The coupling of VG separation and enrichment
with in-atomizer trapping of hydrides or other
vapors for ETAAS quantitation has developed
into a modern, automated, sensitive and success-
fully commercialized technique, VG᎐ETAAS,
which has been treated extensively in recent
reviews w21,53,58x and monograph w15x. The num-
ber of relevant publications on VG᎐ETAAS has
already exceeded 100 w21x. Attractive features of
VG᎐ETAAS as well as some problems faced are
summarized in Table 7, while comparative scores
of this approach vs. other AAS techniques are
given in Table 2. The absolute and relative LODs

Table 8
Examples of HG᎐ETAAS applications to some biological and environmental CRMs or SRMs by Zeeman THGA employing
permanently Ir᎐Zr-treated integrated platforms Žin ␮g gy1 or ␮g mly1 . w71,130x

Analyte CRM or SRMa Certifiedb Foundc Noted

As NRCC SLRS-3 0.72" 0.05 0.70" 0.03 FI-HG᎐ETAAS; Cys

NRCC BCSS-1 11.1" 1.4 11.8" 0.03 FI-HG᎐ETAAS; Cys
BCR CRM 277 47.3" 1.6 46 " 1 FI-HG᎐ETAAS; Cys
BCR CRM 320 76.7" 3.4 79 " 2 FI-HG᎐ETAAS; Cys

Cd NIST SRM 2670 Ž0.40. 0.43" 0.01 SB-VG᎐ETAAS

Žnormal level.
NIST SRM 2670 88 " 3 84 " 5 SB-VG᎐ETAAS
Želevated level.
NRCC SLRS-3 0.013" 0.002 0.014" 0.003 SB-VG᎐ETAAS
0.014" 0.005 CF-VG᎐ETAAS
NRCC SLRS-1 0.015" 0.002 0.014" 0.005 SB-VG᎐ETAAS
0.012" 0.002 CF-VG᎐ETAAS
NRCC CASS-3 0.030" 0.005 0.027" 0.006 SB-VG᎐ETAAS
0.034" 0.003 CF-VG᎐ETAAS

Sb NRCC SLRS-3 0.12" 0.01 0.13" 0.07 FI-HG᎐ETAAS; Cys

NRCC BCSS-1 0.59" 0.06 0.57" 0.02 FI-HG᎐ETAAS; Cys
0.63" 0.04 FI-HG᎐ETAAS; Cys
BCR CRM 320 Ž0.6. 0.53" 0.05 FI-HG᎐ETAAS; Cys
NRCC MESS-1 0.73" 0.08 0.73" 0.09 FI-HG᎐ETAAS; Cys
BCR CRM 277 Ž4.0. 3.3" 0.02 FI-HG᎐ETAAS; Cys

SeŽIV. NRCC CASS-3 0.020" 0.005 0.016" 0.008 CF-HG᎐ETAAS

Se NRCC MESS-1 0.34" 0.06 0.31" 0.04 FI-HG᎐ETAAS

NRCC BCSS-1 0.43" 0.06 0.43" 0.04 FI-HG᎐ETAAS

Sn BCR CRM 320 Ž6.0. 6.25" 0.05 FI-HG᎐ETAAS; Cys

a
NRCC, from The National Research Council of Canada, Ottawa, Canada; BCR, from the Institute for Reference Materials
and Measurements, Geel, Belgium; NIST, from the National Institute of Standards and Technology, Gaithersburg, MD, USA.
b
Mean " 95% confidence interval Žinformation values only in parentheses ..
c
Mean " standard deviation, n s 3.
d
Details of sample decomposition and pretreatment procedures given in refs. w71,130x; Cys, pre-reduction with L-cysteine; SB,
semi-batch system for HG.
928 D.L. Tsale¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 917᎐933
are excellent ᎏ in the low pg and ng ly1 range,
respectively. Nevertheless, increasing sample
volumes above 1᎐2 ml is inconvenient in flow
injection mode and may not bring a proportional
improvement in relative LODs w126x. Larger sam-
ples could be processed in continuous-flow and
batch-type mercuryrhydride generators Žup to
10᎐50 ml.; control of reagent and procedural
blanks is a serious concern w53x.
Hydrides and vapors are best trapped on
chemically-modified graphite surfaces, particu-
larly on noble metals w127,128x, some carbides
ŽZr, W. w102,103,121,129x and thermally-stabilized
noble metals on carbide-treated platforms, e.g.
Ir᎐Zr or Ir᎐W w58,71,72,90,130x. More detailed
discussion on chemical modifiers w21,56x and par-
ticularly on permanent modification w58x in
VG᎐ETAAS could be found in recent reviews
and references therein.
In Table 8 are compiled some examples of
VG᎐ETAAS applications to certified reference
materials ŽCRM. and standard reference materi-
als ŽSRM.: environmental waters, plant, and sedi-
ments and urine.
6. Conclusion
On the basis of a set of metrological, methodo-
logical, technical and economic considerations,
the AAS techniques are highly ranked as ‘excel-
lent’ ŽFAAS, CVAAS and VG᎐ETAAS. and ‘very
good’ methods ŽETAAS and HGAAS. for trace
element quantitation. They are widespread, cost-
effective, adequately sensitive for most routine
tasks and supplementary to each other. Admit-
tedly, AAS is nowadays facing a serious challenge
by modern ICP methodologies because of their
simultaneous multi-element capabilities for assays
within broad concentration ranges and straight-
forward coupling with chromatographic appara-
tus.
Attractive specific features of ETAAS are
excellent absolute LODs, microsampling for slur-
ries, solids and liquids, relatively simple pre-
instrumental treatment, reliable contamination
control and coupling with flow-injection enrich-
ment techniques ᎏ down to ng ly1 LODs.
VGAAS offers certain speciation potentialities,
competitive LODs for analytically-difficult ana-
lytes and good sampling frequencies but calls for
more elaborate sample digestion, control of
chemical parameters and potential interferences.
The hyphenated VG᎐ETAAS is the current
technique of choice at ng ly1 levels of hydride-
forming and relevant elements ᎏ so far not very
popular but promising owing to speciation capa-
bilities and good metrological characteristics.
Economic parameters of ETAAS and
VG᎐ETAAS are less favourable vs. other AAS
techniques.
Acknowledgements
Financial support by the Organising Committee
of the Colloquium Spectroscopicum Internatio-
nale XXXI, Ankara, Turkey, is gratefully ac-
knowledged.
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