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Atomic absorption spectrometry pregnant again after 45 years

原子吸收光谱(AAS)

  • Atomic absorption spectrometry } pregnant again after 45 years

    Bernhard WelzU
    Departamento de Quımica, Uni¨ersidade Federal de Santa Catarina, 88040-900 Florianopolis, SC, Brazil ´ ´
    Received 1 June 1999; accepted 4 October 1999

    Abstract
    Because atomic absorption spectrometry AAS seems to be so simple at first glance, its forthcoming end and replacement by more exciting techniques has been forecasted more than once over the past 45 years. However, AAS has received strong impetus again and again, e.g. by the introduction of the graphite furnace technique, and of flow injection, to mention but a few. Although more and more researchers, and even more instrument manufacturers are turning their back on AAS these days, this author believes that AAS is about to give birth to new offspring in the very near future. The most important ones are solid sampling and speciation analysis on the application side, a much deeper exploitation of the potential of flow injection analysis, the use of diode lasers as radiation sources, and the
    introduction of continuum-source AAS on the instrumental side. The latter could replace conventional line-source AAS in the foreseeable future because of its obvious advantages in essentially all analytical aspects. Q 1999 Elsevier Science B.V. All rights reserved.

    Keywords: Continuum source AAS; Diode laser AAS; Flow injection; Solid sampling; Speciation analysis
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  • 第1楼2005/04/11

    1. Introduction

    Atomic absorption spectrometry AAS is not a
    technique that one gets excited about at first
    glance. One has to come a little bit closer and
    look twice in order to find out about its charm.
    Maybe this is the reason why, after the first
    complete description of the processes of absorption
    and emission of radiation by atoms in flames
    w x by Kirchhoff and Bunsen 1]3 in the 1860s, it
    was optical emission that caught the interest of
    spectroscopists, and not atomic absorption. And it
    has taken almost a century until Alan Walsh
    began to wonder why molecular spectra were
    usually obtained in absorption and atomic spectra
    w x in emission 4 . And he came to the conclusion
    that there was no good reason for neglecting
    atomic absorption spectra; on the contrary, they
    appeared to offer many vital advantages over
    atomic emission spectra, and so he started to
    carry out his first experiments. Even though Alkew
    x made and Milatz 5,6 published two papers about
    AAS in the same year when Walsh’s first paper
    w x 7 appeared, it was Alan Walsh who had the
    vision of a bright future for this technique, and
    who was supporting and ‘preaching’ AAS with the
    dedication of a missionary, until it finally found
    acceptance in the mid-1960s.
    However, even with the support of a visionary
    scientist such as Alan Walsh, AAS is not necessarily
    exciting at first glance. When Alan, back in
    1952, called his colleague John Willis, and showed
    him his first experiments with the words ‘look,
    that’s atomic absorption...’ the disappointing
    w x response was only ‘so what?’ 4 . This lack of
    interest continued when an atomic absorption
    spectrometer was publicly demonstrated for the
    first time in Melbourne in 1954. The only person
    who got excited about AAS at first glance in these
    early years was Boris L’vov, who decided to check
    the validity of the author’s ideas immediately
    after he had stumbled over Walsh’s first publicaw
    x tion in 1956 8 , which qualifies him as another
    visionary scientist who could recognize the importance
    of a discovery that was disregarded by
    almost everyone else. And L’vov should become
    another dedicated missionary of AAS, after he
    had succeeded to slowly escape the ‘splendid
    isolation’ of the socialist system of his country.

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  • 第2楼2005/04/11

    But similar to the experience that Alan Walsh
    had to make, the excitement of Boris L’vov was
    not shared by his colleagues, and it is obvious that
    Alan and Boris were the exception, whereas this
    author was more the rule, if I may insert some of
    my personal history. I remember very well my first
    contact with AAS. It was when I applied for a
    position as an application specialist for infrared
    spectroscopy at Bodenseewerk Perkin Elmer in
    1966, and they offered me a position as application
    specialist for AAS instead. ‘Atomic what...?’
    was my first question, and when I was digging into
    Alan Walsh’s paper soon after, there was a complete
    lack of excitement on my part. You aspirate
    a solution into a flame and you get a result
    immediately } something was missing; there is
    no spectrum that needs interpretation as in
    molecular spectroscopy. This technique was too
    simple for me to be exciting, and I really don’t
    know why I nevertheless accepted the position as
    an application specialist for a technique that I did
    not know anything about at that time. However,
    the excitement came soon, I only had to meet
    with the two missionaries of AAS, Alan Walsh
    and Boris L’vov, the latter at the First Atomic
    Absorption Spectrometry Symposium in Prague,
    1967. It was at that conference when the spark of
    excitement ignited a flame that would continue to
    burn throughout my career, and that is reflected
    in more than 250 publications that carry my name,
    including a book on AAS that just appeared in its
    w x third edition 9 .
    It may well be the apparent simplicity of AAS
    that made me wonder back in 1966 if there is
    . anything of interest in this technique that caused
    renowned scientists again and again to forecast
    the end of AAS for the very near future. There
    must have been a good reason for Alan Walsh to
    write his article Atomic Absorption Spectroscopy
    w x } Stagnant or Pregnant 10 back in 1974, i.e.
    there must have been rumors in the air about a
    forthcoming decay of AAS. But obviously, by that
    time AAS had already given birth to a new kid,
     . the graphite furnace GF which, however, was
    not yet well understood, and it required the input
    w x of L’vov 11 , and the introduction of the Stabilized
     . Temperature Platform Furnace STPF concept
    w x by Slavin et al. 12 before it could become the
    driving force for AAS in the 1980s.

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  • 第3楼2005/04/11

    But at a time when AAS was in use in every
    laboratory, and research groups all around the
    world were unveiling atomization and interference
    mechanisms of GF AAS, and the increasing
    knowledge made this technique more and more
    rugged, there was again a renowned scientist prew
    x dicting the forthcoming end of AAS. Hieftje 13
    applied a third order polynomial to the annual
    number of publications on AAS, and predicted
    from the extrapolation of that function that ‘with
    the current rapid growth in ICP atomic emission
    and ICP mass spectrometry and with new incursions
    being made by methods based on glow-discharge
    lamps, AAS is heading for difficult times.
    If current trends continue, I would not be sur
    prised to see the removal of commercial AAS
    instruments from the marketplace by the year
    2000.’ By that time, however, AAS was already
    pregnant again, and the name of this new off-
     . spring was flow injection FI , a technique the
    input of which can be considered revolutionary in
    w x almost all aspects of AAS analysis 14 . It has
    been shown repeatedly that FI is far more than
    an elegant sample handling and sample introduction
    technique, and the potential of FI has not at
    all been exploited completely, as will be discussed
    later in this paper.
    Obviously only a few milestones in the development
    have been discussed in this review of the
    last 45 years of AAS } if 1954, when the first
    atomic absorption spectrometer was exhibited in
    w x Melbourne 10 , is taken as the starting point.
    Zeeman-effect background correction, simultaneous
    multi-element AAS, and the introduction of
    solid-state detectors should at least be mentioned
    as other important contributions. But now, at the
    end of this millennium, isn’t it time to look for
    new goals, new challenges, and send AAS to
    retirement in the same way as this author was
    sent to retirement, because AAS is an ‘established
    technique’ that does not justify any more
    research. Obviously this author has a different
    opinion and is expecting a whole series of exciting
    new developments, both in the field of application
    and in instrumentation. AAS is clearly pregnant
    again.

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  • 第4楼2005/04/11

    2. New fields of application


    When new fields of application are discussed, it
    is necessary also to consider alternate techniques
    that might be capable of solving the same problem
    equally well or even better. It must also be
    kept in mind that there is no single analytical
    technique that can solve all problems, and that
    each technique performs best only in its optimum
    working range, and that the results may deteriorate
    quickly when it is used outside this range.
    The practical analyst looks for a solution to his
    analytical problems and, if he can choose, he
    selects the analytical technique that offers the
    best solution with respect to simplicity, time and
    cost. Obviously, analytical aspects such as accuracy,
    and frequently also detection power, play an
    equally important role.
    Inductively coupled plasma mass spectrometry
     . ICP-MS is undoubtedly the technique that is
    most en ¨ogue today for trace element analysis,
    and there is no doubt about its detection power,
     . its multi-element -mass capability, and its speed
    of analysis. The possibility of doing isotope analysis,
    in addition, offers a unique field of application
    that is proprietary to MS. On the other hand,
    ICP-MS is undoubtedly one of the relatively
    expensive techniques, both in purchase price and
    in running cost. ICP-MS also requires considerable
    operator’s skill, and is certainly not free of
    interferences, particularly in the presence of complex
    and concentrated matrices. Because of its
    popularity and competitiveness, ICP-MS will be
    the prominent technique for comparison with the
    new fields that AAS may enter soon.

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  • 第5楼2005/04/11

    2.1. FI on-line preconcentration and separation for
    GF AAS
    It has been mentioned earlier that the potential
    of FI has not been fully exploited for its
    application in AAS. One of these fields is
    undoubtedly FI on-line preconcentration and separation
    for GF AAS, using sorbent extraction in
    packed microcolumns andror precipitation and
     . collection in knotted reactors KR . Although the
    first papers using these techniques already apw
    x peared in the early 1990s 15,16 , this idea was
    never really supported by instrument manufacturers.
    This is surprising because the combination of
    FI and GF AAS offers ideal conditions for fully
    automatic ultra-trace analysis in the low ngrl
    range in complex matrices under normal routine
    laboratory conditions. Detection limits of GF AAS
    w x in samples such as seawater 17,18 or high-purity
    w x reagents 19 are lowered by 2]3 orders of magnitude
    with a relatively minor instrumental requirement,
    only an insignificant reduction in sample
    throughput, compared to direct GF AAS analysis,
    and no need for clean-room facilities.
    An example of the capability of this technique
    Table 1
    Determination of four elements in doubly deionized water
    DDW and in NASS 2 open ocean sea water standard
    reference material National Research Council Canada using
    flow-injection on-line sorbent extraction separation and prea
    concentration for GF AAS


    is given in Table 1, which shows the determination
    of four trace elements in a sea water reference
    material by GF AAS after on-line sorbentextraction
    preconcentration and separation. The
    results demonstrate first of all that the technique
    is capable of obtaining accurate results in the
    ngrl range in a complex and concentrated matrix
    such as sea water. Secondly it is shown that all
    commonly occurring elements can be determined
     . in doubly deionized water DDW , making an
    on-line purification of reagents a necessity.
    Thirdly, by comparing the standard deviation obtained
    in the sea water sample and in DDW it
    becomes apparent that it is no longer the matrix
    that determines the precision, but obviously the
     lamp flicker noise nickel is well known to be a
    . noisy lamp . This means the matrix has been
    separated completely and has no more influence
    on the determination.
    FI on-line preconcentration and separation
    clearly brings GF AAS detection limits close to
    those of ICP-MS, and it even surpasses the capabilities
    of the latter technique when the matrices
    are considered in which the detection limits are
    obtained. Obviously, FI on-line preconcentration
    and separation could also be coupled to ICP-MS,
    but not with the same ease, considering the elu-
     . ents that are typically used organic solvents and
    their volume which is usually -0.1 ml. Last, but
    not least, the running cost for the GF AAS
    approach is probably an order of magnitude lower
    than that for the comparable ICP-MS system.

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  • 第7楼2005/04/11

    2.2. Solid sampling for GF AAS

    Although Alan Walsh in his first approach proposed
    ‘that the sample is dissolved and then
    w x vaporized in a Lundegardh flame’ 5 , which for
    good reasons became the preferred technique in
    the 1960s and 1970s, solid sampling is as old as
    w x AAS 20 . Boris L’vov used a graphite furnace and
    a few crystals of sodium chloride in his first
    experiment back in 1957 to demonstrate the principle
    of AAS, and several other groups developed
    a variety of furnaces for solid sample analysis in
    the following years. Fig. 1 shows an early application
    of solid sample analysis that was carried out
    in our laboratory using a prototype of what was
    later called the HGA-70, and that was presented
    at the International Atomic Absorption Spectroscopy
    Conference in Sheffield, 1969. Although the
    conditions were very primitive at that time, with
    no reliable tools for solid sample introduction
    into the furnace and no means for background
    correction, the results were surprisingly good.
    The direct analysis of solid samples, using all
    kinds of furnaces and devices for sample introduction
    was continued throughout the past 30
    years, as reviewed in a recent book, edited by
    w x Kurfurst 21 , but it was typically supported by ¨
    isolated research groups only. This is surprising
    because GF AAS is an ideal technique for direct
    solid sample analysis, because it is very flexible
    with respect to the sample size, which can range
    from approximately 0.01 mg up to almost 100 mg
    w x 22 , and also with respect to the form in which
    the sample is presented. This is among other
    things due to the way the sample is introduced,
    e.g. on a platform, the thermal pretreatment in
    the graphite furnace, and the long residence time
    of the atoms in the atomizer. The introduction of
    a commercial system for automatic slurry samw
    x pling 23 , based on the extensive work of Millerw
    x Ihli 24 , could have been the turning point, but
    the acceptance was not as expected.
    More recently, however, there appears to be an
    increasing market requirement for solid sample
    analysis, coming predominantly from the producers
    of modern high-tech materials, such as hard
    metals, superalloys and ceramic superconductors,
    etc. All these materials have two things in common:
    their quality depends extremely on their
    purity with respect to a number of critical trace
    elements, and they are very difficult to bring into
    solution. It was particularly the group of Viliam
    Krivan in Germany who did excellent pioneering
    work in that field, demonstrating that detection
    limits of solid sampling GF AAS are superior to
    all other techniques available for this kind of
    analysis, including ICP-MS, simply because the
    risk of contamination associated with any acid
    w x digestion technique, is avoided 22,25]27 . A typical
    example is shown in Table 2 for the detection
    limits achievable for a number of elements in the
    analysis of powdered tungsten trioxide and tungsten
    blue oxide, using a variety of analytical techw
    x niques 27 .
    Even more important for the practical analysis
    is that the efforts of Krivan and his group have
    resulted in the recent introduction of commercial
    equipment that automates solid sampling GF AAS
    and makes it accessible for routine application
     . Fig. 2 . It has been shown that modern furnace
    technology using platform atomization in a transversely
    heated graphite tube, and integrated
    absorbance for signal evaluation, has increased
    accuracy dramatically, making solid sample analysis
    possible with calibration against simple aquew
    x ous standards 22,25]27 .

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  • 第9楼2005/04/11

    2.3. Speciation analysis

    In the 1960s, determination of summation
    parameters such as total heavy metals in water by
    sulfide precipitation and gravimetry, was replaced
    by the determination of the individual elements,
    as it was recognized that the various heavy metals
    differ significantly in their toxicity. One of the
    driving forces at that time was the introduction of
    AAS which made these determinations easy. In
    the meantime it is well established that the total
    content of an element does not give sufficient
    information, as several elements may be essential
    for humans or animals, and may be toxic at the
    same time, depending not only on their concentration,
    but even more importantly on their oxidation
    state or the chemical form in which they are
    present. A typical example is chromium, which is
    essential in its trivalent form, but carcinogenic in
    its hexavalent compounds. Another example is
    arsenic, the inorganic forms of which are well
    known to be highly toxic, whereas organic com-
    pounds, such as arsenobetain, which are found in
    high concentration in some seafood, are non-toxic,
    and may even be essential.
    A limiting factor for the introduction of speciation
    analysis into routine use is undoubtedly that
    most of the research work in that field is currently
    done using high-pressure liquid chromatography
     . HPLC as a separation technique, and ICP-MS
    for detection. This combination, although very
    powerful, is far too expensive for routine use,
    considering that a fast multi-element system is
    typically waiting 10]20 min for a few species of a
    single element arriving at the detector. There is
    no doubt that this kind of research has to be
    carried out in order to gain all the knowledge
    necessary for speciation analysis. However, for
    routine purposes, a good percentage of speciation
    analysis can be done without prior separation of
    w x the individual compounds by chromatography 28 .
    A simple procedure has, for example, been proposed
    to distinguish between ‘toxic’, i.e. inorganic,
    mono- and di-methylated arsenic, and non-toxic
    arsenobetaine using hydride generation HG
    w x AAS 29 . FI on-line column preconcentration
    and separation is typically selective for one oxidation
    state of an element only, and may hence be
    used for the separation of redox species, as was
    demonstrated for the differential determination
     . w x of Cr VI and total chromium in water 30 .
    Another example of speciation analysis by on-line
    separation and preconcentration is shown in Fig.
    3 for an activated alumina microcolumn, which at
     . pH 2 selectively preconcentrates Cr VI , whereas
     . w x Cr III is retained selectively at pH 7 31 . There
    is no question that this field of routine speciation
    analysis is far from being completely explored.
    In addition, AAS with a quartz tube atomizer is
    an extremely attractive detector for gas chro-
     . matography gc , as already proposed back in
    w x 1976 by Van Loon and Radziuk 32 . This door
    was, however, closed by instrument manufacturers
    with the introduction of digital electronics in
    the 1980s that no longer permitted the recording
    of a series of peaks over an extended period of
    time, i.e. the duration of a chromatogram. It
    should not be difficult to open this door again,
    and AAS could then become a sensitive, highly
    specific, and not too expensive detector for gc
    w x 33 , and after post-column derivatisation, even
    for HPLC 34]36 . This aspect of AAS as an
    attractive detector for chromatography in speciation
    analysis will be brought up one more time in
     connection with diode laser AAS see Section
    . 3.2 .

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