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Walter Slavin

The Perkin-Elmer Carporation


901 Ethan Allen Highway
Ridgefield, Conn. 06877

1
I---

An analytical technique is rarely re- analytical instrumentation, but the


placed or made obsolete by a newer most widely used by far is the ICP.
one. Techniques usually complement The ICP provides detection limits for
each other and provide an arsenal for most elements that are within a factor
the attack on analytical problems. The of two or three times those of flame
analyst must choose from these weap- AA,for some metals a little better, for
ons that which is most appropriate for some a little poorer. Detection limit
his or her specific problem. The task comparisons are considered below.
of choosing among analytical tecb- However, the very refractory elements
niques is a difficult one. It requires a can be easily determined with the
clear understanding of the analytical ICP, and those elements that are only
problems in your laboratory and of the partially dissociated in the ilame are
capabilities of the different techniques usually completely dissociated by the
available. Those who are expert in sev- high temperatures achieved by the
eral techniques do not always agree on ICP. It is for this reason that the ICP
which to use because the grounds for has been spoken of as freer of chemi-
decision are often judgmental and cal interference than flame AA. How-
subtle. Many of us are particularly ex- 0 ever, interferences of other sorts are
perienced in one technique and tend But the more refractory elements, present in the ICP. For instance, high
to he partial to that technique. Those for example, B, V, Ta, and W, are only concentrations of inorganic matrix can
who have an extreme case of this dis- partially dissociated in the flame and shift the location of the hot portion of
ease of partiality may tell you that the are therefore not readily accessible by the plasma and therefore alter the sig-
best analytical technique is atomic ab- flame AA. Samples containing metals nal for specific analytes. Spectral in-
sorption (AA), or inductively coupled such as Mo and the alkaline earths are terferences are an important consider-
plasma (ICP) emission, or electro- not fully dissociated in the flame, ation for the ICP, and different lines
chemistry . . . There is no “best” tech- which sometimes leads to troublesome are preferred for a specific element in
nique; the choice depends on your interferences. Elements that have different matrices. This sometimes re-
skills and on the analytical situation. their resonance lines in the very far quires that spectroscopic skills he
UV are not easily determined, and used to solve some difficult analytical
Spdmcopk technk#ms these include P, S , and the halogens. problems. However, the ICP is inher-
Flame AA. Flame AA is very well Although the technique is rapid, AA ently multielement, and modem in-
established. It has few interferences, instruments are rarely automated to strumentation takes advantage of this
and these are well identified and often permit simultaneous determinations by using many detectors arranged
easily controlled. Standardization is of several elements. along the focal plane of the monochro-
usually simple. The equipment is, by Plasmas. There are several kinds of mator or by very rapid, sequential
now, relatively inexpensive and easy plasmas that have been considered for scanning of the monochromator. The
to use. Of the techniques being com- automation aspects, one of the most
pared, it requires the least operator Presented at the Australian Speetmsmpy Con- valuable features of the ICP, will he
experience. ference. Melbourne, April 1985 discussed later.

00052700/86/0358-589ASO1.50/0 ANALYTICAL CHEMlSl‘RY. VOL. 58, NO. 4. APRIL 1986 588,.


0 1986 American Chemicai Society
Histo* Textile
and Paper
Materials
Conservation and
Characterization

Howard L. Needles and S. Haig


Leronian, Editors
Universify of California-Davis
Explores the conservation and char-
acterization of historic textile and
paper materials, an active area of
interest to wnservstors, chemists,
mnd other physical scientists for
w e n i decades. Focuses on the
preservation of textiles with historic
and artistic valua. Promotes the
aharing of knowledge on preserva-
lion and restoration techninues
between the scientific and wniervs- Flpuro 1. Comparison of detection limits fw flameAA, CP, and furnace AA plotted
lion communities. on a log scale of concentration in micrograms per liter
CONTENTS Because furnace detection llmiig ere Inherently In mass unit6 (plcogams). thq haw been convwbd lo
Conservation Principlesof Henry Francis du Concentration by assuming a 20yL sample
POnt *Age Determination 01 Single-Fiber
Textiles * Degradation in Museum Textiles * Those who are attracted to the ICP tion of the graphite furnace was the
Fiber Damage in Textile Malefials by SEM
Franography of Historic Silk Fibers * Degra- for reasons other than automation are many chemical and physicakhemical
dation of Silk by Heal and Lighl * Paintsd- usually particularly interested in those interferences reported extensively in
PrintedChinese and w8Sfern Silks Identiti- metals that can't be determined by the literature. Those problems are
Cation of Dyes in HistoricTextile Materials
f
flame AA. An important advantage of now largely controlled using a combi-
Analysis of Nalural Dyes on Wool Substrates
Characterization01 Hyacinthine Purple the plasma is that no special sources nation of platform technology, new
(Tekheleo * Mordanted. Natural-DyedWool are necessary. For instance, one can high-quality graphite materials, mod-
and Silk Fabrics * Ellect 01 Aqueous and determine Rh the one time per year it ern, fast photometric instrumentation,
Nonaqueous Treatments * Characferizalion is required without having to retain a and Zeeman background correction.
01 Metallic Yarns * PrehiSforic Fabrics 01
lamp inventory. The concentration Although not totally interference free,
-
Southeastern N. America * Slandards b r
Archival Materials Kinelics 01 Cellulose
Deterioralion * Use of FTlR and ESCA
Estimating the Elkctot Water Washing *
range of the ICP usually spans three
or four orders of magnitude. This is an
the level of interferences for the
graphite furnace is now no greater

-
Discaloralion01 Paper Influence of Copper
and Iron on Paper Accelerated Aging 01
Cellulosic Texlilss
important requirement for automated
analyses. Flame AA spans only two or-
ders of magnitude.
than flame AA or ICP. Nevertheless,
furnace determinations are slow-ty-
pically several minutes per element
Furnace. If the lowest detection per sample. They are generally single
Basedon a symposium sponsored by me
Divislm 01 Cellulose. Paper. end Textile limits that can be obtained with spec- element; multielement analyses often
Chemistry of the American Chemicei Socisly troscopic techniques are necessary for are not practical. The analytical range
your problem, the graphite furnace is is not very large-typically a little less
Advances in Chemislry Series No. 212
452 pages (1985) Clothbound
the technique of choice. On a relative than two orders of magnitude. Thus,
LC 8520094 ISBN M)412-09008 or concentration basis, furnace detec- the furnace is presently used when the
US (L Canada $94.95 Export 1113.98 tion limits are 10 to 100 times better flame or ICP provides inadequate de-
than flame AA or ICP. On an absolute tection limits.
mass basis, furnace detection limits Detection limits. In Figure 1 (right
are often 1000 times more sensitive side) flame AA and ICP are compared.
because only a very small sample is re- In addition to indicating that the de-
quired for the furnace. tection limits of the two techniques
In the recent past, the major limita- are similar, it can also be seen that

59OA ANALYTICAL CHEMISTRY, VOL. 58, NO. 4, APRIL 1986


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trix, if the Zeeman technique is used mainly used for trace analysis work,
for background correction. This is the the simplicity and speed of both tech.
reason for the increasing interest in niques make them valuable for major
Zeeman background correction. element analysis. Probably, flame AA
The comparison of detection limits is still under-used for major element
can be confusing when techniques analysis in competition with X-ray
such as flame AA, ICP, and furnace fluorescence or gravimetric proce-
AA are compared. ICP and flame AA dures. At high concentrations of the

-
are steady-state techniques. The sig- analyte metal, flame AA signals are re-
nal is determined after the sample has markably stable, and it is easy to dem-
1 been aspirated long enough for the onstrate a precision of 0.2% relative
signal to come to some final equilibri- standard deviation (RSD).Because in.
um value. Thus, flame or ICP detec- terferences are also typically negligi-
tion limits are usually related to con- ble, this means that an accuracy close
theyaren compl tary. Re- centration, with the assumption that to the same level is available if accu-
fractory metals like Ti, v, and Ba tend the amount of sample is unlimited. On rate standards can be prepared. Many
to be poor on the flame AA chart, but the other hand, the furnace technique mining companies use this advantage
better on the ICP. In contrast, the uses the entire sample and detects an of flame AA for buying and sellinn
very volatile, heavy metals such as Cd absolute amount of the analyte element. precious metals, wher; very smali
and Zn are very good on the AA chart To compare the three techniques changes in percentage points can
and slightly poorer on the ICP chart. on the basis of concentration ignores equal large amounts of money. The
The left side of Figure 1shows the the advantage of the furnace, which standard reference method for Ca in
detection limits in picograms for the can handle very small samples. But it serum uses flame AA, using standards
bulk of the elements determined with is meaningful to the analyst who has that are carefully prepared to bracket
furnace AA. The scale on the right unlimited sample and does not care the analytical result from the sample.
side of the figure indicates the concen- about small sample volumes. To com- Precision of 0.5% to 2% is easily ob-
tration detection limits with assump- pare the techniaues on the basis of ab- tained with the ICP and. with recent
tion of a 20-rL sample. Most instru- solute detection.limit (say in pico- improvements, ICP may become com-
ment companies make these numbers grams) is meaningful for those ana- petitive with flame AA for acrurate
look about five times better by assum- lysts who are working with very small major metal determinations. The ICP
ing a 100-pL sample. In fact, the con. amounts of biological tissue, semiron- advantage of a very wide linear analyt-
centration detection limits that we ductor materials, or fragments offo- ical range makes it less necessary to
show in the figure are achievable in rensic or art materials. redilnte a sample that may have ex.
real sample solutions, even in the Major element determinations. ceeded the range.
presence of a massive amount of ma- Although both flame AA and ICP are Automation. It is easy to misrepre-

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592A ANALYTICAL CHEMISTRY. VOL. 58, NO. 4. APRIL 1988
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sent the different analytical tech- modern fast, sequential ICP can de- the present graphite furnace technol-
niques and particularly different in- termine 40 to 50 elements per min- ogy is its slowness. In principle, a way
struments with respect to their ability ute-2000-3000 determinations per to speed up the technique is to deter-
to handle large numbers of determina- hour-if the analytical lines are within mine several elements simultaneously
tions. The situations in which large an appropriate range. If we consider, in each sample. O’Haver has adapted
numbers of samples must be analyzed however, a more realistic situation, say a high-resolution spectrometer and a
for a limited number of elements, for a water lab doing about 15 elements continuum source to accomplish si-
example, in the clinical lab or the agri- per sample all morning or all day, this multaneous multielement furnace AA.
cultural test station, favor automated equipment will process more than At the same time, he and his col-
flame AA. The situations in which 1000 determinations per hour, com- leagues have expanded the photomet-
many elements must be determined in plete with standardization, time for ric range beyond that available in
many samples, such as a water test lab the autosampler to recycle, and time present commercial furnace AA. How-
or a geological survey situation, favor for each sample to come to equilibri- ever, his technique suffers from sever-
the ICP. This is because each flame um in the plasma. al problems that are not easy to cor-
AA determination is rapid, but a sig- So, for throughput, the ICP is fast- rect. To obtain sensitive, interference-
nificant amount of time is required to er. Some partisans might argue that free furnace results, conditions must
change the element being determined. simultaneous ICP would be faster be chosen that are specific for each el-
In contrast, because separate light than a sequential system. If you are ement. Also, the continuum source has
sources are not needed for the ICP, measuring both trace and major con- inadequate brightness in the far UV
changing between elements is rapid. stituents of the same sample, the per- and, for example, As and Se are usual-
But it takes longer for the sample to sample time is controlled by the time ly excluded from the panel of ele-
come to equilibrium in the ICP, so needed to collect the data from the ments. But the search for much faster
that each sample takes a longer time weakest line that is used, even though furnace analyses continues, and sever-
than in flame AA. most other elements do not require a al furnace emission procedures may
The automation of flame AA is long integration time. The simulta- become viable alternatives.
highly developed. For example, a typi- neous instruments cannot realistically Solid samples. If your samples are
cal automated system can determine work faster than a few minutes per already solutions they are ideal for
six elements in 50 samples in <35 min, sample to accomplish all of the tasks spectroscopic techniques, generally re-
complete with standardization, etc. that they must do in series. In con- quiring little more than simple dilu-
This works out to about 500 analyses trast, while the sequential instrument tion. Solid samples usually require
per hour. These modern instruments collects the elemental data in series, dissolution, and frequently a large
are easily coupled to elaborate com- the autosampler change and plasma enough sample must be dissolved to
puter systems for handling the mas- equilibration are done while the grat- ensure homogeneity of the sample. In
sive amounts of information that the ing is returning to its start position. those cases where a small homoge-
instrumentation can generate. The Probably the major disadvantage of neous sample of the solid phase must

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594A ANALYTICAL CHEMISTRY, VOL. 58, NO. 4, APRIL 1986


be analyzed, solid-sampling tech- availability of sophisticated electron-
niques have been used for flame AA,
ICP, and the furnace. These opportu-
ics at low cost has stimulated further
interest in the field. For many metals,
Microelectronics
nities deserve greater attention. electroanalytical methods are about
equally sensitive to flame AA or ICP.
Processing
Slurries are sometimes satisfactory
samples for flame AA, ICP, or the fur- They are generally less sensitive than norganic Materials
nace if they are not allowed to settle. furnace AAS. Zharacterizatlon
Ultrasonic agitation of the auto- It is usually necessary to pretreat a
sampler table is useful for automated sample prior to electroanalytical mea-
sampling. For the ICP the Babbington surement to put all of the analyte met-
nebulizer is helpful for viscous sam- al into the same chemical form. In
ples or slurries. The graphite furnace other words, interferences occur as a
is particularly useful for solid sam- result of differences in the chemical
pling in situations in which a few hun- state of the analyte metals. This can
dred micrograms provides a homoge- sometimes be turned to advantage.
neous representation of the sample. For instance, in seawater analysis, the
The modern furnace technology per- free ionic metal is sometimes pre-
mits such samples to be calibrated by ferred over total metal, which includes
solution working curves. the metal adsorbed to particles. Elec-
Hydride methods. Metals such as troanalytical techniques will distin-
As, Se, Sb, Bi, and others can be readi- guish between these two states of the
ly converted to their metal hydrides, metal, whereas the spectroscopic tech-
which are gaseous at room tempera- niques measure total metal.
tures. This permits relatively large X-ray fluorescence. X-ray fluores-
samples-10 to 50 mL-to be extract- cence has been used for many years to
ed with minimal sample handling and measure major metal content of many
L A . Casper, Editor
quantitated by thermal decomposition classes of samples, especially alloys. Honeywell, Inc.
of the hydride in flame AA instru- X-ray fluorescence provides high pre-
ments. Designs are now available that cision, often 0.1% or 0.2% RSD. Stan- Highli hts leadinpedge research in
extend the signals over sufficient time dardization requires reasonably close the fieyd of materials development.
Provides a thorough overview of
to permit ICP analysis in rapid se- matching of standard and sample. In techniques used in analyzing and
quential systems. Furnaces have also recent years improvements have been characterizing inorganic materials in
been used for the hydride technique. made in the sensitivity of X-ray fluo- integrated circuits. Covers all major
By now, hydride methods provide rescence so that the technique is now aspects of materials science, along
with applications to a wide variety of
parts-per-billion sensitivity for As and also applied to trace metals. However, high-technology areas. Includes
Se in simple matrices such as environ- it seems to me that modern flame AA extensive discussion on the role of
mental waters and plant and animal and ICP are simpler to use (except for chemistry in high-technology materi-
fluids and tissues. All chemical forms very routine analyses), somewhat less als.
of the element of interest must be con- expensive, and can achieve equal pre- CONTENTS
verted to a single valence state prior to cision and accuracy-and usually bet- Analytical Approaches and Expert Systems
hydride generation, and some interfer- ter sensitivity. Electrical Characterization of Semiconductor
ences persist. The relative sensitivity Mass spectroscopy. Isotope dilu- Materials Dopant Profiles by the Spreading
Resistance Technique Semiconductor
(ppb) of hydride methods is similar to tion mass spectroscopy (IDMS) has Materials Characterized by SEM Semicon-
that of the furnace, and the hydride been highly recommended by many ductor Materials Defect Diagnostics Mi-
equipment is less expensive. Modern workers who are trying to reach the croelectronic Materials Characterized by
furnace methods have fewer interfer- very lowest detection levels in un- SIMS Applications of AES in Microelec-
ences for As and Se. tronics X-ray Photoelectron Spectroscopy
known and complex matrices. IDMS is NDP Applied to Microelectronic Materials
the only technique permitted by the Processing Thermal-Wave Measurement of
Nonspectroscopic techniques National Bureau of Standards for es- Thin-Film Thickness Optical Reflectance
There are techniques other than tablishing reference values on stan- and Ellipsometric Techniques Oxygen and
Carbon Content of Silicon Wafers Raman
spectroscopy that are used for the de- dard reference materials. The tech- Microprobe Applied to Analytical Problems
termination of metals both at major nique requires considerable handling Characterization bf GaAs Thermal-Wave
and at trace levels. Some of these of the sample and a great deal of time Imaging in an SEM Microelectronics Serv-
techniques have advantages in certain for each sample. Also, the equipment ice Laboratory Elemental and Isotopic
Analysis Activation Analysis of Electronics
situations. Others are quite general is very expensive. Only those with spe- Materials Trace Element Survey Analysis
and are recommended by their sup- cialized skills can obtain good results. Plasma Phosphorous-Doped Oxides
porters. Using my own judgment, I The new technique of ICP-mass Vacuum-Deposited Nickel-Chromium Spin-
will try to put them into perspective spectroscopy (ICP-MS) can be used On Glass Film as a Planarizing Dielectric *
Silicon-Wafer Cleaning Monitoring Gas
compared with spectroscopic tech- effectively in some IDMS applica- Particles Microelectronics Processing
niques. tions. The ICP is an ideal ion source Problem Solving
Electroanalytical techniques. for the mass spectrometer. It is still a Based on a symposium sponsored by the
Electrochemical methods are probably little early to assess the eventual suc- Division of Industrial and Engineering
the most widely used competition for cess of ICP-MS, although it is likely Chemistry of the American Chemical Society
spectroscopy in trace metal determi- to become a highly useful technique. ACS Symposium Series No. 295
nations. Of these methods, anodic Neutron activation analysis. Neu- 440 pages (1985) Clothbound
LC 85-30648 ISBN 0-8412-0934-0
stripping voltammetry is the most tron activation analysis (NAA) has US & Canada $79.95 Export $95.95
widely used. The technique predates been used for a long time for trace Order from:
AA, and flame AA took over many an- metal determinations. Neutron activa- American Chemical Society
alytical problems previously solved by Distribution Dept. 95
tion can be accomplished by a pile or 1155 Slxteenth St., N.W.
electroanalytical means. However, by instrumental techniques, and the Washington, DC 20036
or CALL TOLL FREE 800-424-6747
electroanalytical techniques have been choice between these two options will and use your credit cardl
greatly improved in recent years. The determine the sensitivity and the cost.

ANALYTICAL CHEMISTRY, VOL. 58, NO. 4, APRIL 1986 595A


Either way, NAA is less sensitive for think flame AA is the technique to
Reverse Osmosis most metals than furnace AAS. Never- choose.
theless, workers experienced with the And don’t let a plasma zealot con-
technique generally believe that it is vince you that the ICP has no interfer-
more accurate than the several spec- ences and is, thus, easier to use than
troscopic techniques. flame AA. It is free of some of the AA
Although the judgment is personal, chemical interferences, but it has
I have not understood why IDMS or many more of its own. Certainly, I
NAA should be considered superior to don’t claim the platform Zeeman fur-
furnace AAS for reference methods. nace is free of interference; otherwise,
With any of these methods, the most why have we spent so much time find-
frequent analytical problem results ing appropriate matrix modifiers?
from contamination, which is equally Flame AA is the easiest and most
difficult to control in any of the meth- trouble-free metal determination
ods. Workers who must determine Pb, technique. This probably will change
Cd, Zn, etc., a t levels below 1 pg/L gradually with respect to ICP, but it is
must take considerable precautions to certainly true today and will be for
use reagents that have been specially several years to come.
purified and to keep dust from set- Compared with ICP, flame AA is a
tling on the samples. If care is taken in much less expensive way to use spec-
S. Sourirajan and Takeshi Matsuura, the control of contamination, graphite troscopy for metal analysis. Flame AA
Editors furnace AAS will provide results that costs from $10,000 to $40,000, depend-
National Research Council of Canada are a t least as accurate as NAA or ing on the level of automation. The
Reports significant advances in the IDMS. For most elements, furnace ICP costs from $60,000 to $150,000,
technological improvement and funda- AAS is more sensitive, thus requiring depending on speed and automation.
mental understanding of reverse-osmo-
sis-ultrafiltration membranes and pro- less sample handling. A new laboratory not yet using spec-
cesses. Features topics such as new Chromatography. Over the years, troscopic methods for metal analysis
studies in gas separations and pervapo- gas chromatography (GC) has been can expect to be operational much
ration by RO membranes, fundamental
studles in membrane formation and used by some workers to determine more rapidly using flame AA.
membranes transport, pro ress in trace metals in complex organic mix- ICP. If you have a well-equipped
develop.ment and industria? use of tures. Because GC separates com- AA lab, you may want to expand this
inorganic membranes, and more.
CONTENTS pounds, the different metallic species capability to additional analytes: B, V,
Materials Sclence of Reverse-Osmos~s-Lltral,~tration are determined. For those compounds P, Zr, W, Nb, Ta, S, and some others.
Memoranes PoiyethersulfoneUltraf Itrat.on
Memoranes Nature of Dynamically Formea
for which the technology is appropri- Sequential ICP is the way to do it. It is
Ultrafdtration Memoranes Polvolena Membranes n ate, very sensitive measurements can versatile and flexible. The routine wa-
Hyperfiltration of Electrolyte Solutions Structure,
Permeability, and Separation Characteristicsof be made. However, the technique re- ter test lab that determines a large
Porous Alumina Membranes 9 Plasma-Polymerized
Membranes of 4-Vinylpyridine Gamma Ray-
quires specialized skills. number of elements on each sample
Induced Enhancement Effect on Salt Rejection In the past several years ion chro- and analyzes many samples will be
Properties of Irradiated Membranes 9 Polyether
Composite-1000Spiral.Wound Membrane Element matography has been developed as an better off with the ICP than with
Transport in Pressure-DrivenMembrane Separation
Process Physicochemical Interpretationof Behav-
offshoot from modern liquid chroma- flame AA because the simple matrix of
ior of Pressure-Driven Membrane Se aration tography. When ion chromatography natural waters is easy to handle on the
Process Effect of Hydrolysis on C e h o s e Acetate
RO Transport Coefficients Application of Multicom- is used for metal determination, the ICP. But the ICP requires more skill
ponent Membrane Transport Model to RO Separation
Processes Predictability of Membrane Perform-
metallic compounds are separated and than does flame AA.
ance in RO Systems Involving Mixed loni;ed Solutes an appropriate detector is used to Furnace AA. However, if the most
in Aqueous Solutions Solute Separation and
Transport Characteristics Through Polyether Com- quantitate the compounds. The tech- important activity for which new in-
posite-1000 RO Membranes Hydrodynamic
Properties of Skin and Bulk of Asymmetric RO
nique is particularly convenient for strumentation is being obtained is to
Membranes Limiting Flux in Ultrafiltration of anions that are not easily determined determine metals at ultratrace levels,
Macromolecular Solutions Mineral Ultrafiltration especially in inorganic or partly inor-
Membranes in Industry Membrane Eioreactors for by spectroscopic methods (for exam-
High-PerformanceFermentation Single-Stage
Seawater Desalting with Thin-Film Composite
ple, halides, sulfate, and phosphate). ganic materials, furnace AAS is called
Membrane Elements Boiler-FeedQuality Water Groups of metals can be separated by for. The Zeeman system provides ma-
from Bitumen-Heav Oil Oil in Water Emulsions jor advantages for furnace analysis in
Treatment of Paoer-&lantWaBt;water bv Ultrafiltra- ion chromatography and detected at
levels that begin to be competitive almost every case in which real sam-
with flame AA or ICP. However, sam- ples are being analyzed.
ples must be treated so that appropri- Note that the furnace should no
of Fruit Juices Halogen Interaction with Polyamide ate compounds are formed. Ion chro- longer be considered an accessory to a
RO Membranes RO Membrane Fouling at Yuma
Desalting Test Facility Fluid Mechanics 01 Dilute matography is unlikely to be as specif- flame AA instrument. It is a complete-
Solutions RO and Ultrafiltrat,ionMembrane
Compaction and Fouling Studies Using Ultrafiltration ic as spectroscopic methods, but the ly independent analytical technique
Pretreatment 9 Gel Volume Deposits on Ultrafiltration cost for equipment is likely to be simi- requiring optimized instrumentation.
Membranes Pretreatment, Fouling, and Cleaning in
Membrane Processino of Industrial Effluents Gas lar to the simplest flame AA instru- In practice, every well-equipped lab
Permeability of Poiypgptiae Membranes So vent- doing metal analysis is frequently re-
Excnange Dry ng of Celldose Acetate Membranes ments and, of course, the anions can
for Separatfon01 nyarogen-Methane Gas M xtdres be determined. quired to reach the low levels in diffi-
Pervaporat on Memoranes Dehydration of A,cono -
Water Mlxtures TnroLgn Composite Memoranes oy cult matrices that demand the Zeeman
Pervaporation Choosing a technique platform furnace system. The Zeeman
Based on a symposium sponsored by the Division
of Industrial and Engineering Chemistry of the Flame AA. Given all of these con- platform furnace AA,technique is ap-
American Chemical Society siderations, how do you choose an ap- propriate for every well-equipped
ACS Symposium Series No 281 metal analysis lab. It has properties
501 pages (1985) Clothbound propriate technique? If your primary
LC 85-0921.9 ISBN 0-8412-0921-9 requirements relate to a limited num- that make it unique.
U S &Canada $89.95 Export $107.95
Order from: American Chemical Society
ber of metals at higher levels, you will The single overriding complaint
Dlstrlbution Office De t 36 almost always be best off with flame about the furnace, which curtailed its
1155 Sixteenth St.,
Waahlngton, DC 20036
t4.k AA. If an analyst is new to metal anal- growth for many years, was that it was
or CALL TOLL FREE 800-424-6747
and use your credit card.
ysis or if an experienced spectrosco- greatly error prone because of inter-
pist is not available to run the lab, I ferences. There are many comments in

596A ANALYTICAL CHEMISTRY, VOL. 58, NO. 4, APRIL 1986


published papers to that effect, such compares ICP, the DCP, flame AA, nology. Given the various characteris-
as the two quoted below: furnace AA, and electrochemical tics that make up the modern furnace,
methods for 10 trace metals in electro- including Zeeman background correc-
Investigatorsusing such common analytical lytes-that is, in metal chlorides: tion for difficult samples, the graphite
techniques as flame and graphite furnace
atomic absorDtion ... have made enormous For the large laboratory the best combina-
furnace technique is now no more dif-
errors in measuring lead concentrations in ficult than flame AA and probably less
biological and environmental materials. tion of techniqueswould be an ICP and elec- difficult than ICP.
[Everson J.: Patterson. C. Clin. Chem. 1981, trothermal AAS, whereas for the smaller
27,765.1 lab, . . . flame and electrothermalAA would
suffice. [Skidmore P. R.; Greetham, S. S.
Analyst 1983,108,171].
[Furnace AAS] should at this time still be
considered an art rather than a reliable ana- And finally, George Morrison, the
lytiealscience... . the large number of inter-
ferences and the inabilitv of the standard Editor of ANALYTICAL CHEMISTRY,
additions technique to c6mpensate far in- did a critical review of the analytical
terferences make graphite furnace AAS procedures available for trace metal
highly unreliable in many cases. Foyer, determinations in biological materials.
K. W. J. Assoc. Off. Anal. Chem. 1981,64,
396.1 His final summary is:
There is a tendency to believe that We see that while many trace element tech-
Zeeman background correction should niques are available for biological analyses,
be recommended only when it is prov- on the basis of the criteria of sample size,
pretreatment,sensitivity.accuracy and pre-
en that an ordinary furnace system cision,and coat,the technique of ETA-AAS
does not work. I believe this recom- [electrothermalatomization AA spectrome-
mendation is totally incorrect. In our try] offers the greatest opportunity. [Morri-
experience a quicker, more reliable, son, G. H.Crit. Reu. Anal. Chem. 19'19.8, Walter Slauin is a senior scientist at
281.1
and less troublesome procedure can be Perkin-Elmer, working in atomic
developed using the combination of Therefore, I would conclude that spectroscopy. He is a 1949graduate of
the stabilized-temperatureplatform flame AA and ICP are the preferred the Uniuersity of Maryland in phys-
furnace with the Zeeman background analytical techniques at levels where ics and math. He has led Perkin-El-
corrector. these two techniques are useful. The mer's efforts in the field of AAS and
choice between the two has to do with has contributed extensively to the de-
conclusion the particular metal and to some ex- uelopment of AA techniques and ap-
As I have included negative quota- tent with the matrix. But any labora- plications. Slauin has also published
tions from the literature about the tory that must occasionally do deter- widely on instrumentation and appli-
past furnace technique, I want M fin- minations at levels below those avail- cations of fluorescence spectroscopy,
ish with several examples of the many able on flame AA or the ICP should be far-UV spectroscopy, chromatogra-
more flattering papers. A recent paper equipped to use graphite furnace tech- phy, and clinical chemistry.

OFTHE Chromatographersthe world over choose Hamilton syringes over all uthers.
The reason is plain: the better the syringe,the hetter the results.

IBPERT when microliters count, there's no substitute for a Hamilton.

).IAMIlaxuu
The measure of excdlence.

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