Spectrochimica Acta Part B 57 (2002) 1835–1853

Review
Modifiers and coatings in graphite furnace atomic absorption
spectrometry—mechanisms of action (A tutorial review)夞
H.M. Ortnera,*, E. Bulskab, U. Rohra, G. Schlemmerc, S. Weinbruchd, B. Welze
a
Department of Chemical Analytics, Institute of Material Science, Darmstadt University of Technology, Petersenstr 23,
D-64287 Darmstadt, Germany
b
Department of Chemistry, University of Warsaw, Warsaw, Poland
c ¨
Analytik Jena GmbH, Uberlingen, Germany
d
Institute of Mineralogy, Darmstadt University of Technology, Darmstadt, Germany
e
Department of Chemistry, Federal University of Santa Catarina, Florianopolis, Brazil

Received 15 May 2002; accepted 1 August 2002

Abstract

A multitude of different and often contradictory mechanisms for the effects of modifiers and coatings have been
proposed. Many of these proposals lack sufficient experimental evidence. Therefore, a series of statements based on
our own investigations is given as ‘facts’. Another series of statements is made as ‘fictions’ related to erroneous
proposals on the functioning of modifiers and coatings in the pertinent literature. Two basic concepts are developed
for the sequence of processes leading to analyte stabilization for the two most important groups of modifiers:
refractory carbide forming elements of the IVa–VIa groups of the periodic system on the one hand and Pt-group
metals on the other hand. These concepts are based on the main reactions of graphite with elements and compounds:
carbide formation and intercalation. Most important experimental results leading to this understanding are described:
Penetration measurements for modifiers and analytes indicated the subsurface zone down to approximately 10 mm as
the essential place for graphite–analyte–modifier interactions. The reason for this phenomenon is an open porosity of
the pyrocarbon coating of 5–10% (vyv) into which liquids penetrate upon sample application. This also indicates
that modifiers are best applied by impregnation or electrolysis whereas dense coatings are not advantageous. It is also
shown that graphite tube assemblies are dynamic systems with a limited lifetime and carbon losses are an essential
feature of tube corrosion. Most frequently found erroneous statements are discussed: (a) Particles on the tube surface
are responsible for analyte stabilization and retention during pyrolysis. (b) Analyte stabilization is taking place by
formation of intermetallic compounds or thermally stable alloys. (c) Experiments are performed with unrealistic
concentrations of analytes andyor modifiers. (d) Dense coatings are advantageous. Finally, a functional schedule is
given for the three steps of graphite furnace atomic absorption spectrometry (GFAAS): sample application and

夞 This paper was presented at the 7th Rio Symposium on Atomic Spectrometry, held in Florianopolis,
´ Brazil, April 2002 and is
published in the Special Issue of Spectrochimica Acta Part B, dedicated to that conference.
*Corresponding author. Tel.: q49-61-51-166-379; fax: q49-61-51-166-378.
E-mail address: h.ortner@hrzpub.tudarmstadt.de (H.M. Ortner).

0584-8547/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 5 8 4 - 8 5 4 7 Ž 0 2 . 0 0 1 4 0 - 4
1836 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853

drying; pyrolysis; atomization. Contrary to the vast amount of literature on this topic it tried to provide the
analyst working with GFAAS and in an increasing number working with Solid Sampling-GFAAS with a set of most
important statements. This might spare the experimentalist a lot of useless optimization procedures but should lead
him to a basic understanding of the complex phenomena taking place in his instrument and during his analytical
work.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: GFAAS; Graphite atomizer; Chemical modification; Mechanisms of action; Coatings

1. Introduction possible in order to facilitate the study of such an

Mechanisms of action of modifiers in electro-
thermal atomic absorption spectrometry (ETAAS)
is a topic of great scientific and practical interest.
Volynsky recently published a respective review
with 284 literature citations for the most popular
group of modifiers, i.e. the platinum group metals
w1x. This demonstrates the worldwide efforts in the
search of basic principles of action of modifiers.
Coatings can also be considered as permanent
modifiers w2,3x, and are, therefore, included in the
discussion.
The pertinent literature is full of very different
and often contradictory proposals for mechanisms
of action of modifiers and coatings w4,5x. A series
of statements based on our own investigations are
presented as ‘facts’. This should not indicate that
only our own investigations in this wide field are
correct. What should be expressed by this formu-
lation is that the ‘facts’ in this paper are observa-
tions based on experimental evidence rather than
on mere speculation. On the other hand, some
frequently proposed mechanisms of action are
shown to be erroneous and only these are sum-
marized under ‘fictions’. This way it is hoped to
raise the ongoing discussion on a safer and largely
experimentally based level. This concept was
already used by us previously w6x but it is now
elucidated in much greater detail. Matrix—analy-
te—and modifier behavior in connection with
graphite tube changes with rising temperature of
an analysis cycle as well as with a rising number
of analysis cycles are very complex processes and
it is difficult to keep all these phenomena properly
in mind for a sound interpretation of graphite
furnace atomic absorption spectrometry (GFAAS)-
procedures. It therefore, tried to structure this
remarkably voluminous knowledge as clearly as
overview.
An exciting and relatively new version of
GFAAS is now approaching maturity—Solid Sam-
pling-GFAAS (SS-GFAAS). Of course, the method
has for quite some time been in critical discussion
and maybe ten years ago even very reputed ana-
lysts did not think that this is a reliable approach
to real type samples. However, the obvious advan-
tages have ultimately led to the construction of
impressive new instrumentation like the Atomic
Absorption Spectrometer (AAS) ZEEnit 60 of
Analytik Jena (Germany) which lends itself to
relatively simple quality control, e.g. for the deter-
mination of traces of Cu, Pb, Cd, Zn and Fe in
calcium fluoride w7x, an important new substance
for fluoride–phosphate glasses used in laser optics
dedicated to nanostructuring processes in the
microelectronics industry. The most prominent
advantages of this analytical approach for powders
and other solid samples are:
● Trace element sensitivity down to the ppb-level
in favorable cases.
● Avoidance of contamination by minimum sam-
ple preparation with no dissolution procedures.
● Small sample weights in the single mg-range,
which also allow heterogeneity investigations
on this sample weight level.
However, it has been observed in our area that
the analysts active in this field in industry have
little experience in this very special type of
extreme trace analysis and still less knowledge in
graphite corrosion phenomena. This is typical for
today’s industrial situations caused by over-ration-
alization w8,9x. Consequently the nice instrumen-
tation which still does bear some instrumental and
software bugs, is not handled adequately. Analyti-
cal optimization is not properly carried out and
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
some basic problems, e.g. related to respective
graphite corrosion which often is disastrous in
solid sampling into graphite boats is not reduced
by adequate measures. It is, therefore, one of the
main incentives of this paper to provide the exper-
imentalist with a series of relatively simple state-
ments which maybe can help to avoid respective
pitfalls and might lead to a more profound under-
standing of the essentials of GFAAS which still is
one of the most important trace analytical methods
available.
2. Facts
2.1. Fact 1
2.1.1. Reaction of carbon with the elements of the
periodic system: carbide formation
If one considers the vast variety of inorganic
carbon compounds with the elements of the peri-
odic system it is observed that only few elements
do not form any compounds with carbon, Table 1.
At first sight one even wonders whether graphite
should be the proper material for atomizers in
atomic absorption spectrometry. However, as it
turned out in the long evolution of ETAAS, carbon
is the most adequate material for this purpose in
spite of all these carbon compounds w10,11x. With
almost all metals, carbon is forming carbides of
very varying structures and properties.
The most stable carbides are the ones of the
IVa–VIa-groups of the Periodic System of the
Elements (PSE). Many of these metallic carbides
belong to the hard materials, which are extensively
used in technology w12–14x. Metallic or interstitial
carbides are also formed by Mn, the iron metals
and by P and As. The diamond-like carbides of B
and Si also exhibit a high thermodynamic stability
and high melting points. Of the salt-like carbides
of the Ia-, IIa- and III-Groups of the PSE including
the lanthanides and actinides the latter are the most
stable ones. Most of these carbides are decomposed
to acetylene by water and are hence called acetyl-
ides. Group I-metals form quite a series of inter-
calation compounds. The elements of group VI
and VII and nitrogen form volatile or liquid,
covalent carbon compounds.
Some of these carbides range amongst the ther-
mally most stable compounds we know (e.g. HfC,
1837
TaC, ZrC, NbC) with melting points around and
above 3500 8C w13x. That these elements are
difficult to atomize in a graphite tube system is
obvious. It should also be understood that technical
carbonization of these very stable carbide formers
is occurring at significantly lower temperatures
than their melting points: carburization to WC at
1500–1700 8C, to TaC at 1600 8C, to TiC at
2000–2200 8C w13,14x.
2.2. Consequences in GFAAS
2.2.1. Negative effects: low analyte sensitivity w15x
and pronounced tube corrosion
● Lacking sensitivity for thermally stable carbide
forming elements, especially lanthanides (acti-
nides), IVa–VIIIa-group elements namely Ti,
Zr, Hf, V, Nb, Ta, Mo, W and elements forming
diamond like carbides (B, Si). Of course, car-
bide formation is especially detrimental in
GFAAS if the thermal stability of the formed
carbides exceeds the pyrolysis temperature and
especially if it approaches or also exceeds the
atomization temperature.
● Acetylides cause dramatic corrosion due to
hydrolysis of respective carbides with water in
the sample application step and due to the
formation of acetylene. Possibly the formation
of gaseous carbides at high temperatures also
plays a role w16–18x.
2.2.2. Positive effects: analyte stabilization, matrix
decomposition and prolonged tube lifetime
● Some of these elements are good permanent
modifiers (impregnants): Especially some of
those of groups IV a (Zr, Hf), Va (Nb, Ta), VI
a (Mo, W) w19,20x.
● Some matrices are better decomposed during
pyrolysis by the catalytic activity of the formed
modifier-carbides w21x.
As was pointed out by Volynsky w19x, it has
been observed by many analysts that the lifetime
of carbide-modified graphite tubes is significantly
longer than that of standard graphite tubes in many
practical applications. This is probably due to the
resistance of refractory carbides against the attack
of many acids and acid mixtures and their high
temperature stability.
1838 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
2.2.3. Proposal for the mechanism of action of
refractory carbide forming elements as modifiers
The question now arises, where such modifier–
graphite–analyte interactions take place.
Furthermore, the question is why these elements
are good modifiers similar in their analyte stabiliz-
ing effects to the VIIIa-platinum group elements
which do not form carbides at all.
It is interesting to observe that especially anal-
ytes with a tendency to form oxo-anions are
stabilized by IVa–VIa-group modifiers, i.e. the
III–VI-group elements. It is known from carbide
chemistry that refractory metal (RM) carbides are
easily oxidized on their surface. It is also known
that many metal oxides form bronzes, i.e. mixed
metal oxides with RM-oxides w22x. These exhibit
a high thermal stability. Oxoanions are well known
to form heteropoly-acids with RM-isopoly acids in
acidic aqueous media. These heteropoly acid sys-
tems will be dehydrated to thermally quite stable
mixed oxides w22x. Although there is no hope
presently to investigate analyte–modifier–com-
pound formations at the extreme trace levels of
the analytes present in GFAAS it is reasonable to
propose such a compound formation as stabilizing
effect of the carbide forming modifiers. The break-
ing of these bonds at high temperatures by a
reconversion of the modifier oxides to carbides
with CO-formation and subsequent analyte atomi-
zation would be a logical process leading to an
effective analyte atomization with the analyte
atomic vapor being carried into the tube atmos-
phere by the evolving CO. Subsequent sample
introduction will again lead to the necessary sur-
face oxidation of the RM-carbides to form heter-
opoly acids again with the newly introduced
analytes. Fig. 1 should illustrate this novel
approach by a new mechanism of action for a
large group of permanent modifiers.
It is now also understandable why an oxidative
treatment of graphite surfaces should improve
analyte retention in some cases w24–27x. Here,
too, complex formation with surface hydroxyl- and
carboxyl-groups will take place with many analy-
tes. Dehydratization will again lead to oxide and
carboxide systems, followed by analyte reduction
1839
and CO-formation as described above. However,
the retention will not be as effective as the one by
heteropoly-compounds of RM-carbides.
It should be mentioned that apart from, e.g. tube
lifetime observations for carbide coated tubes, no
experimental evidence for the proposed mechanism
is yet available. We are, however, planning to
study refractory metal carbide oxidation by syn-
chrotron X-ray induced photoelectron spectrometry
(XPS).
It should be emphasized that the universal inter-
pretation of the retention mechanism of the palla-
dium modifier as dissociative chemisorption w28x
is too narrow for the broad variety of high tem-
perature chemical interactions taking place
between analytes, modifier and graphite. It is
especially the absence of the consideration of the
graphite as a highly reactive material at atomiza-
tion temperatures which underestimates respective
reactions with carbon in this context. In order to
understand the action of the second large group of
modifiers of the platinum metals it is necessary to
first consider some essential aspects of graphite
interaction with liquid samples.
2.3. Fact 2
2.3.1. Penetration measurements for modifiers and
analytes into the depth of graphite tube systems
● Modifiers and analytes penetrate up to 10 mm
into the pyrographite (PG)-coating of longitu-
dinally heated graphite atomizer-(LHGA) and
transversally heated graphite atomizer (THGA)-
tube systems already upon sample application
and drying w29,30x. This is not a diffusion
process but a liquid penetration primarily into
the open porosity of the PG. For the Pd–Mg-
modifier, there is significantly less MgO than
PdO below the surface. Arsenic as analyte also
penetrates into the PG to the same depth as the
Pd-part of the modifier w29x.
● After pyrolysis the Pd penetrated deeper into
the PG-layer (up to 30 mm) whereas the analyte
together with the MgO did not change their
depth distribution.
● Good modifiers appear to remain in the near
1840 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853

Fig. 1. Potential permanent modifiers among refractory carbide-forming elements and noble metals (in italics) according to w23x
and proposed mechanism of analyte retention for carbide-forming modifiers.

surface region (example: WC from tungstate
solutions, noble metals w30x). Similar observa-
tions were made by Majidi and Robertson using
Rutherford backscattering spectrometry w31x.
However, they interpreted their results as pure
diffusion because investigations were only per-
formed after pyrolysis.
● Other modifiers or matrices quickly penetrate
the whole wall thickness (examples: La, Nb).
This might be due to the formation of gaseous
carbides and in the case of La also due to
extensive corrosion and exfoliation by acetylene
formation during aqueous sample application
w16–18,32x.
● Some matrices such as iron do not penetrate
into the PG-layer at all (especially covalently
bound carbide formers) w18x.
2.4. Fact 3
2.4.1. The pyrographite coating on polycrystalline
electrographite: micro- and nanometer-scale-sur-
face morphology and porosity measurements
The microstructure of PG-surfaces was exten-
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
sively studied by scanning electron microscopy
(SEM) w33x. From these studies it was concluded
that the PG forms a dense and essentially poreless
layer on the EG-base material with a high oxida-
tion resistance and an extremely low permeability
as a result of the high crystalline order of the PG.
It must be mentioned that no high resolution SEM-
studies were performed since at that time (at the
end of the 1980s) field emission gun SEMs were
still very rare. First investigations by scanning
tunneling microscopy (STM) and atomic force
microscopy (AFM) did demonstrate great changes
in surface nanoroughness during graphite tube
lifetime of PG-surfaces w34x. However, detailed
studies with very high lateral resolution were not
feasable at the very beginning of the fantastic
instrumental development of these new methods
of surface investigation. Only fairly recently Van-
dervoort et al. w35x demonstrated the presence of
nanometer scale cracks already on virgin PG-
surfaces of modern THGA-tube systems. Since the
lattice in these domains of the PG-surface is
oriented almost perpendicularly to the surface, the
resistance toward oxidative attack is much lower
than in areas where the lattice is oriented parallel
to the surface. Consequently, these domains will
be corroded much faster which will give rise to a
growing open porosity. Therefore, porosity meas-
urements on LHGA- and THGA-tube systems are
of great importance in order to further elucidate
this important property of PG-surfaces. Such meas-
urements are, however, not quite easy to perform.
The conventional method of porosity measurement
by mercury intrusion is not applicable to graphite
materials because of the danger of changing the
porosity by the breakdown of the graphite pore
structure by the high mercury pressures which
have to be applied w36x. Therefore, a pycnometric
procedure was applied w36,37x which yielded a
most surprising result w29x: the open porosity of
PG-coated LHGA-systems with platform is in the
range of 5–10% (vyv) (compare also with w38x)
and that of pyrographite is reported up to 3% (vy
v) for well ordered PG w39x. With these results
the penetration measurements discussed above
become better understandable.
1841
2.5. Fact 4
2.5.1. The significance of intercalation compounds
in GFAAS for matrices, modifiers and analytes
Intercalation is the key issue for graphite-inter-
actions w40x with many:
● Analytes.
● Matrices.
● Modifiers.
Preferably intercalated elements and compounds
w40x:
● Alkali and alkaline earth metals, noble metals.
● All mineral acids except HNO3 (which is rather
thermally decomposed).
● Many metal oxides and halides.
● Halogens and halides (especially from organic
solvents after thermal decomposition of the
latter).
One of the reasons of the failing of glassy
carbon as a candidate material for GFAAS is its
inability to form intercalation compounds! Of
course, other important reasons are its becoming
fairly reactive at temperatures above 2200 8C and
its relatively low temperature resistance: it is rap-
idly destroyed at temperatures above 2500 8C w41x.
2.5.2. Positive effects of the formation of interca-
lation compounds in GFAAS: studies on the func-
tioning of modifiers of the platinum-group metals
The advantageous use of modifiers of the plati-
num group metals (PGM) seems to be based on
the formation of intercalation compounds and a
subsequent activation of these intercalated metal
atoms. The such activated metal atoms are pro-
posed to form strong covalent bonds with easily
volatile analyte elements which leads to their
stabilization to remarkably high appearance tem-
peratures w29,42x.
The first step in this process, the intercalation
of Pd has been experimentally verified by X-ray
emission line shift measurements in the electron
microprobe. This line shift of the selected Pd
Lb2y15 line for various Pd-compounds is extremely
small. This made the development of a special
procedure of peak-flank intensity ratio measure-
ments necessary w29x. A comparison of the
1842 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853

observed line shift for Pd in areas, where no Pd- on or below the surface with samples of prepared
particles are seen in respective scanning electron PdCl2-graphite intercalation compounds unambig-
micrographs (SEM-micrographs) but Pd is present uously demonstrated the presence of intercalated

Fig. 2.
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853 1843

Pd in THGA-platforms. Details of this investiga-
tion will be published separately. In addition,
elution experiments were carried out after the
drying step on LHGA-platforms treated with a
conventional PdyMg-modifier. It was found that
20% of the Pd could not be eluted any more with
6 M HCl. This also clearly indicates that the
retained Pd cannot any more be present as nitrate
or oxide but must have reacted with carbon to
form compounds which are resistant against the
elution. The Mg was recovered to 100% by the
same elution procedure w29x.
So far the experimental evidence of the Pd-
modifier intercalation has been described. We can
unfortunately only speculate about the subsequent
analyte retention mechanism because we have no
experimental possibility to study the bonding of
nanogram amounts of analytes with all the instru-
mental possibilities of today’s impressive range of
methods of analysis on solid state systems w43,44x.
We propose a mechanism of bonding, e.g. of As
to the Pd-atoms which are activated by their
intercalation, above a graphite lattice plane in the
following way w45x. Fig. 2 should demonstrate the
process of Pd-oxide intercalation and the proposed
way of bonding of As-analyte atoms. There are
chemical bonds between the p-electron system of
the graphite lattice on the surface of a lattice plane
to the coordinatively unsaturated Pd-atoms on the
outer surface of a Pd-cluster adjacent to the graph-
ite lattice. The electrons missing to noble gas
configuration for these Pd-atoms are, therefore,
taken over from the p-electron system of the
graphite. This causes an elevated electron density
for these Pd-atoms which are, therefore, activated
for an interaction with, e.g. As(OH)3 to function
as electron donors. This is an analogy to the
ferrocenes where the iron atom also exhibits elec-
tron donor properties: Fe(C5H5)2qHq™
wFeH(C5H5)2xq w45x.
If the Pd, on the other hand, would act as
electron acceptor, then analytes in higher oxidation
states we.g. As(V)x or metal cations as e.g. Cd2q
or Pb2q could not be bound. The bonding between
the p-electron system of the graphite lattice and
the coordinatively unsaturated Pd atom in the
periphery of a cluster is symbolized by a perpen-
dicular line in Fig. 2. The thus activated Pd-atom
then reacts with, e.g. arsenic acid in the way
shown in Fig. 2. It should again be emphasized
that only the Pd-atoms on the phase boundary Pd-
clusterygraphite are activated. This is in agreement
with the observation that the analyte is already
bound during the drying step. This bond is not
destroyed by a temperature rise in spite of the
ongoing reduction of the PdO under the conditions
of the pyrolysis. It should also be stressed that the
activated domain of the Pd-modifier is the subsur-
face region to a depth of approximately 10 mm,
i.e. the volume of the open porosity and adjacent
domains between the graphite layers of the PC-
structure. It should also be mentioned that by the
strong bonding of the analyte to the Pd its mobility
at pyrolysis temperature is practically suppressed.

Fig. 2. (a) Description of the bonding in PdO: the bonding of Pd2q with (4=O2y) 1y4 leads to dsp2—hybridization and not
completely filled 5p-orbitals. The oxygen coordination of Pd-atoms is 4-fold and leads to polar covalent bonds. (b) Intercalation of
PdO in graphite: from EPMA-investigations it can be concluded that cluster formation with diameters of several micrometers and
a height of 1–2 nm takes place when PdO is intercalated near the surface of the PC. With rising temperature up to pyrolysis the
reduction of PdO by inner surface carbon atoms with subsequent CO evolution takes place. Maybe some O2 is also formed without
reductive action of the carbon. (c) Chemical bonds are formed between the Pd-atoms adjacent to the graphite lattice planes by
interaction of the p-electron cloud of the graphite, which fills up the 5p orbitals of the Pd to noble gas configuration (in analogy
to ferrocenes). Within the Pd-clusters, the bonds to oxygen prevail and later on metallic bonds between the Pd-atoms which do not
have a chance to interact with the p-electron cloud of the graphite. (d) This interaction of Pd-near surface atoms with the graphite
lattice seems to activate the Pd to become an electron donor for metalloids. The lower part of the figure should show how such a
bonding situation could look like. The ferrocene-like bonding between the graphite and the coordinatively unsaturated Pd-atoms
adjacent to the graphite lattice plane is symbolized with a perpendicular bond in a broken line. The two other valency bonds
symbolize bonds to the Pd-cluster. Such an activated Pd atom now reacts with, e.g. arsenic acid in the way shown. The formation
of a double bond between the Pd and the metalloid is not an exotic situation. It was also observed in other metal-organic compounds,
e.g. in (OC)3NisAsR3. It should be emphasized that only Pd-atoms on the phase boundary between the Pd-cluster and the graphite
can act in such a manner.
1844 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
Hence, the analyte atoms cannot diffuse further
into the graphite nor to the inner tube surface.
Hence, neither a broadening of the atomization
peak occurs nor are analyte losses during the
pyrolysis step possible.
A more in depth study of the respective atom
formation for As, Se, Te can be found in w29x and
will be discussed later under Fiction 2.
2.5.3. Negative effects of matrix- or modifier-
intercalation
The intercalation of mineral acids, on the other
hand, also leads to a tight binding of many analytes
resulting in a pronounced deterioration of their
determination w46x.
In still other cases, the formation of intercalation
compounds leads to PG-layer scrolling and a fast
subsequent exfoliation. This was observed, e.g. for
the matrices iron and lanthanum although the mode
of corrosive attack is quite different for these two
matrices w18x. This again results in bad analytical
performance and a dramatic decrease of analytical
as well as total tube lifetime.
2.6. Fact 5
2.6.1. Permanent modifiers need high temperature
stability and are best applied by impregnation or
electrolysis
Recently, the concept of permanent modifiers
became very popular w47x. The elements most
commonly used for this purpose are either Pt-
group metals with high melting points (Pt 1772
8C, Rh 1966 8C, Ru 2310 8C, Ir 2410 8C) or very
stable carbide forming elements (W, Ta, Zr, etc.).
These modifiers may also be used as ‘in situ’
collectors of analyte hydrides w47x.
Due to the lower melting point of Pd (1552 8C)
as compared to Ir (2410 8C) Pd is inferior to Ir as
permanent modifier. This was demonstrated by
respective results of Pd- and Ir-determination by
instrumental neutron activation analysis after appli-
cation of 200 mg Pd and 25 mg Ir and analysis
under conditions for Sn: after 300 analysis cycles,
the modifier is still operative, but 99% of the Pd
are lost. 53% of the Ir are still present mostly
below the graphite surface w29x.
Tube impregnation is the easiest way to apply
permanent modifiers to GFAAS-tube systems
w3,48x.
Still more effective than impregnation is the
deposition of permanent modifiers by electrolysis.
The reservoir of, e.g. noble metal modifiers depos-
ited in the elemental form below the surface is
thus greater and, hence, available for the total
analytical lifetime of the tube system, i.e. for
several hundred analysis cycles. This saves rea-
gents and shortens analysis time. Blanks are also
kept to a minimum this way w30x. It should have
been pointed out already that too high amounts of
permanent modifiers can decrease the sensitivity
for some elements, and can lead to other negative
effects. This is especially true for (dense) coatings
applied by Physical Vapor Deposition (PVD) or
Chemical Vapor Deposition (CVD).
2.7. Fact 6
2.7.1. Graphite tube assemblies are dynamic sys-
tems with a limited lifetime w49,50x
For PG-coated tubes three distinct stages of tube
system performance can be distinguished w50x:
● A preliminary phase of approximately 20 anal-
ysis cycles with greater deviations in sensitivity
and large relative standard deviation (R.S.D.).
This is caused by high mass losses, a developing
smoothing of surface roughness and a reduction
in closed porosity due to recrystallization phe-
nomena in the binder phase of the polycrystal-
line electrographite tube system body.
● A phase of nearly constant and high sensitivity
with a minimum in R.S.D. follows the initial
phase, caused by minimum mass losses, a min-
imum in closed porosity and a largely smooth
pyrocarbon surface with eventually rising cor-
rosion. This range is often prolonged by sec-
ondary carbon coating in the platform region
and can last for several hundred analysis cycles.
● A final phase with decreasing sensitivity and
increasing R.S.D. The analytically useful life-
time is reached if the sensitivity dropped by
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
more than 20% of the maximum sensitivity, and
the R.S.D. rose to )2.5%. In this stage, surface
roughness is rising due to corrosion, mass losses
are also rising. Permeability of carbon for anal-
yte atoms through the tube wall increases. Car-
bide formation in the gas phase increases.
The total lifetime of a tube system is reached
when tube breakage occurs.
Table 2 gives an overview of respective phe-
nomena in AAS-behavior of the analytes, their
underlying phenomena of relevant graphite chang-
es together with important interpretations.
2.8. Fact 7
2.8.1. The significance of carbon losses w46,50x
The mass loss and carbon loss of a tube system
are identical since the tubes consist of )99.9%
carbon.
The carbon loss amounts to several percent of
the total tube mass over the analytical lifetime of
a tube system w29,50x.
This loss occurs predominantly during the atom-
ization and the tube scavenging period. The main
causes are carbon evaporation and carbon particle
emission rather than oxidative processes.
However, oxidative processes mainly occurring
during pyrolysis are important phenomena leading
to activated carbon areas from which carbon evap-
oration takes place during the high temperature
phase of analysis cycles. Carbon losses may
amount up to )150 mg per analysis cycle. In-tube
losses are around 50% lower than this. They are
best characterized by electrothermal vaporization-
inductively coupled plasma-mass spectrometry
(ETV-ICP-MS) w50x.
Of course, corrosive and high temperature tube
attack and carbon losses are interrelated.
3. Fictions
The most important and experimentally estab-
lished facts for understanding the action of modi-
fiers have been elucidated. In the following, some
1845
of the most frequently found erroneous interpreta-
tions of observations on the mechanism of action
of modifiers will now be discussed as ‘fictions’.
3.1. Fiction 1
3.1.1. Particles on the graphite surface are respon-
sible for analyte stabilization and retention during
pyrolysis
This is one of the most frequently given expla-
nations for analyte stabilization by modifiers w1x.
However, qualified thoughts on how analytes
should be stabilized in particles are scarce. Here
are our own considerations and experimental
results on this topic:
● The particle abundance for the universal modi-
fier (Pd, Mg) is surprisingly low if actual
amounts are applied we.g. 15 mg Pd(NO3)2, 10
mg Mg(NO3)2x w29x. Since the particles are
decomposing during pyrolysis (at the latest)
they become porous.
● Only for amounts used for permanent modifi-
cation, the particle abundance is initially high
(200 mg Pd, 25 mg Ir). However, after 300
analysis cycles (Sn-conditions) the particles
have all disappeared, but the modifier is still
operative w29x. This was the most convincing
observation for us that analyte stabilization can-
not be effected by particles.
● There is no reason, why the Pd or Ir in the
particles should retain the analytes during pyrol-
ysis due to high diffusion rates and short dis-
tances for outward-diffusion in porous particles
of 0.1–10 mm in diameter.
● In many cases, an improved modifier action
was observed for very fine particles of the
modifier with particle diameters in the range of
several tens to hundreds of nanometers w51x.
This is understandable since a finer and more
homogeneous distribution of the modifier will
be more effectively intercalated than few larger
modifier particles. On the other hand, such small
particles cannot possibly retain the analyte by
mere diffusional processes.
● Particles or better drops of molten Pd (TMs
1552 8C) cannot retain analytes (e.g. As, Se,
1846 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853

Table 2
Lifetime profile of PC-coated graphite tubes of polycrystalline electrographite

Analytical phenomena Reasons in structural changes Interpretation

of the graphite
Preliminary phase of tube stabilization
Greater variations in Caused by: This leads to:
(a) analyte sensitivity (a) high mass loss (a) high tendency of carbide
(b) reproducibility (b) secondary coating formation in the gas
(R.S.D. too large) (c) decrease of the closed phase
porosity by heating (b) Reduction and unifi-
processes especially in the cation of PC-surface-
binder of the electrographite roughness by secondary
coating; this leads to a
decrease in the activity
for carbide formation of
the PC coating.
(c) Reduction of closed
porosity leads to a
more homogeneous
temperature distribution
throughout the tube.
Range of optimal tube performance
Optimal tube perfor- (a) Minimal closed porosity (a) High analytical
mance: (b) Corrosion of pyrocarbon performance caused
(a) Highest and constant coating low by minimal carbide
sensitivity (c) This range is frequently formation, in the gas
(b) lowest and constant extended by pronounced phase as well as on the
R.S.D. secondary coating of platform and tube
platforms. surface
(b) Minimal analyte
diffusion into the
graphite
Range of decreasing tube performance terminating analytical tube lifetime and finally total
tube lifetime by tube cracking and breakage
(a) Loss of sensitivity (a) Rise in closed porosity Loss of sensitivity and
and increase in R.S.D. due to hysteresis of reproducibility caused
End of analytical thermal expansion by:
tube lifetime if (b) Rise of surface roughness (a) Rising tendency to
R.S.D. exceeds 2 due to corrosion carbide formation in the
to 5% (relative) (c) Rise of mass loss gas phase
(d) Rise of wall permea- (b) Rising carbide formation
bility due to thinning on the corroded platform
or complete destruction and tube surface
of PC-coating (c) Pronounced analyte
diffusion into the graphite
with subsequent carbide
formation and subsurface
intercalation

Te) to the observed appearance temperatures of activation energies, e.g. for As and Se with the
approximately 1900, 1500 and 1600 8C, respec- conventional Pd–Mg-modifier were determined
tively. Activation energies of diffusion in liquids to 1300 kJymol and 500 kJymol, respectively,
range from 1 to 30 kJymol only w29x. Contrary, w29x.
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
3.2. Fiction 2
3.2.1. Analyte stabilization by formation of inter-
metallic compounds or thermally stable alloys
● In the review by Volynsky w1x, a whole chapter
is dedicated to the ‘Application of binary phase
diagrams for clarification of the mode of action
of platinum group metals (PGM)—modifiers’,
stating that binary phase diagrams are a source
of important information concerning stabiliza-
tion of analytes by means of metallic modifiers.
This is unfortunately a typical ‘fiction’ for the
following reasons:
● The modifier to analyte mass ratio amounts to
1000:1–100 000:1 in all practical cases. On the
other hand, all intermetallic compounds or ther-
mally stable alloys are only formed at mass
ratios between 1:1–100:1 w52x. Such com-
pounds cannot, therefore, be formed in ETAAS,
contrary to the findings of some authors who
unfortunately used unrealistic mass ratios
between analytes and modifiers andyor between
analytes plus modifiers and the graphite tube
w53,54x.
● Volynsky stated w1x, ‘phase diagrams cannot be
used for an exact description of the character-
istics of nanogram quantities of analytes as the
amounts are too small to create a phase.’ This
is unprobable since the nanogram range and
even the picogram range are far above the mass
of single atoms or atom clusters (10y22 –10y20
g) where phases would not any more exist.
However, the only realistic possibility is the
formation of solid solutions of analytes with the
modifier present in the metallic form. Of course,
grain boundary aggregations or incoherent pre-
cipitates could also be formed at low analyte
solubility in the metal and in the solid state.
There again, however, outward diffusion would
occur at pyrolysis temperature and above unless
some strong bonds are formed between analyte
and the activated metal as described above.
3.2.2. Antithesis: on the atomization mechanism of
As, Se, Te—a demonstration of the complexity of
such investigations
Contrary to a mere speculation on the stability
of intermetallic compounds it should now be dem-
1847
Table 3
Appearance temperatures and activation energies (Ea ) for As,
Se, Te, measured according to the method proposed by R. Stur-
geon in presence of the PdyMg-modifier w55x
Element Appearance Ea
Temperature w8Cx wkJymolx
As 1900 1300
Se 1500 500
Te 1600 250
onstrated how one can arrive at some experimen-
tally based conclusions on respective atomization
mechanisms. This is a tedious process, which also
requires special instrumentation not readily avail-
able in laboratories dedicated to GFAAS work.
The temperature dependence of the rate of
atomization and the appearance temperature of the
atomization step are influenced by the compound
into which the analyte is transformed during pyrol-
ysis. The appearance temperature is defined as the
temperature at which the analyte becomes detect-
able in the atomization step. Sturgeon et al. w55x
developed a method for the determination of the
temperature dependence of the rate of atom for-
mation and a physical model, which allows con-
clusions concerning the compound of the analyte
before the atomization. In presence of the PdyMg-
modifier higher pyrolysis temperatures are feasible
for easily volatile elements w56–58x. It is therefore,
most likely that the analyte is transferred into a
more stable compound. Table 3 shows the appear-
ance temperatures and activation energies which
were measured by U. Rohr w29x and which are
quite high. The interpretation of these data in
terms of compounds, which are atomized, is dif-
ficult. Literature data for energies of some selected
processes for the atomization of As, Se, Te point
towards a combined effect of analyte retention by
strong bonding and hindered diffusion, Table 4.
Some compounds can be excluded as candidate
compounds for the given system:
● Although the enthalpies of formation of the
oxides would agree well with the experimentally
determined activation energies, the high volatil-
ity of these compounds would lead to essentially
lower appearance temperatures.
1848 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853

Table 4
Literature data for energies of some selected processes for the atomization of As, Se, Te

Type of process energy Compound Value in wkJymolx Reference

Enthalpy of formation As2O3 y654.4 Chemiker Kalender w59x

Enthalpy of formation SeO2 y240.6 Chemiker Kalender w59x
Enthalpy of formation TeO2 y325 Chemiker Kalender w59x
Enthalpy of formation As 32.43 Chemiker Kalender w59x
Enthalpy of formation Se 19.33 Chemiker Kalender w59x
Enthalpy of formation Te 50.6 Chemiker Kalender w59x
Enthalpy of formation PdSe y50.24 B.W. Mountain et al. w60x
Enthalpy of formation PdAs y24.3 H. Isper et al. w61x
Enthalpy of formation PdTe y37.7 O. Kubashevsky w62x
Activation energy of diffusion in metals 60–300 R. Freer, J. Mat. Sci. w63x
Activation energy of diffusion in oxides, 100–600 R. Freer, J. Mat. Sci. w63x
e.g. S in NiO 370 R. Freer, J. Mat. Sci. w63x
Activation energy of diffusion in liquids 4–25 ¨
Landolt-Bornstein; Jost w64,65x
Enthalpy-values are tabulated for 298 K. Correction for the respective appearance temperatures was not possible (no data avail-
able). However, corrections would be insignificant (several kJ per 1000 K)

● If the evaporation of the elements would be the
process of atom formation, the activation energy
should be approximately equivalent to the
enthalpy of formation because the activation
energy of diffusion in the gas phase is low.
Since the enthalpies of formation are quite low,
this is not the way the atomization of As, Se,
Te is taking place.
● The route over the intermetallic compounds can
not be considered due to the concentration ratios
of the modifier with the analytes as discussed
above. In addition, the respective enthalpies of
formation are also too low.
● The high values for the activation energy of the
atomization point into the direction of a ther-
modynamically controlled as well as a diffusion
controlled process: the analyte-modifier com-
plex dissociated and the diffusion of the analyte
out of the graphite into the gas phase is the
process determining the reaction velocity. There
is a fair agreement between the determined
activation energies and the activation energies
for the diffusion in metals and oxides. Only by
the existence of a rather stable Pd-analyte com-
pound (with DH of formation around 100 kJy
mole) and a fairly high activation energy of
diffusion it is possible to understand the high
values of the activation energies listed in Table
4. The example for the activation energy of
diffusion of S in NiO was included in Table 4
in analogy to the diffusion of Se in PdO. It can
be expected that elements with a rather large
ionic radius as compared to the oxygen ion and
which form stable compounds with the metal
of the crystal lattice of the matrix will exhibit
a high activation energy of diffusion.
3.3. Fiction 3
3.3.1. Experiments with unrealistic concentrations
of analyte andyor modifier
All such experiments result in misleading
conclusions.
This should be clear from the previous discus-
sion. In the three component system pyrographite
coating–modifier–analyte completely different sit-
uations will occur if relative concentrations andy
or subsurface conditions are changed. Therefore,
even experiments with a realistic mass ratio of
analyte to modifier but with an unrealistic relation
of the applied masses to the mass of the graphite
tube system will lead to erroneous results.
3.4. Fiction 4
3.4.1. Dense coatings are advantageous in GFAAS
● All coating procedures which lead to at least
initially dense and homogeneous layers in
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
graphite tube systems are not meaningful. Due
to our findings, they block the active subsurface
zone of the PG-layer responsible for analyte
retention w29,42x.
● All impregnation—or electrolysis procedures—
do not lead to such dense layers but to subsur-
face penetration of the applied modifiers via the
open porosity of the PG-coating. Good modifi-
ers appear to be those which do not penetrate
too quickly very deep. They concentrate the
analyte in the first 10 mm below the surface
and do not allow the analyte to be trapped too
deep below the surface w3,30,48,49x.
● Incidentally, impregnation and electrolysis are
much cheaper and experimentally easier prac-
ticed than coating by CVD- or even PVD-
processes. They usually yield longer stability of
analytical parameters in routine practice
w3,30,48x.
● Furthermore, there is no CVD- or PVD-coating
which would not dramatically deteriorate during
tube lifetime due to corrosive attack and differ-
ent thermal expansion of graphite and coating.
Hence, tube system performance will change
drastically with increasing penetrability of the
originally dense layer. Finally, dense layers
change the electrical resistance and the emissiv-
ity of the tube system. Hence, temperature
adjustment by resistance will lead to different
temperatures than for mere graphite tube sys-
tems for which the calibration has been carried
out w10,11,33x.
3.5. Fiction 5
3.5.1. The oblivion of carbide formation in GFAAS
In spite of the significance of carbide formation
discussed under FACT 1 this important phenome-
non remains largely unconsidered in many impor-
tant studies on phenomena occurring in GFAAS
w5,28x. Carbide formation has been experimentally
verified by precision peak shift measurements of
the C Ka-line with the electron microprobe for Fe
and La w18,29x. This is not easy to measure since
the much higher peak for the C Ka of the pyro-
graphite is only slightly influenced by the C Ka
peak of carbides present especially in surface near
regions of the pyrographite. These regions can be
1849
easily located by Fe Ka and La La measurements
prior to the C Ka precision measurements with the
method of tangents w29x. Respective details will
be published in a subsequent paper. It should be
noted, however, that the significance of carbide
formation in GFAAS has been extensively treated
by Volynsky w19,20x and our group
w3,6,10,11,29,33,48,66x.
3.6. Fiction 6
3.6.1. The dream of simple approaches to GFAAS
atomization mechanisms instead of the use of
highly instrumental techniques
It has been propagated by B. L’vov, one of the
most prominent researchers in GFAAS that
‘‘«... in many respects this approach (of dissociative
chemisorption and evaporation) seems to be more preferable
(being more efficient and simple) in comparison with
different instrumental techniques used nowadays for this
purpose: X-ray diffraction, X-ray photoelectron spectros-
copy, Rutherford backscattering (spectrometry), «.’’ w28x.
Unfortunately this concept may work for some
special cases but it cannot be generalized as an
ultimate solution to the elucidation of all atomi-
zation mechanisms in GFAAS. We hope to have
demonstrated how complex such situations can be
and most of these findings are based on highly
instrumental investigations, e.g. by line shift pre-
cision measurements in electron probe microanal-
ysis (EPMA). Most of the things we know in this
field of high temperature chemistry on and in
graphite stems from investigations with above
mentioned methods and this is the only safe way
of collecting such information w18,29–31,33–
35,40,42,43,46,47,50x. As already pointed out, the
eventual development of a concept of what hap-
pens in GFAAS work is not only a satisfaction of
the ever existing strive of mankind for knowledge
but an essential help for optimization procedures
leading to reliable methods in quality control in
industry and many other important institutions in
life sciences and elsewhere.
4. Conclusion
4.1. Functional schedule for GFAAS work
As a result of the presented discussion a basic
concept for the sequence of processes leading to
1850 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
thermal stabilization of analytes by the application
of modifiers could become visible through the fog
of right and wrong interpretations of a vast amount
of experimental data. Most of the phenomena
which are outlined in the following are, however,
based on own experimental work:
4.1.1. Sample application and drying step
● Penetration of analyte (and modifier in case of
non-permanent modifiers) into the first 10 mm
of the PG-layer of the platform (or tube wall).
● Formation of particles containing modifier and
analyte on the surface mainly in the valleys
between the dimples of the PG-coating.
● Partial decomposition of nitrates to respective
oxides. However, Mg(NO3)2 which is present
remains unchanged.
● PGM-modifiers are partially intercalated as
oxides and form mixed oxides with analytes.
Permanent RM-modifiers which have formed
carbides already in the tube pretreatment stage
are oxidized on their surface and also form
mixed oxides or heteropolyacid-compounds
with analytes which form oxoanions in aqueous
solutions.
● The retention of analytes from their hydrides is
very effective for many analytes by the presence
of permanent PGM-modifiers. This is again not
an effect of the modifier present in particles on
the surface but of activated modifier atoms in
the near surface region. Activation is effected
by modifier intercalation. Presumably ferrocene-
like compounds are formed with analytes also
after catalytic hydride decomposition.
4.1.2. Pyrolysis
● PGM-modifiers and other oxides are reduced to
the elemental state. A larger percentage of PG-
metals is intercalated as compared to the drying
stage, if the modifier is applied together with
the sample.
● Stable oxide bronzes or heteropoly-compounds
are stabilizing analytes which form oxoanions
on the surface of carbide forming modifiers.
● In no case a dense layer of a metal or a carbide
is formed.
● The analyte usually remains just below the
graphite surface, i.e. its depth distribution stays
constant.
● Metal particles with single mm diameters or
less on the graphite surface cannot retain anal-
ytes to observed appearance temperatures. Mol-
ten metal particles cannot at all retain analytes
due to enhanced out-diffusion.
● Neither (binary) alloys nor intermetallic com-
pounds can be formed due to the great modifier
excess over analyte quantities. Only the forma-
tion of solid solutions is possible.
4.1.3. Atomization
● Dissociation of the covalent analyte-metal-
bonds, out-diffusion of analyte (and modifier
followed by partial evaporation, if it exhibits a
rather low melting point like Pd) and thus
transfer into the gas phase.
● Some analytes like Pb are retained too strongly
by PGM-modifiers. The result is a pronounced
memory effect.
● Similar effects are known for, e.g. Ti, Zr, Cr,
Mo, V which form mixed carbides with RM-
modifiers of great thermal stability. These mixed
carbides are non-stoichiometric compounds
which can be formed at any mass ratio of the
components.
● RM-modifier oxo-compounds with analytes are
reduced under CO-formation. The evolving CO
carries the also formed analyte atom vapors into
the gas phase.
● The combined action of the upper layers of PG
together with the modifier seems to be operative
for most modifier actions on analytes. This is
the reason why dense coatings are not advan-
tageous. If they are formed, e.g. by PVD-
methods, they are not stable for the analytical
tube system lifetime.
5. Nomenclature
AAS: Atomic absorption spectrometry
AFM: Atomic force microscopy
CVD: Chemical vapor deposition
EG: (Polycrystalline) electrographite
EPMA: Electron probe microanalysis
ETAAS:Electrothermal atomic absorption
spectrometry
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
ETV-ICP-MS: Electrothermal vaporization-
inductively coupled plasma-mass
spectrometry
GFAAS: Graphite furnace atomic absorption
spectrometry
LHGA: Longitudinally heated graphite atomizer
PG: Pyrographite
PGM: Platinum group metal(s)
PSE: Periodic system of the elements
PVD: Physical vapor deposition
RM: Refractory metal (with a melting point
above 2000 8C)
RSD: Relative standard deviation
SEM: Scanning electron microscopy
SS-GFAAS: Solid sampling-graphite furnace
atomic absorption spectrometry
STM: Scanning tunneling microscopy
THGA: Transversally heated graphite atomizer
TM: Melting point
XPS: X-ray induced photoelectron
spectrometry
References
w1x A.B. Volynsky, Mechanism of action of platinum group
modifiers in electrothermal atomic absorption spectrom-
etry, Spectrochim. Acta Part B 55 (2000) 103–150.
w2x C.J. Rademeyer, B. Radziuk, N. Romanova, N.P. Skaug-
set, A. Skogstad, Y. Thomassen, Permanent iridium
modifier for electrothermal atomic absorption spectrom-
etry, J. Anal. At. Spectrom. 10 (1995) 739–745.
w3x H.M. Ortner, H. Krabichler, W. Wegscheider, Beschich-
¨
tung und Impragnierung von Graphitrohren, in: B. Welz
(Ed.), Fortschritte in der atomspektrometrischen Spuren-
analytik, 1, Verlag Chemie, Weinheim, 1984, pp.
73–114.
w4x A.B. Volynsky, Investigation of the mechanisms of the
action of chemical modifiers for electrothermal atomic
absorption spectrometry: what for and how?, Spectro-
chim. Acta Part B 53 (1998) 139–149.
w5x D.L. Styris, D.A. Redfield, Perspectives on mechanisms
of electrothermal atomization, Spectrochim. Acta Rev.
15 (1993) 71–123.
w6x H.M. Ortner, E. Bulska, U. Rohr, G. Schlemmer, S.
Weinbruch, B. Welz, Modifiers and coatings in
GFAAS—Facts and fictions in: Contemporary state,
development and applications of spectroscopic methods,
in: E. Krakovska, (ed.), Proceedings of the 4th European
Furnace Symposium and the XV Slovak Spectroscopic
Conference, 2000, p. 11–20.
1851
w7x W. Schron,¨ A. Detcheva, B. Dressler, K. Danzer, Deter-
mination of copper, lead, cadmium, zinc and iron in
calcium fluoride and other fluoride–containing samples
by means of direct solid sampling GF-AAS, Fresenius
J. Anal. Chem. 361 (1998) 106–109.
w8x H.M. Ortner, Der Faktor Mensch in der Qualitatssicher-
¨
ung, Teil 1 und Teil 2, GIT Labor-Fachz. 41, 1997,
756–761 and 1010–1013.
w9x H.M. Ortner, The human factor in quality management,
Accred. Qual. Assur. 5 (2000) 130–141.
w10x H.M. Ortner, W. Birzer, B. Welz, G. Schlemmer, A.J.
Curtius, W. Wegscheider, V. Sychra, Surfaces and mate-
rials of electrothermal atomic absorption spectrometry-
more than a merely morphological study, Fresenius Z.
Anal. Chem. 323 (1986) 681–688.
w11x H.M. Ortner, B. Welz, G. Schlemmer, V. Sychra, Mater-
ialien fur¨ die ETAAS—ein materialwissenschaftlich-
analytisches Resumee; in: K. Dittrich, B. Welz (Eds.),
CANAS 1993 Colloquium Atomspektroskopie, Univer-
¨ Leipzig und UFZ-Umweltforschungszentrum Leip-
sitat
zig-Halle GmbH 1993, p. 51–78.
w12x F. Benesovsky: Carbides, 4th edition, Ullmanns Enzyk-
¨
lopadie der technischen Chemie, 9, Verlag Chemie,
Weinheim, 1975, pp. 122–136.
w13x F. Benesovsky, Pulvermetallurgie und Sinterwerkstoffe,
2. Auflage, Metallwerk Plansee AG and Co. KG, Reutte,
1980.
w14x W. Schedler, Hartmetall fur ¨ den Praktiker, VDI-Verlag
¨
GmbH, Dusseldorf, 1988.
w15x B. Welz, M. Sperling, Atomic Absorption Spectrometry,
Wiley-VCH Verlag GmbH, Weinheim, 1999.
w16x B. L’vov, A.A. Vasilevich, A.O. Dyakov, J.W.H. Lam,
R.E. Sturgeon, Reduction of metal oxides by carbon in
graphite furnaces. Part 1. Temporal oscillations of atom-
ic absorption in the process of slow evaporation of A.,
Bi, Cr, In, Mg, Mn, Pb, Sb, Sn and Te oxides, J. Anal.
At. Spectrom. 14 (1999) 1019–1024.
w17x B. L’vov, A.O. Dyakov, A.A. Vasilevich, J.W.H. Lam,
R.E. Sturgeon, Reduction of metal oxides by carbon in
graphite furnaces. Part 2. Temporal oscillations in atom-
ic absorption during the process of slow evaporation of
Al, Mn and Yb oxides is spatially isothermal and non-
isothermal graphite atomizers, J. Anal. At. Spectrom.
15 (2000) 115–120.
w18x H.M. Ortner, U. Rohr, G. Schlemmer, S. Weinbruch, B.
Welz, Corrosion of transversely heated graphite tubes
by iron and lanthanum matrices, Spectrochim. Acta Part
B 57 (2002) 243–260.
w19x A.B. Volynsky, Review: Application of graphite tubes
modified with high melting carbides in electrothermal
atomic absorption spectrometry, I General approach,
Spectrochim. Acta Part B 53 (1998) 509–535.
w20x A.B. Volynsky, Graphite atomizers with high-melting
carbides for electrothermal atomic absorption spectrom-
etry. II. Practical aspects, Spectrochim. Acta Part B 53
(1998) 1607–1645.
1852 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
w21x A.B. Volynsky, Catalytic processes in graphite furnaces
for electrothermal atomic absorption spectrometry,
Spectrochim. Acta Part B 51 (1996) 1573–1589.
w22x E. Lassner, W.D. Schubert, Tungsten-Properties, Chem-
istry, Technology of the Element, Alloys and Chemical
Compounds, Kluwer ¨ Acad.yPlenum Publ., New York,
1999, p. 121, 122 and 157–164.
w23x D.L. Tsalev, V.I. Slaveykova, P.V. Mandjukov, Chemical
modification in graphite furnace atomic absorption spec-
trometry, Spectrochim. Acta Rev. 13 (1990) 225–274.
w24x L. Hahn, G. Muller-Vogt,
¨ W. Wendl, Role of oxygen in
the determination of oxide-forming elements by electro-
thermal atomic absorption spectrometry. Part 1. Effect
of oxygen on the reactions of thallium, J. Anal. At.
Spectrom. 8 (1993) 223–227.
w25x G. Muller-Vogt,
¨ ¨
L. Hahn, H. Muller, W. Wendl, D.
Jacquiers-Roux, Role of oxygen in the determination of
oxide forming elements by electrothermal atomic
absorption spectrometry. Part 2. Effect of oxygen on the
reactions of thallium, bismuth and lead in uncoated
furnaces, pyrolytic coated furnaces and on platforms, J.
Anal. At. Spectrom. 10 (1995) 777–783.
w26x G. Muller-Vogt,
¨ F. Weigend, W. Wendl, Role of oxygen
in the determination of oxides forming elements by
electrothermal atomic absorption spectrometry, Part 3,
Spectrochim. Acta Part B 51 (1996) 1133–1137.
w27x U. Brennfleck, G. Muller-Vogt,
¨ W. Wendl, Effect of
oxygen on the reactions of tin in uncoated, pyrolytically
coated and zirconium carbide coated graphite tube
atomizers, Spectrochim. Acta Part B 51 (1996)
1139–1145.
w28x B. L’vov, Mechanism of action of a palladium modifier,
Spectrochim. Acta Part B 55 (2000) 1659–1668.
¨
w29x U. Rohr, Korrosionsphanomene und Wirkungsmechan-
ismen in der Graphitrohr-Atomabsorptionsspektrometrie,
Ph.D. Thesis, Darmstadt University of Technology,
1996.
w30x E. Bulska, B. Thybusch, H.M. Ortner, Surface and
subsurface examination of graphite tubes after electro-
deposition of noble metals for electrothermal atomic
absorption spectrometry, Spectrochim. Acta Part B 56
(2001) 363–373.
w31x V. Mahidi, J.D. Robertson, Investigation of high tem-
perature reactions on solid substrates with Rutherford
backscattering spectrometry: interaction of palladium
with selenium on heated graphite surfaces, Spectrochim.
Acta Part B 46 (1991) 1723–1733.
w32x B. Welz, A.J. Curtius, G. Schlemmer, H.M. Ortner, W.
Birzer, Scanning electron microscopy studies on surfac-
es from electrothermal atomic absorption spectrometry-
II. The lanthanum modifier and the determination of
phosphorous, Spectrochim. Acta Part B 41 (1986)
1175–1201.
w33x B. Welz, G. Schlemmer, H.M. Ortner, W. Wegscheider,
Scanning electron microscopy studies of surfaces from
electrothermal atomic absorption spectrometry, Prog.
Anal. Spectrosc. 12 (1989) 111–245.
w34x J. Habicht, T. Prohaska, G. Friedbacher, M. Grasser-
bauer, H.M. Ortner, Nanotopographical changes on
graphite tube surfaces in electrothermal atomic absorp-
tion spectrometry experiments as studies by atomic force
microscopy, Spectrochim. Acta Part B 50 (1995)
713–723.
w35x R.E. Vandervoort, D.J. Butcher, C.T. Brittain, B.B.
Lewis, Scanning tunneling microscope images of graph-
ite substrates used in graphite furnace atomic absorption
spectrometry, Appl. Spectrosc. 50 (1999) 928–938.
w36x E. Hoinkis, E. Robens, Surface area and porosity of
unmodified graphitic matrices A3–27 and A3–3 and
oxidized matrix A3–3 (1950), Carbon 27 (1989)
157–168.
w37x DIN ISO Standard 5018, Determination of the density
of refractory ceramic materials, 1989.
w38x Produkte fur¨ die Analysentechnik, company brochure of
Ringsdorff-Werke GmbH, E 555y91, Bonn, Germany.
w39x Kohlenstoff und Graphit-Herstellung und Eigenschaften,
company brochure of Ringsdorff-Werke GmbH, A 545y
92, Bonn, Germany.
w40x E. Bulska, H.M. Ortner, Intercalation compounds in
atomic absorption spectrometry, Spectrochim. Acta Part
B 55 (2000) 491–499.
w41x B. Welz, G. Schlemmer, H.M. Ortner, W. Birzer, Scan-
ning electron microscopy studies on surfaces from
electrothermal atomic absorption spectrometry—V.
Glassy carbon tubes, Spectrochim. Acta Part B 45
(1990) 367–407.
w42x H.M. Ortner, U. Rohr, S. Weinbruch, G. Schlemmer, B.
Welz, Modifiers in ETAAS-How do they work? 2nd
European Furnace Symposium, Book of Abstracts, O
IVy2, St. Petersburg, 1996.
w43x H.M. Ortner, in: H. Gunzler
¨ (Ed.), Ortsaufgeloste
¨ oder
¨
topochemische Analytik—ein Uberblick, in: Analytiker
Taschenbuch, 19, Springer, Berlin, 1998, pp. 217–261.
w44x H.M. Ortner, Perspectives and trends of modern mate-
rials analysis, Quim. Anal. (Suppl. 1) 16 (1997)
S15–S20.
w45x C. Eschenbroich, A. Salzer, Organometallchemie, Teub-
ner Verl, Stuttgart, 1998, pp. 366–438.
w46x U. Rohr, H.M. Ortner, G. Schlemmer, S. Weinbruch, B.
Welz, Corrosion of transversely heated graphite tubes
by mineral acids, Spectrochim. Acta Part B 54 (1999)
699–718.
w47x D.L. Tsalev, V.I. Slaveykova, L. Lampugnani, A. D’Uli-
vo, R. Georgieva, Permanent modification in ETAAS:
Advances, anticipations, and reality, Spectrochim. Acta
Part B 55 (2000) 473–490.
w48x H.M. Ortner, E. Kantuscher, Metallsalzimpragnierung
¨
von Graphitrohren zur verbesserten AAS-Siliziumbes-
timmung, Talanta 22 (1975) 581–586.
w49x H.M. Ortner, B. Welz, G. Schlemmer, V. Sychra, Mater-
¨ die ETAAS—ein materialwissenschaftlich-
ialien fur
¨
analytisches Resumee, in: K. Dittrich, B. Welz (Eds.),
Colloquium Analytische Atomspektroskopie, CANAS
 H.M. Ortner et al. / Spectrochimica Acta Part B 57 (2002) 1835–1853
‘93, Univ. Leipzig und UFZ—Umweltforschungszen-
trum, Leipzig-Halle, 1993, pp. 51–78.
w50x ¨
H.M. Ortner, U. Rohr, P. Bruckner, R. Lehmann, G.
¨
Schlemmer, U. Vollkopf, B. Welz, G. Feucht, Untersu-
chungen zur Graphitrohrkorrosion mittels Gravimetrie
und ETV-ICP-MS, in: B. Welz (Ed.) CANAS’95 Col-
loquium Analytische Atomspektrometrie, Bodenseewerk
Perkin Elmer GmbH, 1996, pp. 89–96.
w51x A.B. Volynsky, V. Krivan, Colloidal palladium—a prom-
ising chemical modifier for electrothermal atomic
absorption spectrometry, Spectrochim. Acta Part B 52
(1997) 1293–1304.
w52x T Call, in: T.B. Massakski, H. Okamoto, P.R. Subra-
manian, L. Kacprzak (Eds.), Binary alloy phase dia-
grams 2nd edition, 1–3, ASM The Materials
Information Soc, Metals Park, OH, USA, 1990.
w53x W. Wendl, G. Mueller-Vogt, Chemical reactions of lead
in graphite furnace atomic absorption spectrometry, J.
Anal. At. Spectrom. 3 (1988) 63–66.
w54x K. Yasuda, Y. Hirano, T. Kamino, T. Yaguchi, K.
Hirokawa, Observation of vaporization in palladium-
indium intermetallic compounds by graphite furnace
atomic absorption spectrometry using transmission elec-
tron microscopy, Anal. Sci 11 (1995) 437–440.
w55x R.E. Sturgeon, C.L. Chakrabarti, C.H. Langford, Studies
on the mechanism of atom formation in graphite furnace
atomic absorption spectrometry, Anal. Chem. 48 (1976)
1792–1807.
w56x G. Schlemmer, B. Welz, Palladium and magnesium
nitrates, a more universal modifier for graphite furnace
atomic spectrometry, Spectrochim. Acta Part B 41
(1986) 1157–1165.
1853
w57x R.W. Dabeka, Refractory behavior of lead in a graphite
furnace when palladium is used as a matrix modifier,
Anal. Chem. 64 (1992) 2419–2424.
w58x H.-J. Heinrich. G. Emrich, E. Schierkorn, Investigation
of stabilisation mechanism for arsenic by palladium in
graphite furnace AAS in: Selected Papers of the 26th
CSI, D.L. Tsalev, editor, July 2–7, 1989, Sofia, 239.
w59x C. Synowietz, K. Schafer,¨ Chemiker Kalender, 3rd
edition, Springer, Heidelberg, 1984, pp. 539–571.
w60x B.W. Mountain, S.A. Wood, Chemical controls on the
solubility, transport and deposition of platinum and
palladium in hydrothermal solutions: a thermodynamical
approach, Econom. Geol. 83 (1988) 492–510.
w61x H. Isper, R. Krachler, G. Hamminger, Thermodynamic
properties of palladium–arsenic alloys, Z. Metallkde. 82
(1991) 470–477.
w62x O. Kubashevsky, C.B. Alcock, P.J. Spencer, Materials
Thermochemistry, 6th edition, Pergamon, Oxford, 1993,
p. 303.
w63x R. Freer, Bibliography—Self diffusion and impurity
diffusion in oxides, J. Mat. Sci. 15 (1980) 803–824.
¨
w64x Landolt-Bornstein: Zahlenwerte und Funktionen, Band
II: Eigenschaften der Materie in ihren Aggregatzustan-¨
¨
den, 5. Teil Transportphanomene—Kinetik—Homogene
Gleichgewichte, Springer, Berlin, (1968), 4–23.
w65x W. Jost, Diffusion—Methoden der Messung und
Auswertung, Steinkopf-Verlag, Darmstadt, 1957.
w66x M.R.A. Michaelis, W. Wegscheider, H.M. Ortner, Tan-
talum carbide coated platforms for atomic absorption
spectrometry with electrothermal atomisation: perform-
ance characteristics for tin, selenium and rhodium, J.
Anal. At. Spectrom. 3 (1988) 503–509.