EPA-650/2-74-125
DECEMBER 1974
Environmental Protection Technology Series
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EPA-650/2-74-125
POLLUTANT ANALYSIS
COST SURVEY
by
Bernard Greifer and John K. Taylor
U.S. Department of Commerce
National Bureau of Standards
Washington, D. C. 20230
Interagency Agreement No. 215
ROAP No. 21ADD-BJ
Program Element No. 1AB013
EPA Project Officer: Frank E. Briden
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
December 1974
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor docs mention of trade names or commercial products constitute
endorsement or recommendation for use.
ii
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TABLE OF CONTENTS
Page
INTRODUCTION 1
Bernard Greifer
1. REPORT FORMAT 1
A. Scope of Report 1
B. Organization of Report 3
2. TRACE ANALYSIS OF REAL SAMPLES 4
A. Materials Balances 4
B. Matrices of Interest 6
C. Sampling 7
D. Choice of Analytical Method 9
3. REFERENCES 9
NUCLEAR METHODS 10
Donald A. Becker
1. INTRODUCTION 10
2. NUCLEAR METHODS 10
A. Activation Spectrometry 10
B. Neutron Activation Analysis 11
C. Fast Neutron Activation Analysis 11
D. Charged Particle Activation Analysis. . . 11
E. Photon Activation Analysis 11
F. Nuclear Track Technique 12
G. Isotope Dilution Analysis 12
3. ANALYTICAL APPLICATION TO SPECIFIC MATERIALS. 12
A. Fly Ash 13
B. Coal 13
C. Oil 13
D. Ores and Minerals 14
E. Metals and Alloys 14
F. Organometallics 14
G. Incinerator Particulates 15
H. Slurry Streams, Feeds to/from Flotation
Processes, and Sediments in Flotation
Processes IS
4. RESULTS AND DISCUSSION 15
5. REFERENCES 20
ill
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SPARK SOURCE MASS SPECTROMETRY 30
Paul J. Paulsen
1. INTRODUCTION 30
A. Interferences 31
B. Sample Requirements 31
C. Sensitivity 31
2. PRECISION OF MEASUREMENTS BY SSMS 32
3. ACCURACY OF ANALYSIS BY SSMS 32
A. No Standards Used; Concentrations
Estimated 32
B. Analysis Using Standard Reference
Materials (SRM's) 33
C. Analysis Using Synthetic Standards .... 33
D. Analysis Using Stable Isotope Dilution . . 34
4. PROCEDURE FOR ANALYSIS OF MATERIALS 35
A. Group I Matrices 35
B. Group II Matrices 36
C. Group III Matrices (metals and alloys) . . 36
5. ANALYSIS BY ISOTOPE DILUTION 37
6. ELEMENT COVERAGE OF SSMS ANALYSIS 39
7. COST (TIME) OF ANALYSIS BY SSMS 39
8. CONCLUSION 40
9. REFERENCES 44
X-RAY FLUORESCENCE AND ELECTRON MICROPROBE METHODS . . 49
Stanley D. Rasberry and Kurt F. J. Heinrich
1. X-RAY FLUORESCENCE 49
Application to Matrices of Environmental
Interest 54
1. Fly Ash and Incinerator Particulates . 54
2. Coal 54
3. Oil 54
4. Ores, Minerals and Cement 54
5. Metals and Alloys 55
6. Organometallics 55
IV
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7. Slurry Streams, and Feeds and Sedir
ments in Flotation Processes 55
8. Slags and Glass 56
2. ELECTRON PROBE MICROANALYSIS 56
3. ION PROBE MICROANALYZER 58
4: REFERENCES 68
ATOMIC ABSORPTION SPECTROMETRY 80
Theodore C. Rains
1. INTRODUCTION 80
2. INSTRUMENTATION AND TECHNIQUE 80
A. Interferences 81
3. SAMPLE REQUIREMENTS 82
A. Sampling 83
B. Sample Preparation 83
4. APPLICATION TO MATERIALS OF ENVIRONMENTAL
INTEREST 84
5. RESULTS AND CONCLUSIONS 85
A. Tabulated Information 85
B. Costs 85
C. Conclusions 86
6. RliFERENCl-S 93
ABSORPTION SPECTROPHOTOMETRY 99
R. W. Burke
1. INTRODUCTION 99
2. ANALYSIS OF SPECIFIC MATERIALS 100
3. CONCLUSIONS 101
4. REFERENCES . .' 104
ATOMIC EMISSION SPECTROSCOPY 110
Danold W. Golightly
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1. INTRODUCTION 110
A. Optical Emission Sources 110
B. Chemical Preconcentration 113
2. APPLICATION TO MATERIALS OF ENVIRONMENTAL
INTEREST 113
A. Group 1 - Streams to and from Air
Scrubbers 113
B. Group 2 - Metals and Alloys (Fe, Al, Cu,
Pb, Zn) 114
C. Group 3 - Ores, Minerals, and Sediments
from Coal Flotation Processes 114
D. Group 4 - Coal, Feeds to Coal Flotation
Processes, Organometallics (formed by
Combustion Processes) 115
E. Group 5 - Fly Ash and Incinerator
Particles 115
3. COST (TIME) OF ANALYSIS 115
A. Survey Analyses 115
B. Quantitative Analyses 116
4. REFERENCES 123
VOLTAMMETRY (POLAROGRAPHY) 134
E. June Maienthal
1. INTRODUCTION 134
2. APPLICATIONS TO ENVIRONMENTAL ANALYSIS ... 136
3. CONCLUSIONS 140
4. REFERENCES 148
5. BIBLIOGRAPHY 150
A. Fly Ash, Coal, Oil, Organometallics,
Incinerator.Particulates and Minerals. . 150
B. Metals, Alloys, and Ores 155
C. Slurry Streams, Feeds to and from
Flotation Processes, Sediments in
Flotation Processes, and Water (general) 165
POTENTIOMETRY (ION-SELECTIVE ELECTRODES) 170
Richard A. Durst
VI
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1. INTRODUCTION 170
2. APPLICATIONS 171
A. Cadmium 172
B. Calcium 172
C. Copper 172
D. Cyanide 173
E. Fluoride 173
F. Lead 173
G. Silver/sulfide 174
H. Sodium 174
I. Potassium 174
3. DISCUSSION 175
4. REFERENCES 176
STANDARD REFERENCE MATERIALS 179
John K. Taylor
1. INTRODUCTION 179
2. SRM'S OF DIRECT ENVIRONMENTAL INTEREST .... 180
A. Fly Ash 180
B. Coal 181
1. Trace Elements in Coal 181
2. Mercury in Coal 182
3. Sulfur in Coal 182
C. Fuel Oil 182
1. Trace Elements in Fuel Oil 182
2. Sulfur in Fuel Oil 183
D. Inorganic Materials 183
1. Minerals 183
2. Ores 184
3. Cements 184
4. Refractories 186
E. Metals and Alloys 186
F. Metal-Organics 187
3. SRM'S OF INDIRECT ENVIRONMP.NTAL INTEREST ... 187
A. Trace Elements in Glass 188
B. Orchard Leaves 189
C. Bovine Liver 190
SUPPLEMENTAL REFERENCES 192
VII
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LIST OF TABLI-.S
NUCLEAR MRTHODS
1. Trace Elements in Environmental Materials . . 18
2. Rlemcnt Index to References Nuclear Methods . 19
SPARK SOURCE MASS SPECTROMETRY
1. Simultaneous Determination of Twenty-seven
Elements by Spark-Source Mass Spectrometry
in Typical Coal and Fly Ash Samples 42
2. Subject Index to References 43
X-RAY FLUORF.SCF.NCi: AND ELECTRON MICROPROBE
1. Analysis of Fly Ash and Incinerator
Particulates by X-Ray Fluorescence 60
2. Analysis of Coal by X-Ray Fluorescence. ... 61
3. Analysis of Oil and Organometallics by
X-Ray Fluorescence 62
4. Analysis of Ores, Minerals and Cements by
X-Ray Fluorescence 63
5. Analysis of Metals and Alloys by X-Ray
Fluorescence 64
6. Analysis of Slurry Streams, Feeds and
Sediments by X-Ray Fluorescence 65
7. Analysis of Slags and Glasses by X-Ray
Fluorescence 66
8. Analysis of Particulates by the Electron
Probe Microanalyzer 67
ATOMIC ABSORPTION SPECTROMETRY
1. Analysis of Metals and Alloys by Atomic
Absorption Spectrometry - Flame Method. ... 87
2. Analysis of Fly Ash, Ores and Minerals by
Atomic Absorption Spectrometry - Flame
Methods 88
3. Analysis of Fly Ash, Ores, Minerals, Metals
and Alloys by Atonic Absorption Spectrometry -
Non-Flame Methods 89
4. Analysis of Slurry Streams and Process
Streams by Atomic Abosrption Spectrometry -
Flame Methods 90
5. Analysis of Coal, Oil, Organometallics by
Atomic Absorption Spectrometry - Flame
Methods 91
6. Analysis of Coal, Oil and Organometallics
by Atomic Absorption Spectrometry - Non-
Flame Methods 92
vi ii
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ABSORPTION SPF.CTROPMOTOMETRY
1. Analysis of Coal, Oil, Organometallics,
Metals, and Alloys by Absorption
Spectrophotometry . 102
2. Analysis of Fly Ash, Ores, Minerals,
Incinerator Particulates, Slurry .
Streams, Process Feeds by Absorption
Spectrophotometry 103
ATOMIC I-MISSION SPI-CTROSCOPY
I. Summary of Spectrographic and Spectrometric
Detection Limits 117
2. Summary of Spectrographic and Spectrometric
Analysis of Various Materials 118
). Index to Emission Spectroscopy References . . 119
4. Estimates of Time Required for Several
Types of Spectrographic and Spectrometric
Analyses 120
VOLTAMMI-TRY (POLAROGRAPHY)
1. Analysis of Fly Ash, Coal, Oil, Organo-
metallics, Incinerator Particulates, and
Minerals by Polarography 142
2. Analysis of Ores, Metals, and Alloys by
Polarography. . ". 143
3. Analysis of Slurry Streams, Sediments,
Process Feeds, and Water by Polarography. . . 144
4. lilement Index to References for Table 1 ... 145
5. Element Index to References for Table 2 ... 146
6. Lilement Index to References for Table 3 ... 147
IX
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LIST OF FIGURES
INTRODUCTION
1. Applications of trace element analysis to
monitoring materials, process streams, and
effluents of a typical industrial process ... 5
X-RAY FLUORESCENCE AND ELECTRON MICROPROBE
1. X-ray fluorescence analyzer 51
2. X-ray fluorescence spectra of liquid paints
having two different levels of toxic metal
content; obtained using a tungsten target
tube operated at 50 kV, 50 mA, and LiF
crystal and a scintillation detector 51
3. Calibration curve for determination of lead in
dry paint powder, following preparation by
dilution with a common matrix (ZnO); obtained
using the same conditions as given in figure 2. 52
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POLLUTANT ANALYSIS COST SURVEY
Final Report
June 1972 - June 1974
by
Bernard Greifer and John K. Taylor
ABSTRACT
The report summarizes various approaches to the chemical
analysis of heavy industry process materials and effluents
for trace element constituents that might contribute to
environmental pollution. It assesses the capabilities and
costs of nuclear methods, spark source mass spectrometry,
x-ray fluorescence and electron and ion microprobe spectro-
metry, atomic absorption spectrometry, absorption spectro-
photometry, atomic emission spectroscopy, voltammetry
(polarography) and potentiometry (ion-selective electrodes)
for determining traces (less than 100 ppm) of Hg, Be, Cd,
As, V, Mn, Ni, Sb. Cr, Zn, Cu, Pb, Se, B, F, Li, Ag, Sn, Fe,
Sr, Na, K, Ca, Si, Mg, U, and Th in such matrices as fly
ash, coal, oil, ores, minerals, metals, alloys, organo-
metallics, incinerator particulates, slurry streams, and
feeds to and from sedimentation processes. The report
includes a selected bibliography of the current literature,
and a review of the Standard Reference Materials available
for environmental analysis.
This report supersedes NBSIR 73-209, "Survey of Various
Approaches to the Chemical Analysis of Environmentally
Important Materials", of which it is a revision and
extension.
XI
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CHAPTER 1
INTRODUCTION
Bernard Greifer
1. REPORT FORMAT
This report is an evaluation of various approaches to
the chemical analysis of heavy industry process materials
and waste products for constituents that may find their way
into the environment and be considered pollutants. The
applicability and costs of suitable methods of measuring
the trace metal content (less than 100 ppm) of industrial
process feeds, product streams, and effluents are presented
for comparison so that the optimum analytical support pro-
grams for particular situations can be selected from among
the available alternatives.
Heavy industrial processes have come under scrutiny as
contributors to environmental contamination. While sulfur
dioxide and particulate emissions have been investigated
extensively, the trace elements in these and other effluents
have been relatively unexplored. These trace elements may
be a source of valuable by-products that could be recovered,
or they may constitute a toxic hazard that should be removed;
but they ought not to remain an unknown quantity. Modern
instrumental methods of analysis have the capability to
determine the trace elements in industrial effluents at
a reasonable cost. This report summarizes current procedures
suitable for the analysis of these and similar materials.
The information provided is based on a bibliographic
survey and evaluation of the current literature by members
of the staff of the Analytical Chemistry Division, Institute
for Materials Research, of the National Bureau of Standards.
The work was carried out under an interagency agreement
between the Department of Commerce and the Environmental
Protection Agency dated June, 1972.
A. Scope of Report
The report assesses the capability and costs of various
methods of determining the concentration of trace elements
(< 100 ppm) in the following basic sample matrices: fly ash,
coal, oil, ores, minerals, metals, alloys, organometallics,
incinerator particulates, slurry streams, and feeds to and
from sedimentation processes. As the occasion presents
itself, additional matrices may be mentioned, as water,
sediments and coagulates.
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The trace elements of analytical interest include:
mercury, beryllium, cadmium, arsenic, vanadium, manganese,
nickel, antimony, chromium, zinc, copper, lead, selenium,
boron, fluorine, lithium, silver, tin, iron, strontium, sodium,
potassium, calcium, silicon, magnesium, uranium, and thorium.
In this listing the elements may be considered as major or
minor constituents according to their relative concentrations
in the matrix materials, but most of the attention will be
directed toward elements present at or below the 100 ppm
(100 pg/g) level.
The analytical methods included in this review embrace
nuclear methods, mass spectrometric methods, x-ray, optical,
and electrometric methods of analysis, specifically:
1. Nuclear methods
2. Spark source mass spectrometry
3. X-ray fluorescence and electron microprobe
spectrometry
4. Atomic absorption spectrometry
5. Absorption spectrophotometry
6. Atomic emission spectroscopy
7. Voltammetry (polarography) and potentiometry
(ion-selective electrodes)
The methods considered are those which are capable of rapidly
and accurately determining trace elements in a variety of
materials with a minimum of sample manipulation. Analytical
methods requiring long and careful sample processing such
as isotope-dilution mass spectrometry have not been included
in this survey because of their prohibitively high labor
cost and slow accumulation of analytical data. For this
same reason, wet chemical procedures are considered only
as they are involved with instrumental methods such as
spectrophotometry.
The performance of the analytical methods is considered
from the viewpoint of their capability to carry out the
required trace element determinations on the matrices of
interest, at a reasonable cost. The parameters of interest
include:
1. Instrumentation requirement
2. Detection limit
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3. Accuracy
4. Sample preparation
5. Sample size
6. Manpower skills requirement
7. Cost per analysis
The performance parameters are listed in no special order.
The information for each analytical method is taken from
the literature wherever possible, and supplemented from
the personal experience of the NBS staff members in other
cases where literature references are not available. These
performance parameters provide guidelines for comparing
the various analytical methods but they do not contain
sufficient information to permit a decision to be made that
one method is superior to another in a specific appli-
cation.
B. Organization of Report
The report is divided into chapters describing the
analytical methods under consideration. The chapters contain
bibliographies citing general sources of information and
specific references keyed to the elements of interest in the
matrices being analyzed. Tables summarizing the analysis of
each element according to detection limit, cost, and other
performance parameters are included for each method. The
accompanying chapter texts provide comments and connecting
narrative.
Various indexes are provided to facilitate access to the
tabular information pertaining to the determination of each
trace element likely to be present in the matrix materials.
Details of methods of analysis of specific matrices, or
determination of specific elements, or costs of such deter-
minations may be located in the chapter texts, tables, and
bibliographies by reference to these indexes or to the
Table of Contents.
The sample matrices are grouped differently in each
chapter depending on the common characteristics of importance
to each analytical method. For example, one analytical method
may group the matrices according to their silica content or
their solubility in mineral acids, while another method may
find a common denominator to be the organic content. The
table headings provide entry into the analytical informa-
tion and the references.
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Costs are listed in the tables as the cost of analyzing
a single sample. In some cases each element is the sole
constituent being determined, as in atomic absorption
spectrometry; and in other cases each element is considered
to be one of a group of elements being determined sequen-
tially, as with x-ray fluorescence, or simultaneously on the
same sample, as with spark source mass spectrometry. The
costs of trace element determinations will generally fall
between the two extremes of low-cost multi-element survey
methods and high-cost single-element determinations. Also,
the cost per sample for large numbers of routine determina-
tions can be expected to be less than indicated in the
tables. Accordingly, the tabulated values should be consid-
ered as guidelines to maximum reasonable costs when the
analyses are done by experienced, trained analysts.
Tables in each chapter list performance parameters for
each method of analysis according to matrices and trace
elements of interest. Where possible, information is pro-
vided on sample sizes required, analytical accuracies expected,
and costs of determining elements present at concentrations
about 1, 10, or 100 ppm. Some methods of analysis not
particularly suited for trace determinations (e.g. x-ray
fluorescence) are described for element concentrations
considerably above 100 ppm in order to present a complete
picture of the methods' capabilities.
The tabulated information and supporting references
are presented without judgments as to the relative merits
of the various analytical instruments and procedures. De-
cisions regarding the suitability of alternative methods
for trace element determinations should be based on experi-
ences with real samples.
2. TRACE ANALYSIS OH RliAL SAMPLES
A. Materials Balances
An assessment of the environmental impact of an
industrial process or subprocess requires analytical data
of several kinds. Figure 1 is a flow diagram showing the
different chemical analyses that might be used to monitor
the material flow in and out of a typical process. Ores
and scrap metals are analyzed before they are smelted in a
blast furnace, and the commercial metals and crude inter-
mediates are analyzed as products. The effluent gases,
solids, and liquids are analyzed before being recycled,
recovered as by-products, or treated and released to the
environment as wastes. As indicated in Figure 1, these
data might be expected to indicate a materials balance
because all of the inputs and outputs are being analyzed.
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RAW MATERIALS
Ores
Concentrates
Scrap metal
Fuel (coal)
Chemicals
Catalysts
Solvents
ANALYSIS)^>
)
INDUSTRIAL
PROCESS
Smelting
Refining
Etc.
_^> /ANALYSIS!^.
PRODUCTS
Metals
Chemicals
Acids
Plastics
ANALYSIS
GASES
Furnace gas
Metal vapors
Sulfur dioxide
Nitrogen oxides
EFFLUENTS
SOLIDS
Fly ash
Coal ash
Slags
Oxide dusts
Metal particles
LIQUIDS
Slurry streams
Coagulates
Sediments
RECYCLE-
ANALYSIS
T
RECOVERY-
WASTES
Permissible levels
Figure 1. Applications of trace element analysis Co monitoring materials,
process streams, and effluents of a typical industrial process.
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However, achieving a complete materials balance among all
of the trace constituents may be a difficult undertaking,
especially if trace elements interchange between process
materials and walls of pipes and vessels, or if there are
minute losses or additions from the environment (i.e. con-
tamination). Many engineers would be pleased with a pro-
duct purity of 99.9 percent, but the analytical chemist sees
1,000 ppm of other constituents in this product. This
difference in outlook between the engineering viewpoint
and the chemist viewpoint is crucial to an understanding
of the relative merits of the different analytical methods.
The materials balance which is complete to 100.0 percent
from an engineering viewpoint is not good enough to account
for trace elements; it must be complete to 100.0000 percent
to account for a 1 ppm constituent.
For a material balance of trace constituents to be
reliable, the analyses must be not only precise, they must
above all be accurate. A small error in the analysis of
a major component of the raw material could lead to a serious
error of judgment regarding the need for, or the reliability
of the analyses in the final products, or waste products, or
emissions. Accurate measurements are best ensured when
dependable, evaluated methods of analysis are used, and
requisite calibrations made with reference materials are
interspersed in the course of the analyses to provide
quality control.
B. Matrices of Interest
Trace element analyses can be carried out routinely
after suitable procedures have been established and the
requisite instrumentation installed. The materials under
consideration for trace determination may be thought of
primarily among the products and effluents if the main
concern is environmental contamination; however, ores, fuels,
and other process inputs should be included in the interest
of a suitable materials balance. The diversity of materials
to be analyzed is demonstrated in this listing of matrices
which may contain trace elements of environmental importance:
1. Raw materials such as ores, concentrates, scrap
metals, coal and coke, chemicals, catalysts.
2. Products and intermediates including commercial
metal, slags, sinters, blister metal, and bullion.
3. Gaseous emissions including acid mists, fly ash
and other particulates as metallic and metal-oxide dusts,
partly burned fuels.
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4. Process waste waters including coagulates, sedi-
ments, and sludges produced in the course of upgrading
effluents for pollution control.
5. Plant working environment including dusts, filters,
water and solvents, lubricating oils, vapors from molten
metals.
The number and variety of sample materials and their
expected complexity and inhomogeneity can give rise to
difficult problems in sample collection and analysis. Just
as chemical analysis is a specialized field, the sampling
of process streams requires sophisticated planning by
engineering specialists to assure that the samples are repre-
sentative of the materials of interest. Since such an
assurance is vital to the success of the trace element
determinations, some of the problems encountered in sampling
will be discussed.
C. Sampling
One of the most important considerations in chemical
analysis is the assurance that the samples in the laboratory
are truly representative of the bulk materials from which
they have been taken; and this is especially true in the case
of trace determinations. It is obvious that analysis can give
information only about the particular samples in the labo-
ratory. If these are not the same composition as the slags,
sediments, process streams, etc. which they purport to repre-
sent, then the chemical results can have no value whatever
and may even be misleading. Obtaining a representative
sample may not be a simple matter. The matrix materials are
typically inhomogeneous, consisting of two or more poorly
mixed phases most of the time. The trace element composi-
tions may be changing continually since they depend upon the
interaction of a great many process variables, e.g. impurities
in the ores, process side reactions, transfer of material to
or from vessel walls and pipes, loss of volatile elements
during roasting, transfer of material to or from filters; all
these may affect the trace element content of the matrix
materials.
Sampling of heterogeneous combinations of liquids,
solids, and gases such as gas-borne particulates, mists,
slurries, and sludges requires careful planning. It is
essential that the number and selection of samples taken
for analysis be such as to assure that all the trace elements
present in the matrices are represented in their correct
concentrations. The problems encountered in sampling process
streams for trace constituents may arise from such sources as
(1) the inhomogeneity of the matrix materials, (2) composition
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changes with time or some process variable, f3) sample altera-
tion during sampling and transport to the receiver, (4) sample
alteration within the receiver, and (5) inefficient collectors
which do not capture 100 percent of the trace elements along
with the samples. Collection of representative samples from
process streams may require the combined efforts of engineer-
ing specialists in stream analysis, fluid mechanics, chemical
reactions, corrosion, and materials separation to name a few
disciplines.
It is important to understand why the sampling is being
done, what streams and what phases in the streams are to be
sampled, where are the best places to sample, when are the
best times to sample, how big a sample to take, how long a
sampling time, how to collect and retain all the trace
elements. [1]
An often overlooked factor in sampling is the detailed
and unambiguous identification of analytical samples. Such
vital information as date, time, and location of sampling
should be recorded. Other pertinent information such as
process parameters at the time of sampling, and even the
then-existing environmental conditions may he of importance
in many cases to a proper interpretation of the analytical
data. The name of the person taking the sample, and reference
to the notebook or log sheet should also be indicated. All
of these matters assume special importance when legal consid-
erations may be involved.
The analytical chemist ordinarily requires only a part
of the sample collected. In this event it is imperative that
the portion used for analysis be representative of the sample
submitted to the laboratory. Trained analytical chemists are
aware of such matters, but the availability of analytical
instruments that can be used by laymen prompts this note of
caution. liven the trained analyst needs to be reminded to
properly identify each sample analyzed and document the
experimental conditions used. Calibration procedures and
quality control measures should be recorded to provide authenti-
cation which might be needed at a later date. In some cases
a bank of analyzed samples may be retained for further
analysis, for verification, for later reference, or for other
purposes.
Since the analytical chemist has no control over the
samples before they reach the laboratory, the forthcoming
discussions of instrumental chemical analysis will assume
that the samples presented for analysis have been obtained
knowledgeably and are free from losses or outside contamina-
tion.
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D. Choice of Analytical Method
Although the performance parameters which comprise the
bulk of the tabulated information seem to provide a basis for
comparison of the relative merits of the alternative methods
of analysis, it is possible that such a comparison might have
little application to the real world of dirty samples and
fallible people. In fact, it may be generally impossible to
decide a priori that one method will be superior to another
in a specific situation, because of the numerous subjective
considerations which cannot be accounted for, in a report of
this type. The rationale behind the choice of performance
parameters establishes the general acceptability of the
analytical methods according to accepted standards of
accuracy, detection limits, analytical costs, etc. However,
there are many opportunities for experimental error and
operator bias which may be caused by the effects of the
matrix constituents themselves on the analyses; or by
differences in reagents and standards used by the various
laboratories; or by the ability of analysts to obtain the
optimum results with their instruments and operating proce-
dures; or the extent to which the samples reflect the actual
bulk matrix compositions, and so on.
The "best" methods of analysis will be those that
perform most reliably in the actual analysis of real samples.
Such methods probably cannot be identified until a body of
analytical results is accumulated. It is realistic to
acknowledge that the "best" methods often are those with
which the laboratories have the greatest experience. New
and unfamiliar analytical methods require an investigative
or break-in period whose cost must either be recovered
through volume analyses or considered a worthwhile invest-
ment in improved technological capability, before such new
methods are adopted. The value of this report and other
compendiums of analytical methods [2] lies in their utility
as guidelines to show what others have done to solve similar
problems in trace analysis. Judgments as to what can be
done in specific situations should be based on careful
observation of test results.
REFERENCES
[1] Fair, J. R. , Crocker, B. B., and Null, II. R., Sampling
and Analyzing Trace Quantities, Chem. Engineering 79,
146 (1972).
[2] Pinta, M., "Detection and Determination of Trace
Elements," original edition Dunod, Paris (1962) in
French. English edition, Ann Arbor Science
Publishers, Ann Arbor, Michigan, fourth printing (1972).
9
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CHAPTER 2
NUCLEAR METHODS
Donald A. Becker
1. INTRODUCTION
Nuclear methods of analysis have for many years been
deeply involved in the analysis of trace levels of numerous
elements in a wide variety of sample matrices. This chapter
lists the capabilities of the various nuclear methods and
provides references to demonstrate their feasibility. How-
ever, since most nuclear techniques depend more on the
specific elements present in the sample, rather than the
broad category of matrix type, no specific matrix differen-
tiation has been made in the accompanying table. Some
discussions of the individual matrices of interest are
included under Section 3.
2. NUCLEAR METHODS
The broad category of nuclear methods includes almost
all methods which depend upon the measurement of a radio-
isotope resulting from an irradiation process. A brief
description of the more important methods presently in use
follows:
A. AS - Activation Spectrometry (Instrumental Neutron
Activation Analysis)
This is the method of choice if sufficient sensitivity
and specificity are available. In this technique, a sample is
irradiated in a neutron source (usually a nuclear reactor,
to obtain the required sensitivity) for a period of time,
and, after withdrawing the sample, the resulting induced
radioactivity is observed. This radioactivity is usually
detected and quantitated using a high resolution lithium-
drifted germanium semiconductor detector [Ge(Li)] for
greatest specificity. In this technique, each radioisotope
may be uniquely identified through the observation of a.) its
gamma-ray energy; b.)its half-life; and c.) its peak ratios
(if it has two or more gamma-ray peaks). It is limited
primarily by the total radioactivity induced in the sample
under evaluation, and often long decay times are required for
many elements. However, it is usually possible to determine
many elements simultaneously with one or two irradiations and
2 or 4 counts of a particular sample and associated standards.
10
-------
B. NAA - Neutron Activation Analysis
This method is similar to the previous technique, except
that a radiochemical separation can be employed after irradi-
ation, but before measuring the radioactivity. This separa-
tion, if done competently, can remove all or most of the
interfering radioactivities while retaining all or a known
portion of the radioisotope(s) of interest. Thus, while
additional effort is required for the separation, the resulting
product is one of a few radioisotopes of interest with little
or no other interfering radioactivities. Thus, it is usually
possible to obtain maximum sensitivity along with high preci-
sion and accuracy with this technique.
C. FNAA - Fast Neutron Activation Analysis
This is another method of activation analysis in which
fast neutrons are used as the irradiation source. This fast
neutron source could be a Cockcroft-Walton neutron generator
producing 14 MeV neutrons, another type of particle accelerator
used for generating fast neutrons, or a radioisotope source
such as californium-252, producing neutrons by spontaneous
fission with energies peaking around 2-3 MeV. However, this
technique is seldom used for trace analysis due to a lack of
sensitivity caused primarily by the relatively low fast neutron
fluxes currently available.
D. CPAA - Charged Particle Activation Analysis
This method of activation analysis depends upon the use
of radioisotopes produced in the sample by a charged particle
beam from accelerators such as a tandem-Van de Graaf or a
cyclotron. This method has the capability of detecting
several elements difficult to determine by other nuclear methods,
and thus has found some limited usefulness. The technique
is limited 'to a great extent by the nature of its irradiation
beam, since it can penetrate to only a few micronmeters depth in
the sample. Thus, while found to have great applicability
in the field of surface analysis, it is quite limited for the
types of samples under consideration here.
li. PAA - Photon Activation Analysis
The method of photon activation analysis utilizes the
bremsstrahlung radiation produced by the deceleration of very
energetic electrons in a high Z material. One excellent source
of such radiation is the Linear Electron Accelerator, or LINAC.
These high energy photons are very penetrating, thus producing
an irradiation source quite useful for several elements,
especially those which are difficult to determine by neutron
activation analysis. This technique also uses a Ge(Li) detector
11
-------
system for counting, and can also have a radiochemical separa-
tion step included in the analysis. Two of the important
disadvantages, however, include the lack of generally available
LINAC's and the general similarity of gamma-ray energies of
the radioisotopes produced by the prevalent (y,n) nuclear
reactions (usually positron emitters).
F. NTT - Nuclear Track Technique
The nuclear track technique makes use of the fission or
alpha particle decay of a nucleus undergoing neutron bombard-
ment. If a smooth surface of the sample or a solution of the
sample is placed in intimate contact with a special type of
plastic, then irradiated (usually with thermal neutrons),
several elements produce a track in the plastic which can then
be chemically etched and counted microscopically. At present,
of the elements of interest here, only boron and uranium can
be determined by this technique.
G. IDA - Isotope Dilution Analysis
A number of elements can also be determined using the
technique of isotope dilution analysis. This heading includes
both isotope dilution analysis and its related technique
of substoichiometric isotope dilution analysis. In these
methods, a radioisotope of the element of interest with known
specific activity is added to the sample, after which all or a
portion of the "diluted" element is separated from the sample.
The changed specific activity of the separated radioisotope
allows the calculation of the concentration of the element in
the sample. This technique is listed in table 1 as a secondary
method for several elements. '
3. ANALYTICAL APPLICATION TO SPECIFIC MATERIALS
The applicability of nuclear methods for the analysis of
fly ash, coal, oil, ores, minerals, metals, alloys, organo-
metallics, incinerator particulates, slurry streams, feeds
to/from flotation processes, and sediments in flotation pro-
cesses has been investigated. It does not seem to be feasi-
ble to consider each of these materials separately for all
of the elements of interest. Very few papers have been
published for these materials even though these methods,
especially neutron activation analysis, are eminently suitable
JThis is not to be confused with Isotope Dilution Mass
Spectrometry which uses enriched stable isotopes as
tracers, rather than radioactive isotopes.
12
-------
for most of the elements in all of the matrices. Thus, only
an overview of the different sample matrices will be given
here, with some references to specific publications, if
available. It must also be remembered, however, that dis-
solution of the sample after irradiation, with an appropriate
radiochemical separation of the element of interest, will
yield a determination which is essentially similar for all
sample matrices. This is not only possible, but is currently
being done in the NBS laboratory as well as many other acti-
vation analysis laboratories. This fact, coupled with the
ability to verify radioisotopic purity by at least two and
possibly three different parameters (i.e., gamma-ray energy,
half-life, and peak-ratios) enables reliable analytical
data to be obtained for most elements for almost all types
of samples.
A. Fly Ash
The primary difficulty in the analysis of fly ash is the
high radioactivity level resulting from neutron irradiation.
However, since impurity levels are also generally high, the
sensitivity loss should not be a problem. Many elements can
be determined non-destructively, however, the shortlived
radioisotopes (e.g., calcium, magnesium, vanadium) may be
impossible to detect at low concentrations. This material
can be dissolved in acid mixtures and the element(s) of
interest separated, with some increase in cost but with much
improved sensitivity. Unfortunately, very little analytical
data have been published on fly ash.
B. Coal
This matrix is elementally similar to biological materials,
and thus can be tentatively considered in terms of neutron
activation analysis results on human tissue (86) and botanical
samples (87). In the first publication 30 elements were
determined in individual samples by radiochemical separations
and gamma-ray spectrometry (86). In the second publication
15 elements were determined non-destructively in samples of
dried kale leaves. Again, sample dissolution is simple and
separations can be performed to improve the sensitivity and
specificity for individual elements or small groups of
elements. Many additional activation analysis references are
available for trace element analyses in biomedical samples
(90,91,92), but only one was found in which a coal was the
sample matrix (68).
C. Oil
The activation analysis of oil samples has been demon-
strated several times, notably the determination of 13 trace
elements by AS in crude petroleum (81), and the systematic
13
-------
determination of 11 trace elements in crude oils, distillation
fractions, asphalts, etc., by NAA with radiochemical separa-
tions (88). In this latter paper, comparisons were made for
some elements with results by other analytical techniques, and
precisions of ±10 percent claimed for the NAA results. Addi-
tional papers present work on the characterization of marine
oil pollution sources by AS (89,97).
D. Ores and Minerals
The activation analysis technique has been applied to
large numbers of geological type samples (93,94,95) and to
some ore and ore processing product samples (96). In one case,
a single sample weighing less than one gram was analyzed by
neutron activation with radiochemical separations, and 39
elements were determined with precisions of better than ±5
percent claimed for over half of the elements (95). In a
second situation, a neutron generator (FNAA) was used to
activate samples and rapid, nondestructive analyses were made
for several elements with sensitivities of about 1 mg (96).
In an ore and mineral type of sample, the capability of any
nondestructive activation technique depends to a significant
extent on the concentration of other elements in the matrix.
Thus, some preliminary evaluation will usually have to be
made before an established analytical procedure can be
applied.
Li. Metals and Alloys
Much analytical data have been published on the activa-
tion analysis of trace elements in metals and alloys.
Several particularly useful references other than those from
table 2 are included here (98,99,100). The ease of analysis
depends significantly on the activation of the matrix material.
Thus, much of the work reported in the literature has been
made on sample matrices which are relatively easy, such as
aluminum, iron, lead and bismuth. Metals and alloys which
activate strongly (such as manganese, copper, gold, antimony)
or fission under neutron irradiation (such as uranium or
thorium) are much more difficult to analyze for trace element
concentrations.
'' Qrganometal lies
Organometallics have been analyzed by activation
analysis for major constituents (101,102), but not often for
trace contaminants. This is most likely due to a lack of
interest in trace element information, since thermal neutron
activation analysis would seem to be especially suited to this
type of sample. However, some restrictions might be found
necessary for the irradiation of very volatile liquids or
explosive compounds in a nuclear reactor.
14
-------
G. Incinerator Particulates
The characteristics of this type of sample would probably
be somewhere between fly ash and coal. No particular problems
are foreseen that were not already mentioned, but no publica-
tions are available which specifically treat this material.
H. Slurry Streams. Feeds to/from Flotation Processes, and
Sediments in Flotation ProcessTs
These sample types are grouped together because there is
so little published information on their analysis by nuclear
methods. The only references that could be found were two
papers, one previously mentioned under ores and minerals (96),
plus one additional paper on the use of isotopic neutron
sources for process control in the metallurgical industry
(103). Again, most of the sample types included here would
appear to be very suitable to at least one of the activation
analysis methods.
4. RESULTS AND DISCUSSION
The results of this survey of the analysis of environmental
materials by nuclear methods are found in table 1. Each
element is listed along with pertinent information concerning
its determination. As discussed in the introduction, no
further breakdown of the data by sample type will be made;
general comments can be found in Section 3 of this chapter.
In the explanation of table 1, each column will be
commented upon here. For the second, third and fourth columns,
(TECHNIQUE USED, ACTIVATION EQUIPMENT, and DETECTION EQUIPMENT,
respectively) the definitions can be found at the bottom of the
table, and are discussed here and elsewhere.
The instrumentation required for most of the activation
procedures listed in table 1 are first, an irradiation source
(for AS and NAA, usually a high flux nuclear reactor) or
access to one, and second, a pulse height analyzer and high
resolution lithium-drifted germanium detector system for
detecting and quantifying the induced radioactivites resulting
from the irradiation. The activation analysis technique has
the substantial advantage over most other trace analytical
techniques in that after the sample has been irradiated (i.e.,
the trace element of interest has been made radioactive)
normal contamination problems no longer exist. In fact, when
radiochemical separations are used usually macro quantities
(10-20 mg) of the element of interest are added to the sample
as carrier to minimize separation and adsorption problems.
Thus, to retain this advantage, handling and manipulation of
the sample before irradiation, (preconcentration, dissolution,
etc.) should be kept to a minimum.
15
-------
Column 5, PREPARATION TIME, is an estimate of the time
required for preparation of a sample for analysis. This
time does not include the time necessary for counting a
sample or calculation of the results, nor does it include the
time required for dissolving the sample or for a chemical
separation, should that be required. However, such factors
are considered in estimating the cost of an analysis.
Column 6 contains the estimated DETECTION LIMIT, in
micrograms. Most of the values for AS and NAA have been
obtained from published compilations of experimental sensi-
tivity values (104,105). In all cases the value quoted is
for the "interference free" situation, using irradiation
time of a few hours at a thermal neutron flux of 5xl013n.cm 2
sec"1. Where necessary, corrections have been made for
counting with a Ge(Li) detector system. These detection
limits are realistic, however, especially when employing an
effective radiochemical separation to remove any interfering
radioactivities from the sample. In fact, the listed detec-
tion limit can often be exceeded when specialized counting
equipment is used. For instance, even though the listed
detection limit for sodium in table 1 is 10~3 yg, as little as
4xlO~6 pg of sodium has been determined with a precision of
better than ±10 percent, using a 8-y-Y sum-coincidence spectro-
meter (36,101).
In column 7, the estimated SAMPLE SIZE (grams) has been
listed. This sample size is very flexible for neutron activa-
tion analysis and photon activation analysis, although less
so for the other nuclear techniques. Samples have been
analyzed which range from a few micrograms to tens of grams.
However, general sampling considerations limit the sample
size to more than 10 mg, while potential self-shielding
effects usually limit the sample size to a gram or less.
In column 8, the MANPOWER SKILL LEVEL is assumed to be
that of a skilled technician for the AS determinations. This
has been shown to be true in a number of laboratories,
providing the assumption in the next column is true, that an
established analytical procedure is available. To provide
that procedure, usually a scientist is required. Also, in many
cases where a technician is indicated, a chemist will often
be necessary if a radiochemical separation is required. In
the table, a chemist is listed whenever special procedures are
indicated.
In column 9, the COST PER ANALYSIS .is estimated on the
basis that an established analytical procedure is available,
and that at least 100 samples are to be analyzed. Thus, the
values given are for routine analyses, rather than special
research type analyses.
16
-------
In column 10, the SELECTIVITY has been evaluated on the
basis of ease of determination by the primary nuclear analytical
method. In the case of AS, this is a function of the gamma-
ray energy, the half-life, and the general ability of the
technique to successfully determine the element nondestructively
in a variety of sample types. If a rapid and simple radio-
chemical separation would be very effective, this may also
have been taken into consideration.
Column 11, COMMENTS, includes the evaluation of half-life,
decay time, and/or radiochemical separations on sensitivity
and specificity, and also lists the alternate nuclear method(s)
of analysis for that element along with the pertinent
reference (s).
Table 2 contains a listing of references for each indivi-
dual element in a variety of matrices, often by a number of
different nuclear methods. No attempt has been made to be
exhaustive, but rather the aim has been to illustrate the
analytical determination of that specific element.
No report on an analytical technique would be complete
without a few comments on the potential errors and biases
involved. These areas have been discussed extensively in the
literature and so will not be further discussed here (106,107,
108). It is sufficient to say that the uncertainties
involved are well understood, so that with these techniques
levels of accuracy and precision of ±5 percent are possible
in many cases, and ±25 percent in almost all cases, ui capable
laboratories.
In conclusion, the various nuclear techniques of analysis
have been shown to be capable of the determination of the
elements listed in many sample matrices. These techniques,
especially neutron activation analysis, activation spectrometry,
and photon activation analysis, should be very useful in the
analysis of trace elements in environmental samples.
ACKNOWLEDGMENT
The extensive and able assistance of Ms. Lottie McClendon
in the compilation of the bibliography for this chapter is
acknowledged with much appreciation.
17
-------
Table I. Tree* Elements la tailroneeatal Malorlale
00
Deti.-r«-ned
»«icur»
Brrylliue
Cad* me
Arsenic
IjnjJma
uin.jnese
M.lrl
Anl unny
Chrtniua
Z in..
Copper
Lead
bclcniua
Bvron
f lucr me
Lilhiun
Silver
Fin
1 ron
M lonl lua
Sodiu.
POIJ..IU>
ClIciM
Silicon
*ti|nesiue
Uraniue
Ihoriua
Used
AF
CPAA
AS
AS
AS
AS
AS
AS
AS
AS
AS
PAA
AS
tit
IS
\s
AS
AH
IS
NXA
AS
AS
AS
NAA
AS
AS
IS
Eauio.
RfACT
TV DC
RIICT
RLACT
RLACT
HI ACT
RIALT
KLILT
Rl ACT
RLALT
RFICT
LINAC
RLILT
RIAC7
RIAIT
RIACI
Rl II i
RIICT
Rl kCT
RIAIT
RfACT
REACT
RE'CT
or-trr
REICT
REACT
RLACT
Fnulp.
»»« r.r
PHA Nal
PHI i.e
PIIA r.e
PHA Ce
PI 'A Ce
PHI -r.e
PIIA r.e
PIIA r.o
PHA re
PMA-'.e
PHI- r.e
PHA be
SPtC
P"A v.e
SPli
PH< Ce
PIIA -r.e
PIIA-Cc
Plll-Ce
PI>l-Ce
PIIA-Ce
PHA -r.c
PHA -r.c
PIIA -r.e
PIIA Cc
PIIA-Cc
T!
IS
10
IS
IS
IS
IS
IS
IS
IS
IS
IS
JO
IS
10
IS
10
It
11
IS
10
IS
IS
IS
10
IS
IS
IS
it.* LUlltuft) Sutfl) Skill Level Antlysi*
I**"
1
» 10
K 10
|A*
10"
1 0"
1 0"
lO'2
e 10
e 10
B S
io-'
,0 '
10-'
B 10*
10
B 10'*
B 1
B 10
B 10
B 10*
B 10*
1
B 1
10*1
IO*1
.01-1
<0 1
.01-1
01-1
01 1
.01-1
01 -1
.01 1
01 -1
01-1
.01-1
01-1
.01-1
.001-
01-1
.01-1
01-1
.01-1
.01 1
.01-1
.Ol-'l
01-1
.01-1
.01-1
.01-1
.01-1
.01-1
.0
.0
.0
.0
0
0
0
0
.0
.0
.0
.0
.1
.0
.0
0
.t
.0
.0
.0
.0
.0
.e
.0
.0
.0
TFCII
riifii
TECH
TECH
TrCH
TICII
TFfli
TECH
TLCII
TLCII
TLCII
TLCII
TECH
TECH
TECH
CHEN
TECH
TECH
TlTH
ClltM
TrCH
TECH
TECH
ClltM
TCCH
TECH
TFCII
(SO-100
100-200
SO-'IOO
SO-100
SO-100
SO-IOO
SO 100
SO 100
SO-ion
to 100
so-ioo
100-200
SO-100
100-100
SO-IOO
100-100
SO-IOO
SO-IOO
SO-IOO
100-200
SO-IOO
SO-IOO
SO-IOO
100-100
SO-100
so-ioo
SO-IOO
f I . .
5e t ec 1 1 v 1 1
( Non-del t.
Cood
Poor
r.ood
V. Coed
V Good
tic
Good
V. Cood
Cood
V. Coed
Cood
Good
Good
V Good
Fair
Cood
Fair
V. Coed
--
Eic.
V Cood
Eic
--
Cood
Good
flood
5 Comets'
Chca. Sepn.»; Alt*: IDA (0)
Alao: Photoaeutron Teck(2*. >I.)0) ; AS 140)
Of tea requires Chea. Sepn.; AI»*:F1AA (If)
CheB. Sepn.-
Short half-life
Cheo. Sepn."
Also IDA (7)
Often reoulres leaf, decay lie* er Chea. Seee.
Filher of lue lietopea caa »e used; Alto: IDA (t)
Ckee. Sepn. ; Alsa IDA (0.11)
Chea. Sepn. ; Also- AS (40)
Often requires leap decay tie*
Alto AS (41); CPAA (14)
Short balf-ltfe; Alt* CPAA (24); PAA (11)
V. short half-lit*, uses reader pulse; Alto:
acquires loeg decay or Cnce. S*pa.
Require! CheB. Sepn., Alto CPA4 (41)
Short half-life; Alae: CPAA fit)
quire* ChcB.Sepa.: Alte: FHAA (SI)
Short half-life. Alae: F1AA (If)
Chea. Sepn. >. Alae nTT (14); Deleyed ant roe (SO
Alao: Deleyed eeutrea ceuatlaf (SO)
AS Actlvitloa tpectroaetr* (lattruecntil aeutroa actlntloa »*l*ili); MAA N*uiroa actlvitloa aaalyili,
hVJLA Fait neutroa activattea aaalyin; CPAA - Charted particle acttvailoa aaalyili; PAA Photon actliratloej
analyili; KTT Nurlcar trick teckalquc; IDA liotope dllullei idllyilt
RIACT Muclear reactor; TVDC - Tandee Vaa de Craaf accelerator; LI MAC Linear alectroa accelerator
r(1lA Ce Pulic helikt anil>ier kltb Kl|h rciolutioa |*raaniua laeaa-ray detector; PIIA-Ma I PHA vlih (odlue led Id*
detector; 1PIC Special countlia. technl^uei (* reference!).
Detrition linm are alcrofrini of the element, for the interference-free li mat Ion; ten.
CTKII ililleJ technician. CULM t rimed analytical cheeist
Cttineicd on the baili of Uric (>IOO) nuaheri of laaple*. uiln| aa established analytical procedure.
CHEM SEPN Sifniflcantly laprovcd deterelnatioa vlth ilaple chealcal separation; CIIEM SEPN freatlr leproved
detcratnitlon mth aleple cheaical separation, for eiplanatlon of ether tochnloues used, sec a.
-------
Table 2
Element Index to References
Nuclear Methods
Element
Mercury
Beryllium
Cadmium
Arsenic
Vanadium
Manganese
Nickel
Antimony
Chromium
Zinc
Copper
Lead
Selenium
Boron
Fluorine
Lithium
Silver
Tin
Iron
Strontium
Sodium
Potassium
Calcium
Silicon
Magnesium
Uranium
Thorium
References
9,16,47,67,68,69,81
20,22,23,24,48,70
17,26,29,67,71
29,30,57,67,75,76,81
29,46,57,58,80
3,14,29,65,76
31,45,77,81
7,28,29,76,81
15,27,29,32,59,66,77,81
9,14,27,29,32,60,61,65,67,76,77,81
8,13,14,18,27,29,62,65,76,77
42,48
44,63,67,81,82
24,34,48
24,33,48
38,48,64,74
1,2,29,37,77,83,84
29,30,56,81
10,14,40,66,76,77,81
29,41,54,55
19,29,36,65
25,27,29,85
6,29,39
52,53,77,78
29,43,78
4,5,25,34,35,50,51,74,79,81
25,49,50,72,73,74
19
-------
REFERENCES
1. Adam, F.; Hoste, J.; Speecke, A., Detection of Silver in
Lead by Neutron Activation Analysis, Talanta 10, 1243
(1963).
2. Nakai, T.; Yajima, S.; Okada, M., Activation Analysis hy
Short-Lived Nuclides. IV. Determination of Silver hy
Silver-110, Nippon Kagaku Zasshi 8j_, 1422 (1960).
3. Bouten, P., lloste, J., "Activation Analysis of Manganese
in Cast Iron and High-Alloy Steels, Talanta 8_, 322 (1961).
4. Decat, D., Van Zanten, H., Determination of Trace Quanti-
ties of Uranium by Neutron Activation Analysis, Anal. Chem.
3.5, 845 (1963).
5. Smales, A. A., Mapper, D., The Determination of Uranium in
Fairly Pure Beryllium Metal by Neutron Activation and Gamma
Spectrometry, Anal. Chim. Acta 125, 587 (1961).
6. Atchison, CI. J., Beamer, W. H., Determination of Trace
Impurities in Magnesium by Activation Analysis, Anal.
Chem. 2±, 1812 (1952).
7. Tejam, B. M., Haldar, B. C., N-Benzoyl-N-Phynylhydroxyl-
amine as a Substoichiometric F.xtractant in Activation
Analysis, IV. Determination of Antimony, Radiochem.
Radioanal. Lett. 9, 189 (1972).
8. Miloslov, Krivanek, Frantisek, K.f Substoichiometric
Determination of Copper in High-Purity Metals by Acti-
vation Analysis, Talanta 12, 721 (1965).
9. Stary, J., Ruzicka, J., Isotope-Dilution Analysis by
Solvent Extraction, II. Highly Selective Determination
of Zinc with Dithizone, Talanta 81, 296 (1961).
10. Ibid, A New Principle of Activation Analysis Separations,
1_0, 287 (1963).
11. Trascenko, S. M., Extraction Radiometric Determination
of Microgram Amounts of Lead by Isotope Dilution,
"Radiometric Methods of Determ. of Microelem.," p. 93
Nauka, Moscow-Leningrad, 1965.
12. Carmichael, I. A., Whitley, J. E., Determination of
Fluoride by Substoichiometric Isotope Dilution, Analyst
9^, 393 (1970).
20
-------
13. Ruzicka, J. Stary, J. Isotope Dilution Analysis by
Solvent Extraction - IV, Selective Determination of
Traces of Copper with Dithizone, Talanta 9_, 617 (1962).
14. Brooksbank, W. A., Leddicotte, G., Neutron Activation
Analysis of Aluminum-Base Alloys, Anal. Chem. 30, 1785
(1958).
15. Fasalo, G. B., Malvano, R., Solvent Kxtraction of Cr
with Tribenzylamine, Anal. Chim. Acta 2£, 569 (1963).
16. Westermark, T., Activation Analysis of Mercury, Intern.
J. Appl. Radiation Isotopes 9_, 11 (1960).
17. Ricci, I-., Mackintosh, W. D., Neutron Activation Method
for the Determination of Traces of Cadmium in Aluminum,
Anal. Chem. 3_3, 230 (1961).
18. Chinaglia, B., The Determination of Some Elements in
Aluminum by Non-Destructive Radioactivation Analysis,
l-nergia Nucl. 8, 571 (1961).
19. Plumb, R. C., Measuring Trace IMements, Nucleonics
L4, 48 (1956).
20. Levine, C. A., Surls, J. P., Rapid, Nondestructive
Determination of Beryllium Using Van de Graff X-Rays,
Anal. Chem. 34, 1614 (1962).
21. ALdankin, B. C., etc., A Method for Beryllium in Ores
by Means of Photoneutrons, AEC-TR-4498, 99-105 (1961).
22. Mezhiborskaya, K. B., Radioactivation Determination of
Beryllium, Atomic Energy, USSR 6, 416 (1959).
23. Guinn, V. P., Lukens, H. R., The Photoneutron Deter-
mination of Beryllium and Deuterium, Trans. Amer. Nucl.
Soc. 9, 106 (1966).
24. Ricci,I:., Ilahn, R. L,, Sensitivities for Activation
Analysis of 15 Light Elements with 18 MeV Helium-3
Particles, Anal. Chem. 3£, 794 (1967).
25. Aruscavage, P. J., Millard, H. T., A Neutron Activation
Analysis Procedure for the Determination of Uranium,
Thorium and Potassium in Geologic Samples, J. Radioanal,
Chem. 11, 67 (1972).
21
-------
26. Lieberman, K. W., Kramer, H. M., Cadmium Determination
in Biological Tissue by Neutron Activation Analysis,"
Anal. Chem. 4^, 266 (1970).
27. Vasiler, I. Y., Razumana, G. N., Determination of Trace
Impurities in Indium Antimonide by a Neutron Activation
Method, Radiokhimiya 1J., 573 (1969).
28. Adams, F., Hoste, J., Activation Analysis of Antimony
by Sum-Coincidence Spectrometry, Nucleonics £2,55 (1964).
29. LaFleur, P. D., and Becker, D. A., Editors, Activation
Analysis Section: Summary of Activities, July 1969 to
June, 1970, NBS Tech. Note 548 (1970).
30. Neirincka, R., Adams, F., Hoste, J., Determination of
Impurities in Ti and Ti Dioxide by Neutron Activation
Analysis. 1. Simultaneous Determination of 16 Trace
Elements, Anal. Chim. Acta 46, 165 (1969).
31. Nceb, K. A., Martin, J., Activation Analysis of Small
Quantities of Tellurium, Chlorine, Thallium and Nickel
in Selenium, Z. Anal. Chem. 247 (1962).
32. Ballaux, C., Dams, R., Hoste, J., Neutron Activation
Analysis of High-Purity Selenium. Part V. Simultaneous
Determination of Metallic Impurities, Anal. Chim. Acta
3£, 141 (1966).
33. Wilkniss, P. I:., The Determination of F, Cl, Br, and I
in a Single Sample by Photon Activation Analysis,
Radiochim. Acta. 1^, 138 (June 1969).
34. Carpenter, B. S., Determination of Trace Concentrations
of Boron and Uranium in Glass by the Nuclear Track Tech-
nique, Anal. Chem. £4, 600 (1972).
35. Becker, D. A., LaFleur, P. D., Determination of Trace
Quantities of Uranium in Biological Materials by Neutron
Activation Analysis Using a Rapid Radiochemical Separation,
Anal. Chem. 4£, 1508 (1972).
36. Becker, D. A., Neutron Activation Analysis of Sodium
at the Picogram Level, Trans. Amer. Nucl. Soc. 12 495
(1969). ~~
37. Morris, D. F. C., Killick, R. A., Determination of
Silver and Thallium in Rocks by Neutron Activation Anal-
ysis, Talanta 4, 51 (1960)
22
-------
38. Wiernik, M. , Amiel, S. , Activation Analysis of Lithium
by Means of 8Li and a Cerenkov Detector, IA-1190, 115-16
(1969).
39. Pretorius, R., Schweikert, E. A., A Method for Determining
Calcium by Alpha Activation Analysis, SUNI-10, 19-20
(1969).
40. Mantel, M., Alhu, Yaron, Amiel, S, Trace Element Anal-
ysis of Standard Reference Materials, IA-1190, 118-19
(1969).
41. Debrun, J. L. , Albert, P., Irradiation of Some Natural
Elements by 35 MeV Photons. Application in Activation
Analysis, Bull. Soc. Chim. Fr. ^» 102° (1969).
42. Lutz, G. J., Determination of Lead in Environmental
Samples by Photon Activation Analysis, Proc., Conf. on
Nucl. Methods in Environ. Res. 144-49, ANS, Columbia,
MO. (1971).
43. Smathers, J. B., Duffey, D., Derivative Neutron Acti-
vation Determination of Magnesium, Nucl. Appl. Technol.
I, 84 (1969).
44. Nadkarni, R. A., Haldar, B. C., Substoichiometric
Determination of Selenium by Neutron Activation Analysis,
Radiochem. Radioanal. Letters ]_, 305 (1971).
45. Ibid, Substiochiometric Determination of Nickel in
Steel by Neutron Activation Analysis, 339 (1971).
46. Linstedt, K. D. and Kruger, P., Determination of
Vanadium in Natural Waters by Neutron Activation Anal-
ysis, Anal. Chem. 4_2, 113 (1970).
47. Gillette, R. K., Investigations into the Determination
of Mercury in Copper, Mound Laboratory Report No. MLM-
1772 (TID-4500), Monsanto Research Corp. (1970).
48. Lukens, H. R., A Neutron Activation Analysis Method
for the Determination of Be, Li, B, F and Pb. J.
Radioanal. Chem. 1_, 349 (1968).
49. Smith, G. W., and Mongan, D. M., The Determination of
Thorium in Cerium Matrices by Neutron Irradiation: Use
of Argonne Pneumatic Facility, Int. J. Appl. Rad. Iso.
1£, 81 (1965).
50. Amiel, S. Analytical Applications of Delayed Neutron
Emission in Fissionable Elements, Anal. Chem. 34,
1683 (1962).
23
-------
51. Campbell, F. T. and Svteele, 12. L., Uranium Assay by
Nondestructive Neutron Activation Analysis, Radiochem.
Radioanal. Letters 11, 245 (1972).
52. Nadkarni, R. A., and Haldar, B. C., Determination of
Silicon, Phosphorus and Sulfur in Alloy Steel by Neutron
Activation Analysis, Anal. Chim. Acta £2_ 279 (1968).
53. Vogt, J. R. and Ehmann, W. D., Silicon Abundances in
Stony Meteorites by Fast Neutron Activation Analysis,
Geochim. Cosmochim. Acta 2£, 373 (1965).
54. Higuchi, H., et al., Simultaneous Determination of
Strontium and Barium by Neutron Activation Analysis
with a Ge(Li) Detector, Anal. Chim Acta 44, 431
(1969).
55. Qureshi, I. II., and Meinke, W. W., Radiochemical Sepa-
ration of Strontium by Amalgam Exchange, Talanta 10
737 (1963).
56. Hamaguchi, H., et al., Determination of Trace Quanti-
ties of Tin by Neutron Activation Analysis, Anal.
Chim. Acta 30_, 335 (1964).
57. Fukai, R., and Meinke, W. W., Activation Analysis
of Vanadium, Arsenic, Molybdenum, Tungsten, Rhenium,
and Gold in Marine Organisms, Limnology and Ocean-
oyraphy T_t 186 (1962) .
58. Das, 11. A., et al. , Routine Determination of Vanadium
in Silicate Rocks by Neutron Activation Analysis,
Radiochem. Radioanal. Letters 4_, 307 (1970).
59. Hrunfelt, A. 0., and Steinnes, E., Determination of
Chromium in Rocks by Neutron Activation and Anion
Exchange, Anal. Chem. 39, 833 (1967).
60. Ball, T. K., and Filby, R. H., The Zinc Contents of
Some Geochemical Standards by Neutron Activation and
X-ray Fluorescence Analysis, Geochim. Cosmochim. Acta
29_, 737 (1965).
61. Bakes, J. M., and Jeffery, P. G., Determination of
Zinc in Ores and Mill Products by Neutron Activation
Analysis, Anal. Chem. 3£, 1594 (1964).
62. Grimanis, A. P., Rapid Determination of Copper in
Plants by Neutron Activation Analysis, Talanta 15, 279
(1968).
24
-------
63. LaFleur, P. D., "Activation Analysis Section: Summary
of Activities, July 1968 to June 1969," NBS Tech. Note
508 (1970).
64. Smith, G. W., et al., The Neutron Activation Determina-
tion of Lithium in the Presence of Alkali Metals and
Magnesium, Anal. Chim. Acta 33, 1 (1965).
65. Becker, D. A., and LaFleur, P. D., Neutron Activation
Analysis: Application of Trace Elements Analysis of
Biological and Environmental Materials, "Proceedings,
Fifth Ann. Conf. on Trace Substances in Environmental
Health," Univ. of Mo., Columbia, Mo. 447 (1971).
66. Benson, P. A., and Gliet, C. E., Neutron Activation
and Radiochemical Determination of the Molybdenum,
Chromium, and Iron Content of Individual Stainless
Steel Microspheres, Anal. Chem. 35., 1029 (1963).
67. Orvini, E., Gills, T. , LaFleur, P., Nuclear Activation
Analysis of Se, As, Zn, Cd, and Hg in Environmental
Matrices, Trans. Amer. Nucl. Soc. 15, 642 (1972).
68. Rook, II. L., LaFleur, P. D. , and Gills, T. E., Mercury
in Coal: A New Standard Reference Material, Environ-
mental Letters i2, 195 (1972).
69. Kennedy, Ii. J., et al. , Environmental Studies of
Mercury and Other Elements in Coal and Lake Sediments
as Determined by Neutron Activation Analysis, "Proc.
Conf. on Nuclear Methods in Environ. Research," ANS,
205, Columbia, Mo. (1971).
70. Mezhiborskaya, K. B., A Radioactivation Method for the
Determination of Beryllium in Minerals, Raw Materials
and in Hydrometallurgical Products, J. Anal. Chem. USSR
15., 323 (1960).
71. Bilefield, L. I., Determination of Cadmium in Rocks
by Neutron Activation Analysis, Analyst 86^, 386 (1961).
72. Leddicotte, G. W., Mahlman, H. A., Determination of
Microgram and Submicrogram Quantities of Thorium by
Neutron Activation Analysis, "Intern. Conf. Peaceful
Uses of At. Energy," £, 250 (1955).
73. Mantel, M., Propai, S. T., Amiel, S., Neutron Activation
Analysis of Thorium in Rocks and Ores by Multiple Gamma
Ray Peak Ratio Determination, Anal. Chem. .42, 267 (1970)
25
-------
74. Amiel, S., New Methods of Radio-Activation Analysis
Based on Delayed Neutron Emission and Secondary Reactions,
"Utilization of Research Reactors," Vol. 3, 307-14, Vienna
1AI:C, London (1962).
75. Saskoloka, II., Rowinska, L. The Search for Internal
Isotopic Tracers in Metallurgical Materials. I. Determi-
nation of In, W, As, Au, Sc, Re, Ir, and Ca by the
Neutron Activation Method, .1. Radioanal. Chem. 7
29 (1971).
76. Lamb, J. F., et al., Application of Lithium-Drifted
Germanium Gamma-Ray Detectors to Neutron Activation
Analysis. Non-Destructive Analysis of a Sulfide Ore.
\nal. Chem. 38_, 813 (1966).
77. Leddicotte, G. W. et-al., The Determination of Trace
l-le-nents in Reactor Materials by the Method of Neutron
\ctivation Analysis, TID-7555, 192-215 (1958).
78. Lobanov, F.. M., Mingalier, G. G., Rapid Neutron Acti-
vation Determination of Si, Al, Ba and Mn in Synthetic
Micas, Aktivatsionnyii Analiz Elementiogo Sastava
Geologicheskikh Obekter, 77-83, Tashkent (1967).
79. DcLanHe, P. !V., et al., Critical Evaluation of Spiking
of Low Grade Tro Samples in Activation Analysis for
Gold and Uranium, Talanta 15, 1488 (1968).
80. '.Vahl , W. !!., Molinski, V. .J. , Rapid Radiochemical
Separation Procedures for Activation Analysis Indicators,
"nroc., Inter. Conf. Modern Trends in Act. Anal."
44, College Station, Texas (1965).
81. Shah, K. R., Filby, R. II., Holler, W. A., Determi-
nation of Trace Clements in Petroleum by Neutron Acti-
vation Analysis. II. Determination of Sc, Cr. Fe, Co,
Ni, Zn, As, Sc, Sb, Eu, Au, llg and U, J. Radioanal.
Chen. 6, 413 (1970).
82. Pillay, K. K. S., Thomas, C. C., Neutron Activation
Analysis of the Selenium Content of Fossil Fuels,
Nucl. Anpl. Technol. 7, 478-(1969).
83. Turkstra, J., Pretorius, P. J., Nondestructive Deter-
mination of Platinum Metals in Ores, Matte and Lead
Assay Beads by Reactor Activation Analysis and High
Resolution Gamma Spectrometry, Anal. Chem. 42, 835
(1970).
26
-------
84
85,
86
87
Morris, !3. F. C. , Killick, R. A.
of Silver in Galena and
vsLs, Anal. Chim. Acta.
The Determination
Blende by Radioactivation Anal-
20, 587 (1959).
Sorin, M., Ponescn, G., Determination of Potassium in
Geological Samples Using Neutron Activation Analysis,
Ann. Soc. Heol. Belg. 94_, 132 (1971).
Samsahl, K., Brune, 0. and Wester, P. 0., Simultaneous
Determination of 30 Trace Elements in Cancerous and
Non-Cancerous Human Tissue Samples by Neutron Activation
Analysis, Internat. J. Appl. Rad. Isotopes 16, 273
(1965).
Nadkarni, R. F
Trace Elements
, and Ehmann,
in Biological
Activation Analysis, J. Radioanal
(1969).
W. D., Determination of
Standard Kale by Neutron
Chem. 3, 175
et al., Systematic
89
90
91
92
93
94
Colombo, U. P
Technique for the Determination of Trace
Petroleum, Anal. Chem. 36, 802 (1964).
Neutron Activation
Metals in
Guinn, V. P. and Bellanca, S. C., Neutron Activation
Analysis Identification of the Source of Oil Pollution
of Waterways, "Proceedings, 1968 Internat. Conf. Mod.
Trends in \ct. Anal.," MRS Spec. Publ. 312, Vol. I,
p. 93 (1969).
Internat. Atomic Energy ^gency, Uses of Activation
Analysis in Studies of Mineral Element Metabolism in
Man, Report of a Panel Meeting, Teheran, IAEA Report
No. 122, Vienna (1970) (11 pages).
Internat. Atomic Energy Agency,
-- :- the Life Sciences," . 0_ __ _
IAEA, Vienna (1967).
Internat. Atomic Energy Agency,
Techniques in the Life Science*
Symposium, Amsterdam, May 1967
'Nuclear Activation
Proceedings of a
DeVoe, J. R., Editor, "Modern Trends in Activation
Analysis. Chapter 2. Biomedical Applications," Pro-
ceedings of the 1968 International Conference on
Modern'Trends in Activation Analysis, NBS Spec. Publ.
312, Vol. 1, n 98-212 (1969).
Ibid, "Chapter 4. Geochemical and Cosmochemical Appli-
cations," pp 288-413.
Brunfelt, A. 0.
in Geochemistry
Oslo (1972).
, and Steinnes, E.,
and Cosmochemistry,
27
'Activation Analysis
1 Universitetsforloget,
-------
95. Allen, R. 0., ct al., Neutron Activation Analysis for
39 Elements in Small or Precious Geologic Samples, J.
Radioanal. Chem. 6, 115 (1970).
96. Navalikhin, L. V., et al., Simultaneous Determination
of Lead, Copper, and Zinc in Multimetal Ores and Their
Processed Products by Activation Analysis, J. Radioanal.
Chem. 11_, 257 (1972).
97. Huinn, V. P., et al., The Trace Element Character-
ization of Crude Oils and Fuel Oils Via Instrumental
Neutron Activation Analysis, "Proc., Nuclear Tech. in
r.nvironmental Pollution," Salzburg, p. 347, IAEA, Vienna
(1971).
98. Malvano, R. , \eutron Activation Analysis in Metallurgy,
Atompraxis 11, 309 (1965).
99. Albert, P., Apnlication of Radioelements to Investi-
gating the Purification of Metals by the Zone Refining
Method: Systematic Analysis After Irradiation with
Neutrons (From the book "New Physical and Chemical
Properties of Metals of Very High Purity," New York,
Gordon and Beach Science Publishers) pp 1-51 (1965).
100. Bunshah, R. F., editor, "Modern Analytical Tech-
niques for Metals and Alloys: Part 2," Interscience,
New York (1970). (Above includes six chapters on
activation analysis, including chapters on thermal
neutron activation, fast neutron activation, and
photon and charged particle activation.)
101. LaFleur, P. D., Editor, "Activation Analysis Section:
Summary of Activities, July 1968 to June 1969."
NBS Tech. Note 508, p 76 (1970).
102. DeVoc, J. R., Editor, "Radiochemical Analysis:
Activation Analysis, Instrumentation, Radiation
Techniques, and Radioisotope Techniques, July 1965
through .June 1966, "NBS Tech. Note 404, p 29 (1966).
103. Kuusi, J., The Application of Isotopic Neutron
Sources to Chemical Analysis for Process Control in
the Metallurgical Industry, "Proc., 1968 Internal.
Conf. Mod. Trends Act. Anal.," NBS Snec. Publ. 312,
Vol. I, p. 450 (1969).
104. Yule, H. P., Experimental Reactor Thermal-Neutron
Activation Analysis Sensitivities, Anal. Chem. 37,
129 (1965).
28
-------
105. Yule, H. P., Reactor Neutron Activation Analysis:
Instrumental Sensitivities in Six Matrix Materials,
Anal. Chem. 38, 818 (1966).
106. Smith, G. W., et al., Determination of Trace
Elements in Standard Reference Materials by Neutron
Activation Analysis, Anal. Chim. Acta. 38, 333
(1967). ~~
107. DeVoe, J. R., Editor, "Proceedings, 1968 Inter-
national Conf. Modern Trends in Activation
Analysis, Chapter 15, Accuracy, Precision and
Standards." NBS Spec. Publ. 312, Vol. II, (1969).
108. Cook, G. B., et al., International Comparison
of Analytical Methods for Nuclear Materials - I,
Talanta 10, 917 (1963).
29
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CHAPTER 3
SPARK SOURCE MASS SPECTROMETRY
Paul J. Paulsen
1. INTRODUCTION
In spark source mass spectrometric (SSMS) analysis,
samples are introduced as solid "electrodes" into the
source chamber which is evacuated to a pressure of IxlO"7
to IxlO"8 torr! Ions are produced from a pair of sample
electrodes by imposing a pulsed radiofrequency voltage of 20
to 80 keV between them. The spark produced vaporizes and
ionizes all elements in a small volume of the sample with
each pulse. The high energy available in the spark results
in the production of multiply charged as well as singly
charged ions of all elements. The +1 ions, however, are the
most abundant species with+a dejreasj in abundance with each
increasing charge (i.e. Fe *>Fe 2>Fe 3, etc.). The ions are
accelerated by a 24 kV D.C. potential and pass through an
electrostatic sector and then a magnetic sector. The ions
are resolved into individual beams in the magnetic sector
and dispersed according to their mass to charge ratio. A
photographic plate at the exit of the magnet simultaneously
detects all elements from Li (mass 7) to U (mass 238) on
each exposure. By making a graded series of exposures
covering 5 to 6 orders of magnitude, it is possible to
determine elements present from the ppb level up to the
100 percent level.
Recently instruments have been produced which have
electronic detection as well as photographic detection. These
instruments use an ion multiplier to measure ion currents of
a single mass line at a time. The full mass range is
covered by scanning the ions of the individual lines sequen-
tially across the ion multiplier (by changing the magnetic
field strength).
Spark source mass spectrometry is ideally suited to
survey an unknown sample for all possible elements from major
constituents to those present at the ppb level. The spark
source has no inherent "blind spots" for any element and
detects all elements with approximately the same sensitivity,
Under optimum conditions a detection limit of a few ppb can be
obtained for all elements while consuming as little as 10 to
100 mg of sample. This high absolute sensitivity makes the
technique applicable to both the analysis of low levels of
concentration and the analysis of small samples (such as
particulates from a low-volume air sample).
Jl torr = 133 Pascals.
30
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A. Interferences
Although the SSMS cap potentially detect all elements,
there will be interferences present which may hinder or
prevent the analysis of some elements in real life samples.
There are two main sources of possible interferences, the + 2,
+3, etc. multiply charged ions and molecular ions (hydrocarbons,
metal dimers, oxides, etc.) having the same nominal mass to
charge ratio as the singly charged line of the element being
determined.
Control of experimental conditions and proper plate
interpretation techniques minimize the number of potential
interferences. An experienced SSMS operator is not likely
to misidentify the interference as an element. The existence
of actual interferences and the concentration level where
the interference starts will depend on what other elements are
present in the sample and their concentrations. The actual
sample must be run to determine which elements have inter-
ferences (at what concentration levels), however from
previous experience we know it will be only a small per-
centage of the possible elements. In a recent publication
in American Laboratory, R. Brown [1] reported the simultaneous
determination of from 40 to 60 elements in single samples by
SSMS. The sample types ranged from lung tissue and coal
dust to fly ash.
U. Sample Requirements
The spark source requires conducting or semiconducting
samples for sparking which are stable under the 10"7 to
10~* torr vacuums present in the instrument. Powders can be
mixed with graphite or silver powder and compressed into
electrodes suitable for analysis. Techniques are available to
analyze essentially any form of sample from liquids to insu-
lating solids by SSMS, however it is important to note that
any sample manipulation will result in some degree of contami-
nation of the sample when analyzing at the sub-ppm level for
all possible elements.
The high absolute sensitivity of the spark source
requires good sample homogeneity in order for the small volume
of sample consumed in the analysis to be representative of
the bulk of the sample. Powders used for analysis should be
'v-lOO mesh size and be well mixed in order to meet this homo-
geneity requirement.
C. Sensitivity
Modern spark source instruments can obtain 1 ppb detec-
tion limits with 1 hour of sample sparking at ^2000 resolu-
31
-------
tion (_m.ass) using photographic detection. If the instru-
A mass oi-
ment has electrical detection, 0.1 ppm detection limits are
obtained when scanning the entire mass range in ^10 minutes,
Detection limits at the ppb level are obtained from electrical
detection when using the peak switching mode (1 to 30 sec
integration of each peak), however this mode only allows
examination of a limited number of elements in each sample
(10 to 20 elements). Both modes of electrical detection are
normally operated at a resolution of only 500, making it
incapable of resolving any interference involving a line
having the same nominal mass as the analytical line being
measured.
2. PRECISION OF MEASUREMENTS BY SSMS
The uniformity of the photographic plates used in
SSMS analysis limits the precision of measurements to ^±5
percent, and this level of precision is usually only obtained
in the measurement of the isotopic ratios for an element,
provided the ratio is measured within a single exposure.
When measurements are made involving the absolute intensities
between exposures, (as in most types of analysis) precisions
of ±15 to 20 percent are usually obtained. The scanning mode
of electronic detection gives precisions of ±10 to 30 percent
[2] and in the peak switch mode of electronic detection, pre-
cisions can approach ±1 percent [2] under favorable conditions,
3. ACCURACY OF ANALYSIS BY SSMS
The accuracy of a spark source analysis on the other
hand will usually dependon the availability of a suitable
reference standard with the same composition (same basic
matrix). With a good reference standard the obtainable
accuracies can equal the precision values just mentioned.
The following is a general outline of different approaches
to the standards problem:
A. No Standards Used; Concentrations Estimated
It was mentioned previously that the SSMS detects all
elements with approximately the same sensitivity. The
accepted method of computing results for SSMS analysis when
no standard is available is to assume that all elements have
the same atomic sensitivity as the matrix and equate relative
line intensities to element concentrations. Results calcu-
lated in this manner are usually reported to be within a
factor of 3 to 10 of the correct result. A study at NBS of
12 Standard Reference Materials (all metals or metal alloys)
by SSMS yielded analysis with 75 percent of the computed
impurity concentrations within a factor of 3 and 95 percent
within a factor of 5 of the certified concentrations.
32
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Although this range in accuracy may not be adequate for
the final analysis of a sample, the complete elemental
coverage and the sub-ppm detection limits make it the ideal
survey technique. An analysis of this type will provide the
information necessary to make the decision as to which
elements need to be determined more accurately by other
techniques.
While an analysis without a standard can be in error by
a factor of 3 to 10, it is possible to compare the relative
concentrations of impurity elements in different samples to
within ±20 percent, providing the basic matrix composition
does not change. A significant number of useful SSMS analyses
in the past have involved the detection and correlation of
relative changes in concentration even though these changes
were small compared to the uncertainty in the reported
absolute concentration levels.
B. Analysis Using Standard Reference Materials (SRM's)
Many certified SRM's arc available from NBS and other
sources which can be used as reference standards for SSMS
analysis. As long as the major components of the standard
and the unknown samples are the same, a single standard is
valid for a wide concentration range. (Halliday et al; [3]
showed a linear response for gold through five orders of
magnitude in a titanium matrix.)
Use of a standard, and careful control of all instrument
parameters produce ±15 percent accuracy with the photo-
graphic plate detection; ±6 to 8 percent accuracy has been
obtained under special conditions [4]. Electrical detection
in the scanning mode can yield ±10 to 30 percent accuracy
[2] depending on the number of scans, and peak switching ±4 to
7 percent [2,5], At the lower error levels and low concen-
trations the uncertainties in the certified standard may be
a significant source of error. Unfortunately, most standards
will have only 20 to 30 elements certified, these may cover
only half of the elements detected in a survey analysis and
thus still present a problem.
C. Analysis Using Synthetic Standards
Powdered samples which are normally mixed with graphite
(silver, etc.) powder and pressed into electrodes for analysis,
and other types of samples can be conveniently compared to
synthetic standards prepared in an identical manner. Griffith
et al. [6] used this method for determination of rare earths
in rare earth oxides, and Nicholls et al. [7] used it for
determining elements in geological materials. Accuracies from
±20 to ±5 percent are claimed using photoplate detection. The
accuracy of analysis will depend upon the synthetic standard
33
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having elements chemically combined in the same way as they
are in the sample. Thus, CrCl3 (or K2Cr207) added to a
graphite mix in a known concentration could not serve as a
reference standard for the determination of Cr in a ruby
powder (mixed with graphite) where the Cr is locked inside the
highly refractory A1203 matrix. It could serve quite ade-
quately, however, for determining Cr in water solutions which
were prepared for sparking by evaporation with graphite
powder, mixing, and pressing into electrodes.
D. Analysis Using Stable Isotope Dilution
Isotope dilution analysis with the SSMS can provide an
absolute method of analysis (requiring no standards) to
accuracies of ±5 percent for any element having two or more
stable isotopes. With this technique a known amount of an
enriched separated isotope (spike) of an element is added to
the sample being analyzed; following chemical and physical
equilibrium of the "spike" isotope with the natural isotopes
of the element, the element is separated from the matrix and
the altered isotopic ratio is determined with the SSMS. Only
three measured quantities are required to compute a concen-
tration: (1) the sample weight, (2) the amount of separated
isotope added and (3) the altered isotopic ratio. In most
samples several elements can be determined simultaneously by
SSMS isotope dilution, from a single sample treatment. This
is the only technique used at NBS for the SSMS analysis of
Standard Reference Materials for certification. Elemental
concentrations have ranged down to the low ppb level [8,9,10],
and to sub-ppb levels [11] for systems amenable to precon-
centration.
In all SSMS analysis techniques, other than isotope
dilution, the accuracy of an analysis ultimately depends on the
ability to run both the sample and reference standard under
identical conditions. The sample homogeneity, the gap between
sample electrodes during sparking, their alignment with the
ion optical axis of the instrument, the voltage of the R.F.
spark, plus other operational parameters can affect the abso-
lute intensity of an element line when compared to the total
ion current or the intensity of an internal standard element.
Although these parameters affect the absolute intensity of an
element's lines, they have no measurable effect on the isotope
ratio of an element (photographic detection) measured on a
single exposure. The precision and accuracy of an analysis
by SSMS isotope dilution is therefore limited only by the ±5
percent uniformity of the photographic plate.
34
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4. PROCEDURE FOR ANALYSIS OF MATERIALS
The materials covered by this report can be grouped
according to the treatment required to get the samples into
forms suitable for sparking in the mass spectrometer. The
forms used will, in turn, be controlled by the standardization
method (precision and accuracy) desired.
Group I
Coal, oil, organometallics (organic content)
Group II
Fly ash, ores, minerals, incinerator particles,
slurry streams, feeds to and from flotation
processes, sediments in flotation processes
(all inorganic solids [after evaporation of
water], nonconducting)
Group III
Metals, alloys (conducting samples which can be
run as is, with no treatment other than cutting
to size)
A. Group I Matrice-s
The SSMS has about the same sensitivity for organic
compounds as it does for inorganic elements. The ^2000
resolution normally obtained with photographic detection
will completely resolve equal-intensity hydrocarbon and
element lines having the same nominal mass. In the
presence of a gross excess of hydrocarbons from Group I
samples, however, higher resolution w.ould be required to
maintain separation of the lines. SSMS instruments now
being sold can be adjusted to resolutions of 10,000 and
higher, but at the expense of sensitivity. The 500
resolution of the electronic detection mode is incapable
of resolving hydrocarbons from elements at the same
nominal mass and cannot be used when hydrocarbon lines
are present. Coal is presently being run directly [1,12]
and after dry ashing. Dry ashing not only permits the use
of the higher sensitivity 2000 resolution range, it also
preconcentrates the inorganic material being analyzed from
10 to 100-fold. Dry ashing can lose volatile elements such
as Hg, Te, Cd, As, etc. If analysis of such elements is
desired, a wet ash procedure would be better. Both oils
and organometallics can be handled by wet ashing, possibly
in sealed tubes or bombs.
35
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B. Group II Matrices
The slurry streams, feeds to and from flotation
processes, and sediments in flotation processes require
removal of water by drying. In the dry form all of this
group could be handled the same way. Direct sparking
of these nonconducting materials requires mixing with a
conducting powder such as graphite (silver, etc.). Sample
grinding may be necessary to obtain the ^100 mesh size
required for sample homogeneity. Geological survey
samples could be used as reference standards for some
minerals, ores, and materials from the flotation process
but certainly not for all of them and not for either
fly ash or slurry streams. A synthetic standard mixed
with graphite would certainly give better results than
estimating concentrations, but the fact that the
synthetic standard does not match the physical-chemical
form of the actual samples could cause relatively large
errors. The problem of producing a synthetic standard
identical to a sample could be solved by dissolving all
samples in mineral acids (this also applies to Groups I
and III). Such solutions could then be exactly dupli-
cated with a synthetic mixture.
C. Group III Matrices (metals and alloys)
No special sample treatment is normally required.
Standard Reference Materials are most readily available
for these type samples. If a standard is not available
or if critical elements have not been certified in the
SRM's, the sample can either be dissolved for a compari-
son to a synthetic standard or analyzed by isotope
dilution.
It has been pointed out that to obtain a synthetic
standard that is identical to a sample, the sample
itself may have to be dissolved. Any such sample pro-
cessing will introduce contamination of the samples.
Dissolution of samples (wet ashing) would normally be
done with excess amounts of acids. The problems
actually encountered will depend on what elements are
to be determined and their concentration levels with
respect to the purity and amounts of acids being used
for dissolution. In addition, dissolution dilutes
the sample and hence reduces sensitivity. However, even
if the subsequent processing involves redrying of the
sample, the added acid anions still represent a significant
amount of sample dilution. The added anions are even more
troublesome as a source of molecular interference when
combined with cations. The alkalis and alkaline earths are
particularly inclined to combine with anions to form ionized
molecular species in the spark source.
36
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Samples starting as water solutions or samples
dissolved for purpose of analysis can be handled a
number of ways:
1. They can be frozen in a liquid nitrogen cooled
"cup" and sparked directly using a high purity counter
electrode [13].
2. They can be evaporated to dryness on a high
purity substrate and sparked against a high purity
counter electrode [14],
3. The solution can be slurried with graphite,
evaporated to dryness, mixed, and pressed into
electrodes [1],
4. The solution can be "spiked" and analyzed
by isotope dilution analysis.
System 3 would be most amenable for use with the
"synthetic" reference standard.
5. ANALYSIS BY ISOTOPE DILUTION
Isotope dilution is the most accurate means of
analysis available to the SSMS. However, it does not
have the element coverage that is available in the
direct sparking of a sample. Factors involved in
isotope dilution analysis by SSMS are:
1. It applies only to elements with two or
more isotopes and cannot be used for gases.
2. The requirement of mixing the spike isotope
with the natural element isotopes physically and
chemically (both in oxidation states and in chemical
form) means that all samples must be put into solu-
tion as a minimum treatment.
3. Measurement of an isotope ratio by SSMS
requires about 10"8 to 10"s grams of an element for
consumption in the sparked volume (<10 mg).
4. Item 3 plus problems of interferences in
essence require a preconcentration step for any
isotope dilution analysis of elements below a few
hundred ppm. The preconcentration should include the
removal of water, the major (unanalyzed) cations
and anions. Since only the isotope ratio is measured
for each element, the efficiency of a preconcentration
procedure is not important so long as enough material is
recovered to measure the ratio. General group separation
37
-------
procedures such as electrodeposition, anion or cation
exchange and solvent extraction have been used in our labo-
ratory for preconcentration. Generally the last step has
been electrodeposition onto pure gold wires for sparking.
Preconcentration of water and acids [11] is obtained simply
by evaporation onto the gold wires used for sparking.
5. Analysis by isotope dilution requires that
the measured altered ratio be significantly different
from both the natural and "spike" isotopic ratios.
A photpplate will give the best accuracy if the final
ratio is ^1 (2 if the natural ratio is 1).
6. Item 5 plus the limited dynamic range of
intensity covered by a single exposure on a photoplate
restricts the concentration range covered by a
single spiking to a factor of ^10 up or down from
the optimum ratio.
7. Our laboratory has not attempted isotope
dilution analysis on SRM's above several hundred ppm
since other techniques are normally available at NBS
which can give better accuracy than the SSMS at these
high concentrations. For elements attempted below
this concentration, a single group separation technique
has enabled successful isotope dilution analysis of
approximately half of the elements present in the
sample. Six to eight elements are usually determined
simultaneously in each sample.
There is a specific application of environmental
interest where isotope dilution by SSMS can be both
very effective and relatively inexpensive to use. It
is the analysis problem of testing a material to see
whether it meets certain legal concentration specifi-
cations for trace elements (e.g., pollution standards!!).
In thissituation,the sample would be spiked with
the exact amount of spike isotope that gives an altered
isotope ratio of 1 at the critical specified concen-
tration. A visual inspection of isotope ratios on the
SSMS photoplate would rapidly identify any element that
is present in an amount grossly above or below the
specification levels. Only those elements whose con-
centrations are close to meeting or failing specifica-
tions would have to be measured with a densitometer.
The analysis would give its most reliable results exactly
at the critical, specified concentrations. If this
technique were applied to the analysis of water supplies,
evaporation-preconcentration techniques could give
detection limits as low as 0.01 to 0.1 parts per billion
on ^50 ml of water [11].
38
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6. ELEMENT COVERAGE OF SSMS ANALYSIS
All analyses by SSMS will involve the determination
of many elements simultaneously from each sample. Since
the only "blind" spots in SSMS analysis are generated
by the constituents of the sample itself, the sample
must be analyzed before it is known which elements
cannot be determined. The total number of interferences
will be always less than ^30 percent of all the elements.
Table 1 is taken from a recent publication by Brown
et al. [1]. He was able to detect over 60 elements
in both fly ash and coal samples by SSMS. Table 1 lists
all 27 of the desired elements detected in fly ash
and 26 of the 27 desired elements found in coal. Overall,
for group I, II, and III samples, we can estimate that
at least 20 elements of the 27 listed tor this report
could be determined for each sample; however, the specific
elements would not be known until the samples were run.Tn
general, the low mass elements are the ones having most
interferences.
Isotope dilution would have the lowest element
coverage of any SSMS technique. The NBS laboratory has
determined in various sample matrices, 16 of the 27
elements listed. (Hg, Cd, Ni, Sb, Cr, Zn, Cu, Pb, Se,
Ag, Sn, Fe, Sr, K, Ca and Nig.) U and Th should also be
readily determinable. Experience with NBS SRM samples
indicates that about 10 to 12 of the elements can be
separated as a group with a single separation procedure
and be determined simultaneously by SSMS isotope dilu-~
tion.One-gram samples would give analyses down to
'v/O.l ppm with accuracies of ±5 to 10 percent at 1 ppm
and higher.
7. COST (TIME) OF ANALYSIS BY SSMS
It is assumed that the number of similar samples
to be analyzed will be large enough so that the initial
set up times can be ignored. These estimates are based
on experiences of a one-man laboratory; larger
laboratories should be more efficient. Only two
examples will be given which represent extremes for
cost, coverage and accuracy; (a) an all inclusive
survey analysis with estimations of concentrations
(factor of 3 to 10) and (b) isotope dilution analysis
of a limited number of multi-isotope elements.
1. Survey analysis for all possible elements, no
reference standard used, visual interpretation of
photographic plate (no densitometry), all samples
except possibly oil and organo-metallics.
39
-------
a. Sample preparation ^1 hour or less.
b. SSMS instrument and photoplate development
^1 hour.
c. Photoplate interpretation ^1 hour.
TOTAL Two to four samples tested for ^60 elements
per man day - results ±5 to 10 fold.
2. Isotope dilution analysis. Accurately spiked
sample, densitometry of photographic plate, computer
calculations of results for all samples.
a. Sample dissolution, spiking, preconcen-
tration ^1/2 day.
b. SSMS instrument time and plate development
^1 hour.
c. Densitometry of plate and computation of
results ^-3 hours.
TOTAL One sample for 8 to 12 elements per man day -
results to ±5 to 10 percent accuracy.
8. CONCLUSION
There are two types of applications where the SSMS
can be clearly superior to any other single analytical
method.
1. To survey a completely "unknown" sample for
all possible trace elements to concentrations well below
1 ppm. A direct sparking without standards (x3 to xlO
accuracy) would give an analysis adequate for making
decisions as to which elements were at high enough
concentrations to require an accurate analysis. This
SSMS survey analysis would also contain enough informa-
tion to permit decisions to be made as to which
analytical techniques should be used for each element,
based on the concentration levels sought and possible
interferences from other elements.
2. Use of SSMS isotope dilution to test environ-
mental samples for compliance to preset standards of
acceptable concentration levels for toxic elements
(many elements simultaneously).
Such samples can be spiked so that each element being
tested gives an altered isotope ratio of 1 (or 2 for some
elements) at its critical level. In this case rapid visual
40
-------
plate interpretation would identify all elements which
grossly pass or fail. Only elements near the critical con-
centrations would require the more precise densitometry data,
and these results would be most reliable at the specified
concentration. Easily preconcentrated samples, such as
drinking water supplies, could have detection limits as low
as 0.1 to 0.01 parts per billion from SO ml samples.
41
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Table 1. Simultaneous Determination of Twenty-seven Elements
by Spark-Source Mass Spectrometry in Typical Coal
and Fly Ash Samples(a)
Matrix
Element
Hg
fie
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
P
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
CoalU)
(ppm)
0.08
1.2
0.19
0.30
12
30
2.7
0.14
~ 4.5
10
25
3.9
0.32
42
5.7
0.22
0.83
1600
100
5000
410
4000
Major
4500
1.9
4.5
Fly Ash(l)
(ppm)
<0.01
8.0
0.70
22
50
400
50
4.5
110
260
200
60
0.30
230
150
42
0.50
60
Major
2000
Major
7000
Major
Major
Major
30
40
(a)
In addition to the above elements of interest, reference
(1) lists values for 34-38 additional elements.
42
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Table 2. Subject Index to References
I. Precision and/or Accuracy of SSMS Analysis
1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 16, 17, 18, 23, 25, 26,
28, 32, 33, 34, 35, 36, 37, 38, 40, 41, 43, 51
II. Survey Analysis, Concentrations Estimated to Factor 3 to 10
1, 3, 12, 14, 18, 20, 21, 22, 23, 24, 25, 27, 29, 31, 39,
42, 45, 46, 49, 50, 53
III. Analysis Using Synthetic Reference Standard
6, 7, 17, 25, 26, 28, 32, 35, 36, 37, 38, 41, 48
IV. Analysis Using Certified Standard Reference Materials
2, 3, 4, 7, 8, 9, 10, 16, 18, 26, 32, 33, 34, 37, 40, 46,
47, 51, 52
V. Analysis Using Isotope Dilution SSMS
8, 9, 10, 11, 19, 43, 44
VI. Analysis of Solutions or Samples Dissolved for Analysis
1, 8, 9, 10, 11, 13, 14, 17, 19, 20, 21, 25, 27, 28, 30,
37, 38, 39, 42, 43, 44, 45, 49
VII. Group I Samples - Coal, Oil, Organometallies and'High
Organic Content Samples
1, 12, 17, 20, 22, 23, 24, 26, 28, 41, 43, 45, 53
VIII. Group II Samples - Fly Ash, Ores. Minerals, Slurry
Streams, etc.
1, 7, 16, 17, 20, 22, 24, 32, 33, 34, 35, 36, 37, 40, 46,
47, 48, 50
IX. Group III Samples - Metals and Alloys
1, 2, 3, 4, 5, 6, 8, 9, 10, 18, 19, 26, 27, 31, 36, 37,
42, 52
X. Analysis Using Electronic Detection
1, 2, 5, 20, 22, 30, 31, 36, 37, 45, 49, 51, 52
43
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References
[1] Brown, R., Jacobs, M. L., and Taylor, H. E., A Survey of
the Most Recent Applications of Spark Source Mass
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[2] Bingham, R. A. and Elliott, R. M., Accuracy of Analysis
by Electrical Detection in Spark Source Mass Spectrometry,
Anal. Chem., 4J5, 43 (1971).
[3] Halliday, J. S., Swift, P., Wolstenholme, W. A.,
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[4] Franzen, J. and Schuy, K. D., The Effect of Electrode
Shape on Analytical Precision in Spark Source Mass
Spectrometry, Int. Mass Spectrometry Conference, Berlin,
25-29 September 1967.
[5] Evans, C. A., Jr., Guidoboni, R. J., and Leipziger, F. D.,
Routine Analysis of Metals Using a Spark Source Mass
Spectrograph with Electrical Detection, Appl. Spec., 24,
85 (1970).
[6] Griffith, D. A., Conzemius, R. J., and Svec, H. J.,
Determination of Rare Earths in Selected Rare Earth
Matrices by Spark Source Mass Spectrometry, Talanta,
1£, 665 (1971).
[7] Nicholls, G. D., Graham, A. L., Williams, E., and
Wood, M., Precision and Accuracy in Trace Element
Analysis of Geological Materials Using Solid Source
Spark Mass Spectrography, Anal. Chem., 39, 584 (1967).
[8] Paulsen, P. J., Alvarez, R., and Kelleher, D. E.,
Determination of Trace Elements in Zinc by Isotope
Dilution Spark Source Mass Spectrometry, Spectrochimica
Acta, 24B, 535 (1969).
[9] Alvarez, R., Paulsen, P. J., and Kelleher, D. E.,
Simultaneous Determination of Trace Elements in Platinum
by Isotope Dilution and Spark Source Mass Spectrometry,
Anal. Chem., 41_, 955 (1969).
[10] Paulsen, P. J., Alvarez, R., and Mueller, C. W., Spark
Source Mass Spectrographic Analysis of Ingot Iron for
Silver, Copper, Molybdenum, and Nickel by Isotope Dilution
and for Cobalt by an Internal Standard Technique., Anal.
Chem., ££, 673 (1970).
44
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[11] Kuehner, E. C., Alvarez, R., Paulsen, P. J., and Murphy,
T. J., Production and Analysis of Special High-Purity
Acids Purified by Sub-Boiling Distillation, Anal. Chem.,
44_, 2050 (1972).
[12] Kessler, T., Sharkey, A. G., Jr., and Friedel, R. A.,
Spark-Source Mass Spectrometer Inyestigation of Coal
Particles and Coal Ash, 19th Annual Conf. on Mass
Spectrometry and Allied Topics, May 2-7, 1971, Atlanta,
Georgia.
[13] Owens, E. B., Analysis of Frozen Aqueous Solutions by
Spark Source Mass Spectroscopy, Anal. Letters, 3, 223
(1970).
[14] Ahearn, A. J., Mass Spectrographic Detection of Impurities
in Liquids, J. Appl. Phys., 3£, 1197 (1961).
[15] Blosser, E. R. and Thompson, R. J., Elemental Analysis of
Air Particulates Using Spark Source Mass Spectrography,
19th Annual Conf. on Mass Spectrometry and Allied Topics,
May 2-7, 1971, Atlanta, Georgia.
[16] Roaldset, E., Relative Sensitivity of Rare Earth Elements
In Spark-Source Mass Spectrometry, Talanta, 17, 593,
(1970).
[17] Tong, S. C., Gutenmann, W. II., St. John, L. E., Jr., and
Lisk, D. J., Determination of Fluorine and Bromine in
Halogenated Herbicide Residues in Soil by Spark Source
Mass Spectrometry, Anal. Chem., 44, 1069 (1972).
[18] Franklin, J. C., Time-Resolved Spark-Source Mass
Spectrometry; The Effect of Spark Duration on Relative
Sensitivity Factors, Ion Intensity, and Precision of
Analysis, Union Carbide Corporation, Nuclear Division,
Y-1757, Oak Ridge, Y-12 Plant, Contract W-7405.
[19] Leipziger, F. D., Isotope Dilution Analyses by Spark
Source Mass Spectrography, Anal. Chem., 37, 171 (1965).
[20] Brown, R., The Quantitative Analysis of Inorganic
Pollutants in Air and Water Using Spark Source Mass
Spectrometry, presented at ISIMEP, Ottawa, June 1971,
AEI Scientific Apparatus, Publ. TP 36.
[21] Chupakhin, M. S., Kazakov, I. A., and Kryuchkova, 0. I.,
Determination of Impurities in Liquids on a Spark Ion
Source Mass-Spectrometer Communication 1. Analytical
Technique and the Mechanism of Ion Formation, Z. Anal.
Khimii, 24, 3 (1969).
45
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[22] Brown, R. and Vossen, P. G. T.f Spark Source Mass
Spectrometric Survey Analysis of Air Pollution Particles,
Anal. Chem., £2, 1820 (1970).
[23] Jones, R. M., Kuhn, W. F.t and Varsel, C., Spark Source
Mass Spectrographic Analysis of Tobacco Ash, Anal.
Chem., 40, 10 (1968).
[24] Harrison, W. W., Clemena, G. G., and Magee, C. W.,
Forensic Applications of Spark Source Mass Spectrometry,
J. of the AOAC, 5£, 929 (1971).
[25] Yurachek, J. P., Clemena, G. G., and Harrison, W. W.,
Analysis of Human Hair by Spark Source Mass Spectrometry,
Anal. Chem., 41_f 1666 (1969).
[26] Harrison, W. W. and Clemena, G. G., Factors Affecting the
Use of External Standards for Spark Source Mass
Spectrometry, Anal. Chem., 44, 940 (1972).
[27] Cherrier, C. and Nalbantoglu, M., Determination of Trace
Impurities in Mercury and Some High Purity Acids by
Spark Source Mass Spectrometry, Anal. Chem., 39, 1640
(1967).
[28] Tong, S. S. C., Gutenmann, W. H., and Lisk, D. J.,
Determination of Mercury in Apples by Spark Source Mass
Spectrometry, Anal. Chem., 4_1, 1872 (1969).
[29] Clegg, J. B., Millet, E. J., and Roberts, J. A., Direct
Analysis of Thin Layers by Spark Source Mass Spectrography,
Anal. Chem., 4_2, 713 (1970).
[30] Brown, R., Powers, P., and Wolstenholme, W. A.,
Computerized Recording and Interpretation of Spark Source
Mass Spectra, Anal. Chem., 43, 1079 (1971).
[31] Socha, A. J., Analysis of Thin Films Utilizing Mass
Spectrometric Techniques, Vac, Sci. Tech., 7_, 310 (1970).
[32] Taylor, S. R., Geochemical Application of Spark Source
Mass Spectrography-II. Photoplate Data Processing,
Geochim. Cosmochim. Acta, 35, 1187 (1971).
[33] Morrison, G. H. and Rothenberg, A. M., Homogenization of
Nonconducting Samples for Spark Source Mass Spectrometric
Analysis, Anal. Chem., 44, 515 (1972).
[34] T.iylor, S. R., Muir, P., and Kaye, M., Trace Element
Chemistry of Apollo 16 Lunar Soil from Fra Mauro, Geochim.
Cosmochim. Acta, 35, 975 (1971).
46
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[35] Taylor, S. R., Geochemical Analysis by Spark Source Mass
Spectrography, Geochim. Cosmochim. Acta, 29, 1243 (1965).
[36] Conzemius, R. J. and Svec, H. J., An Electrical Detection
System for a Spark-Source Mass Spectrograph, Talanta,
1£, 365 (1969).
[37] Morrison, G. H. and Colby, B. N., Precision of Electrical
Detection Measurements of Powdered Samples in Spark Source
Mass Spectrometry, Anal. Chem., 44, 1206 (1972).
[38] Kai, J. and Watanabe, M., Mass Spectrographic Determination
of Impurities in Liquids, Mass Spectroscopy, 16, 241 (1968)
[39] Chastagner, P. and Tiffany, B., Analysis of Curium and
Californium by Single-Exposure Spark Source Mass
Spectrometry, Int. J. Mass Spectrom. Ion Phys., 9, 325
(1972).
[40] Morrison, G. H. and Kashuba, A. T., Multielement Analysis
of Basaltic Rock Using Spark Source Mass Spectrometry,
Anal. Chem., 4^, 1842 (1969).
[41] Evans, C. A., Jr. and Morrison, G. H., Trace Element
Survey Analysis of Biological Materials by Spark Source
Mass Spectrometry, Anal. Chem., 40, 869 (1968).
[42] Chastagner, P., Analysis of Microsamples by Single-
Exposure Spark Source Mass Spectrometry, Anal. Chem.,
4_1, 796 (1969).
[43] Carter, J. A. and Sites, J. R., Determining PPB Mercury
Concentrations Using a Spark-Source Mass Spectrometer
Sample Changer, Anal. Letters, 4_, 351 (1971).
[44] Taylor, J. K., Alvarez, R., Paulsen, P. J., Paulson,
R. A., Rains, T. C., and Rook, H. L. Interaction of
Nitrilotriacctic Acid with Suspended and Bottom Material,
Water Pollution Control Research Series, 16020 GFR
07/71, U.S. Environmental Protection Agency.
[45] Taylor, C. E., McGuire, J. M., and McDaniel, W. H.,
Computerized Interpretation of Spark Source Mass Spectra
for Water Analysis, 20th Annual Conf. on Mass Spectrometry
and Allied Topics, June 4-9, 1972, Dallas, Texas.
[46] Ikeda, Y., Umayahara, A., Kubota, E., Aloyama, T., and
Watanabe, E., Trace Element Analysis of Glass by High
Resolution Spark Source Mass Spectrometry, 20th Annual
Conf. on Mass Spectrometry and Allied Topics, June 4-9,
1972, Dallas, Texas.
47
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[47] Morrison, G. II., Kashuba, A. T., and Rothenberg, A. M.,
Elemental Abundances in Lunar Materials by Spark Source
Mass Spectroscopy, 18th Annual Conf. on Mass Spectrometry
and Allied Topics, June 14-19, 1970, San Francisco, Calif,
[48] Socha, A. J., Updegrove, W. S., and Oro, J., Mass
Spectrograph Analysis of Lunar Materials by Probe
Technique, 18th Annual Conf. on Mass Spectrometry and
Allied Topics, June 14-19, 1970, San Francisco, Calif.
[49] Bingham, R. A., Brown,, R., and Powers, P., On Line
Analysis with a Spark Source Mass Spectrometer, 18th
Annual Conf. on Mass Spectrometry and Allied Topics,
June 14-19, 1970, San Francisco, Calif.
[50] Hunt, M. H., The Analysis of Non-Conduct ing Solids by
Spark Source Mass Spectrography, 18th Annual Conf. on
Mass Spectrometry and Allied Topics, June 14-19, 1970,
San Francisco, Calif.
[51] Leipziger, F. D., Photographic vs. Electrical Detection
for Spark Source Instruments, 18th Annual Conf. on Mass
Spectrometry and Allied Topics, June 14-19, 1970,
San Francisco, Calif.
[52] Socha, A. J., Baker, C. W., and Masumoto, E. M., An
Electronic Detection System Utilizing Integration
Techniques for a Spark Source Mass Spectrometer, 17th
Annual Conf. on Mass Spectrometry and Allied Topics,
May 18-23, 1969, Dallas, Texas.
[53] Sasaki, N. and Watanabe, E., The Application of Spark
Source Mass Spectrometry to the Trace Element Analysis
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St. Louis, Missouri.
48
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CHAPTER 4
X-RAY FLUORESCENCE AND F.LECTRON MICROPRO!!!: METHODS
Stanley D. Rasberry and Kurt I-. J. lleinrich
1. X-RAY I:LUORHSCliNCI:
X-ray fluorescence analysis is noted for its applica-
bility to a diversity of sample types and it has gained
extensive industrial use for monitoring the composition of
both raw materials and finished products. An introduction
to the technique and descriptions of many applications are
given in several books (references 1-6). The elements
above atomic number 11 can be routinely determined in ores,
minerals, fuels, bulk particulatcs, liquids, slurries,
filtrates, powders, metals and other sample types. The
applications of x-ray fluorescence analysis are being des-
cribed in about 500 published papers per year. References 7-
100 and 123-126, appended to this chapter, have been selected
to represent recent applications.
The name x-ray fluorescence analysis is used to cate-
gorize several analytical techniques which have the same
physical basis; inner-shell excitation of atoms induced via
energy transfer from an incident flux of x-rays and the sub-
sequent decay from excited state coupled with electron-atom
recombination. The energy transfer, in both excitation and
emission (decay) is dependent upon the atomic number (ele-
ment) of the atom involved in the interaction. That is, an
emitted fluorescent x-ray is characteristic in energy of the
atom from which it is emitted. This gives the analyst a
useful means of qualitatively identifying which elements are
present in a specimen. As we shall see later, accurate quan-
titation depends in part on measuring the rate (intensity)
at which x-rays of a given energy are emitted.
The apparatus necessary for x-ray fluorescence analysis
includes a source of x-rays for excitation and a means of
determining the rate of x-rays emitted from the specimen at
discrete energies (the analyzer, detector and counting
electronics). A variety of choices exists for each module
of the instrument.
The excitation source may be an x-ray tube arranged to
excite the specimen directly or through a filter so selected
as to alter the excitation spectrum to more useful wave-
lengths. Another possible choice for excitation is the use
of radioisotopes; here too, filters can be used. Outside the
precise definition of fluorescent spectroscppy, excitation
can also be effected by bombarding the specimen with electrons
(10-100 keV), protons (1-200 MeV), or a variety of ions.
49
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At the next stage in the apparatus, precise specimen
positioning is required, and the excitation x-rays must be
apertured so as to fall only on the specimen. The main
options at this point consist of automated specimen chang-
ing or equipment for direct examination of continually flow-
ing liquid, slurry or powder streams.
Various arrangements of collimation may be used either
to aid reduction of background or improve energy resolution
characteristics.
Separating the emitted x-rays into a spectrum of re-
solved energies is usually accomplished by one of three
different means: diffraction, balanced filters, or "energy
dispersive" analyzer. Diffraction of the x-ray beam by a
crystal can be used to disperse the energies as an inverse
function of beam-to-crystal angle. The dispersion character-
istics are also a function of the lattice spacing of the
crystal; but, this aspect is held constant with a given
crystal selection. In the use of balanced filters, the
filters are selected so that they transmit equal intensities
at all energies except those between their absorption edges,
and so that the energy of interest falls within this "band
pass".
In both the diffractive and balanced filter modes, an
x-ray detector must be employed to measure the presence and
intensity of x-rays at a given energy. Scintillation detec-
tors, gas-filled proportional detectors and gas-flow propor-
tional detectors are used in different ranges of energies
and count rates.
In the "energy dispersive" mode no physical separation
of energies is used prior to the detector. Instead, energy
separation is accomplished on the basis of pulse height
analysis of the output signal of the detector. This is
practicable because each x-ray energy produces an electronic
pulse which is proportional in energy and thus susceptible
to analysis. The detectors usually used in this mode are
the Si(Li) solid state detectors because of their good
energy resolution characteristics.
Each of the three means of energy analysis described
has a large number of possible variations. This, together
with the wide variety of excitation and detection possibi-
lities, causes the number of permutations of instrument con-
figurations to be large. One of the most generally effective
arrangements for quantitative elemental analysis is shown
in figure 1. This is the arrangement which has been used in
most of the applications referred to in the bibliography.
We have used it at NBS in the analysis of many different
types of specimens. As an example, in figure 2 we show
50
-------
Figure 1. X-ray fluorescence analyzer. Flat crystal
spectrometer geometry: (A) x-ray tube,
(B) specimen, (C) collimator, (D) dispersing
crystal, (E) detector, frequently preceded by
a collimator (from reference 2).
II -I- 71 LIQUID MINT
e
i
0.01%
0.09% Hf
03% M|
101. Pk
ZMto
10
A
26
14
«a eo 10 «
DIFFRACTION ANOLC (II)
42
00
Figure 2. X-ray fluorescence spectra of liquid paints
having two different levels of toxic metal
content; obtained using a tungsten target
tube operated at 50 kV, 50 mA, and LiF
crystal and a scintillation detector.
51
-------
the x-ray spectra of two samples of liquid paint. The spec-
trum on the right is for a paint with presence of antimony,
cadmium, strontium, arsenic and mercury six-fold greater than
in the paint represented on the left. At energies (x-ray
lines) characteristic of these five elements, there is a
nearly proportional increase in intensity -- demonstrating
the feasibility of quantitative, as well as qualitative,
analysis.
Quantitative determination of elements which do not vary
over wide ranges of concentration (more than a few percent,
by weight) in specimens of nearly constant composition is
accomplished by use of standard reference materials or other
known "type standards". It is important for the standards
to be nearly the same in composition as the unknowns because
of interelement effects which will be mentioned later. An
example is given in figure 3 of a calibration curve pre-
pared, at NBS, for the determination of lead in dry paint
powder. The dry paint powder has been mixed with a common
matrix to dilute the effects of differences in the remainder
of the compositions.
woo
too
S.OO
g«00
200
a-a-n
ICAO KTCftMINATlON M
WV MINT MMMJUTlON
T HUICI Of FOUR
1 HIMUMtNTt
1194
LCM> AOOCO (WEIGHT %J
Figure 3. Calibration curve for determination of lead in
dry paint powder, following preparation by
dilution with a common matrix (ZnO); obtained
using the same conditions as given in figure 2.
52
-------
Usually, x-ray fluorescence analysis can be performed
directly on a sample with little or no preliminary treat-
ment; this results in low labor costs. For some types of
samples, notably slurries, on-stream analysis is done for
control purposes using automated equipment. The detection
limit for direct analysis is usually 50-1000 ppm depending
on the matrix and weight of sample available. For the more
sensitive elements, or by using special preconcentration
techniques, lower detection limits are achievable. Normally,
one or two grams of material are used when this quantity is
available. However, specimens as small as a few milligrams
may be analyzed, possibly with reduced sensitivity, by
using special methods. In industrial examples, the preci-
sion and accuracy available have permitted the economical
analysis of such materials as steel, aluminum, glass and
portland cement powder on an essentially real-time basis.
The accuracy required in industry is typically ±1/2 percent
to ±1 percent for the major elements, ±2 percent for the
minor elements, and ±10 percent for the trace constituents.
X-ray fluorescence equipment is available for simulta-
neous determination of as many as ten or more elements, in
the same sample, in a two-minute measurement period.
Virtually every phase of the technique is susceptible to
automation, from specimen preparation and insertion into
the instrument through all measurement aspects, data
collection, computation, interpretation and display.
Especially when large volumes of analyses are done, auto-
mation is economically attractive owing to substantially
decreasing labor costs. The instrument operators may be
high school, vocational school or junior college-trained
technicians; however, the supervision of the effort should
be in the hands of a graduate chemist, chemical engineer
or equivalent.
Interferences of two different types can occur in x-ray
fluorescence. In the first (line interferences), an x-ray
line of the analyte may be so near a line produced by another
element that the two are not resolved by the spectrometer.
Usually, this problem can be solved by selecting another x-
ray line of the analyte to measure. The second kind of
interference (matrix interelement effects) is caused when
large differences in composition exist among the various
standards and unknowns. The intensity of the x-ray line of
the analyte is influenced not only by the analyte concentra-
tion, but also by the composition of the matrix (other
elements). Correction procedures, either through chemical
preparation or mathematical data manipulation are available
to resolve this type of interference. Standard Reference
Materials play a key role in the accurate calibration of x-
ray fluorescence analysis.
53
-------
Application to Matrices of Environmental Interest
]. Fly Ash and Incinerator Particulates. (references
7-19) Methods for the x-ray fluorescence analysis of fly
ash and incinerator particulatcs were not actively researched
until about five years ago. Since that time, extensive work
has been done on the subject. As can be seen in the appended
summary sheet, x-ray fluorescence methods are applicable
for the determination of 24 of the 28 elements of principal
interest. In routine direct analysis, the cost of deter-
mining one element should not exceed $1.00. Lower concen-
trations can be obtained by chemical pretreatment of the
sample, with an attendant increase in cost (see references
18 and 19). The need for Standard Reference Materials seems
to be especially pressing for fly ash and incinerator par-
ticulate matrices.
2. Coal. (references 20-23) L. T. Kiss (21) has
made one of the best and most thorough studies of x-ray
fluorescence analysis of coal presently available. Using a
procedure of drying, fine-grinding and briquetting ten-gram
samples of coal, x-ray measurement, and a special interele-
ment correction procedure, Kiss was able to accurately deter-
mine from 0.02 percent to 3.90 percent of iron, titanium,
calcium, potassium, chlorine, sulfur, silicon and aluminum
in coal. Both synthetically prepared and chemically
analyzed standards are used in calibration.
3. Oil. (references 24-37) X-ray fluorescence
analysis of oils and gasolines is one of the oldest routine
applications of the method -- dating back to the 1940's.
Outstanding work has been done in this area by Birks, Brooks,
Friedman and Roe (34), Dwiggins and Dunning (27-28), Hale
and King (26) and Gunn (24-25). All elements above sodium
can be determined in oil by x-ray fluorescence methods.
Particular attention has been given to lead, bromine,
molybdenum, nickel, iron, manganese, titanium, vanadium, zinc,
calcium, and barium. Hale and King (26) report direct
determination of nickel at the 0.1 ppm level, and Bergmann,
Ehrhardt, Granatelli and Janik (30) report sub-ppm deter-
minations using ion exchange preconcentration. The method
is finding increased use (including work at NBS) in monitor-
ing wear metals in engine and gearcase oils.
4- Ores, Minerals and Cement. (references 38-54)
X-ray fluorescence analysis has Found wide industrial accep-
tance in these areas over the past twenty years. This is
especially true in the cement industry, where tc-ns of
thousands of determinations are performed each day using
x-ray fluorescence spectrometers, many of which are highly
automated. The work of Rose and Brown (38), Rose, Adler and
54
-------
Flanagan (44) and Campbell and Thatcher (52) is especially
important to the mining industry. Bean (48-49) and
Andermann (50) are widely cited among investigators of x-ray
fluorescence methods for the analysis of cement. When
matrix variations are large, physically corrective techniques,
such as dilution or mathematical treatment to correct the
results are usually required. The need for standards is
especially large in this area, and many have been produced by
NBS, the most recent being seven new SRM's for portland
cement to replace and supplement five others which were
issued ten years ago.
5. Metals and Alloys. (references 55-79) Similar to
the case of ores, minerals and cement, this area has been
widely developed and used in industry over the past twenty
years -- with significant improvement and further extension
of application over the last five to ten years. The
literature dealing with the analysis of metals and alloys
by x-ray fluorescence is large (approximately 10,000 papers).
The references given here are representative, but hardly do
more than scratch the surface. The usual range for direct,
accurate analysis is 0.01 percent to 95.0 percent for the
elements above sodium in atomic weight. Research and
development is active in this area, especially concentrating
in: lower detection limits, more complete automation, more
accurate standardization, and improved mathematical treat-
ment. Several hundred Standard Reference Materials for
metals and alloys have been issued by NBS. Alloy reference
standards are also sold by U. S. Steel, Carpenter Technology,
Brammer Standards, Alcoa and others.
6. Organometallics. (references 80-82, also see papers
in section; Oil)The analysis of metallo-organic compounds
is not a common subject in the x-ray fluorescence literature.
However, metallo-organic compounds are used as additives in
the preparation of synthetic oil standards. The literature
pertinent to the x-ray fluorescence analysis of oil is
described in the appropriate section. NBS has issued 24
metallo-organic compounds primarily to be used for the
calibration of spectrochemical equipment used in the deter-
mination of wear metals in lubricating oil.
7. Slurry Streams, and Feeds and Sediments in Flotation
Processes"(references 83-94)Smallbone (85 and 87) and
Smallbone and Davidson (84 and 86) have been leaders in the
design and construction of the special sample handling
apparatus needed for "on-line" x-ray fluorescence applications.
Calibration for these techniques is made difficult by the
variability of water content in the moving material; correc-
tions are required. Sampling is also un important aspect
of the problem. Standardization is difficult, because to
simulate the material under analysis requires flowing a
55
-------
large volume of standard through the on-line sample handling
apparatus. These problems cause undesirable losses in
accuracy; further R and D appears to be needed in this area.
8. Slags and Glass. (references 95-100) An increasing
amount of quality control analysis in the glass industry is
done by x-ray fluorescence analysis. It is also a popular
method for evaluating slags. Glasses are analyzed directly
on solid material, with calibration by standards. NBS is
supplying two Standard Reference Materials of solid glass
and the ASTM is assisting in establishing several more on
an inter-company basis. Until now, most companies have
had only standards made in their own plants. The x-ray
method is in a good state of development relative to glass
analysis. Slags are usually treated with preparation tech-
niques similar to those used for ores: crushing and
briquetting, diluting and briquetting or diluting and fusion.
The preparation of standards must follow the same process.
2. ELECTRON PROBE MICROANALYSIS
l.lectron probe microanalysis has been available, with
commei'cially produced instruments, for about 15 years.
During that time many industrial applications have been
described in the literature. A survey of these is given in
references 101-122.
Electron probe microanalysis is the sum of procedures
using a focused electron beam (of energy between 1 and 50 keV)
to obtain, from the zone of beam impact upon a specimen,
information concerning -its properties. This is achieved in
an instrument similar in some aspects to the electron
microscope. Electrons emitted from a heated tungsten wire
are focused into a beam of a diameter of less than 0.5 vim.
This beam is directed toward the specimen. The interaction
of the specimen with the impinging electron beam results in
the emission of x-ray lines from the microscopic region of
the specimen which has been excited by the electrons. The
characteristic x-ray spectra emitted by the specimen reveal
its elemental composition.
The emitted x-ray lines can be observed, and their
intensities measured, by means of curved-crystal
spectrometers. The instrument at NBS has three such
spectrometers, so that three elements can be measured simul-
taneously. The wavelength range is from 1 to 100 A; this
permits the observation and analysis of all elements of
atomic number above 5, and with high sensitivity for the
elements of atomic number above 10. Another device installed
in the NBS electron probe is the energy dispersive solid
state detector. This device permits the simultaneous
detection of all elements of atomic number above 11, and
56
-------
thus provides for a rapid means for qualitative and semiquan-
titative analysis, which is particularly useful in the
analysis of small particles.
i
Other phenomena (emission of backscattered and
secondary electrons, cathodoluminescence, etc.) also produce
useful information. The analyzed region on the specimen
which is excited by the electron beam is usually about
2x2x2 un. Since Cosslett and Duncumb (128) introduced
the scanning beam technique in electron probe microanalysis,
the instrument has become a microscope as well as a
spectrometer. The interactions between scanning electron
microscopy and x-ray spectrometry account for the great
versatility of this instrument. It has found wide industrial
application both for the analysis of free-standing micro-
particulates and for microscopic features on the surfaces
of bulk materials.
The forte of the electron probe is microanalysis (.small
size) as opposed to trace analysis (low concentration);
however, detection limits between 100 and 1000 ppm are
available for most elements. Accuracies of ± 5 percent, or
better, are routinely available and careful, quantitative
work can produce accuracies of ±2 percent. The precision of
measurement, for elements above 1 percent in concentration,
is generally ±1 percent or better.
Sample preparation depends on the nature of the specimen.
If the specimen is larger than one inch in diameter, a sample
must be cut so that it will be small enough (one-inch
diameter) to load in the instrument. Discrete micro-parti-
culates can be isolated, mounted and restrained. Quantitative
analysis of metals requires a flat polish, equivalent to that
obtained with 1/4-um diamond polishing compound. Non-
conductive specimens are given a sub-un coating of a con-
ductor (usually carbon) in a vacuum evaporator so that static
charging will not occur when the samples are subjected to
the electron beam. In some cases, especially for qualitative
work, no sample preparation is required.
The cost for purchase of an electron probe microanalyzer,
auxiliary equipment and sample preparation facilities is
about $150K to $200K. Operational cost for an electron
probe laboratory, including labor costs, may be expected to
range between $250 and $500 per day. A single element
determination on a single point on a sample requires about
one-half hour; economies may result when several elements
are determined at several points on the same sample. As
with x-ray fluorescence, the instrument operators may be non-
degree technicians, but supervision should be in the hands
of a graduate chemist, or equivalent.
57
-------
The conditions for electron probe microanalysis and the
results to be expected are quite similar for all sample
types which can be analyzed, therefore, a single guideline
for application is appended. Usually the electron probe
analysis is considered applicable to particulates isolated
from fly ash or from incinerators; or even, particulates
from slurry streams or in sediments from-flotation processes.
In addition, it is applicable to analyses in coal, ores,
minerals, cement, metals, alloys, slags and glasses. To
the best of our knowledge it has not been applied to analysis
of oil or organometallics. It would be feasible, however,
to perform such analyses on solid particulate wear residues
in lubricating oils.
3. ION PROBE MICROANALYZJ-R
The usefulness of the electron probe microanalyzer
in the determination of trace levels is limited by the back-
ground which is inherent to primary x-ray spectra. This
background is principally produced by the continuous
(bremsstrahlung) spectrum. As to the elements which can be
investigated, the electron probe is inefficient or use-
less for the investigation of elements of atomic number
below ten.
The ion probe microanalyzer offers a promising alter-
native to the electron probe. In this instrument, the probe-
forming agent is an ion beam, which can be of either negative
or positive charge. Ions of several elements can be used,
although oxygen is presently the preferred species. The
beam can be focused into a focal spot in the ord?r of one
or a few micrometers, and it can be scanned in line-
or raster form, in the same manner as the electron beam in
a scanning electron microscope. The secondary ions formed
in the sputtering of the specimen are collected in a mass
spectrograph, and the spectrum thus obtained is used to
identify the elements present in the specimen.
Secondary mass spectra can be obtained from all elements
of the periodic table, with particularly high sensitivity
for the atomic numbers below ten which cannot be efficiently
handled with the electron probe. Further advantages of the
ion probe are: the shallow sampling (100 angstroms or less),
the possibility of measuring isotope ratios, and the possi-
bility of producing depth profiles* due to the etching action
of the primary beam which removes successive layers of the
specimen material. The method is, however, still in an
experimental stage, particularly with reference to its
potentials for quantitation. Due to the complexity of the
underlying ohysical process, the accuracy of ion probe
analysis is probably inherently lower than that of electron
58
-------
probe analysis, except for isotope ratio measurements,
which can be performed to one percent accuracy or better.
mens.
The technique is applicable to a large range of speci-
The analysis of individual microscopic particles of
air purticulates has been demonstrated in practice, and it
thus appears that this instrument may have an important
role in the study of environmental and pollution problems
(129).
59
-------
Table 1. Analysis of Fly Ash and Incinerator Particulates
by X-Ray Fluorescence
,
Element ^a-
Hg
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Ag
Sn
Fe
Sr
Na
K
Ca
Si
MS
U
Th
S
, Expected
1 Conc'n.
(ppm)
(d)
10-100
100
500
1000
500
10
100
5000
1000
5000
(d)
(d)
100
1-10*
(e)
(e)
(e)
(e)
(e)
(d)
(d)
(e)
Accuracy
(T)
5-25
15
15
5
5
5
25
15
5
5
5
15
5
15
5
5
5
5
5
Time to
Prepare
Sample
(mm)
5
11
11
"
"
11
M
II
II
II
II
II
II
II
1 1
II
It
II
II
II
II
II
II
,,^ Cost1'"'
Sample
Size
(g)
1-10
M
ti
M
M
n
n
n
ti
ti
ti
ti
it
M
it
n
ii
n
n
ti
M
n
ti
Detection1 J Per
Limit
(ppm)
500
100
100
50
50
10
100
50
50
50
200
100
100
100
50
200
1-2%
200
100
200
1000
500
500
200
Analysis References
(S)
See 7-19,
1-5 especially
n
n
"
M
n
11
"
14
n
12,16,17
11
11
M
11
11
11
11
11
"
n
"
7,19
(a) Determination of Be, B, F, Li not feasible by XRF.
(b) See text for equipment required, manpower skills, and interferences expected.
(c) Ten elements may be determined for $10-50 total, in routine analysis.
(d) Expected levels not known. May be 1-10 ppm or less.
(e) Major constituents.
-------
Table 2.
, , Expected
Element1 ' Conc'n. ;
Hg
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
AB
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
S
Al
Ti
Cl
(ppmj
0.5-10%
0.01-3%
0.01-0.5%
0.1-10%
0.5-10%
0.1-1%
0.3-6%
0.5-10%
2000
0.04-0.20
Accuracy
Analysis of Coal by X-Ray Fluorescence
Time to ,, ^
Prepare Sample Detection^ *
Sample Size Limit
(min)
25
25
5
5
5
5
5
5
15
30
M
M
It
II
It
It
It
II
It
It
M
It
II
II
It
TgT
10
II
It
It
II
tl
II
II
II
II
It
II
It
tt
It
II
It
It
II
II
II
II
II
It
It
tppmj
500
100
100
50
50
10
100
50
50
50
200
100
100
100
50
200
1-2%
200
100
200
1000
500
500
200
200
10
200
Per
Analysis
(T5
5-10
References
See 29-23,
especially:
21,23
23
21,23
21,23
21,23
23
20,23
21,23
21,23
21
(a) Determination of Be, B, F, Li not feasible by XRF.
(b) See text for equipment required, manpower skills, and interferences expected.
(c) Ten elements may be determined for $50-100 total, in routine analysis.
-------
ON
tsj
Table 3. Analysis of Oil and Organometallics
Time to
, > Expected Prepare Sample
Element^ ' Conc'n. Accuracy Sample Size
Hg
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
S
Al
Ti
(ppm) (%) (min) (g)
5 10
n n
n n
100-500 5
5% 1
0.1-100 5
n n
it n
100-500 15
n ii
500 15
n ti
n n
n ti
1-100 15 " "
ti n
n it
n n
0.1-1% 5
n ti
it it
n n
n M
0.1-5% 15 " "
n M
II M
Detection ^ J
Limit
(ppm)
500
100
100
2
50
0.1
100
50
50
50
200
100
100
100
1
200
1-2%
200
100
200
1000
500
500
100
200
10
by X-Ray Fluorescence
_ Cost^
Per
Analysis
References
4-10
n
M
II
II
II
II
II
II
II
24-37,80-82,
See
especially:
28
35
24
31
31
28
31
28
27
(a) Determination of Be, B, F, Li not feasible by XRF.
(b) See text for equipment required, manpower skills, and interferences expected.
(c) Five elements may be determined for $20-50 total, in routine analysis.
-------
Table 4. Analysis of Ores, Minerals and Cements by X-Ray Fluorescence
(e)
Element
(a)
Expected
Conc'n.
1 '
Accuracy
, ->
^ )
CppmJ
Hg
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
S
m
5
U
"
ii
M
11
II
II
It
II
M
1 1
II
f I
II
1 1
II
II
II
II
It
II
M
II
Time to
Prepare
Sample
[min)
5-30
Sample
Size
2-10
It
It
II
II
It
II
tt
II
tt
It
II
It
II
Detection
Limit
Cppm)
500
100
100
50
50
10
100
50
50
50
200
100
100
100
50
200
1-2%
200
100
200
1000
500
500
200
^ ^
Cost
Per
Analysis
(T5
1-10
it
tt
it
M
II
It
II
References
See 38-54,
especially:
(a) Determination of Be, B, F, Li not feasible with XRF.
(b) Concentrations depend on samples and stages of processing.
(c) Accuracy generally ±5 percent for main elements.
Cd) See text for equipment required, manpower skills, and interferences expected.
(e) Cost in direct, automated systems less than $1 per element; in manual systems
with preparation, $10 per element.
-------
Table 5. Analysis of Metals and Alloys by X-Ray Fluorescence
,, . Time to
, -j Expected1- J , -. Prepare
Element*- ' Conc'n. Accuracy1- ' Sample
Hg
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
S
(a)
(b)
(c)
(d)
(e)
CppnU (%) (min)
2-5 1-10
II M
II II
11 11
11 II
It II
II 11
II II
II II
II 11
II 11
I II
1 1 1
1 It
1 1 1
1 It
1 II
1 II
1 t
1 1 1
II I
II 1
It 1
II 1
( f( ~\ t-OSt
Sample Detection1 J Per
Size Limit Analysis References
(ppm) ($)
See 55-79
Usually 500 1
Bulk 100
100
50
50
10
100
50
50
50
200
100
100
100
50
200
1-2%
200
100
200
1000
500
500
200
Determination of Be, B, F, and Li not feasible with XRF.
Concentrations depend on metal samples .
Accuracy generally ±2-5 percent for main and minor elements.
See text for equipment required, manpower skills, and interferences expected.
In industrial applications, usually less than $1 per element.
-------
Table 6. Analysis of Slurry Streams, Feeds and Sediments
by X-Ray Fluorescence
Element^
Hg
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
S
,, . Time to
Expected1- J , . Prepare Sample
Conc'n. Accuracv*- ) Sample Size
(ppm) (%) (min) (g)
15 0-30 1-10
M n M
M M ii
n n ii
ii it .1
M n M
M it M
n n n
ii 11 it
n n n
11 ii ii
n it ii
it ii
n M
ii ii
n ii
ii ii
n n ii
n n n
M II II
II II II
II II II
* I C 1
Detection^ ' Per
Limit Analysis References
(ppm) ($)
See 83-94
500 1
100
100
50
50
10
100
5U
50 "
50
200
100
100
100
50
200
1-2%
200
100 "
200
1000
500
500
200
(a) Determination of Be, B, F, Li not feasible with XRF.
(b) Concentrations depend on materials being analyzed.
(c) Accuracies frequently not better than ±15 percent because of calibration difficulties.
(d) See text for equipment required, manpower skills, and interferences expected.
(e) In industrial applications, usually less than $1 per element.
-------
Table 7. Analysis of Slags and Glasses by X-Ray Fluorescence
ON
Element^
Hg
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
S
Expected1- J
Cone 'n.
tppm)
(e)
(e)
(e)
(e)
(e)
(e)
(e)
0-5%
(e)
(e)
0-3%(f)
fe )
0-20%
0-5%
Cg)
(g)
0.01-5%
i
Accuracy ^bJ
C%)
5
5
15
15
5
1
5
Time to
Prepare
Sample
(mm)
5-30
II
It
II
* i
11
Sample
Size
(g)
2-10
11
M
II
II
II
II
II
M
II
11
II
II
II
Detection^0'
Limit
500
100
100
50
50
10
100
50
50
50
200
100
100
100
50
200
1-2%
200
100
200
1000
500
500
200
Per
Analys is References
cn
See 95-100
1-10
(a) Determination of Be, B, F, Li not feasible with XRF.
(b) Elemental concn. and accuracy of determination are sample-dependent.
(c) See text for equipment required, manpower skills, and interferences expected.
[d) Direct, automated systems less than $1 per element; manual systems with preparation,
$10 per element.
(e) Possibly present in both slags and glasses.
(f) Higher in slags.
(g) Major constituent in slags and glasses.
-------
Table 8.
Element
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
Analysis of Particulates by the Electron Probe Microanalyzer
Expected^ , , Detection^- '
Conc'n. Accuracy1- J Limit
(ppm) (*,) (ppm)
0.1%
200
200
100
100
100
200
100
100
100
200
200
200
200
100
200
11
200
100
100
500
500
500
CostCc)
Per
Analysis References
C$3
See 101-122
5-50
M
It
1 1
II
ti
II
I*
1 1
1 1
II
1 1
1 1
11
1 1
II
II
II
It
II
ti
II
II
II
II
II
It
(a) Elemental concentration and accuracy of determination are sample-dependent.
(b) See text for equipment required, time to prepare sample, sample size, manpower
skills, and interferences.
(c) Automated systems about $5 per element, manual systems with preparation about
$50 per element.
-------
References
Books Related to X-ray Fluorescence Analysis
1. II. A. Liebhafsky, II. (i. Pfeiffer, I-. II. Winslow and
I'. 1). Zemany, "X-ray Absorption and Lmission in
Analytical Chemistry," Wiley, New York (1960).
2. L. S. Birks, "X-ray Spectrochemical Analysis," 2nd
Ed., Intersciencc, New York (1969).
3. R. Jenkins and J. L. Ue Vries, "Practical X-ray
Spectromctry," Spr inger-Ver lag, Kcv* York (1969).
4. L. P. Bertin, "Principles and Practice of X-ray
Spectrochemical Analysis," Plenum, New York (1970).
5. R. 0. Miillcr, trans, by K. Kcil, "Spectrochemical
Analysis by X-ray Fluorescence," Plenum, New York
(1972) .
6. K. F. .J. lleinrich, C. S. Barrett, J. B. Newkirk and
C. 0. Ruud, eds., "Advances in X-ray Analysis," Vol.
5, Plenum, New York (1972). The preceding 14 volumes
of this series also contain numerous articles on the
use of x-ray fluorescence analysis.
My Ash and Incinerator Part iculates
7. S. C. doadby and J. l:. Stephens, "Determination of
Sulphur in l:ly-ash by X-ray Emission Spectroscopy,"
Fuel 4£, 19 (1967).
8. J. Lcroux and M. Mahmud, "Flexibil ity of X-ray Emission
Spectrography as Adapted to Microanalysis of Air
Pollutants," J. Air. Poll. Control Assoc. 2_0, 402
(1970) .
9. C. II. Anderson, "Application of the VXQ-72000 X-ray
Spectrometer to the Analysis of Air Particulates,"
Applied Research Laboratories Methods Report 825.91,
Sunland, Calif. (1971).
10. F. S. Moulding and J. M. Jaklevic, "Trace Element
Analysis by X-ray Fluorescence," Lawrence Berkeley
Laboratory, Report UCRL-20625 (May 1971).
68
-------
11. D. A. Landis, F. S. Goulding and B. V. Jarrett, "Some
Aspects of X-ray Fluorescence Spectrometers for Trace
Element Analysisi" Lawrence Berkeley Laboratory,
Report LBL-320 (Sept. 1971).
12. J. M. Jaklevic and F. S. Goulding, "Semiconductor
Detector X-ray Fluorescence Spectrometry Applied to
Environmental and Biological Analysis," Lawrence
Berkeley Laboratory, Report LBL-743 (Mar. 1972).
13. R. D. Giauque, F. S. Goulding, J. M. Jaklevic and
R. H. Pehl, "Trace Element Analysis with Semicon-
ductor Detector X-ray Spectrometers," Lawrence
Berkeley Laboratory, Report LBL-647 (July 1972).
14. J. C. Wagner, E. II. Bicknese and F. R. Bryan, "X-ray
Determination of Zinc in Basic-Oxygen Flue Dust and
Blast-Furnace Sinter," Appl. Spectrosc. 21, 176 (1967)
15. T. R. Dittrich and C. R. Cothern, "Analysis of Trace
Metal Particulates in Atmospheric Samples using
X-ray Fluorescence," J. Air. Poll. Control Assoc. 21,
716 (1971). ' ~~
16. II. R. Bowman, J. G. Conway and F. Asaro, "Atmospheric
Lead and Bromine Concentration in Berkeley, Calif.
(1963-1970)," Envir. Sci. and Tech. 6, 558 (1972).
o o
17. P. Greenfelt, A. Akerstrbm and C. Brosset, "Deter-
mination of Filter-Collected Airborne Matter by
X-ray Fluorescence," Atmos. Envir. 5_, 1 (1971).
18. C. L. Luke, "Uctcrmination of Traces of Lithium,
Beryllium or Phosphorus by X-ray Analysis," Anal.
Chim. Acta 4_S, 365 (1969)'.
19. C. L. Luke, "Determination of Traces of Fluorine or
Sulfur by X-ray Analysis," Anal. Chim. Acta 43, 245
(1968). ~~
Coal
20. M. Berman and S. Ergun, "Analysis of Sulphur in Coals
by X-ray Fluorescence," Fuel 4_7, 285 (1968).
21. L. T. Kiss, "X-ray Fluorescence Determination of Brown
Coal Inorganics," Anal. Chem. 38, 1731 (1966).
69
-------
22. E. Davidson, A. W. Gilkcrson and S. G. Shequen, "X-ray
Fluorescence Analysis with a New High Speed Multi-
channel Instrument," Reprint from Applied Research
Laboratories, Sunland, Calif. (1965).
23. C. H. Anderson and R. L. Jones,
Inorganic Constituents of Coal
Reprint from Applied Research Laboratories,
Calif. (1968).
"Determination of
by X-ray Fluorescence,
Sunland,
Oil
24.
25.
26.
27.
28.
29.
E. L. Gunn, "Problems of Direct Determination of Trace
Nickel in Oil by X-ray Emission Spectrography,"
Anal. Chem. 36, 2086 (1964).
E. L. Gunn, "Absorption Effects in
Measurement of Elements in Oil,"
Anal. 6, 403 (1963).
X-ray Fluorescence
Advan. in X-ray
C. C. Male and
minations in
Level
Anal
W. H. King, Jr., "Direct Nickel Deter-
Petroleum Oils by X-ray at the 0.1-P.P.M,
, Chem. 33, 74 (1961).
W. Dwiggins,
Determination
raphy ," Anal.
Jr. and H. N. Dunning, "Quantitative
of Nickel in Oils by X-ray Spectrog-
Chem. 31, 1040 (1959).
C. W. Dwiggins, Jr. and II. N. Dunning, "Quantitative
Determination of Traces of Vanadium, Iron, and Nickel
in Oils by X-ray Spectrography," Anal. Chem. 32, 1137
(1960).
C. C. Kang, L. W. Keel and E. Solomon, "Determination
of Traces of Vanadium, Iron, and Nickel in Petroleum
Oils by X-ray Emission Spectrography," Anal. Chem. 52,
221 (1960).
30. J. G. Bergmann, C. H. Lhrhardt, L. Granatelli and J. L.
Janik, "Determination of Sub-PPM Nickel and Vanadium
in Petroleum by Ion Exchange Concentration and X-ray
Fluorescence," Anal. Chem. 39^ 1258 (1967).
31. W. E. Burke, L. S. Hinds, G. E. Deodato, E. D. Sager, Jr.
and R. E. Borup, "Internal Standard X-ray Spectrographic
Procedure for the Determination of Calcium, Barium,
Zinc and Lead in Hydrocarbons," Anal. Chem. 36, 2404
(1964).
70
-------
32. E. N. Davis and R. A. Van Nordstrand, "Determination
of Barium, Calcium and Zinc in Lubricating Oils -
Use of Fluorescent X-ray Spectroscopy," Anal. Chem.
26_, 973 (1954) .
33. E. N. Davis and B. C. Hoeck, "X-ray Spectrographic
Method for the Determination of Vanadium and
Nickel in Residual Fuels and Charging Stocks,"
Anal. Chem. 2]_, 1880 (1955).
34. L. S. Birks, E. J. Brooks, H. Friedman and R. M. Roe,
"X-ray Fluorescence Analysis of Ethyl Fluid in
Aviation Gasoline," Anal. Chem. 22, 1258 (1950).
35. J. L. Caley, "The Use of X-ray Emission Spectrography
for Petroleum Product Quality and Process Control,"
Advan. in X-ray Analysis 6, 396 (1963).
36. R. Jenkins, "Applications of X-ray Fluorescence Analysis
in the Oil Industry," J. Inst. Petroleum 48, 246
(1962).
37. U. Jovanovic, "Development of an X-ray Emission Spec-
trography Method for the Determination of Molybdenum
in Oils," Anal. Chem. 42, 775 (1970).
Ores, Minerals and Cement
38. II. J. Rose and R. Brown, "X-ray Fluorescence Analysis
of Niobate-Tantalatc Ore Concentrates," Advan. in
X-ray Analysis 7_, 598 C1964).
39. A. P. Langheinrich, J. W. Forster and T. A. Linn, Jr.,
"Energy Dispersion X-ray (EDX) Analysis in the Non-
Ferrous Mining Industry," Analysis Inst. 9_, F-3 (1971)
40. R. S. Rubinovich, "Determination of Iron in Rocks and
Ores by X-ray Fluorescence," Inderst. Lab. 30, 539
(1964) .
41. Anon. "The Application of the ARL Model 72000 X-ray
Quantomctcr to the Analysis of Agglomerates, Slags
and Ores," Reprint from Applied Research Laboratories,
Sunland, Calif. (1972).
42. B. P. Fabbi and W. J. Moore, "Rapid X-ray Fluorescence
Determination of Sulfur in Mineralized Rocks from
the Bingham Mining District, Utah," Appl. Spectrosc.
2£. 427 (1970).
71
-------
43. B. P. Fabbi, "X-ray Fluorescence Determination of
Barium and Strontium in Geologic Samples," Appl.
Spectrosc. 25_, 316 (1971).
44. H. J. Rose, Jr., I. Adler and F. J. Flanagan, "Sug-
gested Method for Spectrochemical Analysis of Rocks
and Minerals Using an X-ray Spectrometer, E-2 SM 11-13,"
in Methods for Emission Spectrochemical Analysis, 5th Ed.,
p. 778, ASTM, Philadelphia (1968).
45. G. K. Czamanske, J. H. Hower and R. C. Millard, "Non-
proportional, Non-linear Results from X-ray Emission
Techniques Involving Moderate-Dilution Rock Fusion,"
Geochim. et Cosmochim. Acta 3p_, 745 (1966).
46. K. Norrish and J. T. Mutton, "An Accurate X-ray Spec-
trograph Method for the Analysis of a Wide Range of
Geological Samples," Geochim. et Cosmochim. Acta 53,
431 (1969).
47. I. C. Stone, Jr. and K. A. Rayburn, "X-ray Spectrographic
Determination of Rare Earths in Silica-Alumina Cata-
lysts," Anal. Chem. 39_, 357 (1967).
48. B. L. Bean, "A Method of Producing Sturdy Specimens of
Pressed Powders for Use in X-ray Spectrochemical
Analysis," Appl. Spectrosc. 20^ 191 (1966).
49. B. L. Bean and B. W. Mulligan, "X-ray Spectrochemical
Analysis of Materials: Cement and Dental Alloys,"
ASTM-STP 373, 25 (1965) .
50. G. Andermann, "Suggested Method for Spectrochemical
Analysis of Cement Raw Mix by the Lithium Tetraborate
Fusion Technique Using an X-ray Spectrometer," in
Methods for Emission Spectrochernical Analysis, 5th Ed. ,
p. 706, ASTM, Philadelphia (1968).
51. H. T. Dryer and H. Renton, "Influence of the Origin
of Raw Materials on the X-ray Analysis of Cements,"
Developments in Applied Spectrosc. 4_, 83 (1964).
52. W. J. Campbell and J. W. Thatcher, "Determination of
Calcium in Wolframite Concentrates by Fluorescence
X-ray Spectrography," U.S. Bur. of Mines Rept. of
Investigation 5416 (1958).
53. U. F. Sermin, "The Application of the ARL 72000 X-ray
Quantometer to the Analysis of Raw Cement Materials,"
Reprint from Applied Research Laboratories, Sunland,
Calif. (1969).
72
-------
54. D. F. Sermin, "The Application of the ARL X-ray Quan-
tometer to the Analysis of Fused Cement Clinker,"
Reprint from Applied Research Laboratories, Sunland,
Calif. (1969).
Metals and Alloys
55. E. F. Spano, T. E. Green and W. J. Campbell, "Evaluation
of a Combined Ion Exchange X-ray Spectrographic Method
for Determining Trace Metals in Tungsten," U.S. Bur.
of Mines Report of Investigation 6565 (1964).
56. C. A. Kienberger and A. R. Flynn, "Determination of
Metallic Impurities in Aluminum by X-ray Fluorescence,"
U.S. AEC Research and Development Report K-1638 (1966).
57. W. W. Houk and 1.. Silverman, "Determination of Iron,
Chromium and Nickel by Fluorescent X-ray Analysis,"
Anal. Chem. 3_1, 1069 (1959).
58. C. M. Davis and G. R. Clark, "X-ray Spectrographic
Analysis of Nickel-Containing Alloys with Varied
Sample Forms," Appl. Spectrosc. 4, 123 (1958).
59. R. M. Brissey, "Analysis of High Temperature Alloys
by X-ray Fluorescence," Anal. Chem. 2^, 190 (1953).
60. J. D. Eick, H. J. Caul, D. L. Smith and S. D. Rasberry,
"Analysis of Gold and Platinum Group Alloys by X-ray
Emission with Correction for Interelement Effects,"
Appl. Spectrosc. 2_^, 324 (1967).
61. S. D. Rasberry, II. J. Caul and A. Yezer, "X-ray Fluor-
escence Analysis of Silver Dental Alloys with Cor-
rection for a Line Interference," Spectrochim. Acta
23B, 345 (1968).
62. A. Chow and F. L:. Beamish, "Determination of Gold by
X-ray Fluorescence Methods," Talanta JL5, 539 (1966).
63. K. Hirokawa, "Determination of Impurities in Some Non-
Ferrous Metals by Fluorescent X-ray Spectroscopy,"
Science Repts. of the Res. Inst. Tohaku Univ. A-13,
263 (1961). English.
64. W. M. MacNevin and h. A. llakkila, "Fluorescent X-ray
Spectroscopic Estimations of Palladium, Platinum,
Rhodium and Iridium," Anal. Chem. 29, 1019 (1957).
73
-------
65. L. S. Birks and E. J. Brooks, "Hafnium-Zirconium and
Tantalum-Columbium Systems," Anal. Chem. 22, 1017
(1950).
66. W. J. Campbell and H. E. Marr III, "Identification and
Analyses of Copper-Base Alloys by Fluorescent X-ray
Spectrography," U.S. Bur. of Mines Rept. of Investi-
gation 7635 (1972).
67. A. Carnevale and A. J. Lincoln, "An X-ray Fluorescent
Method for the Determination of Copper in Silver-
Copper Alloys," Dev. in Appl. Spectrosc. 5_, 113 (1966).
68. T. J. Cullen, "Briquetted Copper Alloy Drillings as a
Sample for X-ray Spectroscopy," Anal. Chem. 33, 1343
(1961) .
69. R. Alvarez and R. Flitsch, "Accuracy of Solution X-ray
Spectrometric Analysis of Copper-Base Alloys," NBS
Misc. Publ. 260-5 (1965).
70. R. E. Michaelis, R. Alvarez and B. A. Kilday, "Deter-
mination of Minor Constituents in Low-Alloy Steels
by X-ray Fluorescence Analysis," J. of Res. Nat.
Bur. of Standards 65C, 71 (1961).
71. B. A. Kilday and R. E. Michaelis, "Determination of
Lead in Leaded Steels by X-ray Spectroscopy," Appl.
Spectrosc. H^, 136 (1962).
72. R. W. Taylor, "X-ray Spectrochemical Determination of
Niobium and Tantalum in High-Alloy and Stainless
Steel," Dev. in Appl. Spectrosc. £, 65 (1964).
73. G. E. Hicho, II. Yakowitz, S. D. Rasberry and R. E.
Michaelis, "A Standard Reference Material Containing
Nominally Four Percent Austenite," Adv. in X-ray
Anal. !_£, 78 (1971).
74. S. D. Rasberry, "Application of Computers in Electron
Probe and X-ray Fluorescence Analysis," Adv. in
X-ray Anal. l_5_f 56 (1972) .
75. L. Backerud, "Determination of Copper in Complex
Brasses by X-ray Fluorescence Spectroscopy,11
Appl. Spectrosc. 2_^, 315 (1967).
76. D. F. Sermin, "The Application of the ARL Model 72000
X-ray Quantometer to the Analysis of Steel," Reprint
from Applied Research Laboratories, Sunland, Calif.
(1968) .
74
-------
77. D. F. Sermin, "The Application of the ARL 72000 X-ray
Quantometer to the Analysis of Stainless Steel,"
Reprint from Applied Research Laboratories, Sunland,
Calif. (1969).
78. D. F. Sermin and K. Slickers, "The Application of the
ARL Model 72000 X-ray Quantometer to the Analysis of
Aluminum Base Alloys," Reprint from Applied Research
Laboratories, Sunland, Calif. (1968).
79. D. F. Sermin and P. Roy, "The Application of the ARL
72000 X-ray Quantometer to the Analysis of Copper
Base Alloys," Reprint from Applied Research Labora-
tories, Sunland, Calif. (1969).
Organometallics (Also see papers in section: Oil)
80. S. A. Bartkiewicz and H. A. Hammatt, "X-ray Fluores-
cence Determination of Cobalt, Zinc and Iron in
Organic Matrices," Anal. Chem. 36, 833 (1964).
81. K. P. Champion and R. N. Whittem, "The Determination
of Calcium in Biological Samples by X-ray Fluores-
cence," Analyst 9_2^ 112 (1967).
82. G. V. Alexander, "An X-ray Fluorescence Method for the
Determination of Calcium, Potassium, Chlorine, Sulfur,
and Phosphorus in Biological Tissues," Anal. Chem. 37,
1671 (1965). ~~
Slurry Streams, and Feeds and Sediments in Flotation Processes
83. P. J. Dunton, "Determination of Total Bromine in Brines
by X-ray Fluorescence," Appl. Spectrosc. 22, 99 (1968).
84. A. H. Smallbone and H. Davidson, "Determination of
Low Z Number Elements in Oils, Slurries and Solutions,"
Reprint from Applied Research Laboratories, Sunland,
Calif. (1972).
85. A. H. Smallbone, "New X-ray Fluorescence Analytical
Techniques and Material Handling Methods," Reprint
from Applied Research Laboratories, Sunland, Calif.
(1965).
86. A. H. Smallbone and Ii. Davidson, "On Stream Analysis
of Solutions," Reprint from Applied Research Labor-
atories, Sunland, Calif. (1972).
75
-------
87. A. H. Smallbone, "Liquid Cell (#128375) for X-ray
Fluorescence Analysis," Reprint from Applied Research
Laboratories, Sunland, Calif. (1970).
88. U. M. Cowgill, "Use of X-ray Emission Spectroscopy in
the Chemical Analysis of Lake Sediments, Determining
41 Elements," Reprint from the author at the Dept.
of Biology, Yale University (1968).
89. U. M. Cowgill, "Method to Determine All Detectable
Exchangeable Cations Using X-ray Emission and Optical
Emission Spectroscopy," Appl. Spectrosc. 22, 415 (1968)
90. K. J. Garska, "Microgram Determination of Chlorides by
Deposition as Silver Chloride and X-ray Fluorescence,"
Anal. Chem. £0, 809 (1968).
91. W. A. Rowe and K. P. Yates, "X-ray Fluorescence Method
for Trace Metals in Refinery Fluid Catalytic Cracking
Feedstocks," Anal. Chem. _y5, 368 (1963).
92. M. Hellman, "Determination of Metals in River Sludge
by X-ray Fluorescence and Its Application in Actual
Practice," Z. Anal. Chem. 254, 192 (1971). In German.
93. Y. K. Park, "Trace Element Determination in Natural
Waters by X-ray Fluorescence Spectrometry after Con-
centration by Evaporation," Dachan Hwabak Hwoejee 13,
41 (1969). In Korean.
94. Y. K. Park, "Trace Element Determination in Natural
Waters by X-ray Fluorescence Spectrometry After
Continuous Dithizone Extraction in a Pulsed Column,"
Dachan Hwabak Hwoejee 13, 45 (1969). In Korean.
Slags and Glass
95. S. H. Laning, "X-ray Study of Glass," The Glass Industry
Mar., 118 (1962).
96. D. F. Sermin and P. Roy, "The Application of the ARL
72000 X-ray Quantometcr to the Analysis of Glass
Powders," Reprint from Applied Research Laboratories,
Sunland, Calif. (1969).
97. C. W. Orrell, "Ceramic Analysis by X-ray Fluorescence -
the Non-Automatic Spectrometer," Br. Ceram. Res. Ass.
Spec. Pub. 50, 70 (1966).
76
-------
98. R. S. Lowe, "Ceramic Analysis by X-ray Fluorescence -
the Automatic Instrument," Br. Ceram. Res. Ass. Spec.
Pub. SjO, 79 (1966).
99. !'. H. Uorr, "Rontgenfluoreszenzanaly tische Methoden
fur die Glasanalyse," Glastechn. Ber. 34, 175 (1961).
100. L). A. Stephenson, "Theoretical Analysis of Quantitative
X-ray Emission Data: Glasses, Rocks and Metals,"
Anal. Chem. 4_3, 1761 (1971).
Applications of Electron Probe Microanalysis (X-ray Microprobe)
101. L. S. Birks and R. E. Seebold, "Use of the Electron Probe
to Measure Low Average But High Local Concentrations,"
ASTM Spec. Tech. Pub. 308 (1961).
102. J. Philibert, "The Castaing Microsonde in Metallurgical
and Mineralogical Research," J. Inst. Met. 90, 241
(1961).
103. J. Philibert and C. Crussard, "Applications of the Elec-
tron Probe Microanalyzer," J. of the Iron and Steel
Inst. 183, 42 (1956).
104. R. J. Bird, "Electron Probe Micro-analysis in a Petroleum
Research Laboratory," Inst. Petroleum 48, 297 (1962).
105. L. S. Birks and R. E. Seebold, "Diffusion of Nb with
Cr, Fe, Ni, Mo and Stainless Steel," J. Nuclear
Materials ,3, 249 (1961) .
106. L. S. Birks, J. M. Siomkjlo and P. K. Koh, "Identification
of Chi and Sigma Phases in Stainless Steel with the
Electron Probe Microanalyzer," AIME Transaction 218,
806 (1960).
107. E. J. Brooks and L. S. Birks, "Electron Probe Analysis
of Segregation in Inconel," ASTM Spec. Tech. Pub. 245,
100 (1958). ,
108. K. C. Carroll, "Metallurgical Applications of the Elec-
tron Microprobe," J. Inst. Met. 9J_, 66 (1962).
109. R. Castaing, J. Philibert and C. Crussard, "Electron
Probe Microanalyzer and its Application to Ferrous
Metallurgy," J. of Metals 9, 389 (1957).
77
-------
110. D. B. Clayton, T. B. Smith and J. R. Brown, "The
Application of Electron probe Microanalysis to the
Study of Microsegregation in Low Alloy Steel,"
J. Inst. Met. 9£, 224 (1961).
111. J. W. Colby, "Electron Microprobe Examination of
Phosphides in Uranium," NLCO-870, Summary Technical
Report, Jan. 1 to March 31, 1963, pp. 83-91, National
Lead Company.
112. V. G. Macres, "Application of Electron Probe Micro-
analysis to Cu-Zn Diffusion," Thesis (MIT) 1958).
113. U. A. Melford and P. Uuncumb, "The Metallographic
Application of X-ray Scanning Microanalysis," Metal-
lurgia S7_, 159 (1958).
114. U. A. Melford and P. Duncumb, "The Application of X-ray
Scanning Microanalysis to Some Metallurgical Problems,"
Metallurgia 61_, 205 (1960).
115. L. S. Birks, E. J. Brooks, I. Adler and C. Milton,
"Electron Probe Analysis of Minute Inclusions of a
Copper-iron Mineral," Am. Mineral 44, 974 (1959).
116. R. Castaing and K. Fredriksson, "Analyses of Cosmic
Spherules with an X-ray Microanalyzer," Geochim. et
Cosmochim. Acta _!£, 114 (1958).
117. K. F. J. Heinrich, "Identification of Inclusions
with the Electron Probe Microanalyzer," ASTM
Spec. Tech. Pub. 393, 39 (1966).
118. A. K. Temple, K. F. J. Heinrich and J. F. Ficca, Jr.,
"Quantitative Electron Microprobe Analysis of Ilmenite
Ores," in The Electron Microprobe, McKinley, Heinrich
and Wittry, eds., Wiley, New York, p. 784 (1966).
119. K. F. J. Heinrich, "Electron Probe Microanalysis: A
Review," Appl. Spectrosc. 22, 395 (1968).
Books Related to Electron Probe Microanalysis
120. T. D. McKinley, K. F. J. Heinrich, D. B. Wittry, eds.,
"The Electron Microprobe," Wiley, New York (1966).
121. K. F. J. Heinrich, "Quantitative Electron Probe Micro-
analysis," NBS Spec. Pub. 298, Washington, D. C.
(Oct. 1968).
122. L. S. Birks, "Electron Probe Microanalysis," 2nd Ed.,
Wiley, New York (1971).
78
-------
Supplemental References
123. H. K. Bumstead, "Application of the X-ray Spectro-
meter to the Needs of the Industrial Hygiene Labora-
tory," Indust. Hygiene J., p. 392 (1964).
124. J. W. Cares, "The Quantitative Determination of Air-
borne Metallic Dusts and Fumes by X-ray Spectrometry,"
Amer. Indust. Hygiene Assn. J., p. 463 (1968).
125. J. R. Rhodes, et al., "Energy Dispersive X-ray Analysis
of Air Particulates in Texas," linviron. Sci. and Tech.
6, 922 (1972).
126. C. L. Luke, et al., "X-ray Spectrometric Analysis of
Air Pollution Dust," Rnviron. Sci. and Tech. 6, 1105
(1972).
127. G. H. Heichel and L. Harkin, "Particulate Contaminates
of Lead, Chlorine and Bromine Determined on Trees
with an Electron Microprobe," Environ. Sci. and Tech.
£, 1121 (1972).
128. V. E. Cosslett, New York Academy of Science Annals 97,
464-481 (1962). ~~
129. C. A. Andersen, Editor, "Microprobe Analysis", John
Wiley 5 Sons, New York (1973).
79
-------
CHAPTKR 5
ATOMIC ABSORPTION SPECTROMETRY
Theodore C. Rains
1. INTRODUCTION
Atomic absorption spectrometry (AAS) has been demon-
strated to be a sensitive and selective technique for inorganic
analysis (1-4). This technique is presently being used to
determine the major, minor and trace elements in a wide
variety of materials such as water, petroleum products, metals,
ores, air particulates and biomedical materials. In atomic
absorption methods of chemical analysis, a portion of the
sample is converted into an atomic vapor, and the absorbance
of light by this vapor is measured at a specific wavelength
which is characteristic of the analyte. The unknown concen-
tration is determined by comparison with absorbance measure-
ments on standards of known composition.
The advantages of AAS may be summarized as (1) the
large number of elements which can be determined with one
instrument, (2) the low limits of detection, (3) the relative
freedom from interferences, (4) the speed of analysis with
no elaborate separations required, and (5) the absence of
need for highly trained technical personnel for most types
of AAS analysis.
2. INSTRUMENTATION AND TECHNIQUE
A wide range of AAS instruments for making accurate and
precise measurements is commercially available. The basic
components of an AAS instrument consist of a primary source
of radiation, a means of producing atomic vapor, a wavelength
isolator, radiation detector and readout system.
In general, hollow-cathode lamps are used as the primary
source of radiation; they are available commercially for all
elements which can be determined by AAS. As a rule they
meet the basic requirements and are readily applicable to
all AAS instruments.
The conventional means of producing atomic vapor of
the analyte is to nebulize the sample solution into a flame.
This is a wasteful and inefficient process but it is simple
and convenient, and hence continues to be used. In recent
years, nonflame sources have been used to produce atomic
vapor (5). Examples of such devices include plasma torches,
stabilized arcs and heated graphite furnaces. Of these
three sources the heated graphite furnace has advantages over
80
-------
flame methods in greater sensitivity, lower detection limits,
and the ability to accommodate very small samples CO-5 to
50 pi). The main factors in the production of atomic vapor
are (a) efficiency of atomization, (b) length of flame or
nonflame cell, (c) oxidant-fuel used to produce atomic
vapor, and (d) position within atomic vapor in which
absorption measurements are made.
Requirements for the wavelength selector may vary con-
siderably from element to element. Basically, it is
essential to be able to separate the one required spectral line
from all others, and to keep any background intensity to a
minimum. The means by which this is achieved may vary from
a simple filter, in the case of sodium, to a high resolution
monochromator with a band pass of 1 A for the determination
of nickel, iron and cobalt. If background radiation is
emitted by the primary source of radiation, a narrow band
pass in the selector will minimize its effect. There are
some special instances where a narrow band pass is required
to avoid interferences due to the selection of more than
one absorption line.
To detect the radiation, a multiplier phototube with
its associated power supply and measuring system are essential
for high sensitivity and precision. Because the detection
system is affected directly by the stability of the measuring
circuit, the multiplier phototube, power supply, amplifier,
and readout system must be sensitive and stable. At present,
many types of multiplier phototubes and associated electronics
are available commercially.
Seventy elements have been determined by AAS with
detection limits in an aqueous media of 10 to 10~" vg/ml.
With non-flame methods such as the carbon rod atomizer, the
detection limits for 33 of these elements have been extended
to an absolute value of 10" ll to 10"llf grams, and this list
of elements is growing almost daily.
A. Interferences
Interferences do occur in varying degrees for all
elements determined by AAS. Interferences can be classified
as physical or chemical (10). Physical interferences are
effects which are caused by a physical property of the sample
solution, or which alter one of the physical processes involved
in the atomization process. Of all the physical interferences,
light scattering by particles in the atomization process
usually is the most troublesome. Techniques have been devel-
oped using background correctors but the analyst must be
alert to the possibility of light scatter, especially for those
elements emitting in the ultraviolet region of the spectrum,
and apply the proper correcting technique.
81
-------
Chemical interferences are classified as condensed phase,
ionization, and mutual. Condensed phase interference occurs
when a concomitant (element, radical, or solute present in
solution) inhibits the dissociation or excitation of the
analyte, thereby suppressing the signal. Ionization inter-
ference occurs when the analyte is ionized in the flame
causing a reduction in signal strength. Mutual or inter-
element interference is not well understood but it has been
observed, particularly in the nitrous oxide - acetylene flame,
that the presence of a particular element may enhance or
suppress the absorption due to an analyte.
To eliminate or control chemical interferences in AAS
it is essential that the various instrumental parameters be
optimized. These include type of burner, oxidant-fuel ratio,
flame temperature, flame region, and sample. The flame or
atomization temperature plays a major role in determining the
extent of chemical interference. With the high temperature
nitrous oxide - acetylene flame the chemical interference of
aluminum, titanium, silicon, sulfate, or phosphate on the
alkaline-earth metals is removed. However, this high-
temperature flame usually introduces another type of inter-
ference which is caused by ionization of the analyte, but
this can be controlled by the addition of a cation having a
similar or lower ionization potential than that of the analyte.
Another way to eliminate condensed phase type of inter-
ference is by the addition of releasing or protective
chelating agents. Releasing or protective chelating agents
are defined as substances which, when added in sufficient
quantity in the presence of an interferent, will restore
the absorption of the analyte to its original value.
In some extreme cases liquid-liquid extraction is used
to remove the interferent; this has an added effect of
increasing the sensitivity of the analysis by preconcentrating
the analyte.
3. SAMPLE REQUIREMENTS
The kinds of samples suitable for analysis by atomic
absorption spectrometry cover a wide range. The analyte
may be present in only trace quantities or it may be a major
constituent. The type and quantity of sample being analyzed
usually affect the selection of a sampling method and sample
preparation. Trace analysis frequently requires special
sampling and preparation techniques. Some factors which
must be considered are (a) the sampling process, (b) pro-
cedures for obtaining samples in solution, and (c) methods
of separation or preconcentration, if required. The nature
of the sample matrix (e.g. coal, fly ash, ores, minerals,
82
-------
metals, etc.) governs the choice of sampling, dissolution,
and preconcentration steps.
A. Sampling
A particular sampling approach which the analyst should
follow is dictated by the concentration of the analyte and
the specific purpose for the analysis. The sampling procedure
or the lack of sample homogeneity have been known to intro-
duce errors much greater than those associated with the
chemical determinations. Calder (65) has, shown that in the
analysis of potassium in herbage, the variance due to sampling
was ten times greater than the variance for the flame deter-
minations .
B. Sample Preparation
The procedures for sample dissolution and subsequent
treatment depend upon the sample matrices being analyzed;
naturally, one method of sample treatment cannot be expected
to work well for all matrices, and it is necessary to choose
the best approach for any particular sample. A review of
various techniques for the preparation of samples for AAS
analysis has been made, which includes biochemical, agri-
cultural, metallurgical, mining, geochemical, industrial,
and other types of samples (5-7).
At the present state-of-the-art, solutions are normally
required for atomic absorption spectrometry. A new technique
using a carbon rod or furnace is currently being developed
which holds promise that solid samples (e.g. fly ash, air
particulates, etc.) may soon be analyzed directly; but the
overwhelming majority of present-day AAS determinations is
made on solutions.
Sample Dissolution
Samples with a high content of organic material respond
well to dry ashing (heating for 2-4 hours at 500°C) with
subsequent dissolution of the residue in a mineral acid.
If wet ashing is preferred, the sample may be heated with a
mixture of nitric and perchloric acids, though other combi-
nations of acids with sulfuric acid are preferred for some
matrices. Most metals and alloys are soluble in hydrochloric
and nitric acids. If silicates and the more refractory
elements are present, the addition of hydrofluoric acid
is essential. To dissolve the more refractory ores and
minerals, the sample may be decomposed in a specially designed
Teflon vessel with hydrofluoric acid and a small quantity
of aqua regia. The time required for decomposition is
30-40 min at a temperature of 110°C.
83
-------
It is important that the acids used for dissolving
the samples be of such purity that they do not contribute
trace elements of their own to the analytical results.
Separation or Preconcentratian
Separation or preconcentration or both are frequently
required as a part of AAS determination of trace elements.
Separation methods, as distinct from preconcentration steps,
are normally utilized to separate the analyte from the matrix
or from other interfering species. Preconcentration steps
are performed when the sensitivity or detection limits of the
method are insufficient for the analysis. Due to the high
specificity of AAS analyses, it is possible in most instances
to perform a general, nonspecific separation and preconcen-
tration step for one or several elements. The methods of
separation and preconcentration are liquid-liquid extraction,
ion exchange and coprecipitation. Of these three methods,
liquid-liquid extraction is preferred and used extensively
in atomic absorption spectrometry. Chelating agents most
frequently used include 8-quinolinol (oxine), dithizone
(diphenylthiocarbazone), cupferron, and several dithio-
carbamate derivatives, particularly diethylammonium diethyl-
dithiocarbamate and ammonium pyrrolidine dithiocarbamate (7).
The chelates formed are extracted into a water - immiscible,
nonaqueous solvent such as methyl isobutyl ketone (MIBK).
After removal of the aqueous phase, the metal-bearing
organic phase is introduced into the flame and the absorption
measured. This technique not only separates the analyte from
the matrix, but also yields an increase in sensitivity due
to the effect of the organic solvent on the flame.
4. APPLICATION TO MATERIALS OF ENVIRONMENTAL INTEREST
Atomic absorption spectrometry has been compared with
other spectrochemical methods (8) and with other techniques
of chemical analysis (9) for a variety of materials. In
many laboratories AAS has supplanted wet chemical methods
due to its specificity, low limits of detection, capability
of determining many elements in one sample solution, freedom
from elapsed-time requirements of those methods in which
reactions must go to completion, and provision for data
output in digital-concentration form.
In the past five years papers have been published
describing AAS techniques for diverse environmentally
impacting materials which include agricultural - fertilizer,
plants, and soils; clinical - air, blood, tissue and hair,
urine and bone; industrial - cement, chemicals, coal, gasoline
and liquid fuels, lubricating oils, Pharmaceuticals, and
polymers; nutritional - beverages, fats and foodstuffs;
84
-------
metallurgical - iron and steel, ferrous and non-ferrous
alloys and refractory materials; mining and geochemical -
minerals, ores, silicates and water samples. It appears
that AAS has been used to analyze almost every known type of
material.
5. RESULTS AND CONCLUSIONS
A. Tabulated Information
Tables 1-6 summarize the literature described in
references 1-65. Detection limits, required sample sizes,
and analytical costs are collected for the elements of
interest at expected concentrations in the range 1, 10, and
100 ppm. At these levels the expected accuracy of AAS
analyses is 25 percent, 15 percent, and 5 percent respec-
tively. This contrasts with the instrumental precision of
AAS analysis of 1-2 percent and analytical accuracy of better
than 2 percent at macro concentration levels. The attainment
of these expected levels of accuracy in the analyses depends
on the continued use of reliable standards.
Stock solutions of standards are prepared from high
purity metals which are available as NBS Standard Reference
Materials (SRM's). Procedures for the preparation of 77
standard solutions are described by Dean and Rains (5).
The quality of the standards used during the analytical
measurements is of great importance in trace element deter-
minations.
Column 10 in tables 1-6 is an element index to the
references, and provides entry to additional information
on individual elements in specific matrices. No literature
was available on the direct determination of fluorine and
thorium by atomic absorption spectrometry.
B. Costs
No great operator skill or experience are needed to
operate AAS instruments, and less operational dexterity is
required with flame methods than with most other types of
spectroscopic sources. However, training in the observation
of possible causes of error is essential for trace element
determinations. Hazards to the operator are few, but proper
safety precautions must be learned and practiced, especially
when using nitrous oxide - acetylene flames.
Atomic absorption spectrometers are relatively inexpensive,
with a price range of $3,500 to $12,000. The estimated
analytical costs may be expected to decrease from the values
listed in the tables, as the number of elements to be deter-
mined in the same solution is increased. Atomic absorption
spectrometry appears to be capable of providing an
85
-------
analytical capability which can meet the financial require-
ments of most industrial and municipal laboratories.
C. Conclusions
Atomic absorption spectrometry is a versatile analytical
tool which can be used to determine 25 of 27 elements of
interest present in macro or trace concentrations as consti-
tuents in environmentally significant matrices. Its high
specificity, moderate instrument and labor requirements,
and simple operating procedure make it eminently suited for
routine trace element determinations at a reasonable cost.
86
-------
Table 1. Analysis of Metals and Alloys by Atomic Absorption Spectrometry
Flame Method
oo
Element
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
Expected
Conc'n.
Ippmj
1,10,100
it
ii
it
it
it
it
it
it
n
U
it
n
10,100
Accuracy
T*J
25,15,5
it
ti
n
it
it
n
n
it
n
ii
ii
n
15,5
Eqpt.
Req'd.
UJ
A
B
C
D
B
C
C
C
C
C
C
C
C
B
Time to
Prepare
Sample
Ihrj
2-4
2-4
2-4
2-4
2
2-4
2
2-4
2
2
2
2
2-4
2-4
Sample
Size
Cg)
1-5
0.1-1
.Ol-.l
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
1-5
Detection
Limit
tPg/gJ
1
0.3
0.1
0.2
0.2
0.1
0.1
0.1
0.5
0.1
0.2
0.1
0.2
10
Cost^J
Per
Analysis
~~T5T
50-100
40-60
20-40
20-40
20-40
40-60
20-40
40-60
20-40
20-40
20-40
20-40
40-60
50-100
Com-
ments
(b)
(b)
(b,e)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
References
38,53
6,7,14
6,7,14,62
7,14,44
7,14,22,19
6,7,14,19
6,7,14.19
14,22,61
6,7,14,19
19,22,62
7,19,22,41
7,22,41,61
7,22,54
7
No information.
1,10,100
it
n
n
n
it
n
n
10,100
1,10,100
10,100
25,15,5
ii
n
n
it
n
it
n
15,5
25,15,5
15,5
C
C
C
C
C
C
C
B
B
C
. B
2
2
2-4
2
2
2
2
2
4-6
2
2-4
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0. Ol-.l
0. Ol-.l
0.1-1
1-5
0.1-1
1-5
0.01
0.1
0.1
0.1
0.1
0.01
0.01
0.1
1
0.1
10
20-40
20-40
40-60
20-40
20-40
20-40
20-40
20-40
40-60
20-40
50-100
(b)
(b)
(b)
(c)
(c,d)
(d)
6,7,19,22
7,19,22,41
43,61
6,7,19,22
7,22,56
6,7,22,56
6,7,22,'S6
7,19,22
7,22
6,7.19.22
No information.
(a) AAS, plus oxidants and fuels: A-Ar+H2; B-N20+C2H2; C-Air+C2H«; D-Air+H2.
(b) Separation and preconcentration required for 1 ppm.
(c) Releasing agent required (LaCli).
(d) lonization suppressor required.
(e) Molecular scatter.
(f) Costs include nontechnical personnel skilled in AAS analyses.
-------
Table 2. Analysis of Fly Ash, Ores and Minerals
Atomic Absorption Spectrometry
Flame Methods
by
Element
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
Expected
Cone ' n .
(ppraj
1,10,100
it
it
it
n
n
n
ii
ii
ii
ii
ii
it
10,100
Accuracy
T*J
25,15,5
ii
ii
ti
ii
ii
ii
n
ii
ii
ii
n
ii
15,5
Eqpt.
Req'd.
(a)
A
B
C
A
B
C
C
A
B
C
C
C
A
B
Time to
Prepare
Sample
"THrJ
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-6
Sample
Size
U)
1-5
0.1-1
0.01-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
1-5
Cost1*'
Detection Per
Limit
(ug/g)
1
0.5
0.1
0.2
0.6
0.1
0.1
0.1
0.5
0.1
0.2
0.2
0.2
10
Analysis
m
50-100
50-100
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
50-100
Com-
ments
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
References
6,53
19,41,49
22,41,50,51
44,47,51
22,51
22,51
25,27,41
6,7,22
6,7,19,51
22,23,45,50^59
22,41,51
22,23,41
22,47,54
48
No information.
1,10,100
ii
ii
ii
ti
1,10,100
II
II
10,100
1,10,100
10,100
25,15,5
ii
ii
ii
ii
25,15,5
II
II
15,5
25,15,5
15,5
C
C
A
C
C
C
C
B
B
C
B
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-4
2-6
2-4
2-4
0.01-1
0.1-1
1-5
0.1-1
0.1-1
0.01-.1
.Ol-.l
0.1-1
1-5
0.1-1
1-5
.01
0.2
1
0.1
0.1
.01
.01
.1
1
.1
10
40-60
40-60
50-100
40-60
40-60
40-60
40-60
40-60
50-100
40-60
40-60
(b)
(b)
(c)
(d)
(c)
7,22,56
22,23,41
22,50
7,22,45,56
22,45
7,27
27,46
6,27,46,51
7,22,46
7,27,45,46
7
No information.
(a) AAS, plus oxidants and fuels: A-Ar+H2; B-NiO+CsHz; C-Air-C2H2.
(b) Separation and preconcentration required for 1 ppm.
(c) Releasing agent required (LaCli).
(d) I6niza.ti.on suppressor required.
(e) Costs include nontechnical personnel skilled in MS analyses.
-------
oo
VO
Table 3. Analysis of Fly Ash, Ores, Minerals, Metals and Alloys
by Atomic Absorption Spectrometry
Non-Flame Methods
Expected EC
Element Conc'n. Accuracy R<
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
[ppmj (V) (
1,10,100 25.15,5
n n
B
ii it
n n
B
n B
n n g
n B
B
n n B
B
.1 n B
n n
No information.
B
B
B
B
n n B
B
n n £
B
n n
B
No information.
No information.
ipt.
iq'd
CaT"
A
B
or
C
C
or
or
or
or
or
or
or
or
B
or
or
or
or
or
or
or
or
B
or
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
Time to
Prepare Sample
Sample Size
(hr)
2-
2-
2-
2-
2-
2-
2-
2-
2-
2-
2-
2-
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
2-4 0.
(g)
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
001-0.
Detection
Limit
Per
Analysis
Com-
ments
References
(wg/gj[cj 1$)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
10"*
10-8
10.;
10-3
10-6
10.5
10-S
10-5
10-6
10-6
10. c
10.J
10-3
10 5
-d
10-7
10-S
10 C
10"e
1° "1
l°-4
10"c
10-6
10 A
10"6
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
40-60
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
(d)
Cd)
Cd)
Cd)
Cd)
37,39,40,53
5,26,33
33,39,60
39,60,63
36,60,63
33,34,36,60
33,34,36,60
60,63
34,60,63
5,36,60,63
5,36,60,63
33,34,36,60
35,39,60,63
36,60
5.60
34,36,39,60
60
33,60.63
36,57,60,63
60,63
5
39,60,63
36,60,63
33,60,63
(a) AAS plus A - cold vapor method; B - carbon furnace; C tantalum ribbon.
(b) Costs include nontechnical personnel skilled in AAS analyses.
(c) Separation and preconcentration required.
(d) Molecular scatter, background correction required.
-------
vo
o
Table 4. Analysis of Slurry Streams and Process Streams by
Atomic Absorption Spectrometry
Flame Methods
Expected
Element Conc'n. Accur
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
(ppm) (1
Eqpt.
acy Req'd
J UT~
1,10,100 25,15,5 A
II 1
f
1
I
1
1
1
1
1
1
If t
tj
C
D
B
C
C
A
B
C
C
C
A
10,100 15,5 B
No information.
1,10,100 25,15,5 C
C
A
C
C
C
C
B
10,100 15,5 B
1,10,100 25,15,5 C
10,100 15,5 B
No information.
Time to
Prepare
Sample
Sample Detection
Size Limit
(hr) (g)
2-4
2-4
2-4
2-
2-
2-
2-
2-
2-
2-
2-
2-
2-4
2-0
2-
2-
2-
2-
2-
2-
2-4
2-4
2-4
2-4
2-4
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
^
0.
0.
1-5
1-1
01-1
1-1
1-1
1-1
1-1
1-1
1-1
1-1
1-1
1-1
1-1
1-5
01-1
1-1
1-5
1-1
1-1
01-. 1
01-. 1
1-1
1-5
1-1
1-5
lug/g)
1
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
10
0.
0.
1
0.
0.
0.
0.
0.
1
0.
10
5
1
2
6
1
1
1
5
1
2
2
2
01
2
1
1
01
01
1
1
Cost'1"
Per
Analysis
(1)
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
'50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
50-100
Com-
ments
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(d)
(e)
References
53
7,49.
50,55
7,55
7,55
24,27
7,27
7,24
24,27
24,27
24,27
24,27
54
48,55
7
55
24,50
24,27
55
7
7
7
7
55
7
55
,50
,55
(a) AAS plus oxidants and fuels: A=Ar+H2; B-N20+C2H2; C-Air+C2H2; D-Air+H2.
(b) Costs include nontechnical personnel skilled in AAS analyses.
(c) Separation and preconcentration required for 1 ppm.
(d) lonization suppressor required.
(e) Releasing agent required (LaClj).
-------
Table 5. Analysis of Coal, Oil, Organometallics
by Atomic Absorption Spectrometry
Flame Methods
Element
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
Expected
Conc'n. Accui
Cppmj H
Eqpt.
racy Req'd
fj ~TaT~
1,10,100 25,15,5 A
B
n
10,100 15,5
No information
C
A
B
C
C
A
B
C
C
C
A
B
>
1,10,100 25,15,5 C
c
10,100 " D
1,10,100 " C
1 I
II I
I
II
10,100
1,10,100
10,100
No information
C
C
c
c
B
C
B
Time to
Prepare
Sample
2
2-4
2
2-4
2
2
2
2
2-4
2
2
2
2-4
2-4
2
2
2-4
2
2
2
2
2
4-6
2
2-4
Sample
Size
U)
1-5
0.1-1
0.01-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
0.1-1
1-5
0.1-1
0.1-1
1-5
0.1-1
0.1-1
0.01-.
0.01-.
0.1-1
1-5
0.1-1
1-5
Detection
Limit
tug/gj
1
0.3
0.1
0.2
0.6
0.1
0.1
0.1
0.5
0.1
0.2
0.5
0.2
10
0.01
0.3
1
0.1
0.1
1 0.1
1 .05
0.1
1
0.1
10
Cost10'
Per
Analysis
m
20-40
40-60
20-40
20-40
20-40
20-40
20-40
20-40
20-40
20-40
20-40
20-40
20-40
50-100
20-40
20-40
40-60
20-40
20-40
20-40
20-40
20-40
50-100
20-40
50-100
Com-
ments
(c)
(c)
(c)
(d)
(d)
(d)
(c)
(d)
Cd)
Cc)
Cc)
Cc)
(e)
Cf)
(f)
(f)
References
6,38,53
6,11
6,35
12,13,47
6,14
6,14,17,38
6,14.16,39
15
6,19.28,31
6.20,35
28,31,32,35
28,32,35
13,47
11,19,48
6,20,45
20,21,31,32
6,28
19,28,31,32
6.7,56
6,19,28
6,7,56,64
38,58,64
6,20,28,42
6,20,21,64
7
(a) AAS plus oxidants and fuel: A-Ar+Hj; B-NjO+CjHi; C-Air*C2Hi; D-Air+Hi.
(b) Costs include nontechnical personnel skilled in AAS analyses.
(c) Separation and preconcentration required for 1 ppm.
(d) lonization suppressor required.
(e) Molecular scatter interferences.
(f) Releasing agent required (LaCl,).
-------
Table 6. Analysis of Coal, Oil and Organometallics by
Atomic Absorption Spectrometry
Non-Flame Methods
Element
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
As
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
Expected
Conc'n. Accuracy
tppmj TTj
1,10,100 25,15.5
ii n
n ii
n ii
n n
n n
ii n
n M
n n
n n
n n
n n
n n
n n
No information.
1,10,100 25,15,5
1 i
1 1
1 i
1 i
i f
1 i
1 f
1 1
i t
No information.
No information.
Eqpt.
Req'd
"TaT"
A
B
B or C
C
C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B or C
B
B or C
Prepare
Sample
(hr)
2-4
ii
n
ii
ii
n
it
ii
ii
ii
it
ii
ii
ii
I
I
ii
ii
ii
i
i
i
1
Sample Detection
Size Limit
(g) (Wg/gJ
001-0.1 10~£
10Ift
10 ?
io:i
10 ^
10 "*
10"?
io~l
10"*
I°l6
10 I
ioli.
10-3
10 *
i°:47
10-5
10 £
10 1
10. 1
ID.;
10-s
10-6
10-6
10 b
Co,t
Per
Analysis
TJ)
40-60
II
II
II
II
II
II
II
II
II
1
II
II
II
II
i
II
II
tl
' II
I
- II
II
it
Com-
ments
(c.d)
it
ii
n
n
n
ii
n
n
ii
ii
n
11
n
References
if.;;. 39.40.
60,63
39,63
47,60,63
36,63
5,60,63
18,60,63
60,63
60,63
39,60,63
18,60,63
18,39,63
5,39,47
60
5,60
5,18,63
60
5,18,36
60
5
5
5,39,63
36,63
5,18,19,63
(a) AAS plus: A»cold vapor method; B-carbon furnace; C-tantalum ribbon furnace.
(b) Costs include nontechnical personnel skilled in AAS analyses.
(c) Separation and preconcentration required to attain stated detection limits.
(d) Molecular scatter, background correction required.
-------
References
1. Hubbard, D. P., "Annual Reports on Analytical Atomic
Spectroscopy," Volume 1, Society for Analytical
Chemistry, London, 1972.
2. Winefordner, J. D. and Vickers, T. J., Flame Spectrometry,
Anal. Chem. £4, 150R (1972).
3. Slavin, W., "Atomic Absorption Spectroscopy," Inter-
science, New York, 1968.
4. David, D. J., The Application of Atomic Absorption to
Chemical Analysis, Analyst 815, 779 (1960).
5. Dean, J. A., and Rains, T. C., Editors, "Flame Emission
and Atomic Absorption Spectrometry," Volume 2, Components
and Techniques, Marcel Dekker, New York, 1971.
6. Slavin, W., Atomic-Absorption Spectroscopy-Critical
Review, Appl. Spectrosc. 20, 281 (1966).
7. Mavrodineanu, R., Editor, "Analytical Flame Spectroscopy,
Selected Topics," Macmillan, London, 1970.
8. Grant, C. L., A Comparison of Atomic Absorption with
Other Spectrochemical Methods, in "Atomic Absorption
Spectroscopy," ASTM STP 443, Ameri-can Society for
Testing and Materials, Philadelphia,. 1969, pp. 37-46.
9. Lewis, L. L., A Comparison of Atomic Absorption with
Some Other Techniques of Chemical Analysis, in "Atomic
Absorption Spectroscopy," ASTM STP 443, American
Society for Testing and Materials, Philadelphia, 1969,
pp. 47-69.
10. Dean, J. A., and Rains, T. C., Editors, "Flame Emission
and Atomic Absorption Spectrometry," Volume 1, Theory,
Marcel Dekker, New York, 1969.
11. Chakrabarti, C. L., Beryllium, Boron, Aluminun, Gallium,
Indium, and Thallium, Chapter in "Flame Emission and
Atomic Absorption Spectrometry," J. A. Dean and T. C.
Rains, Editors, Volume 3, Marcel Dekker, New York, in
press.
12. Fernandez, F. J., and Manning, D. C., The Determination
of Arsenic at Sub-Microgram Levels by Atomic Absorption
Spectrophotometry, At. Abs. Newsl. 10, 86 (1971).
93
-------
13. Manning, D. C., A High Sensitivity Arsenic-Selenium
Sampling System for Atomic Absorption Spectroscopy,
At. Abs. Newsl. 1J), 123 (1971).
14. Slavin, S., Barnett, W. B., and Kahn, H. L., The
Determination of Atomic Absorption Detection Limits by
Direct Measurement, At. Abs. Newsl. 11, 37 (1972).
15. Pollock, E. N., and West, S. J.f The Determination of
Antimony at Submicrogram Levels by Atomic Absorption
Spectrophotometry, At. Abs. Newsl. 11, 104 (1972).
16. Keyworth, D. A., Petroleum Products, Chapter in
"Flame Emission and Atomic Absorption Spectrometry,"
J. A. Dean and T. C. Rains, Editors, Volume 3, Marcel
Dekker, New York, in press.
17. Bartels, T. T., and Wilson, C. E., Determination of
Methyl Cyclopentadienyl Manganese Tricarbonyl in JP-4
Fuel by Atomic Absorption Spectrophotometry, At. Abs.
Newsl. £, 3 (1969).
18. O'Gorman, J. V., Suhr, N. H., and Walker, P. L., Jr.,
The Determination of Mercury in Some American Coals,
Appl. Spectrosc. 26, 44 (1972).
19. Christian, G. D., and Feldman, F. J., A Comparison
Study of Detection Limits Using Flame-Emission
Spectroscopy with the Nitrous Oxide-Acetylene Flame
and Atomic-Absorption Spectroscopy, Appl. Spectrosc.
2,5i, 660 (1971).
20. Oliver, M., The Determination of Trace Metals in Polymers
by Atomic Absorption Spectrophotometry, At. Abs. Newsl.
1_0, 12 (1971).
>
21. Barnett, W. B., Hahn, H. L., and Peterson, G. F., The
Rapid Determination of Several Elements in a Single
Lubricating Oil Sample by Atomic Absorption Spectroscopy,
At. Abs. Newsl. 1£, 106 (1971).
22. "Analytical Methods for Atomic Absorption Spectrometry,"
Perkin-Elmer Corp., Norwalk, Conn., 1968.
23. Thomas, B. G., Determination of Silver, Lead, and
Zinc in High Grade Ores, At. Abs. Newsl. ^0, 73 (1971).
24. Price, J. P., Utilization of Atomic Absorption
Spectroscopy in the Synthetic Fiber Industry, At. Abs.
Newsl. 11, 1 (1972).
94
-------
25. Stresko, V., and Martiny, I.., Determination of Antimony
in Geological Materials by Atomic Absorption Spectrometry,
At. Abs. Newsl. 1_1, 4 (1972).
26. Sighinolfi, G. P., Determination of Beryllium in
Standard Rock Samples by Flameless Atomic Absorption
Spectroscopy, At. Abs. Newsl. 1_1, 96 (1972).
27. Fleming, II. D., Some Applications of Atomic Absorption
Spectroscopy in Metallurgical Laboratories, Atomic
Absorption Spectroscopy Symposium, May, 1970, Melbourne,
Australia (Published by Varian Techtron Pty. Ltd.,
Australis).
28. Sanders, J. B., Application to the Analysis of
Petroleum Products, ibid.
29. Dagnall, R. M., and West, T. S., Observations on the
Atomic Absorption Spectroscopy of Lead in Aqueous
Solutions in Organic Extracts and In Gasoline, Talanta 11,
1553 (1964).
30. Mostyn, R. A., and Cunningham, A. F., Some Applications
of Atomic Absorption Spectroscopy to the Analysis of
Fuels and Lubricants, J. Inst. Petrol. 5J5, 101 (1967).
31. Burrows, J. A., Heedt, J. C., and Willis, J. B.,
Determination of Wear Metals in Used Lubricating Oils
by Atomic Absorption Spectrophotometry, Anal. Chem. 37,
579 (1965). ' ~~
32. Moore, E. J., Milner, 0. I., and Glass, J. R., Appli-
cation of Atomic Absorption Spectroscopy to Trace
Analyses of Petroleum, Microchem. J. 10, 148 (1966).
33. Moffith, A. K., Quinn, P. M., and Limtiaco, L. P.,
Applications of Atomic Absorption Spectrophotometry
in Occupational Health Studies, Aroer. Lab., p. 8
(August 1971).
34. Kahn, H. L., Graphite Furnace Applications in Atomic
Absorption, Amer. Lab., p. 35 (August 1971).
35. Bazhov, A. S., Zherebenko, A. V., and Koko, P. A.,
Atomic Absorption Analysis of Polymetallic Ores,
J. Anal. Chem. of USSR 26_, 1485 (1971).
36. Amos, M. D., Nonflame Atomization in AAS - A Current
Review, Amer. Lab., p. 57 (August 1972).
95
-------
37. Rains, T. C.f and Menis, 0., Determination of Submicro-
gram Amounts of Mercury in Standard Reference Materials
by Flameless Atomic Absorption Spectrometry, JAOAC 55,
1339 (1972).
38. Eider, N. G., Determination of Metals in Paint and
Vinyl Additives by Atomic Absorption Spectrometry,
Appl. Spectrosc. 2JJ, 313 (1971).
39. Gandrud, B. W., and Skogerboe, R. K., Investigation
of the Hollow Cathode Discharge as an Atomic Absorption
Medium, Appl. Spectrosc. 2J[, 243 (1971).
40. Goleb, J. A., The Determination of Mercury in Small
Terrestrial and Nonterrestrial Rock Samples by Atomic
Absorption Spectroscopy, and the Study of Mercury
Release at Elevated Temperatures, Appl. Spectrosc. 25,
522 (1971). "~
41. Sackdev, S. L., and West, P. W., Concentration of Trace
Metals by Solvent Extraction and their Determination by
Atomic-Absorption Spectrophotometry, Environ. Sci.
Technol. £, 749 (1970).
42. Prey, V., Teichmann, H., and Bickler, D., Die
Bestiinmung von Silicium in Organischen Verbindungen
mit Hilfe der Atomarabsorption, Mikrochim. Acta,
138 (1970).
43. Headridge, J. B. and Sowerbutts, A., The Determination
of Tin in Steel by Solvent Extraction Followed by
Atomic Absorption Spectrophotometry, Analyst 97, 442
(1972).
44. Menis, 0., and Rains, T. C., Determination of Arsenic
by Atomic Absorption Spectrometry with an Electrodeless
Discharge Lamp as a Source of Radiation, Anal. Chem. 41,
952 (1969).
45. Abbey, S., Analysis of Rocks and Minerals by Atomic
Absorption Spectroscopy, I, Determination of Magnesium,
Lithium, Zinc, and Iron, Canada Depart, of F.nergy, Mines
Resources, Geol. Survey of Canada, Paper No. 67-37, 1967,
46. Abbey, S., Analysis of Rocks and Minerals by Atomic
Absorption Spectroscopy, II, Determination of Total
Iron, Magnesium, Calcium, Sodium, and Potassium,
Canada Dept. of Energy, Mines Resources, Geol. Survey
of Canada, Paper 68-20, 1968.
96
-------
47. Kirkbright, G. F.f Sargent, M., and West, T. S. , The
Determination of Arsenic and Selenium by Atomic Absorption
Spectroscopy in a Nitrogen-Separated-Air Acetylene Flame,
At. Abs. Newsl. 8_, 34 (1969).
48. Harris, R., Determination of Small Quantities of Boron
by Atomic Absorption Spectrophotometry, At. Abs.
Newsl. 8, 42 (1969).
49. Peterson, Y. A., Determination of Beryllium in Aluminum
Materials by Atomic Absorption Spectrophotometry, At.
Abs. Newsl. 8, 53 (1969).
50. McCracken, J. D., Vecchione, M. C., and Lonpo, S. L.,
Ion Kxchange Separation of Traces of Tin, Cadmium, and
Zinc From Copper and Their Determination by Atomic
Absorption Spectrophotometry, At. Abs. Newsl. £, 102
(1969).
51. Thompson, II. J., Morgan, G. B., and Purdue, L. J. ,
Analysis of Selected Elements in Atmospheric Particulate
Matter by Atomic Absorption, At. Abs. Newsl. 9, 53
(1970).
52. Kalb, G. W., The Determination of Mercury in Water and
Sediment Samples by Flameless Atomic Absorption, At.
Abs. Newsl. 9_, 84 (1970).
53. Manning, D. C., Non-Flame Methods for Mercury Determi-
nation by Atomic Absorption - A Review, At. Abs.
Newsl. 9_, 97 (1970).
54. Nakahara, T., Munemori, M., and Muska, S., Determination
of Selenium in Sulfur by Atomic Absorption Spectro-
photometry, Anal. Chim. Acta £0, 51 (1970).
55. Kopp, J. F., and Kroner, R. C., "Trace Metals in Waters
of the United States," U. S. Dept. of Interior,
F.W.P.C.A., Division of Pollution Surveillance,
Cincinnati, Ohio, 1967.
56. Rains, T. C., Chemical Aspects of Atomic Absorption,
in "Atomic Absorption Spectroscopy," ASTM STP 443,
American Society for Testing and Materials, Philadelphia,
1969, pp. 19-36.
57. Belcher, C. B., and Brooks, K. A., The Determination of
Strontium in Coal Ash by Atomic Absorption Spectro-
photometry, Anal. Chim. Acta 2_9, 202 (1963).
97
-------
58. Kashiki, M., and Oshima, S., Universal Standard Method
for Atomic Absorption Spectroscopy of Organic
Materials, Bunseki Kagaku 20^ 1398 (1971).
59. Allan, R. E., Pierce, J. 0., and Yeager, D., Determi-
nation of Zinc in Food, Urine, Air, and Dust by Atomic
Absorption, Amer. Ind. Hygiene Assoc. J. 29, 469 (1968).
60. Kirkbright, G. F., The Application'of Non-flame Cells
in Atomic-absorption and Atomic-fluorescence
Spectroscopy, Analyst 9_6, 609 (1971).
61. Uurke, K. E., Non-Aqueous Atomic Absorption Spectroscopy
Determination of Microgram Quantities of Antimony,
Bismuth, Lead, and Tin in Aluminum, Iron, and Nickel-
Base Alloys, Paper number 30, presented at Pittsburgh
Conference on Analytical Chemistry and Applied
Spectroscopy, Cleveland, Ohio, February 28-March 5,
1971.
62. Kuroha, T., Tsukahara, I., and Shibuya, S., Determi-
nation of Microamounts of Cadmium, and Zinc in Copper,
Nickel, Aluminum and Uranium Metals by Solvent
Hxtraction - Atomic Absorption Spectrophotometry,
Japan Analyst 2Q_, 1137 (1971).
63. Hwang, J. Y., Trace Metals in Atmospheric Particulates
and Atomic Absorption Spectroscopy, Anal. Chem. 44,
No. 14, 20A (1972).
64. Obermiller, C. L., and Freedman, R. W., Rapid Determi-
nation of Calcium, Magnesium, Sodium, Potassium and
Iron in Coal Ash by Atomic Absorption Spectrophoto-
metry, Fuel 4£, 199 (1965).
65. Calder, A. B., The Statistical Approach in Analytical
Chemistry: Why it is Important, Anal. Chem. 36, No. 9,
25A (1964). ~~
98
-------
CHAPTER 6
ABSORPTION SPECTROPHOTOMETRY
R. W. Burke
1. INTRODUCTION
For the past forty years, absorption spectrophotometry
has played a major role in the analysis of important indus-
trial and research materials. Numerous factors have been
responsible for the popularity of this technique. Foremost
among these are: (11 its modest apparatus requirements,
(2) the possibility of its use by skilled technicians, (3)
its good sensitivity and (41 its high accuracy.
Several ooints should be clearly understood, however,
before discussing specific applications of this technique
to the analysis of the wide variety of materials which are
currently of interest to EPA. First, absorption spectro-
photometry is, for all practical purpose's, a wet-chemical
technique. Samples must therefore alwavs be dissolved
before an analysis can be made. Depending on the type and
complexity of the matrix, sample dissolution can be, and
frequently is, the limiting step in the analytical proce-
dure. This deficiency, however, is common to all wet-
chemical techniques and is best overcome by the analyst's
experience. A second drawback of absorption spectrophoto-
metry is that it is primarily a single element technique.
Consequently, it is not suited for quick, survey-type,
analyses. Finally, the technique is- generally not specific
and, as a rule, its successful application requires that
the element of interest be separated from the remainder of
the matrix. Such a requirement may be considered both a
weakness and a strength. For example, separations may be
tedious and small losses of the desired constituent may
occur. Also, interfering elements may not be completely
eliminated. On the other hand, if satisfactory separations
can be made - and this is more often true than not - the
effect of foreign elements is eliminated, and the spectro-
photometric method becomes essentially an absolute one.
This is often not the case with more sophisticated instru-
mental techniques in which chemical separations generally
are not made. The accuracy of the latter methods depends on
the availability of well characterized standards whose
compositions closely approximate that of the materials
being analyzed. In absorption spectrophotometry, suitable
standards are prepared from high purity elements or com-
pounds which are readily available commercially.
99
-------
2. ANALYSIS OF SPECIFIC MATERIALS
Tables 1 and 2 summarize the relevant information on
the possible spectrophotometric determination of some
twenty-one elements in fly ash, incinerator participates,
coal, oil, ores, minerals, metals, alloys, organometallics,
slurry streams and flotation feeds. Most of the references
cited are not matrix oriented, but instead, deal specifically
with the isolation, preconcentration and spectrophotometric
determination of a particular element. This approach was
necessary for two reasons: (1) there are relatively few
references in the literature dealing with the spectrophoto-
metric analyses of the above matrices and (2) those that
were found employed for the most part, at least from the
viewpoint of the research analyst, inferior methods.
These, findings are not surprising however, since widespread
interest in the analysis of these types of materials has
arisen only in the past few years. The lack of proce-
dures is undoubtedly further accentuated by the fact that
absorption spectrophotometry is primarily a single element
rather than a survey technique.
The criteria used to divide the various matrices into
the two general groups given in tables 1 and 2 were (1)
their complexity and (2) their ease of dissolution. It is
these same two factors which dictate the differences in
accuracy and detection limits listed. Further examination
of the two tables will show that a number of elements have
been marked with an asterisk. These are the elements which
are considered best determined by absorption spectrophoto-
metry.
Perhaps the most variable parameters in these tables
relate to the time and cost of an analysis. The figures
given were taken largely from personal experience and are
the best estimates for a "one-shot," single element deter-
mination. These costs can undoubtedly be substantially
reduced, perhaps even tenfold, by determining several
elements on the same sample and/or by determining the same
element simultaneously in a number of samples of similar
material.
As already mentioned, one of the advantages of absorp-
tion spectrophotometry is its modest apparatus requirement.
This is indeed true since, for about $5,000, a laboratory
can become well equipped to analyze for most of the elements
listed. In spite of its relatively low cost, spectro-
photometric instrumentation is quite rugged with downtime
perhaps averaging no more than 1 percent.
100
-------
3. CONCLUSIONS
The primary purpose of this chapter has been the
delineation of state-of-the-art procedures for the spectro-
photometric determination of some twenty-one elements in
fly ash, incinerator particulates, coal, oil, ores, minerals,
metals, alloys, organometallics, slurry streams and flota-
tion feeds.
The majority of the references cited deal with the
fundamental chemistry involved in the selective separation
and color-forming reactions of these elements. By employing
highly selective separations, the accuracy of the measure-
ment should be scarcely affected by the nature of the
matrix being analyzed, provided adequate dissolution pro-
cedures are used.
In all of the methods referred to above, solvent
extraction has invariably been the method of choice when
separations are necessary. This method is the most widely
used technique because of its simplicity and speed. By
utilizing apparatus no more complicated than a separatory
funnel and requiring at most a few minutes to perform,
solvent extraction offers a superior approach to performing
elemental analyses of these types of materials. They are
especially useful in absorption spectrophotometry since
separation, preconcentration, and, frequently, color develop-
ment can be performed in the same operation.
The greatest impact that absorption spectrophotometry
can make in the near future appears to be in the areas of
standards development and analysis. However, once more
definitive specifications and tolerances are established,
spectrophotometry should play an important role in the
quality control and routine analysis of these materials.
Spectrophotometric procedures have been heavily
automated in the clinical field, and commercially available
auto-analyzers are highly popular. This suggests strongly
that the same can be done for industrial applications,
with attendant savings in costs and convenience for routine
trace element determinations of the future.
101
-------
Table 1. Analysis of Coal, Oil, Organometallics
by Absorption Spectrophotometry (a
Metals, and Alloys
Element(b)
Hg*
Be*
Cd*
As*
V
Mn*
Ni*
Sb*
Cr
Zn
Cu*
Pb
: Se*
o B*
F
Ag
Sn*
Fe*
Si*
U
Th
Expected
Conc'n. /
(ppm)
1-10
1-10
1-10
1-10
1-10
1-10
1-10
1-10
1-10
1-10
1-10
1-10
1-10
^ccurat
c*j
25
15
25
25
5
25
15
15
15
15
25
15
25
Sample
Size
(g)
1.0
1.0
1-2
1-2
1-2
1-2
1.0
1.0
1.0
1.0
1-2
1.0
2-5
Expected
Conc'n. Accuracy
(ppm)
100
1-100
100
100
10-100
100
100
1-100
100
100
1-100
100
1-100
100
10-100
100
100
100
100
10-100
10-100
(*)
5
5
5
5
15
5
5
5
5
5
5
5
15
5
15
5
5
5
5
15
15
Sample Detection Inter-
Size Limit(c) ferences
(g)
0.1
0.1
0.1
0.1
1-2
0. 1
1.0
0.1-0.5
0.1
0. 1
0.1
0.1
0.1
0.1
1.0
0.1
0.1
0.1
0.5
1.0
1.0
(Mg)
0.1
0.1
0.1
0.5
5
5
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.1
2
0.5
1
0.1
0.5
2
2
Cu, Ag
Co
Cu, Co
Au, Tl
Hg, Pci
Mo, V
References
1-5
6,7
8
1A,9,10
1B.2B.11
12,13
38,14,15
16,17
18
2A,3A,19,20
38,21,22
48,23
24,25,26
27-33
4A,34,35,36
37,38
39,40,41,42
68,43,44
45,46
47,48,49
50,51
(a) Precision u.v.-visible spectrophotometer; skilled technician requires 0.5 - 4 hours for
sample preparation; cost $50 - 100 per sample.
(b) Method recommended particularly for elements marked with an asterisk; not recommended for
determination of Li, Sr, Na, K, Ca, Mg.
(c) To convert pg to ppm divide the detection limits (ng) by the sample weights (g).
-------
Table 2. Analysis of Fly Ash, Ores, Minerals, Incinerator Particulates,
Slurry Streams, Process Feeds by Absorption Spectrophotometryta-'
,, N Expected
Element1 J Conc'n.
Hg
Be*
Cd*
As*
V
Mn*
Ni*
Sb*
Cr
Zn
Cu*
Pb
- Se*
n B*
F
Ag
Sn*
Fe*
Si*
U
Th
(ppm)
10
1-10
10
1-10
10
10
1-10
1-10
10
10
1-10
10
1-10
10
10
10
10
1-10
Sample
Accuracy Size
(*)
25
25
15
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
(g)
1.0
1.0
1.0
1-2
1-5
1.0
1.0
1-2
1-5
1-2
1.0
1.0
1.0
1.0
1.0
1-2
1.0
2-5
Expected Sample
Conc'n. Accuracy Size
(ppm)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
10-100
100
100
100
100
10-100
10-100
(*)
5
5
5
5
5
5
5
5
5
5
5
5
5
5
25
5
5
5
5
25
25
(g)
0.1
0.1
0.1
0.1
1-5
0.1
0.1
0.1
1-5
1-2
0.1
0.1
0.1
0.1
1
0.1
0.5
0.1
0.5
1-2
1-2
Detection Inter-
Limit(c) ferences
(ug)
2
0.5
1
0.5
5
5
0.5
0.5
2
2
0.5
2
0.5
2
2
2
2
1
0.5
5
5
Cu, Ag
Co
Cu, Co
Au, Tl
Hg, Pd
Mo, V
1-5
1C,6,7
8
1C,9,10
11
12,13
14,15
16,17
18
19,20
21,22
23
3C,24,25,26
27-33
34,35,36
37,38
39-42
43,44
45,46
47,48,49
50,51
(a) Precision u.v.-visible spectrophotometer; skilled technician requires 2-8 hours for sample
preparation; cost $100-200 per sample.
(b) Method recommended particularly for elements marked with an asterisk; not recommended for
determination of Li, Sr, Na, K, Ca, Mg.
(c) To convert yg to ppm divide the detection limits (pg) by the sample weights (g).
-------
References
1. Committee Report, The Determination of Small Amounts of
Mercury in Organic Matter, Analyst 9J), 515 (1965).
2. Smart, N. A., and Hill, A. R. C., Determination of
Mercury Residues in Potatoes, Grain and Animal Tissues
Using Perchloric Acid Digestion, Analyst 94, 143 (1969).
3. Toribara, T. Y., Shields, C. P., and Koval, L., Behavior
of Dilute Solutions of Mercury, Talanta 17_, 1025 (1970).
4. Miller, W. L., and Wachter, L. E., Determination of
Traces of Mercury in Copper Alloys, Anal. Chem. 22,
1312 (1950).
5. Sandell, E. B., "Colorimctric Determination of Traces
of Metals," 3rd ed., pp. 621-630, Interscience, New
York, 1959.
6. Adam, J. A., Booth, E., and Strickland, J. D. H.,
The Determination of Microgram Amounts of Beryllium
Using Acetyl Acetone, Anal. Chim. Acta 6_, 462 (1952).
7. Kirkbright, G. F. , West, T. S., and Woodward, C.,
Spectrofluorometric Determination of Submicrogram
Amounts of Aluminum and Beryllium with 2-Hydroxy-3-
naphthoic Acid, Anal. Chem. 37, 137 (1965).
8. Sandell, E. B., "Colorimetric Determination of Traces
of Metals," 3rd ed., pp. 350-365, Interscience, New
York, 1959.
9. NBS Tech. Note 424, "Analytical Coordination Chemistry:
Titrimetry, Gravimetry, Flame Photometry, Spectro-
photometry, and Gas Evolution, July 1966 to June 1967,"
Menis, 0., Editor, pp. 64-67 (1968).
10. Nail, W. R., An Improved Method for the Determination of
Arsenic in Steel, Analyst 9_£, 398 (1971)
11. Stary, J., Systematic Study of the Solvent Extraction
of Metal Oxinates, Anal. Chim. Acta 218, 132 (1963).
12. Motojima, K., Hashitani, H., and Imanashi, T.,
Spectrophotometric Determination of Microgram Quantities
of Manganese in Uranium and Aluminum with 8-Hydroxy-
quinaldine, Anal. Chem. 34, 571 (1962).
104
-------
13. Sandell, E. B., "Colorimetric Determination of Traces
of Metals," 3rd ed., pp. 606-620, Interscience, New
York, 1959.
i
14. Stary, J., "The Solvent Extraction of Metal Chelates,"
p. 189, MacMillan Company, New York, 1964.
15. Burke, R. W., and Deardorff, E. R., Simultaneous
Spectrophotometric Determination of Cobalt, Nickel and
Copper with 2,3-Quinoxalinedithiol, Talanta 17, 255
(1970). ~~~
16. Burke, R. W., and Menis, 0., Extraction-Spectrophotometric
Determination of Antimony as a Ternary Complex, Anal.
Chem. 3£, 1719 (1966).
17. Fogg, A. C., Jillings, J., Marriott, D. R., and Burns,
D. T., A Critical Study of Brilliant Green as a
Spectrophotometric Reagent: The Determination of
Antimony, Analyst 9£, 768 (1969).
18. Sandell, E. B., "Colorimetric Determination of Traces
of Metals," 3rd ed., pp. 388-397, Interscience, New
York, 1959.
19. Margerum, D. W., and Santacana, F., Evaluation of Methods
for Trace Zinc Determination, Anal. Chem. 32, 1157 (1960).
20. Stary, J., and Ruzicka, J., Isotopic Dilution Analysis by
Solvent Extraction, Talanta £, 296 (1961).
21. Stary, J., "The Solvent Extraction of Metal Chelates,"
p. 164, MacMillan Company, New York, 1964.
22. Bailey, B. W., Dagnall, R. M., and West, T. S.,
Analytical Applications of Ternary Complexes-II.
Spectrophotometric Determination of Copper as Rose
Bengal Bisphenanthrolinium Copper (II), Talanta 13,
753 (1966).
23. Sandell, E. B., "Colorimetric Determination of Traces
of Metals," 3rd ed., pp. 555-583, Interscience, New
York (1959).
24. Iloste, J., and Gillis, J., Spectrophotometric Determi-
nation of Traces of Selenium with Diaminobenzidine,
Anal. Chim. Acta 12_, 158 (1955).
25. Cheng, K., Determination of Traces of Selenium, Anal.
Chem. 2£, 1738 (1956).
105
-------
26. Kawashima, T., and Tanaka, M., Determination of
Submicrogram Amounts of Sclenium(IV) by Means of the
Catalytic Reduction of 1,4,6,11-Tetraazanaphthacene,
Anal. Chim. Acta 4^, 137 (1968).
27. Spicer, G. S., and Strickland, J. D. H., The Determi-
nation of Microgram and Sub-microgram Amounts of Boron,
Anal. Chim. Acta 1£, 231 (1958).
28. Freegarde, M., and Cartwright, J., The Determination of
Boron in Zircaloy, Analyst 87^ 214 (1962).
29. Hayes, M. R., and Metcalfe, J., The Boron-Curcumin
Complex in the Determination of Trace Amounts of Boron,
Analyst 87^ 956 (1962).
30. Uppstrom, L. R., A Modified Method for Determination of
Boron with Curcumin and a Simplified Water Elimination
Procedure, Anal. Chim. Acta 43, 475 (1968).
31. Dyrssen, D. W., Novkov, Y. P., and Uppstrom, L. R.,
Studies on the Chemistry of the Determination of Boron
with Curcumin, Anal. Chim. Acta 60, 139 (1972).
32. Babko, A. K., and Marchenko, P. V., Photometric Determi-
nation of Boron in Steel, Zavod. Lab. £6, 1202 (1960).
33. Marcantonatoes, A., and Monnier, D., Study of Several
New Fluorescent Reactions of Boric Acid and Fluorimetric
Determination of Nanogram Quantities of Boron (in
French), Helv. Chim. Acta 4_8, 194 (1965).
34. Belcher, R., Leonard, M. A., and West, T. S., A New
Spot Test for the Detection of Fluoride Ion, Talanta 2_t
92 (1959).
35. Bartkiewicz, S. A., and Robinson, J. W., Rapid Method
for the Determination of Fluoride in Liquids, Anal. Chim.
Acta 22_t 427 (1960).
36. Belcher, R., and West, T. S., A Study of the Cerium(III)-
Alizarin Complexan-Fluoride Reaction, Talanta 8, 853
(1961).
37. Dagnall, R. M., and West, T. S., A Selective and
Sensitive Colour Reaction for Silver, Talanta 11, 1533
(1964).
106
-------
38. El-Ghamry, M. T., and Frei, R. W., Spectrophotometric
Determination of Trace Amounts of Silver(I) , Anal. Chem.
4_0, 1986 (1968).
39. Ross, W. J., and White, J. C., Application of Pyrocatechol
Violet as a Colorimetric Reagent for Tin, Anal. Chem. 33,
424 (1961).
40. Dagnall, R. M., West, T. S., and Young, P., The Catechol
Violet Colour Reaction for Tin(IV) Sensitised by
Cetyltrimethylammonium Bromide, Analyst 92, 27 (1967).
41. Smith, J. D., The Spectrophotometric Determination of
Microgram Amounts of Tin with Phenylfluorone, Analyst 95,
347 (1970). ~~
42. Busev, A. I., Shestidesyatnaya, N. L., and Zimomrya,
G. G., Extraction of Tin(II) as its Compound with
Brilliant Green, Zh. Anal. Khim. 2£, 1517 (1971).
43. Moore, F. L., Fairman, W. D., Ganchoff, J. G., and
Surak, J. G., Selective Liquid-Liquid Extraction of
Iron with 2-Thenoyltrifluoroacetone-Xylene, Anal. Chem.
2J_, 1148 (1959).
44. Diehl, H., and Smith, G. F., "The Iron Reagents,"
2nd ed., G. Frederick Smith Chemical Company, Columbus,
Ohio (1965).
45. Ringbom, A., Ahlers, P. II., and Siitonen, S. , The
Photometric Determination of Silicon as a-Silicomolybdic
Acid, Anal. Chim. Acta 20, 78 (1959).
46. llalasz, A., Pungor, E., Properties and Analytical
Applications of the Heteropolymolybdates of Phosphorus,
Arsenic, Silicon and Germanium, Talanta 18, 557 (1971).
47. Stary, J., and Mladky, E., Systematic Study of the
Solvent Extraction of Metal B-Diketonates, Anal. Chim.
Acta 28_, 227 (1963).
48. Florence, T. M., and Farrar, Y., Spectrophotometric
Determination of Uranium with 4-(2-Pyridylazo)resorcinol,
Anal. Chem. 35^ 1613 (1963).
49. Burke, R. W., Exchange Reactions of Ternary Ion-
Association Complexes Directly in the Organic Phase,
Talanta 17, 240 (1970).
107
-------
50. Meinke, W. W., and Anderson, R. E., Method for Continuous
Extraction with a Chelating Agent, Anal. Chem. 24, 708
(1952). ~~
51. Sandell, E. B., "Colorimetric Determination of Traces
of Metals," 3rd ed., pp. 844-851, Interscience, New
York, 1959.
Coal
1A. Abernethy, R. T., and Gibson, F. H., Colorimetric Method
for Arsenic in Coal, U. S. Bur. Mines Rep. Invest.
7184 (1968).
2A. Anand, K. S., Dayal, P., and Anand, 0. N., Determination
of Zinc in Lubricating Oils and Lubricating Oil Concentrates,
Z. Anal. Chem. 259, 33 (1968).
3A. Weaver, C., The Determination of Zinc in Coal, Fuel 46,
407 (1967).
4A. Abernethy, R. F., and Gibson, F. H., Method for
Determination of Fluorine in Coal, U. S. Bur. of Mines
Rep. Invest. 7054 (1967).
Oil
IB. Macmillan, E., and Samuel, B. W., Spectrophotometric
Determination of Low Concentrations of Vanadium in
Petroleum with Hematoxylin, Anal. Chem. 3£, 250 (1966).
2B. Steinke, I., Photometric Determination of Vanadium in
Oil Fractions (in German), Z. Anal. Chem. 233, 265
(1968).
3B. Scoggins, M. W., Ultraviolet Spectrophotometric
Determination of Nickel, Anal. Chem. 4_2, 301 (1970).
4B. Lambdin, C. E., and Taylor, W. D., Determination of
Trace Copper in Petroleum Middle Distillates with
Cuprizone, Anal. Chem. 4_0, 2196 (1968).
SB. Campbell, K., and Moss, R., Determination of Trace
Amounts of Lead in Crude Oil and Petroleum Products, J.
Inst. Petrol. 53, 194 (1967).
6B. Short, F. R., Eyster, C. H., and Scribner, W. G.,
Spectrophotometric Determination of Parts-Per-Billion
Iron in High-Temperature Hydrocarbon Jet Fuels, Anal.
Chem. 3£, 251 (1967).
108
-------
Particulatcs
1C. Sommer, I..t and Kuban, V., Spectrophotometric Determi'
nation of Beryllium with Chrome Azurol S, Anal. Chim.
Acta 44_, 333 (1969).
2C. Stara, V., and Stary, J., Spectrophotometric Determi-
nation of Traces of Arsenic, Talanta 17, 341 (1970).
3C. Dickey, D. W. , Wiersma, J. II., Barnekow, R. G. , Jr.,
and I.ott, P. F., Determination of Selenium by the
Ring Oven Technique, Mikrochim. Acta 605 (1969).
109
-------
CHAPTER 7
ATOMIC 1-MI SSI ON SPHCTROSCOPY
Danold W. Golightly
1. INTRODUCTION
Atomic emission spectra of the elements have long pro-
vided a powerful means for multi-element, chemical trace
analysis. The capabilities of optical emission spectro-
metric analysis have improved with the increasing demands
of our developing technological age and the growing
awareness of the contribution of trace concentrations
of many elements to environmental contamination.
A modern perspective of the state-of-the-art for trace
and sub-trace analysis by optical emission spectrometry (OES)
can be obtained from several books (1B-6B) and reviews (1R-
8R) on the subject. However, neither state-of-the-art
nor details of techniques are simple to elucidate con-
cisely. This chapter summarizes the most recent techniques
for OLS analysis for 27 elements in the matrices: fly
ash, coal, oil, ores, minerals, metals, alloys, organo-
metallics, incinerator particles, slurry streams, and
feeds and sediments in flotation processes.
A. Optical Emission Sources
The basic sensitivity (change in analyte signal per
unit change in analyte concentration) of optical emission
spectrometry is a complex function of analyte element, sample
matrix, emission source, detcctor(s), and spectrometer optics,
Thus, elements that have lov excitation potentials for
resonance lines and little tendency to form stable or
non-volatile compounds are readily detected and have good
sensitivity in most plasma-like discharges. The importance
of compound formation and volatility are most dramatically
incurred with the classical direct-current arc discharge.
DC Arc
The common d-c arc customarily is described as a
source more sensitive, but less precise, than spark-type
electrical discharges (with electrode configurations:
rotating disk, porous cup, vacuum cup, etc.). However,
detectability of elements in solid and powdered matrices is
more a function of the large (10-20 mg) undiluted (usually
only slightly diluted with graphite or buffers) sample
quantity that is vaporized into the arc discharge rather
than inherent sensitivity for all elements. Typical
detection limits for elements in silicate ores (non-
110
-------
voJutile matrix) are listed in table 1, column 1 (1).
Spectroscopic buffers that control volatilization of solid
compounds and stabilize excitation conditions in the arc
plasma enable considerable improvement in spectrographic
dctectability. Harvey (2) has provided tabulated empirical
data that show the importance of matrix and buffers.
Harvey's detection limits for elements in a Li-salt buffer
are shown in table 1, column 2.
Further improvements in detectability of the elements
in spectra and d-c arcs have come from the use of rare-gas
atmospheres (usually Ar) that enclose the discharge (3, 4,
5, 6, 7). Atmospheres of argon, or argon mixed with a
reactive gas (such as oxygen), have made possible the
improved detectati1ity illustrated in table 1, column 3.
Most recently, Gordon and Chapman (8) have reported on
a controlled-atmosphere, d-c arc method that uses AgCl as
a common matrix. Their method, which is similar to residue
methods discussed later in this chapter, requires a solution
of the sample, but enables automated analyses for yg-quanti-
ties of analytes and good precision. Minimum detectable
quantities (8) for elements of interest are illustrated in
table 1, column 4. Hambidge (9) adapted Gordon's method
for analysis of chromium in blood, hair and urine. Serum
aliquots of 0.2 ml provided 1-7 ng quantities of chromium
that could be determined with coefficients of variation of
about 6 percent.
Sparks and AC Arcs
Discharges characterized as high-voltage sparks and
interrupted arcs generally provide means for measurements
more precise than d-c arcs. However, solutions or residues
from solutions are required. Solutions assure homogeneity
ant! a convenient means for addition of internal references
not common to d-c arc powder methods. Some typical detection
limits by porous cup and rotating disk spark methods are
given in table 1, column 5 (10-13a, 13b).
Dilute solutions are particularly amenable to analysis
by the copper-spark or graphite-spark technique. This method
was first described by Ger]ach and Uiedl (14) in 1934, and
later examined thoroughly by Fred, Nachtrieb and Tomkins
(15) [for more recent descriptions, see references 16, 17,
18]. A residue is produced on flat-surfaced impermeable
electrodes by vaporization of a small volume of solution.
This residue then is sampled directly by a spark discharge.
The method is sensitive and capable of high precision (1-3
percent). Typical minimum detectable quantities are shown
in table 1, column 6. The presence of large amounts of
111
-------
matrix material in the residue is detrimental to detectability
and precision, however, chemical separations, such as
extraction, ion exchange, or electrodeposition, possibly
can be used to remove matrix elements and enrich (or
preconcentrate) impurity elements of interest.
Duffendack et al. (19, 20) have utilized a high-voltage
a-c arc, rather than a spark, for analysis of residues on
graphite electrodes. High sensitivity and good accuracy
(19, 21) have been shown for this technique. More recently,
Zhigalovskaya et al. (22, also see 22a, 22b) have described
a short-pulse d-c technique that they found superior to the
copper spark method in determining nanogram quantities of
elements.
Hollow Cathode
Mention also must be made of the hollow-cathode dis-
charge. The hollow cathode provides intense line spectra
of the elements and enables analysis of small samples. In
addition, the source makes possible convenient analyses for
the halogens and other elements with high excitation potentials,
The method is essentially a residue technique because solid
sample is placed or electrodeposited within the hollow
cathode. Some typical absolute detection limits (23, also
see 23a, 23b) are given in table 1, column 7. Matrix effects
are frequently incurred with this source, especially if the
sampling mechanism is not ion sputtering alone. The
hollow cathode lamp has been successfully applied to the
analysis of trace elements in steels (23c) and non-conducting
materials (23d).
Flame Emission
Flame atomic emission spectrometry is an important
analytical technique that too frequently is overlooked in
searches for analytical methods. Nearly 70 elements can be
determined with flames that are in common use: nitrous
oxide-acetylene, oxygen-acetylene, oxygen-hydrogen, etc.
Some detection limits from oxygen-acetylene flames (24) are
surveyed in table 1, column 8.
From among the various microwave discharges, capacita-
tive-coupled and inductively coupled flame-like plasmas, the
induction-coupled argon plasma appears to be a source that
provides stable, bright spectra and thus, good detectability
for many elements. Table 1, column 9 summarizes detection
limits from this source (25, 26).
112
-------
B. Chemical Preconccntration
The key to OES analysis of many elements approaching
part-per-billion concentrations is preconcentration (or
enrichment) of impurities. General methodology and pre-
cautions have been described by Thiers (27), Minczewski (28),
Mizuike (29), and Lighty and Currier (30).
The techniques of most importance to removal of impu-
rities from a matrix and concentration are liquid-liquid
extract ion, ion-exchange and electrodeposition. Some typical
details and commentary on application of these approaches to
optical emission spectrometry have been given by Lighty (30)
and others (16, 27).
Recently, Jackwerth et al. have described DTPA complex
exchange reactions (30a), coprecipitation of trace elements
with thallium iodide, followed by extraction with DDTC (30b),
enrichment of copper as the copper-cuprizone complex on
silver bromide (30c), and trace enrichment by partial disso-
lution of matrices (30d) as sample manipulations preceding
spectrochcmical analysis.
2. APPLICATION TO MATERIALS OF LNVIRONMENTAL INTEREST
The twelve matrices, subjects of this report, can be
beparatcu into five groups for discussion. These groups,
which assemble similar matrices, are:
A. (Iroup 1 - Streams to and frorr Air Scrubbers
The liquids and solids collected in wet scrubbers can
be analyzed by techniques Icr.g established hy Kopp and
Kroner f?la, 31b, ">2a, 33a, p. 1010). Kopp and Kroner
analyzed for Ag, Al, As, H, Ma, Fie, Cd, Co, Cr, Cu, Fe, Mo,
Mn, Ni, I', Pb, Sr, V, and Zn in preconcentrated water
samples by the iotating-disk high-voltage spark method.
Concentrations £ rorr 0.01 to 100 wg/ml were determined on a
direct-reading spectrometer. A voluire of water evaporated
(8 to 10 hrs) to 5 ml contained 20g of fotal solids/liter;
the major portions of solids were salts of Ca, K, Mg, and
Na. ConcentratJon ranges for the various elements analyzed
are shown in table 2, column 1. Four other methods are
discussed in the paper (31a). These techniques and
others f31c, 31d), for spectrometric water analysis should
be directly applicable to analysis of water from wet
scrubbi»."b.
llafi'ty (32b) has described a residue method capable of
detecting almost 60 elements in the ng/ml range. The
technique has been applied to analysis of water sediments.
Barnett (33a, p. 1001) has described a residue method for
113
-------
analysis of water. Concentration ranges are shown in table 2,
column 2. The method is accurate (5-15 percent) and has
a 1-2 percent coefficient of variation.
B. Group 2 - Metals and Alloys (Fe, Al, Cu, Pb, Zn)
Methods for spectrometric analysis of the metals Al,
Cu, He, Pb and Zn are detailed in the ASTM Methods for
Lmission Spcctrochemical Analysis (33a). Only metal
constituents important to bulk metallurgical properties of
these alloys are of concern in the ASTM methods. An example
of elements and their concentration ranges determined in
aluminum by the sensitive point-to-plane spark is given
in table 2, column 3. These concentration ranges typify
the concentrations of interest for analysis of alloys of
copper (33a, p. 445), of iron (33a, p. 215), of lead (33a,
p. 490), and of zinc (33a, p. 532). Balfour, ct al. (33b)
have developed a chemical preconcentration technique
that enables emission spectrochemical analysis to be
carried out for parts-per-million of Ag, As, Au, Bi, Cd, Ge,
In, Mo, Fb, Sn and Tl in alloys of Al, Cr, Co, Fe, Ni and
Ti. Killeen (33c) has used a de-arc for analysis of trace
elements in aluminum.
Tymchuck, et al. (34a, 34b) have found that Cu(OH)F
is a good carrier for analysis of trace impurities, from
volatile arsenic to refractory vanadium, in high-purity
copper. For ppm and sub-ppm determinations, chemical pre-
concentration methods, defined by the specific problem, will
be required.
lilwell and Scholes (35), Uozinel (36), Tolle (36a)
and Publicover (36b) provide further information on spectro-
metric analysis for traces and minor constituents in copper
and its alloys (see table 2, column 5). Four alloy steels
are treated in a special technical publication of the
British Iron and Steel Institute (37). Thornton (23c) has
analyzed for traces in several iron-base alloys with a
hollow-cathode lamp. Atwell and Golden (37a) have
developed a carrier-distillation method for analysis of Pb,
Bi and Sn in nickel-base alloys.
C. Group 3 - Ores, Minerals, and Sediments from Coal
Flotation Processes
Typical standard methods for spectrochemical analysis
of ores, rocks, and minerals (.33a, p. 267, p. 958, p. 968,
p. 982, p. 1027) are concerned with major constituents.
Simultaneous multiple-element analyses for trace elements
in minerals and rocks have been treated by Avni and
Boukobza (48), Tennant and Sewell (49), Moal et al. (50),
114
-------
Schoenfeld (51), de Villiers et al. (52) and in ores by
de Montleau (53). Shapiro (38a) recently has reviewed
methodology for silicate rock analysis. Table 2, column 7
presents typical analyses' of minerals.
Direct analysis of trace elements in ores can be
accomplished with a buffer or with a carrier distillation
method (34, 38). Also, there is an indication that boiler
cap electrodes can provide improved d-c arc analysis for
volatile elements, such as Hg, As and Zn (39, p. 239).
Solution techniques for numerous ores require preliminary
fusion with sodium peroxide or lithium metaborate. Collins
(40) has analyzed waste waters from oil fields for B, Be,
Fe, Mn and Sr by direct optical emission spectrography
with a plasma-arc source.
D. Group 4 - Coal, Feedsto Coal F1 o t a t ion Pr o cesses,
Organometallics (formed T>y Combustion Processes)
The general subject of coal analysis for industry has
been treated by Abernethy et al. (41a, 41b). Sharkey (42)
has determined 53 elements in coal. Gibson and Ode (43)
describe rapid methods for analysis of coal ash and similar
matrices. Prior to solution of samples, a lithium
metaborate fusion of the coal is accomplished in a platinum
vessel (44, 45). Usual analytes and concentration ranges in
the ashed residue are summarized in table 2, column 4 (43).
L. Group 5 - Fly Ash and Incinerator Particles
Principal constituents of fly ash are Si, Fe and Mg.
This matrix is amenable to direct d-c arc analysis; or,
after suitable fusion with lithium tetraborate or hydro-
fluoric acid dissolution, analysis can be performed with
a rotating disk technique. Fusions with lithium borate
flux have been used to reduce sample matrix effects (46, 47).
Automated methods similar to those described by Tennard and
Sewell (49c) for silicate minerals may be applicable to
fly ash and incinerator particles.
3. COST (TIME) OF ANALYSIS
A. Survey Analyses
Qualitative and semiquantitative analyses can be made
for all elements that have resonance lines or other
relatively intense spectral lines within the limits of
photographic plate response and transmission characteristics
of the optics external to the spectrograph. A conventional
d-c arc qualitative analysis provides an identification of
major, minor, and trace constituents (up to 70 elements)
115
-------
typically in 10 mg of solid sample. Qualitative analyses
also can be performed on liquid samples directly by spark
methods or indirectly by residue methods. A semiquantitative
analysis provides additional information on concentrations
in terms of decade ranges defined by available standards and
photographic exposures measured on a scanning microphotometer.
This type of analysis is usually limited to 40 or 45 elements
in a specific matrix material.
The cost for survey analysis is a composite sum of
time (man-hours), and costs of electrodes, reference
standards, buffers, gases for special discharge atmospheres,
photographic plates and reagents. The time required for an
analysis is the most significant of these cost contributors.
Estimated times for qualitative and semiquantitative
analyses are reviewed in table 4 for single sample multiple-
element cases, and for multiple-sample multiple-element
cases. All time estimates include the routine analysis;
however, special samples may require up to several hours
of pretreatment. The time required depends ultimately on
the nature of the analysis and the complexity of the sample.
B. Quantitative Analyses
Quantitative analysis provides concentration informa-
tion for traces and minor constituents that is typically
accurate to within ± 5-10 percent of the true value.
Reference standards such as the NBS Standard Reference
Materials (SRM's) are necessary, and the physical and
chemical similarity of standards and samples are crucial to
the achievement of high accuracy.
Spectrographic methods require time-consuming micro-
photometry and graphical extrapolation methods. However,
direct-reading (photoelectric) spectrometers can minimize
or eliminate either or both of these time-consuming
operations, thereby greatly reducing the time for quantita-
tive measurements. These differences are reflected in
the estimated times (costs) for quantitative analyses
summarized in table 4.
116
-------
Table 1. Summarv of Spectrographic and Spectronetric Detection T.i"iits!
DC
Arc
Element Air
^^ ^^^^.
Hg
3e
Cd
As
V
Mn
Xi
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
ippnj
3000
1
10
100
1
1
30
100
3
100
0.3
1
30
300
30
0.1
3
30
3
100
2000
1
3
0.3
50
100
DC Arc DC Arc
Li-Salt Controlled
Buffer Atmosphere
(ppm)
70
1.5
15
800
0.8
0.6
3
80
O.S
70
0.2
7
15
20
0.8
IS
5
0.2
20
15
0.1
8
0.2
SOO
50
(pprij
0.3
0.005
0.08
0.1
5
0.03
0.1
0.1
O.S
0.1
0.1
0.3
500b
0.4
-r
500b
0.001
0.1
0.4
sh
sooj
1000°
0.01
0.4
0.1
500
500
DC Arc Porous
Reduced Cup g
Pressure Rotating
Argon Disk
TngT
~
0.1
20
1
3
2
2
45
0.4
1
__
1
__
7
0.3
__
7
20
__
3
0.2
(npm)
10
0.02
0.2
3
0.2
0.02
0.5
2
0.1
4
O.OS
4
0.5
_
0.1
0.01
2
0.2
0.06
351?
200b
0.01
1
0.003
100
10
Spark
Copper ^
Graphite
CngT
10
0.2
20
100
1 -
0.2
1
10
1
10
0.5
5
__
0.2
10
0.2
0.5
2.5
SO
10
10 '
10
10
1
100
so
Hollow
Cathode
ir.gj
0.03
3"
__
__
0.03
1
100
1
3
0.03
in
1
__
0.1
0.03
10
3
_
0.03
10
-,-T._
1
0.03
Argon
Induction
Coupled
Flame Plasma
(ug/irlj (.nc/ml)
40
1
6
50
0.3
0.1
0.6
20
P.I
50
0.1
3
__
30
0.000003
0.3
4
0.7
0.004
0.0001
0.003
0.005
S
0.2
10
150
200
30
100
6
6
200
1
9 *
__
8
30
30
__
20
300
5
0.02
_
__
__
S
30
3
M
Index to references in Table 3»
b
Most sensitive line not used.
-------
Table 2. Summary of Spectrographic and Spcctrometric Analysis of Various Materials8
oo
Element
Hg
Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
B
F
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Mg
U
Th
Water
Rotating Disk
Method
lug/ml)
0.005-1.4
0.2-20
4-80
2-40
0.1-20
0.5-40
_
0.2-40
0.5-80
0.2-40
2-40
0.1-20
_
0.1-20
_
0.2-80
0.2-40
_
»
^^
_
^^^
""
Water
Residue Method
(ug/ml)
0.6-30
6-30
1.5-30
1.5-3,000
1.5-30
l.S-30
90-3,000
0.3-300
1.5-30
1.5-300
0.15-30
3-30
1.5-3.000
0.3-300
Aluminum Coal Ash *
Spark-Emission (Major Constituents)
m
0.001-1
0.001-2
0.001-0.05
0.001-S
0.001-10
0.001-4
0.001-10
0.001-30
0.002-0.7
0.001-0.05
0.001-5
0.001-7.5
0.001-4
0.001-0. OS
0.001-0.2
0.001-14
0.001-11
m
E
1^3
0.3-11
0.6-1.4
4-21
14-41
0.8-5.S
Copper,
rUobular
Arc
(ppiT
0.3-3
0.01-0.2
0.1-1
3-40
0.1-l.S
O.l-n.8
2-40
2-40
0.2-3
O.S-10
_
1-1S
0.01-0.3
n.2-in
1-20
0.2-r
1-12
__
1-15
«
0.5-5
^_
0.1-1
__
_
minerals,
Phosnhate
Rock
ippmj
10-400
10-400
10-400
10-400
10-400
in-400
10-400
10-400
in-jnn
10-400
10-400
10-400
10-400
in. 400
10-400
10-400
10-400
10-400
10-400
10-400
^_
10-150
0.5-400
50-400
Minerals,
Powders
ipomj
^^
1-6
5-6
1-2
20-9.0
200-1500
1-2500
0.6-1.2
8-400
40-700
13-8000
6-460
^^^
2.6
2.5-32
1»-2S»
70-570
_
__
100-9%
15-41
0.071-4.31
0.5-2400
2.5-300
?Index to references in Table
Elements reported as oxides.
-------
Table 3. Index to Kmission Spectroscopy References
Column in
Table 1
1
2
.3
4
5
6
7
8
9
Spcctrographic and Spcctrometric
Emission Sources
DC Arc in Air
DC Arc, Li Salt Buffer
DC Arc, Controlled Atmosphere
DC Arc, Reduced Pressure Argon
Spark, Porous Cup Rotating Disk
Spark, Copper and Graphite
Hollow Cathode
Flame
Argon Induction-Coupled Plasma
References
1
2
3,4,5
8
10,11
15,16
.23
24
25
,6,7
,12,13
,17,18
Column in Spectrographic and Spectrometric
Table 2 Analysis of Various Materials
1
2
7>
4
5
6
7
Water, Rotating Disk Method
Water, Residue Method
Aluminum, Spark (-mission
Coal Ash
Copper, Globular Arc
Minerals and Phosphate Rocks
Minerals and Powders
References
32a
32b,
33a,
45
36b
48
52
33a
33b
119
-------
Table 4. Estimates of Time Required for Several Types of Spectrographic and
Spectrometric Analyses.
ro
o
Type of
Analysis
Qualitative,
Spectrographic
Semiquantitative,
Spectrographic
Quantitative,
Spectrographic
Quantitative,
Spectrometric
Number
of Samples
1
15
1
12
1
1
12
1
12
12
Number of
Elements
25
25
25
25
1
25
25
1
25
25
25
Total Time
(Ur.)
1.5
4
4
8
2
5
12
0.25
4
6
0.25
Time/1:1 ement
Analvsis
(Min.)
2-3
0.5-1
8-12
1-3
120
10-15
2-4
15
10
1-3
0.05
(3 Sec.)
Comments
Solids, Powders,
or Liquids.
Solids or Powders.
Ml samp IPS of
like matr ices.
Sol ids, Powders.
Al 1 samplcs
of 11ke mat rices.
Sol ids.Ponders,
or !. in u ids.
Direct-Reading
Spectrometer with
Intensity Ratio
Output.
Direct-Reading
Spectrometer with
Dedicated Computer
and Automatic
Printout in Pre-
determined Format.
(a)
For Spectrographic analysis, this is the number of exposures that can be
conveniently put on a pair of photographic plates in a spectrograph camera.
-------
Optical hmission Spectrometry General References
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Federal Water Control Administration, Cincinnati,
Ohio, 1967.
32b. Haffty, J., Residue Method for Common Minor Elements,
U. S. Uept. of the Interior, Geological Survey, Water
Supply Paper No. 1540-A, U. S. Govt. Printing Office,
Washington, D. C. 1960.
33a. ASTM Committee E-2, Methods for Emission Spectrochemical
Analysis, Sixth Ed., American Society for Testing and
Materials, Philadelphia, Pa., 1971.
33b. Balfour, B. E., Jukes, D., and Thornton, K., A Spectro-
chemical Method for the Determination of Trace Impurities
in Metallurgical Materials, Appl. Spectrosc. 20, 168-171
(1966).
33c. Killeen, 0. P., Spectrographic Detection of Trace
Elements in Aluminum Metal, U.S.A.E.G. Report Y-1532,
15 pp (1966).
34a. Tymchuk, P., Russell, D. S., and Berman, S. S., Ottawa
Symposium on Spectroscopy, Sept. 1964.
34b. Tymchuk, P., Mykytink, A., and Russel, D. S., Spectro-
chemical Analysis of Trace Impurities in Copper Using
Copper Fluoride as a Carrier-Distillation Agent, Appl.
Spectrosc. 22, 268-271 (1968).
129
-------
35. lilwell, W. T., and Scholes, I. R.,'"Analysis of Copper
and Its Alloys," Pergamon Press, New York, 1967.
36. Dozinel, C. M., "Modern Methods of Analysis of Copper
and Its Alloysf"(English translation by G. R. Andraso,
Pittsburgh, Pa.), Charles Dozinel, Brussels, 1960.
36a. Tolle, H., Spectrographic Determination of Trace
Impurities in Pure Copper Using a Globule Arc in
Oxygen, Z. Analyt. Chem. 240, 162-170 (1968).
36b. Publicover, W. E., Spectrochemical Analysis of Oxygen-
Free Illectrolytically Pure Copper by a Globular Arc
Procedure, Anal. Chem. 37_, 1680-1684 (1965).
37. Iron and Steel Institute, Spectrographic Analysis of
Low Alloy Steels, Special Rpt. No. 47, The British
Iron and Steel Research Association, The Iron and Steel
Institute, London, 1952.
37a. Atwcll, M. G., and Golden, G. S., The Emission
Spcctrographic Carrier-Distillation Determination of
Traces of Lead, Bismuth and Tin in Nickel-Base Alloys,
Appl. Spectrosc. 2£, 362-364 (1970).
38. Scribner, B. F., and Mullin, H. R., Carrier-Distillation
Method for Spectrographic Analysis and its Application
to the Analysis of Uranium-Base Materials, NBS
J. Res. 32, 379-389 (1946).
130
-------
38a. Shapiro, I,., Developments in Applied Spectroscopy
£, 143-157 (1970).
39. Mittledorf, A. J., Emission Spectrochemical Methods,
Chapter 6 in "Trace Analysis," Ed. by G. II. Morrison,
Wiley-Interscience, New York, 1967.
40. Collins, A. ("I., Lmission Spectrometric Determination
of Barium, Boron, Iron, Manganese, and Strontium in
Oilfield Waters Using a Plasma Arc, Appl. Spectr. 21,
16-19 (1967).
41a. Aberncthy, K. P., I.rgun, S., Friedel, R. A., McCartney,
.J. T., and Wendcr, I., Coal and Coke, in Pncyclopedia
of Industrial Chemical Analysis, V.10, Pd. hy F. D.
Sncll and L. S. Cttrc, pp. 209-262, Wiley-Interscience,
New York, 1971.
411>. Aberncthy, R. F. , Peterson, M. J. , and Gibson, F. H. ,
Spectrochemical Analysis of Coal Ash for Trace
Elements, U. S. Bur. of Mines Report PB 185554, 1969.
42. Sharkcy, A. C., Shultz, J. L., and Friedel, R. A.,
Advances in Coal Spectromctry - Mass Spectrometry,
U. S. Bur. Mines Kept. Invest. 6318 (1963).
43. Gibson, 1:. II., and Ode, W. II., Applications of Rapid
Methods for Analyzing Coal Ash and Related Materials,
III 6036, U. S. Bur. Mines, 1962.
131
-------
44. Suhr, N. H., and Ingamells, C. 0., Solution Technique
for Analysis of Silicates, Anal. Chem. 38, 730-34
(1966).
45. Karacki, S. S., Coal Ash Analysis with an Argon
Plasma Emission Excitation Source, Paper 96, Pittsburgh
Conference on Analytical Chemistry and Spectroscopy,
Cleveland, March 1972.
46. licrement, F. , Dosage Elem. Etat Traces Roches Autres
Subst. Miner. Natur., Actes Colloq., 173-85 (1968);
C. A. ^5, 83749y (1971).
47. Govindaraju, K., Dosage Elem. Etat Traces Roches
Autres Subst. Miner. Natur., Actes Colloq., 133-44
(1968); C. A. 7S_, 58276J (1971).
48. Avni, R., and Boukobza, A., Cathode-Region Method for
the Direct Spectrochemical Determination of 50 Trace
Elements in Rock Phosphate, Appl. Spectrosc. 25, 483-
489 (1969).
49. Tennant, W. C., and Sewell, J. R., Direct-Reading
Spectrochemical Determination of Trace Elements in
Silicates Incorporating Background and Matrix.
Correction, J. Quant. Spectrosc. Radiat. TrArtSfer 9,
640-645 (1969).
50. Moal, J. Y., Beguinot, J., Ruel, G., and Vannier, M.,
The Quantometer for the Direct-Reading Determination of
Traces of Elements in Natural Materials, C.N.R.S.
Report No. 923, 107-132 (1970).
132
-------
51. Schocnfeld, I., Spectrochcmical Determination of Fluorine
in Standard Rocks, Appl. Spcctrosc. ]A_, 359-361 (1970).
52. dc Villiers, D. B., van Wamelen, D., and Strasheim, A.,
Semiquantitative Procedure for the Simultaneous
Spectrographic Determination of Thirty F.lements in Powder
Samples, Appl. Spectrosc. 20, 298-301 (1966).
53. de Montleau, Ph., Spectrographic Analysis with the Tape
Machine, Method. Phys. Anal. 6, 162-166 (1970).
133
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CHAPTER 8
VOLTAMMETRY (POLAROGRAPHY)
E. June Maienthal
1. INTRODUCTION
Voltammetry (polarography) is a well known analytical
technique that has considerable potential for environ-
mental analysis. While best known for the determination of
trace metals, it can be applied to the determination of
some non-metals and to organic compounds as well. In
fact, any substance that can be electro-oxidized or
reduced in solution is potentially determinable by
voltammetry.
Attractive features of voltammetry include high
sensitivity, good selectivity, moderate cost of instru-
mentation, and the ability to determine several consti-
tuents in the same solution. Modern instrumentation has
improved polarography with respect to sensitivity, selec-
tivity, and ease of operation. Accordingly, it is
surprising that the technique has not found more extensive
use in environmental analysis.
In this chapter, the voltammetric techniques of
analytical importance are described, chemistry pretreat-
ment and matrix effects are discussed, and some of the
experience obtained at NBS is mentioned. In addition,
applications to environmental pollution found in the
literature are reviewed and estimates are given of the
types of results which can be expected.
Background
With a conventional d.c. pen-recording polarograph
and a dropping mercury electrode, solutions containing
as little as 1 pig/ml (0.01 millimolar) can be analyzed.
Accuracies of 2-5 percent are found, and when reduction
potentials are separated by as much as 200 mV, a number
of elements can be determined in the same solution.
The sensitivity and resolution of polarographic
analysis have been greatly extended by the development of
modern instrumentation such as square waye and pulse
polarography by Barker and co-workers (1). Of these,
pulse polarography has been used most often for analytical
purposes, and instruments are commercially available.
With this technique,short voltage pulses of increasing
amplitude are applied to the mercury drop (or a suitable
134
-------
cathode) which is held at the initial potential, and
the current is measured near the end of the drop growth.
For the differential pulse technique, short voltage
pulses of constant amplitude are applied against a linearly
increasing background voltage. In both cases the
charging current is allowed to decay before the measurement
of the faradaic current. Only changes in current are
measured; therefore, increased sensitivity is obtained.
Concentrations as low as 10 ng/ml can be determined and
peaks differing by only 40 mV can be resolved.
Polarographic capabilities have also been improved
by the development of cathode ray polarography by Randies,
with further improvements by Davis and co-workers (2).
With this instrument a linear voltage sweep is applied,
in either the anodic or cathodic direction, during the
last two seconds of the life of a mercury drop which is
mechanically detached every seven seconds. ; The peak
resulting from the electro-oxidation (or reduction) of
the species in question, and which is proportional to
its concentration, is displayed and measured on a cathode
ray tube or a fast recorder. Sensitivities of 10 to
50 ng/ml can be obtained and peaks differing by less
than 100 mV can be resolved.
By use of dual cells, differential operation may
be obtained with this polarograph. Hlectrodes are
matched by cutting a capillary into two pieces of equal
length and using the cut faces as the dropping orifices.
The drop masses are equalized by adjustment of the heads
of the two mercury columns immersed in portions of the
same solution to give identical reduction peak heights
for each cell. For subtractive polarography, the second
cell contains the blank, and its signal is electrically
subtracted from that of the first cell containing the
sample, giving much better defined peaks and higher
sensitivity. In the same way, interfering peaks may be
minimized by putting a similar amount of the inter-
fering ion or ions in the second cell.
The best polarographic precision obtainable, so far,
can be achieved by using the second cell in the compara-
tive mode of operation; that is, placing in it a very
accurately known standard, similar in concentration to
the sample which is in the other cell. The very small
difference between the two is then amplified and measured.
By this technique, standard deviations as low as 2 to 5
parts in 10,000 have been obtained (3, 4). This makes
possible highly accurate determination of macro consti-
tuents on micro amounts of sample.
135
-------
The highest polarographic sensitivity, ranging
from 1 ng/ml to 1 pg/ml can be obtained by anodic
stripping utilizing any of the newer instrumentation
presently available. This technique involves plating
onto a cathodic electrode for a fixed length of time at an
appropriate potential, then applying a voltage scan in
the anodic direction, measuring the increased peak
current resulting from the oxidation of the ion or ions
in question which were accumulated on the electrode. A
variety of types of electrodes may be used - including
hanging mercury drop (either extruded or plated onto
platinum or gold), thin film and solid electrodes, such as
composite mercury-graphite, glassy carbon, etc. Cathodic
stripping, which is the reverse of the procedure des-
cribed above, can be used for determination of anions.
2. APPLICATIONS TO ENVIRONMENTAL ANALYSIS
Voltammetric analysis requires that the substances of
interest be dissolved and contained in an electrolyte
of favorable composition. Proper selection of this
supporting electrolyte can also minimize interferences
in the case of complex mixtures.
For simplification, the 12 matrices of interest
have been combined into three separate groups. In some
respects this is an oversimplication, as any one of the
matrices may require some individual consideration. These
groupings have been based, not necessarily on the simi-
larities of the matrix, but rather on the complexity of
sample dissolution and of other chemical pretrcatments
which may be necessary before the instrumental measurement.
Fly ash, coal, oil, organometallies, incinerator parti-
culates, and minerals are grouped together, because in most
cases the matrix consists of carbon, organic matter,
and/or silica, all of which can be readily eliminated by
wet ashing and nitric, perchloric and/or hydrofluoric
acids, leaving the ion of interest in a soluble form.
The minerals in a few cases may consist, instead, largely of
a heavy metal matrix rather than silica, and in such
cases should be classified with ores, metals, and alloys.
For the first group of matrices, supporting electrolytes
may be chosen so that few direct interferences will exist
for most of the ions of interest. In some cases better
accuracies may be obtained because of increased resolution
after a simple separation such as solvent extraction.
For ores, metals, and alloys, supporting electrolytes
may be chosen for the specific problem at hand so that
few direct interferences exist; however, the matrix
materials (such as iron, lead, or zinc, etc.) may have a
reduction potential in the vicinity of the ion in question,
136
-------
and which in excessive concentrations could decrease the
resolution so that separation may be advisable. Ferric
iron is reduced fairly close to zero volts, in many
supporting electrolytes; hence if it is the major consti-
tuent, it may swamp out trace amounts of other ions reduced
near zero volts. It may be extracted by a variety of means
such as chloroform - cupferron, isobutyl acetate, or methyl
isobutyl ketone. A much simpler solution, however, is to
treat it with a reducing agent such as ascorbic acid or
hydroxylamine hydrochloride converting it to ferrous iron
which is reduced at a much more negative potential.
Lead may be eliminated in most cases by the addition
of sulfate. Subsequent filtration is not necessary as the
precipitated lead sulfate may be allowed to remain in the
solution. Iron, in most cases, cannot be removed as a
matrix interferant in a similar manner by precipitation
with base, because the iron hydroxide precipitate is a
colloidal, gelatinous one which could occlude trace metals
of interest.
The zinc matrix causes no interference in most cases,
as its reduction potential is more negative than most of
the ions of interest.
For slurry streams, feeds to/and from flotation
processes, sediments in flotation processes, effluents
and water in general, water, which may comprise the bulk of
the matrix, can be removed simply by evaporation. The
remainder of residual material will fall under the classi-
fication of one of the first two groups and it can be
treated in a similar manner. The presence of calcium, or
other alkaline earths or alkalis present no problems, as
they are all reduced at a sufficiently negative potential
to cause no interference with the ions of interest in this
study.
Cadmium in air has been determined by a number of
workers after collection on cotton or glass wool plugs,
filter paper, electrostatic precipitators or impingers.
Silverman (5) determined cadmium in dust and fumes using
several of these collection techniques. After dissolution
of the collected sample and oxidation of the organic
material with nitric acid and hydrogen peroxide and
evaporation to dryness, cadmium was measured polarographi-
cally at -0.63V in a supporting electrolyte containing
ammonium hydroxide and potassium chloride. Other workers
(6) have used an ammonium chloride - ammonium hydroxide or
a 30 percent ammonium acetate supporting electrolyte, and
have also determined copper and zinc at the same time.
137
-------
Landry (7) determined lead and zinc in the atmosphere
using cadmium and manganese as internal standards, in an
ammonium chloride-ammonium hydroxide supporting electrolyte.
harlicr workers (8) determined lead in 0.1N KC1 by addition
of a known amount of either zinc or cadmium as an internal
standard. This method requires that zinc or cadmium not be
present in the sample. Kito (9) determined lead in 50-1000 ml
samples of air using a supporting electrolyte of potassium
nitrate, glycine and nitric acid at a pH of 3.
letracthyl lead in air was determined by Khlopin (10)
after absorption of about 0.5 cubic meter of air in castor
oil containing a saturated solution of iodine in methyl
alcohol. The mixture was digested with nitric acid and
evaporated to dryness. The residue was dissolved in dilute
hydrochloric acid and measured in a 30 percent calcium
chloride solution. Khlopin (11) used the same supporting
electrolyte for the determination of zinc, lead, copper,
cadmium, manganese, and bismuth in air. He reports that
all six elements may be determined simultaneously.
Uronc and coworkers (12) have described a micromethod
for the determination of chromium in dusts and mists. After
suitable pretreatment, chromium was oxidized with hydrogen
peroxide and measured in IN sodium hydroxide. The limit of
sensitivity was about 0.05 vg/ml in the final solution
and the error was ±4 percent.
A method has been described for the determination of
manganese, chromium, and iron in air in a trie.thanolamine-
sodium hydroxide supporting electrolyte (13). Pines (14)
used a similar supporting electrolyte and determined
amounts down to 20 ug of manganese in air with coefficients
of variation of 8.5 percent. For SOO-800 ug of manganese,
the coefficient of variation was 2.5 percent.
liabina (15) determined titanium in air after absorp-
tion in 0.5 M sulfuric acid or collection on a PVC filter.
Potassium oxalate was used as a supporting electrolyte and
the pll of the solution was adjusted to 3 - 3.5 with
potassium hydroxide. Errors of :6 percent were obtained,
and more than 50 ug/ml of iron and 1 ug/ml of vanadium
interfered.
Arsine in gas mixtures has been determined by
utilization of its anodic wave in a supporting electrolyte
of ethanol and ammonium nitrate (16). Phosphine and
stibine give waves at the same potential, hence would
interfere.
138
-------
Particulates collected in laboratory air, suburban
air, rural air, and industrial air have been analyzed
at the National Bureau of Standards by cathode ray polaro-
graphy for iron, copper, lead, and cadmium; all four
elements could be measured concurrently without separations,
after wet ashing (17,18). Bulk particulate matter under
study as a possible standard reference material was
readily analyzed for copper, lead, cadmium, and zinc in the
same solution (19).
Metal organics including quinolates and cyclohexane-
butyrates have been readily analyzed for copper, nickel,
manganese, iron, zinc, lead, or cadmium, directly after dry
or wet ashing of the sample (17, 20). Most of these deter-
minations were at the major constituent level, hence the
determinations required only a few mg. of sample. Cadmium
at the 25 percent level was determined directly in cadmium
cyclohexanebutyrate after dry ashing. Standard deviations
of 0.15 percent were obtained using the double cell
comparative method (18).
Iron, copper, nickel, lead and aluminum have been
determined in lubricating oils at the 1-, 50-, and 500-
ppm level respectively, after dry ashing. These mixtures
had been prepared as possible standards for monitoring
engine failure (21).
Glass, rocks, and soils have been readily analyzed
by polarography. Iron, titanium and nickel have been
determined at the 1-, 50-, and 500-ppm levels in a
series of doped glass Standard Reference Materials (22),
with standard deviations of about 1 to 2 percent. The
results agreed very well with those found by several
other techniques (23).
Iron, titanium, and nickel have been determined
in lunar rocks and fine soil from the Apollo 14, 15 and
16 flights. All three elements can be determined in a
single 5-mg sample. The iron values for the different
samples ranged from 3.5 to 15 percent; titanium, from
0.3 to 1.3 percent; and nickel, from 100 to 400 ppm
(24).
Polarography has been useful in the analysis and
certification of several of the NBS bota'nical Standard
Reference Materials which present many of the same
analytical problems as organics and particulates. Iron,
aluminum, lead, cadmium, bismuth and nickel are all
readily determined in amounts ranging from 0.1 to 350
ppm (25).
139
-------
A considerable portion of the polarographic work
at NBS has been concerned with metal and alloy analysis;
hence, the usefulness of polarography in this application
is amply demonstrated (4, 17-21). It has been used for
rapid identification and analysis of metals and alloys in
very small amounts of sample, and it should be applicable
to the analysis of particulates from slurry streams,
sediments, and fly ash. Identification of corrosion
products is another one of NBS experiences that has
applications of environmental interest.
Complete compositional analyses have been made on
samples as small as 90 ug in the case of thin films
composed of antimony-bismuth, lead-tin-tellurium, nickel-
chromium-aluminum-copper, and lead-selenium (17, 18,
20, 21).
Various types of effluents and water systems have
proved to be amenable to polarographic analysis. Periodic
analyses have been made of copper and zinc in the local
water supply to evaluate its suitability for use in a
proposed National Aquarium. Water samples (100-500 ml)
were filtered, the organic material destroyed by acid
treatment, and the samples evaporated to dryness. The
residues were dissolved in dilute hydrochloric acid and
the solutions made ammoniacal. Copper and zinc were
determined concurrently on the cathode-ray polarograph
from peaks appearing at -0.4 V and -1.2 V, respectively.
By use of the sample sizes indicated, the method was
applicable down to at least 5 ppb of copper and zinc.
Samples of water from the NBS reactor have been
routinely monitored for several elements including
copper, cadmium, lead, iron, and aluminum directly, with
no separations, in amounts ranging from 0.6 to 200 ppb.
3. CONCLUSIONS
The examples discussed here demonstrate the appli-
cability of polarography to trace element determination in
materials similar to the matrices under consideration.
Additional applications found in the literature are given
in the Bibliography. Tables 1, 2, and 3 give a summary
of sensitivities, accuracies and costs that can be expected
for typical samples. In many cases the sensitivities
achieved could be significantly greater and the cost of
analysis could be considerably less than those indicated
in the tables, with the expenditure of a little effort
to optimize methodology. The sensitivities indicated in
the tables are in general poorer than those given in
140
-------
instrumentation discussions for pure solutions, because a
realistic evaluation has been made on the basis of pro-
blems which can occur with real samples. One of the
main limits to the sensitivity achievable on real samples
is the magnitude of the blank (both from reagents and
from the environment). If the blank can be kept to a
low level, then higher sensitivity can be achieved.
The prices for commercial voltammetric instrumentation
range from about $3,000 to $16,000. No additional equip-
ment should be required other than that present in an
ordinary chemical analytical laboratory.
A technician, well-trained in analytical manipulations,
should be capable of performing most of the analyses,
provided a detailed procedure is available. A competent
electroanalytical chemist should be available for consulta-
tion.
141
-------
Table 1. Analysis of Fly Ash, Coal, Oil, Organoraetallies,
Incinerator Particulates, and Minerals by Polarography
Time to
Prepare
(c)
Element *
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Sn
Fe
U
' Accuracy^ '
(*)
0.1-10
2-15
2-15
2-15
2-15
2-15
0.2-15
0.2-15
0.2-15
0.2-15
2-15
0.5-15
0.2-15
0.2-15
Sample
(hr)
0.5
1
2
2
1
1
1
1
1
1
2
2
1
2
Detection Sample
Limit Size
Cd)
Per
Analysis
Comments
(e)
10 ppb
0. 5
0. 5
0.1
1
1
1
1
1
0
0
0
0
0
0.1
1
0.5
0.1
0.2
Tg)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
3
6
12
12
6
6
6
6
6
6
12
12
6
12
In interferes
^- '
(f)
(f)
(f)
Pb,Zn interfere
(f)
ffl
^ *
Tl interferes
(f)
(f)
(f)
(a) Polarography not often used for: Hg, Be, B, F, Li, Ag, Sr, Na, K, Ca, Si, Mg, Th.
(b) Accuracy range: standard deviation (%) at macro constituent level to standard
deviation at detection limit, by differential polarography.
(c) Time £ costs based on sets of six samples, single-element determinations. Costs are
considerably less for multi-element determinations in the same sample.
(d) Sample size requirement for elemental determination at stated detection limits.
Larger samples give lower detection limits; smaller samples required for more
abundant elements.
(e) See text for equipment and manpower requirements.
(f) Interfering elements can be separated.
-------
Table 2. Analysis of Ores, Metals, and Alloys by Polarography
Element
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
Se
Sn
Te
U
Accuracv
0.1-10
2-15
2-15
2-15
2-15
2-15
2-15
0.2-15
0.2-15
0.2-15
2-15
2-15
0.2-15
0.2-15
Time to
Prepare
Sample
(c)
1
i
2
>
1
1
1
1
1
1
2
2
1
2
Detect ion
Limit
(PP"0
50
1
1
1
0
1
1
1
0
0
5
1
1
1
ppb
.5
.5
m 2
Sample(d)
Size
~Tgl
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Cost(c)
Per
Analysis
"TIT
6
12
12
12
6
12
12
12
12
6
12
12
12
12
Comments
(e)
In interferes
(f)
^ '
(f)
Pb,Cu interfere
(f)
(f)
(f)
(f)
(O
(f)
B, F, Li, Ag , Sr , Na, K
Ca,
to
Si, Mg, Th
standard
(a) Polarography not often used for: Hg, Be,
(b) Accuracy range: standard deviation (%) at macro constituent level
deviation at detection limit, by differential polarography .
(c) Time § costs based on sets of six samples, single-element determinations
considerably less for multi-element determinations in the same sample.
(d) Sample size requirement for elemental determination at stated detection limits.
Larger samples give lower detection limits; smaller samples required for more
abundant elements.
(e) See text for equipment and manpower requirements.
(f) Interfering elements can be separated.
Costs are
-------
Table 3. Analysis of Slurry Streams, Sediments, Process Feeds,
and hater by Polarography
Element
fa")
* '
Cd
As
V
Mn
Ni
Sb
Cr
2n
Cu
Pb
Se
Sn
Fe
U
Accuracv
CTT^"
0.2-10
2-15
2-15
2-15
2-15
2-15
0.2-15
0.2-15
0.2-15
0.2-15
2-15
0.5-15
0.2-15
0.2-15
Time to
Prepare
Samp 1c
TnT)
0.5
1
1
1
1
5
5
5
2
2
1
?
Detect ion
Limit
(PP"0
10 ppb
Sample
(d)
0
0
0
0
0
0
0
0
0
0
0
5
5
1
1
,1
1
1
,1
1
.5
,5
0.1
0.1
Tg)
i
i
i
i
i
i
i
i
i
i
i
i
i
i
Per
Analvsis
Comments
(e)
12
0
6
6
3
3
3
12
12
6
12
In interferes^
(f)
(f)
(f)
CO
(f)
(f)
1 1 interferes
(f)
(f)
(f)
Sr, Na, K, Ca,
Si, Mg, Th
standard
(a) Polarography not often used for: Hg, Be, B, F, Li, Ag , ,
(b) Accuracy range: standard deviation (%) at macro constituent level to
deviation at detection limit, by differential polarography .
(c) Time fj costs based on sets of six samples, single-element determinations. Costs are
considerably less for multi -element determinations in the same sample.
(d) Sample size requirement for elemental determination at stated detection limits.
Larger samples give lower detection limits; smaller samples required for more
abundant elements.
(e) See text for equipment and manpower requirements .
(f) Interfering elements can be separated.
-------
Table 4. lilement Index to References for Table 1.
Fly Ash, Coal, Oil, Organometalli.es, Incinerator
Participates and Minerals by Polarography
Element
Determined References to Bibliography A
Mercury
Beryllium
Cadmium 2,3,6,7,11,12,13,16,25,29,30,32,42,164
Arsenic 2,17
Vanadium 40
Manganese 2,17,25,30,32,34,35,36,43
Nickel 13,13a,18,164
Antimony 3,17
Chromium 15,32,36,46b,46c
Zinc 2,3,11-14,17,25,29,30,31,32,41-44,46c,164
Copper 2,3,8-14,16,25,30,42,46b,46c,164
Lead 2,3,12,13a,16,17,20-32,42,46b,164
Selenium
Boron
Ruorine
Lithium 33
Silver
Tin 37,46b
Iron 2,13a,17,18,36,46b,164
Strontium
Sod i urn 1
Potassium 1
Calcium
Silicon
Magnesium 19
Uranium 38, 39
Thorium
Reviews 45,46,46a
145
-------
Table 5,
Element
Determined
Mercury
Beryllium
Cadmium
Arsen Lc
Vanadium
Manganese
Nickel
Antimony
Chromium
Zinc
Copper
Lead
Selenium
Boron
Fluorine
Lithium
Silver
Tin
Iron
Strontium
Sodium
Potassium
Calcium
Silicon
Magnesium
Uranium
Thorium
Thallium
Element Index to References for Table 2.
Ores, Metals, and Alloys by Polarography
References to Bibliography B
54,57,58,62,68,69,78,85,86,92,93,96-99,116,117,
121-123,126
47,52,71,81,83,95,100
51 ,53,100
50,53,60,70,78,99,103,113,117
47,53,69,70,78,82,90,94,99,119
70,75
51,55,62,66,75,77,78,80,86,92,98-100,103,104
110-113,116-118
48,55,59,62,68,69,70,72-75,78,84,86,91,94,99,100,
103,113-117,119,121,123,124
48,53,56-59,62,67,69,70,73,74,76-78,84,86,87,92-94,
99,100,103-105,114-116,119-121,125-127
61,62,106
88
47,69,70,78,79,89,90,93,103,107,108,126,128,129
53,69,91,99,104,117,121,124
109
Tellurium
52,63,64,69,
70,106
49,65,85,122,
126,127 Reviews 102,131,132
146
-------
Table 6. Element Index to References for Table 3.
Slurry Streams, Sediments, Process Feeds, and
Water by Polarography
Element
Determined
Mercury
Beryllium
Cadmium
Arsenic
Vanadium
Manganese
Nickel
Antimony
Chromium
Zinc
Copper
Lead
Selenium
Boron
Fl uorine
Lithium
Si Iver
Tin
Iron
St ront ium
Sodium
Potassium
Calcium
Silicon
Magnesium
llran ium
Thorium
Bismuth
Reviews
References to Bibliography C
145,148,149,152,153,155,161-164,166,
180-183,186
140-143,186
161,177
145,151,168
152-155,161,163,166,168,177
139
177
138,145,148,149,151-153,155,157,161,
163,164,166,167,178-184,186
137,145-157,163,165,166,181-183,186
137,145,148,149,152,153,155,156,158,
159,161-167,181,183
170
186
135,186
138,164,186
137,145,151,163,156
133-135,186
133,134
133,134,177,186
133, 134, 136, 1-7, 186
171-176,186
139,144,148,161,186
185,186
147
-------
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B. Metals, Alloys, and Ores
Cadmium
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157
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Pb and Pb-Base Alloys
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158
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84. Gertseva, N. S., Polarographic determination of bis-
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85. Maienthal, K. J. , Bismuth, In, Tl, and Cd in Pb-base
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86. Burlacu, (1., Bot, 0., and /Vntonescu, I., Polarographic
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87. Zagorski, Z., Polarographic determination of oxidised
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88. Zagorski, Z., and Kempinski, K., Concentration of Ag
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89. Shinagawa, M., Murata, T., and Yoshida, T., Polarographic
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90. Kovalenko, P. N., and Lektorskaya, N. A., Polarographic
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Ni and Ni-base Alloys
91. Korshunov, I. A., Suzanova, L. N., and Shchennikova, M. K.,
Polarographic determination of copper and iron in crude
and cathode nickel, Zavod. Lab., IT, 569-71 (1947).
92. Yakovlcv, P. Ya., Razumova, G. P., and Malinina, R. D.,
Polarographic determination of impurities in nickel-based
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Zn) , Zavod. Lab., 25, 1039-41 (1959).
159
-------
9.3. Mukhina, Z. S., Tikhonova, A. A., and Zhemchuzhnaya,
I. A., Determination of traces of lead, bismuth, tin
and cadmium in nickel-base alloys, Zavod. Lab., 22,
535-7 (1956).
Ores
94. Morris, A. C. C. , Determination of traces of antimony,
copper and lead in ferromanganese with a cathode-ray
polarograph, Analyst, £7, 478-84 (1962).
95. Cerny, A., Indirect polarographic and complexometric
determination of very small amounts of arsenic in
iron and ores, Hutn. Listy, 1_3, 715-6 (1958).
96. Oshman, V. A., and Chistyakova, A. P., Polarographic
determination of cadmium in an acid sulphate - iodide
supporting electrolyte, Zavod. Lab., 27, 532-36 (1961).
97. Martynova, L. T., and Sochevanov, V. G., Polarographic
determination of Cd in ores, Zavod. Lab., 26, 792-3
(1960). ~
98. Shcherbov, D. P., and Guzhova, E. P., The polarographic
determination of cadmium and zinc in copper ores, Ref. Zhur,
Khim., 1956, abstract no. 32,761.
99. Yonezaki, S. , Polarographic analysis of metals. III.
Rapid determination of copper in iron ore, pyrite cinder,
and sintered ore; IV. Rapid determination of copper,
antimony, lead, cadmium, nickel, zinc, cobalt and iron
in Babbit metal, V. Determination of zinc on galvanized
iron, Nippon-Kinzoku-Gakkai-Shi., 16, 581-4 (1952).
100. Borlera, M. L., Polarographic analysis of iron ores,
(Cu, Mn, Pb, As, S, and Zn), Ric. Sci., 27, 1492-9
(1957). ~
101. Rooney, R. C., Polarographic determination of trace
elements in Fe, J. Polarographic Soc., 1958, 21-4.
160
-------
102. Scholes , P. II., Cathode-ray polarography: typical
applications to metallurgical analysis, R. § D. , 1962,
38-41.
103. Oclone, G. , and Picasso, (i. , Polarographic analysis of
traces of metals in iron ores, (Cu, Pb, Zn, Ni, and Sn),
Chim. e Ind., 4_2, 598-605 (1960).
104. Semerano, G., and Gagliardo, E., Polarographic determina-
tion of iron, lead, and zinc in some zinc ores, Anal.
Chim. Acta, 4, 422-7 (1950).
105. Zelenina, T. P., Polarographic determination of lead in
chromite ores, Sb. Trud. Vses. Nauch.-Issled. Corn.
-Metaluurg. Inst. Tsvet. Met., 1962, 335-8.
106. Aref'eva, T. V., and Vasil'eva, L. N., Polarographic
determination of selenium and tellurium in complex
ores and products of their working, Sb. Trud. Cos. Nauch.-
Issled. Inst. Tsvet. Met., 1962, 669-75.
107. Alimarin, I. P., Ivanov-Emin, B. N., and Pevzner, S. M.,
Trudy Vsesoyuz. Kinferentsii Anal. Khim., 2, 471-92
(1943).
108. Krai, S., and Rett, V., Rapid polarographic determina-
tion of tin in ferrotungsten, metallic tungsten and
tungsten ores, llutn. Listy, 1£, 638-9 (1960).
109. Shinagawa, M. , Murata, T. , and Okashita, II., Polarographic
analysis of uranium. Separation of concomitant ions with
anion-exchange resin, Japan Analyst, :8, 356-61 (1959).
110. Krai, S., and Kysil, B., Polarographic determination of
very small amounts of zinc in ferromanganese and in
manganese ores containing cobalt, Hutn. Listy, 13, 716-7
(1958). ~~
111. Vesela, M., Polarographic determination Zn in Mn, ferro-
manganese and Mn ores, Hutn. Listy, IS, 805-6 (1960).
112. Ringbom, A., and Torn, L., Polarographic determination
of small quantities of zinc in materials rich in iron,
Finska Kemistsamfundets Medd., 56, 12-7 (1947).
161
-------
113. Cooper, W. C., and Mattcrn, P. J., Polarographic de-
termination of small amounts of metals in iron pyrites,
(Zn, Cu, Ni), Anal. Chem., 2_4, 572-6 (1952).
Te and Te Concentrate
114. Pats, R. G., and Semochkina, T. V., Polarographic de-
termination of lead and copper in tellurium and tellurium
concentrate, Zavod. Lab., 2_8, 800-1 (1962).
Sn and White Metal Alloys
115. Itsuki , K., and Kaji, T., Determination of copper and
lead in crude tin by alternating current polarography,
Japan Analyst, £, 568-71 (1959).
116. Pats, R. G., Tsfasman, S. B., and Semochkina, T. V.,
Determination of Cu, Pb, Cd, and Zn in white metallurgy
products on an a.-c. polarograph, Zavod. Lab., 29, 395-
401 (1963).
117. Faucherre, J., and Souchay, P., Polarographic determina-
tion of traces of metals in alloys containing large
quantities of tin, lead, and antimony, (Cu, Fe, Bi, Cd,
Ni, Zn) , Bull. soc. chim. France, 1949, 722-8.
118. Huang, H., Rapid (polarographic) determination of traces
of zinc in tin alloys, Hua Hsueh Tung Pao, 11, 52 (1962).
Ti02
119. Lagrou, A., Vanhees, J., and Verbeek, F., Determination
of traces of Sb, Cu, and Pb in Ti02 by pulse polarography,
Z. anal. Chemie., 224, 310-17 (1967).
U
120. Saito, K., and Takeuchi, T., Determination of trace im-
purities in metallic uranium. XIV. Determination of
lead by alternating-current polarography, Japan Analyst,
10., 152-6 (1961).
-------
Zn and Zn base Alloys
121. Gajan, R. J., and Geehan, D. M., Rapid determination
of aluminum, iron, copper, cadmium and lead in zinc-
base alloys, Rep. Invest. U. S. Bur. Mines, 5727, 10 pp.
(1961).
122. Ensslin, F., Dreyer, H., and Abraham, K., The polarographic
determination of Cd and Tl in the presence of one another,
Metall u. Erz, 3£, 184-7 f!942) .
123. Pletenev, S. A., and Aref'eva, T. V., Determination of
cadmium and copper in zinc sulfate solution by the
polarographic method, Trudy Vsesoyuz. Konferentsii Anal.
Khim., 2_, 451-5 (1943).
124. Kemula, W. , Rubel, S., and Zakrzewska, G., Polarographic
determination of copper and iron in the presence of a
large excess of zinc, Chem. Anal., Warsaw, 8_, 51-8 (1963).
125. Provaznik, J., and Mojzis, J., Application of inversion
polarography for the determination of microgram quantities
of lead in zinc, gallium, antimony and arsenic, Chem.
Listy, 5_5, 1299-1303 (1961).
126. Seith, W. and vor dem Esche, W., The polarographic de-
termination of trace elements in zinc, (Pb, Cd, Tl, Bi,
Sn) , Z. Metallkunde, 33_, 81-2 (1941).
127. Baev, F. K., Polarographic determination of Pb and Tl
impurities when present in Zn salts and Zn, Uch. Zap.
Rostovsk Univ., £0, 163-72 (1958).
128. Hawkings, R. C., Simpson, D. , and Thode, H. G. , The
polarographic determination of tin in high-purity zinc
and zinc die-casting alloys, Can. J. Research, 25B,
322-40 (1947).
129. Sietnieks , A. J., The polarographic determination of
small amounts of tin in zinc die-casting alloys, Acta
Chem. Scand., 6, 1217-22 (1952).
163
-------
Reviews
130. Rooney, R. C., Polarographic determination of trace
elements in Fe, J. Polarographic Soc., 1958, 21-4.
13L. Scholes, P. H. , Cathode-ray polarography: typical
applications to metallurgical analysis, R. fj D.,
1962, 21-4.
132. Milner, G. W. C., Application of the polarograph to
metallurgical analysis. I. Determination of trace
elements in zinc and zinc alloys, Metallurgia, 33,
321-3 (1946).
164
-------
C. Slurry Streams. Feeds to and from Flotation Processes,
Sediments in Flotation Processes, and Water (general)."
133. Proszt, J., and Gyorbiro, K., Polarographic testing of
drinking and usable water. I. Determination of hardness
and alkali-metal content. (K, Na, Ca, and Mg), Chem. Anal.
Warsaw, ^, 21-8 (1956).
134. Proszt, J., and Gyorbiro, K., Polarographic investigation
of potable water and of water for industrial use. The
determination of hardness and of alkalis, (Ca, Mg. and
Na+K), Anal. Chim. Acta, L5, 585-91 (1956).
135. Reznikov, A. A., and Starik-Smagina, A. S., Polarographic
determination of sodium and lithium in natural waters,
Trudy Vsesoyuz, Konferentsii Anal. Khim., 2, 559-72
(1943).
136. Vancells, L. I:., and Casassas, E., Polarographic determina-
tion of magnesium in presence of calcium with 2,2'
dihydroxyazobenzene. Application to analysis of waters
and calcareous materials, Inform. Quim. Analit. Pura Apl.
Ind., 2£, 1-14 (1970).
137. Nicolson, N. J., The application of pulse polarography
in analysis for some metal ions in water (Al, Cu, Pb
and Fe), Tech. Memo. Wat. Res. Ass., TM59. 22 pp. (1970).
138. Hodgson, H. W., and Glover, J. R., Polarographic determina-
tion of aluminum, zinc, and tin in water, Analyst, 76,
706-10 (1951).
139. Mal'kov, E. M., Fedosecva, A. G., and Stromberg, A. G.,
Determination of nanogram amounts of antimony or bismuth
[in natural water] by anodic-stripping voltammetry after
their separation by extraction, Zh. Analit. Khim., 25,
1748-51 (1970).
140. Whitnack, G. C.f and Brophy, R. G., A rapid and highly
sensitive single-sweep polarographic method of analysis
for As (III) in drinking water, Anal. Chim. Acta, 48,
123-7 (1969).
141. Oliver, H. R., Polaroyraphy of arsenic in the mineral
waters of La Bourboule, Bull, Soc. Chim. Biol., 36,
695-:703 (1954). ~~
142. Kozanski, L., Indirect polarographic determination of
arsenate in mineral waters, Chemia Analit., 16, 793-799
(1971).
165
-------
143. Davidyuk, L. A., New polarographic determination of As
in natural H20, Dopov. Akad. Nauk Ukr. RSR, (1966), 90.
144. Mal'kov, li. M., and Fedoseeva, A. G., Determination of
nanogram amounts of bismuth [in natural water] by anodic
stripping [from a mercury-graphite electrode], Zavod.
Lab., 3£, 912-14 (1970).
145. Souabni, A. Es and Nangniot, P., Determination of traces
of cadmium, cobalt, copper, iron, manganese, lead and
zinc in Belgian mineralised natural waters by differential
oscillopolarography under an imposed voltage, Chim. Analyt.,
5_3, 176-182 (1971).
L46. Odier, M., and Plichon, V., Copper in solution in sea
water: chemical form and determination. Study by a.c.
polarography, Anal. Chim. Acta, 55, 209-220 (1971).
147. Kuroda, K., The copper content of the hot springs of
Yunohanazawa, Hakone, Kanagawa Prefecture, and that of
the hot springs of Osoreyama, Aomori Prefecture, Bull.
Chem. Soc. Japan, 1£, 69-74 (1941).
148. Reznikov, A. A., Polarographic determination of small
quantities of copper, bismuth, lead, cadmium, and zinc
in natural waters, Trudy Vsesoyuz. Konferentsii Anal.
Khim., I, 573-84 (1943).
149. Sinko, I., and Dolezal, J., Simultaneous determination
of copper, cadmium, lead and zinc in water by anodic-
stripping polarography, J. Electroanal. Chem., 25,
299-306 (1970). ~~
150. (ihizhevskaya, M. S., The polarographic determination of
copper in industrial effluent waters, Sb. Nauch. Rabot,
Molotov Med. Inst., Molotov, 1955, 79-82.
151. Whitnack, (I. C., Applications of cath'ode-ray polarography
in the field of oceanography. (Cu, Co,1 Zn, Mn,
J. blectroanal. Chem., £, 110-115 (1961).
152. Abdullah, M. I., and Royle, L. G., Determination of
copper, lead, cadmium, nickel, zinc and cobalt in
natural waters by pulse polarography, Anal. Chim. Acta,
5_8, 283-8 (1972).
153. Ullmann, W. W., Pfeil, B. H., Porter, J. D., and Sanderson,
W. W., Voltammetric determination of metals in low con-
centrations [in trade wastes] (Cu, Pb, Ni, Zn, and Cd),
Anal. Chem., 34_, 213-6 (1962).
166
-------
154. Canals, E., Marignan, R., and Cordier, S., Polarographic
analysis of thermal waters. I. Construction of a labora-
tory polarimeter (Cu, Ni and Co), Trav. Soc. Pharm.
Montpellier, 8_, 57-60 (1948).
155. Porter, J. D., Ullman, W. W., Sanderson, W. W., Purdue
Univ., Eng. Bull., Ext. Ser., 1959, 587. (Publ. 1960)
(Cu, Zn, Cd, Pb, and Ni in trade wastes).
156. Samuel, B. W., and Brunnock, J. V., Polarographic method
for parts per billion [U.S.] of copper and lead in catalytic
reformer feedstocks, Anal. Chem., 3_3_, 203-5 (1961).
157. Virf, L., and Makai, V., Identification and determination
of traces of copper, zinc and cobalt in mineral waters by
polarography, Stud. Univ. Babes-Bolyai, Cluj, Chim., £,
221-4 (1963).
158. Kuroda, K., Lead content of the hot springs of Japan,
Bull. Chem. Soc. Japan, 15, 153-5 (1940).
159. Buchanan, E. B., Jr., Schroeder, T. D., and Novosel, B.,
Square-wave polarographic deterination of lead as a pollutant
in river water, Anal. Chem., 4_2, 370-3 (1970).
160. Pohl, F. A., A quick determination method of trace elements
(ppb range) in the reactor water, Z. Anal. Chem., 197,
193 (1963).
161. Bonsels, W., Linnemann, I:. , and.Pohl, F. A., Automated
analysis of very pure water (M, Bi, Cd, Co, Fe, Ga, In,
Ni, Pb, V, Zn, Zr), Z. Anal. Chem., 222, 210 (1966).
162. Kovalenko, 1'. N., Polarographic determination of small
amounts of lead and cadmium in copper electrolytes (rapid
method), Uch. Zap. Rostov, na Don Univ., 41, 123-134
(1958). ~~
163. Wahlin, li. , Polarographic determination of traces of
metals in organic material. Determination of Pb, Cu,
Cd, Ni, Zn and I:e, Acta Chem. Scand., ]_, 956-68 (1953).
164. Visintin, B., Monteriolo, S., and Giuseppi, S. A.,
Polarographic determination of lead, cadmium, tin and
zinc in water, Ann. Idrol., !_, 212-21 (1963).
165. Mal'kov, E. M., l:edoseeva, A. G., Slastenova, 0. A., and
Stromberg, A. G., Determination of traces of lead and
copper [in natural waters and effluents] by anodic-
stripping polarography on a mercury graphite electrode,
Zavod. Lab., 3_6, 1439-41 (1970).
167
-------
166. Weiss, D., and Fidler, J., Oscillopolarogrpahic determina-
tion of low concentrations of heavy metals in mine waters,
(Pb, Cu, Ni, Cd, and Zn), Rudy, ^2, 204 (1964).
167. Popova, T. P., Polarographic determination of lead and
zinc in natural waters, Sh. Nauch. Tekhn. Inform. Min.
Geol. i Okhrany Nedr., (1955) 129-30.
168. Tikhonov, M. K., and Shalimov, G. A., (Ni and Mn in Ocean
H,0), Gidrofiz. i. Gidrokhim. Issled., Akad. Nauk Ukr,
SSR, (1965) 133.
169. Smith, J. D., and Redmond, J. D., Anodic-stripping
voltammetry applied to trace metals in sea water (17 ions)
J. Electroanal. Chem., 3_3, 169-75 (1971).
170. Cervenka, A., and Korbova, M., Polarographic determination
of selenium in water, Chem. Listy, 49, 1158-61 (1955).
171. Antal, P., Sources of error in the polarographic determina-
tion of microgram amounts of uranium (after enrichment of
solid samples and water), Mikrochim. Acta, 2^, 235-44
(1961).
172. Spivakovski, V. B., Zimina, V. A., and Gavrilyuk, L. S.,
Determination of uranium traces in minerals and in natural
waters, Zavod. Lab., 27_, 390 (1961).
173. Koyama, K., Michelson, C. E., and Alkire, G. K.,
Automatic polarograph for continuous measurement of U
in process waste streams, U. S. Atomic Energy Commission,
HW-30148, (1953).
174. Alkire, G. J., Koyama, K., Hahn, K. J., and Michelson,
C. E., Plant-type polarographic system for determining
uranium in radioactive waste streams, Anal. Chem., 30,
1912-15 (1958). ~~
175. Wilson, J. L)., Webster, R. K., Milner, G. W. C., and
Smales, A. A., A comparison of three methods of determining
the concentration of uranium in sea water, Anal. Chim.
Acta, 23, 505 (1960).
176. Milner, G. W. C., Wilson, J. D., Barnett, G. A., and
Smales, A. A., Determination of uranium in sea water by
pulse polarography, J. Electroanal. Chem., 2_ 25-38 (1961).
177. lletman, J. S., Application of polarography to analysis of
sewgge aod industrial wastes (V, Cr, Ni, Co, Ca, Mg, S~,
SO, ,SO,.~tand CN~), Proc. Effl. and Water Treatment Conv.
(1960) 60.
168
-------
178. Kuroda, K., Zinc content of the Hot Springs of Japan,
Bull. Chcm. Soc. Japan, 15_, 88-92 (1940).
179. Macchi, G., Determination of ionic zinc in sea water by
anodic-stripping voltammetry with use of ordinary capillary
electrodes, J. F.lectroanal.'Chem. , 9_,, 290-98 (1965).
180. Ariel, M., and Hisner, U., Trace analysis by A.S.V.
I. Trace metals in Dead Sea brine 1. Zn and Cd,
J. Electroanal. Chcm., £, 362 (1963).
181. Whitnack, G. C., and Sasselli, U., Application of anodic-
stripping voltammetry to the determination of some trace
elements in sea water (Zn, Cd, Pb and Cu), Anal. Chim.
Acta, 4_7_, 267-74 (1969).
182. Muzzarrelli, R. A., Ricardo, A. A., and Laszlo, S.,
Chitosan for the collection from sea water of naturally
occurring zinc, cadmium, lead and copper, Talanta, 18,
853-8 (1971).
183. Allen, II. E., Matson, W. U., and Mancy, K. H., Trace-
metal characterization in aquatic environments by anodic
stripping voltammetry, (Zn, Cd, Pb, Cu), J. Water Pollut.
Contr. Fed.., 4_2, 573-81 (1970).
184. Cravo, M. do Rosario, Polarographic determination of
zinc and iron in natural water, Rev. Port. Quim., 10,
149-156 (1968).
Reviews
185. Maicnthal, E. J., and Taylor, .1. K., Electrochemical
techniques in water analysis, in Water and Water Pollution
Handbook, 4_, 1751 L. L. Ciaccio, ed., Marcel Dekker, N.Y.
(1973).
186. "Polarographic methods in determination of trace inorganics
in water," (Ca, Mg, Na, Li, Al, Zn, Sn, As, Cu, Cl, 0,
IH, Cd, Br, I, F, U), Maienthal, E. J., and Taylor,
J. K., in Trace Inorganics in Water, 172-82, Advances
in Chemistry Series 73, (1968).
169
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CHAPTER 9
POTENTIOMETRY (ION-SELECTIVE ELECTRODES)
Richard A. Durst
1. INTRODUCTION
Ion-selective electrodes, when applicable, provide
one of the simplest analytical methods for measurement
of the concentration of dissolved substances. Modern
electronic potentiometers provide essentially direct
readout in concentration units, independent of operator
skill or judgment. When the substance of interest is
already dissolved, it may be monitored automatically and
continuously.
i
Selectivity is produced in an electrode by selection
or suitable modification of the electrode membrane
material. Thus the glass electrode which is highly
selective for hydrogen ions and provides the best means for
pH measurement, may be made responsive to other univalent
cations by modification of the glass matrix. Selectivity
for other ions is achieved by the use of electrodes
incorporating solid membranes or by use of liquid ion-
exchange membranes as electrodes. Background information
on these and related matters will be found in the general
references (1, 2).
General Considerations
Applicability to most of the sample matrices under
consideration requires a pretreatment procedure involving
sample dissolution and masking of interferences to pro-
vide an appropriate sample in solution form. In certain
cases, process streams - including feeds, effluents, and
slurries - may be monitored directly by electrode sensors
with minimal pretreatment. Ion-selective electrodes are
logarithmic sensors (emf output is proportional to the
logarithm of the concentiation) hence their response,
i.e., precision, is constant over their entire dynamic
operating range. Strictly speaking, the electrodes
respond to ionic activities rather than concentrations.
The latter,- which is ordinarily the quantity of analytical
interest, must be obtained by dividing the activity by
the activity coefficient. This problem can be over-
come by empirical calibration using solutions of known
concentration. Dissolution of the sample in a medium
of constant ionic environment is another procedure that
has been used (1,2). Under ordinary laboratory condi-
tions, an imprecision of approximately 1-5 percent is
normal, while in plant or remote monitoring situations,
170
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5-10 percent imprecision may be expected. Using titration
procedures, which are usually more complex and time
consuming than direct measurements, imprecisions on
the order of 0.1 percent can be achieved. For routine
analyses, automatic titrations and standard addition
techniques using Gran plot end-point detection can
result in rapid determinations while still retaining
the higher accuracy and precision.
Manpower skills required to make electrode measurements
are minimal once the analytical procedures arc developed,
however, sample preparation and pretreatment may be highly
complex and require a technician trained in chemical
manipulations such as wet ashing, separations, and dilu-
tion.
At the present time, there are over two dozen
different kinds of commercially available ion-selective
electrodes. Of these, almost half are suitable for
the determination of elements of interest in this survey.
The cost of these sensors ranges from $150 to $300,
depending on type (i.e., solid-state, liquid ion-
exchange, combination, etc.). Portable, battery-operated
meters are available in the $100 to $SOO range, while more
sophisticated laboratory-based digital readout meters
cost approximately $1,000. In addition, it is usually
convenient to use a recorder ($300 to $2,000, depending
on features) to monitor emf stability and plot titrations,
although this accessory is not required. Other items
such as stirrers, reagents, and glassware are usually
trivial expenses. Thus, an ion-selective electrode
measurement system can be acquired for as little as
$300, or more typically, $1,000 to $2,000.
Analysis costs will depend on the number of samples
to be analyzed, the pretveatment involved which depends
on the matrix of the sample, and the accuracy and pre-
cision desired which determine the particular electrode
procedure to be used, i.e., direct measurement, titration,
addition technique, etc. In general, automated pro-
cedures can be developed based on electrode sensors.
2. APPLICATIONS
Ion-i>clcctive electrodes have not yet found exten-
sive use in the analysis of the process materials sur-
veyed in this report. On the other hand, they are
being used in closely related situations such as for
the analysis and monitoring of industrial wastes.
Accordingly, it is reasonable to assume that they
could provide advantageous methodology in selected
applications. With this in mind, the characteristics
171
-------
of the presently available electrodes are summarized
and references are given to applications that are
related to, or have some aspects in common with the
materials of interest to this report.
A. Cadmium range: 1M to 10"7M (10 ppb) .
pH range of operation: 1 - 14.
interferences: Ag , Hg , and Cu
must be absent; Pb and Fe
must not exceed Cd level.
Applications include industrial wastes, plating
solutions, non-ferrous alloys, and lubricating oils
and greases (3) .
B. Calcium range: 1M to 10"5M (0.4 ppm) .
pll range: 5.5 - 11.
interferences (in decreasing order
. . _+., + + +
of selectivity): Zn , Fe ,
Pb", Cu", Ni", Sr", Mg",
Ba".
Applications include monitoring of process stream
water (hardness), calcium in food processing, and the
calcium content of minerals (5, 6).
C. Copper (ii) range: 1M to 10~7M (6 ppb).
pH range: 0-14.
interferences: Ag and Hg must
.. i
be absent; he must be less
**
than 1/10 Cu level.
Applications include monitoring plating and etching
baths for printed circuit manufacture, oil refining
processes, industrial anil mining waste waters, and deter-
mining copper in ores, minerals and alloys (7, 8).
172
-------
D. Cyanide ranker 10"2M to 10"6M (0.03 ppm).
pH range: 0-14.
interferences: sulfide ion must
be absent; iodide should not
exceed the cyanide level. To
prolong electrode life, an
operating range of <. 10"3M
CN~ is recommended.
Applications include monitoring industrial metal
extractions and certain petrochemical processes, deter-
mination of cyanide in plating baths, rinse tanks, and
metal finishing solutions (9).
Li. Fluoride range: 1M to 10~6M (0.02 ppm).
pH range: 0-9.
interferences: hydroxide ion is
the only significant inter-
ference: OH" concentration must
not exceed F~ level, i.e.,
pOH > pp.
Applications include monitoring municipal water
supplies, electroplating baths, etching and cleaning
solutions, pesticides, industrial waste waters, stack
gases, and minerals (10-21).
F. Lead range: 1M to 10"7M (0.02 ppm).
pH range: 2-14.
interferences: Ag , Hg , and Cu
must be absent from the sample;
Cd and Fe must not exceed
the Pb** level.
Applications include measurement of lead in electro-
plating baths, petroleum products, and non-ferrous alloys
(22).
173
-------
G. Silver/sulfide range: 1M to 10"7M Ag or S~
(0.01 ppm Ag*; 0.003 ppm S=)
pH range: 0-14.
interferences: mercury is the only
interference - must be absent from
the sample solution.
Applications include measurements of silver or sulfide
in industrial process streams and waste waters, e.g., free
sulfide detection in the manufacture of paper and pulp (23,
24, 25).
H. Sodium range: 1M to 10"6M (0.02 ppm)
pH range: 3 - 12.
interferences: the most serious
interference is Ag* to which the
electrode is 10" times more sensi-
tive; II is also a serious inter-
ference but easily controlled by
pll buffering; Li , K , and
Nlli, are minor interferences.
Applications include monitoring high-purity boiler
water, pulping liquors, and the purification effectiveness
of desalination plants (26, 27, 28).
I. Potassium range: 1M to 10"5M (0.4 ppm).
pH range: 2 - 11.
interferences: major interference
from Cs* and Rb ; minor interfer-
ence from NHU, Na , Ag , and Li .
Applications include monitoring potassium in industrial
process streams and in biological fluids (29, 30).
In addition to the above electrodes, several new sensors
have recently become available commercially. However, because
of the newness of these electrodes, interference data are not
yet available. In all cases, one part of an ionic strength
stabilizer solution is added to 50 parts of the sample solu-
tion. A pH adjustment is then made as required.
174
-------
Arsenic (V)
range: 1M to 10~7M (8 ppb)
pH adjustment: 6-8
Chromium (VI) range: 1M to 10"5M (0.5 ppm)
pH adjustment: none
range: 1M to 10~7M (20 ppb)
pH adjustment: none
range: 1M to 10~6M (0.1 ppm)
3. DISCUSSION
Ion-selective electrodes can
specific elements precisely and at
matrices can be suitably modified
the elements as ions in solution.
under consideration in this survey
carried out by chemical means, e.g
This chemical pretreatnent is time
requires considerable skill but in
mated if large numbers of samples
be used to determine
very low levels if the
or degraded to provide
For most of the matrices
, such a conversion can be
., wet ashing with acids.
-consuming and often
many cases can be auto-
are to be processed.
Once the samples are in the appropriate solution form,
the electrode determination is relatively simple and can be
performed by a variety of techniques depending on the
accuracy and precision desired. Using direct potentiometry
or one of the single-increment techniques, imprecisions on
one percent to 10 percent can be achieved by most electrodes,
if interferences are properly masked, from concentrated solu
tions to the one ppm level. At the sub-ppm level, precision
will degrade due to variable blanks, poor ionic buffering,
and slower electrode response. Direct potentiometry or
addition methods arc rapid, requiring only one to five minutes
and are easily portable for field use. For higher precision,
0.1 percent to one percent, titrations or multiple-addition
techniques can be used with a concomitant increase in experi-
mental complexity and time required for the analysis (3 to
15 minutes).
A wide range of sample sizes can be analyzed by electrode
sensors with the upper limit defined only by homogeneity con-
siderations. With miniaturized electrodes, lower sample
volume limits of 1 pi to 10 yl are feasible. For a 10"5M
solution, only about one nanogram (10 9g) of sample element
is required. The feasibility of such microdeterminations has
been reported, e.g., 0.4 ng of fluoride (10 ul) was deter-
mined with an accuracy and precision of about one percent
using a fluoride electrode (31).
175
-------
REFERENCES
(1) Durst, K. A., Editor, "Ion-Select ivc Electrodes," NBS Spec. Publ.
314, U.S. Govt. Printing Office, WashinRten, D.C., 488 pp, (1969) .
(2) Moody, G. J., and Thomas, J. D. R., "Selective Ion Sensitive
Electrodes," Merrow Publishing Company, Watford, England, 147 pp,
(1971). - -
(3) Frant, M. S., and Ross, J. K., Alkaline Pulping Liquor
Analysis, TAPPI 5^, 1753 (1970).
(4) Frant, M. S., Application of Specific Ion Electrodes to
electroplating Analyses, Plating, 686, (1971).
(5) Woolson, E. A., et al., Soil Calcium Determination Using a
Calcium Specific Ion Electrode, Soil Science 109, 279 (1970).
(6) Nakayama, F. S., and Rasnick, B. A., Calcium Electrode Method for
Measuring Dissociation and Solubility of Calcium Sulfate
Dihydrate, Anal- Chem. 3£, 1022 (1967).
(7) Baumann, L. D., and Wallace, R. M., Cupric-Selective Electrode
with Copper (II) - EDTA for End Point Detection in Chelometric
Titrations of Metal Ions, Anal. Chem. 4_1, 2072 (1969).
(8) Frant, M. S. Applications of Specific Ion Electrodes to
Electroplating Analyses, Plating, 686, (1971)
(9) Frant, M. S., ct al., Electrode Indicator Technique for
Measuring Low Levels of Cyanide, Anal. Chem. 44, 2227
(1972)
(10) Elfers, L. A., and Decker, C. E., Determination of Fluoride in
Air and Stack Gas Samples by Use of an Ion Specific Electrode,
Anal. Chem. 4£, 1658 (1968).
(11) Plucinski, E. C., "Determination of Microgram Quantities of
Fluoride in Metal Oxides," U.S. A.E.G. Report BNWL-601, (1968).
(12) Moeken, H. II., et al., The Potentiometric Determination of Fluorine
in Nuclear Fuel Reprocessing Solutions, Anal. Chim. Acta
4_5, 233 (1969).
(13) Ldmond, C. R., Direct Determination of Fluoride in Phosphate
Rock Samples Using the Specific Ion Electrode, Anal. Chem.
41_, 1327 (1969).
176
-------
(14) Guth, J. L.f and Wey, R., A Rapid Determination of Fluoride in
Minerals and Rocks, Bull. Soc. Franc. Mineral. Crist. 92, 105
(1969).
(15) Collis, D. F.., and Diggens, A. A., The Use of a Fluoride Respon-
sive Electrode for "On-Line" Analysis of Fluoridated Water
Supplies, Water Treatment and Examin. 18, 192 (1969).
i i
(16) Pavel, J., et al., Microdetermination of Fluorine in Organic
Compounds by Direct Measurement with a Fluoride Electrode,
Microchem. J. IJj, 192 (1970).
(17) Younghans, R. S., and McMullen, T. B., Fluoride Concentrations
Found in NASN Samples of Suspended Particles, Fluoride 3_, 143
(1970).
(18) Ficklin, W. H., "A Rapid Method for the Determination of Fluoride
in Rocks and Soils, Using an Ion-Selective Electrode," U.S.
Geology Survey Prof. Paper 700-C (1970).
(19) Buck, M., and Reusmann, G., A .New Semi-Automatic Method for
Fluoride Determination in Plant and Air Samples, Fluoride 4_,
5 (1971).
(20) Rinaldo, P., and Montesi, P., Instrumental Techniques for Titration
of Fluoride in Cryolite and Aluminum Fluoride, La Chemica
e L'Industria 5^, 26 (1971).
(21) Svoboda, K., and Ixfeld, H., Sampling and Automatic Analysis
of Gas Forming Fluoride Emission, Stauh-Reinhalt 31, 1-(1971).
(22) Frant, M. S., Application of Specific Ion Electrodes to
Electroplating Analyses, Plating, 686, (1971).
(23) Swartz, J. L., and Light, T. S., Analysis of Alkaline Pulping
Liquor with Sulfide Ion-Selective Electrode, TAPPI 53, 90 (1970).
(24) Muller, D. C., et al., Determination of Silver in Parts per
Billion Range with a Selective Ion Electrode, Anal.
Chem. 4_1, 2038 (1969).
(25) Brunow, G., et al., Reactions of Sulfur during Sulfate Pulping,
Acta Chem. Scand. 2£, 1117 (1972).
(26) Lenz, B. L., and Mold, J. R., Ion-Selective Electrode Method
Compared to Standard Methods for Sodium Determination in Mill
Liquors, TAPPI 5£, 2051 (1971).
(27) Webber, H. M., and Wilson, A. L., The Determination of Sodium in
High Purity Water with Sodium Responsive Glass Electrodes,
Analyst 9£, 209 (1969).
177
-------
(28) Eckfeldt, E. L., and Proctor, W. E.t Low Level Sodium Ion
Measurement with the Glass Electrode, Anal. Chen. 43,
332 (1971).
(29) Frant, M. S., and Ross, J. W., Potassium Ion Specific
Electrode with High Selectivity for Potassium over Sodium,
Science 167, 987 (1970).
(30) Krull, I. H., et al., A Solid Potassium Ion Selective
Electrode, Anal. Letters 3, 43 (1970).
(31) Durst, R. A., Fluoride Microanalysis by Linear Null-Point
Potentiometry, Anal. Chem. 4_£, 931 (1968).
178
-------
CHAPTIiR 10
STANDARD REFERENCE MATERIALS
John K. Taylor
1. INTRODUCTION
Modern instrumental techniques involve measurements
in which a known sample is compared with an unknown. This
may be a direct comparison or, in the more usual case, an
indirect comparison in which the instrument is calibrated
with knowns to obtain linear or curvilinear concentration-
signal relationships. Such relationships are valid for
establishing the composition of unknowns if the calibrants
are reliable, and if they simulate the composition of the
unknown. In many cases, this simulation must be close to
overcome the influence of the matrix on the calibration.
From the foregoing, it is evident that reliable cali-
brants are a necessity for accurate instrumental analysis.
Moreover, matrix-similar reference materials are required
to verify the absence of bias in a given analytical situa-
tion. Furthermore, it is necessary that such reference
materials be of requisite integrity and be available to all
to provide a means of intercalibration by all interested
parties.
Standard Reference Materials certified by the National
Bureau of Standards fulfill all of the above requirements.
An SRM is a well characterized material, of proven homo-
geneity and stability which NBS certifies and distributes
for calibration of measurement systems. Approximately 700
substances are presently available for use in a wide
variety of analytical situations. Many of these are cer-
tified for their trace-element content, and a number of
them simulate the process materials of this report.
The analyst involved in trace element analysis of
environmentally important materials is well advised to
obtain pertinent SRM's which either match or closely simu-
late his analytical samples. Rather than serving as
working standards, these SRM's are best considered as
primary standards which can be used to verify the accuracy
of a method as it is developed and to a limited extent for
quality control purposes. That is, SRM's may be introduced
into an analytical sequence, on occasion, to replace or
supplement the quality control samples normally used.
SRM's can be invaluable for evaluating analytical
procedures during the development process and also in the
collaborative testing of proposed procedures, where they
179
-------
can be used as one of the control samples. An analyst
who has an occasional need to analyze an unfamilar material
will also find an SRM useful to test his competence in a
special situation.
The growing interest in trace-element analysis of
environmentally important materials has stimulated the
development of several SRM's of this nature. The materials
available at the time of preparation of this report are
reviewed in the following sections of this chapter. These
arc classified as of direct interest if the matrix closely
matches environmentally important substances in the area of
this report. There are several SRM's that are of indirect
interest because they simulate the analytical problems of
the environmental analyst and they have been carefully
characterized for their trace element composition. A
brief description of all of these SRM's is also included
in a following section. Catalogues containing full
details and ordering information and cost are available
from the Office of Standard Reference Materials, National
Bureau of Standards, Washington, I). (.'. 20234.
2. SRM'S OF DIRECT I.NVIRONMENTAL INTEREST
A. Fly Ash
SRM 1633, Trace Moments in Fly Ash, is intended as an
analytical standard for the determination of various trace
elements in coal fly ash. It consists of a blend of coal
fly ash obtained from five electric power plants, selected
to cover a broad spectrum of fuel sources from the mining
industry. Four of the ashes were collected by electro-
static precipitators and one by a mechanical collector.
The material was screened and the portion passing through
a 170 mesh sieve was mixed in a double-coned blender.
The certified values given below are based on the analysis
of at least a 250 mg sample of the dried material and is the
minimum amount that should be used.
Element Content yg/g
Manganese 493 i 7
Zinc 210 i 20
Vanadium 214 .-» 8
Lead 70 ± 4
Chromium 131 ± 2
Copper 128 * 5
Nickel 98 * 3
Arsenic 61 ' 6
Uranium 11.6 * 0.2
Selenium 9.4 \ 0.5
Cadmium 1.45 t 0.06
Mercury 0.14 .' 0.01
180
-------
The following values are not certified because they are
based on a non-reference method, or were not determined
by two or more independent methods. They are included
for information only.
Element Content (vg/g)
Potassium [16800)
Strontium (1380)
Rubidium (112)
Cobalt (38)
Thorium (24)
Beryllium (12)
Thallium (4)
B. Coal
1. Trace Elements in Coal
SRM 1632, Trace Elements in Coal, is intended as an
analytical standard for the determination of trace elements
in coal. The material is a blend of commercially available
coals, obtained from five electric power plants, and
selected to cover a broad spectrum of the coal mining
industry. The material was reground as needed and screened.
The portion passing a 120 mesh sieve but retained on a 325
mesh sieve was taken. The five coals, so processed, were
combined and mixed in a double-coned blender.
The certified values given below are based on the
analysis of at least a 250 mg sample of the dried material
and is the minimum amount that should be used for a deter-
mination.
Element Content vg/g
Iron 8700 ± 300
Manganese 40 ± 3
Zinc 37 ± 4
Vanadium 35 ± 3
Lead 30 ± 9
Chromium 20.2 ± 0.5
Copper 18 ± 2
Nickel 15 ± 1
Arsenic 5.9 ± 0.6
Selenium 2.9 ± 0.3
Uranium 1.4 ± 0.1
Thallium 0.59 ± 0.03
Cadmium 0.19 ± 0.03
Mercury 0.12 ± 0.02
181
-------
The following values are reported but not certified
because they are based on a non-reference method, or were
not determined by two or more independent methods (concen-
trations in wg/g) : Titanium (800); Cobalt (6); Silicon
(3.2); Thorium (3.0); Beryllium (1.5).
2. Mercury in Coal
SRM 1630, Trace Mercury in Coal, is available and
certified for its content of this environmentally important
element. The material is a commercial, low-volatile bitu-
minous coal, ground to a particle size of 210 to 500 micro-
meters and contains 0.13 parts per million mercury by weight.
The mercury content of the SRM was determined by neutron
activation analysis and by flameless atomic absorption spec-
trometry. In addition, the selenium content was deter-
mined and is reported as 2.1 parts per million, but this
value is not certified.
3. Sulfur in Coal
SRM 1631 consists of three different low-volatile
bituminous coals, ground to pass a 60-mesh sieve, packaged
separately. Each coal is certified for its sulfur and ash
contents on an as-received basis.
Coal Sulfur, Percent Ash. Percent
A 0.546 ± .003 5.00 ± .02
B 2.016 ± .014 14.59 ± .09
C 3.020 ± .008 6.17 ± .02
The methods of analysis used for certifying this mate-
rial were essentially those identified as ASTM Method D271.
Four laboratories, experienced in the analysis of coal,
cooperated in the certification of this material and their
analytical values were in close agreement with the NBS values
which provide the basis of certification.
C. Fuel Oil
1. Trace Elements in Fuel Oil
Work is in progress at NBS on SRM 1634, Trace Elements
in Fuel Oil, and it is expected to be released for distribu-
tion by June 1975. Certification of the following trace
elements is expected: mercury, selenium, zinc, nickel, lead,
arsenic, beryllium, manganese, vanadium.
182
-------
2. Sulfur in Fuel Oil
Three samples of residual fuel oil and a distillate oil
are available, certified for their sulfur content. These
are representative fuel oils, obtained from a commercial
producer. The certified values are as follows:
SRM
SRM 1624
SRM 1623
SRM 1622
SRM 1621
Type
Distillate
Residual
Residual
Residual
Sulfur Content. Weight Percent
0.211 ± .004
0.268 ± .004
2.14 ± .01
1.05 ± .02
The method of anal/sis used for certification was
essentially ASTM Method D-129 in which sulfur is determined
gravimetrically as barium sulfate after combustion in an
oxygen bomb.
D. Inorganic Materials
A number of SRM's are available in this category. Trace
elements are certified in some instances and minor elements
in most cases. Those available are listed below.
1. Minerals
Chemical Composition
(Nominal Weight Percent as the Oxide)
SRM
Ib
88a
70a
99a
97a
98a
Type
Limestone, argillaceous .
Limestone, dolomitic .
Feldspar, potash .
Feldspar, wda
Clay, flint ...
Clay, plastic
Wt/Unit
((rams)
50
SO
40
40
60
60
SiO,
492
120
671
6S.2
437
489
Ke.O,
0.75
28
075
065
45
1 34
AI.O,
1.12
019
17.9
20.5
388
332
T,0,
0046
02
01
007
1.90
161
MnO
0.20
.03
CaO
50.9
30.1
0.11
2.14
0.11
.31
SRM
Ib
88a
70a
99a
97a
98a
SiO
0 14
01
18
039
MgO
0 36
21 3
n fi?
.15
42
Cr,0,
0.03
.03
Na,0
004
01
2 cc
67
0.037
082
K,0
0 25
12
Uo
57
0.50
1.04
Li,0
0.11
.070
ZrO,
0.063
.042
BaO
002
26
.078
03
Rb,O
n M
P,0,
008
01
n?
.36
.11
CO,
404
46 6
183
-------
2. Ores
These SRM's are intended for use in checking the
accuracy of assay methods. They are certified for their
content of elements of economic interest, and occasionally,
have additional data given for information only. These
SRM's are supplied in the form of fine powders, usually
passing a 100-mesh or finer sieve.
SUM
15 ~
">?..
79a
I13ii
180
181
182
183
Typo
Manganese .
1 luorspar
Zinc, concentrate
Ruoripar. high-grade . .
Lithium (Spodumcne) .
Lithium (Pelalitc) . .
Lithium (LeptdoUte)
Wl/Unil
(Gram)
inn
IN PRI.P
43
43
45
Cal
O1 \Q
Pe
6A ^N
Mn
S7 »<
li.O
s,o,
2 16
36S
H,0,
0 22
P
0042
Available
Oxygen
16 7
Chemical Composition
(Nominal Weight Percent m the Oxide)
SRM
ftQn
VTA
120b
Type
Ranvttp
DallAHC , , . . . .
Phosphate Rock
(Honda)
Wt/Umt
(gram)
*n
JU
90
A1.0,
e* A
JJ.U
1.06
CaO
09Q
i7
4940
P,0,
A All
u uo
3457
S,0,
A ni
D.ul
468
lc,0,
^ ft
J D
1 10
1
384
00,
279
TiO,
2 78
* 1 O
0.1 5
Na,O
-------
SRM
Chemical Composition
(Nominal Weight Percent as the Oxide)
Wt/Unit
(grams) SiOa AlaQ3 Fe20> TiOi Pa05
633
634
635
636
637
638
6^9
1011
1013
1014
1015
1016
SRM
633
634
635
636
637
638
639
1011
1013
1014
1015
1016
Portland
Portland
Portland
Portland
Portland
Portland
Portland
Portland
Port 1 and
Portland
Portland
Portland
CaO
(*SrO)
64.5
62.6
59.8
63.5
66.0
62.1
65.8
66.60
64.34
63.36
61.48
65.26
'B (red)
C (gold)
D (blue)
F (yellow)
G (pink)
I (green)
J (clear)
SrO MgO
0.31 1.04
.12 3.4
.22 1.25
.04 4.0
.10 0.72
.07 3.84
.15 1.29
.11 1.12
.08 1.39
.26 2.80
.11 4.25
.25 0.42
15
IS
IS
15
IS
SO,
2.18
2.16
7.0
2.3
2.33
2.3
2.4
1.75
1.80
2.70
2.28
2.27
21.9
20.7
18.5
23.2
23.1
21.4
21.6
21.03
24.17
19.49
20.65
21.05
MnjOj
0.04
.28
.09
.12
.06
.05
.08
.03
.05
.07
.06
.04
3.74
5.2
6.2
3.1
3.3
4.5
4.3
5.38
3.30
6.38
5.04
4.97
Na20
0.64
.14
.07
.10
.13
.12
.65
.08
.20
.24
.16
.55
4.2
2.87
2.65
1.62
1.80
3.58
2.42
2.07
3.07
2. SO
3.27
3.71
K20 Li
0.165
.43
.45
.57
.245
.59
.05
.26 (0.
.32 (.
.99 (.
.87 (.
.04 (.
0.24 0.
.30
.32
.17
.21
.25
.31
.25
.20
.25
.26
.34
Z0 RbaO
002) (0.001)
001) (.004)
005) (.007)
004) (.005)
012)(<.001)
24
10
17
09
25
06
08
33
20
32
05
13
Loss on
Ignition
0.75
1.61
3.25
1.16
1.68
0.95
1.0
1.13
0.99
.81
1.70
1.20
185
-------
Chemical Composition
(.-\ominal Weight Percent as the Oxide)
oo
in
Wt/llnit
SRM
633
634
635
636
637
638
639
1011
1013
1014
1015
1016
SRM
633
634"
635
636
637
638
639
1011
1013
1014
1015
1016
Type
Portland
Portland
Portland
Portland
Portland
Portland
Portland
Portland
Portland
Portland
Portland
Portland
CaO
(+SrO)
64.5
62.6
59.8
63.5
66.0
62.1
65.8
66.60
64.34
63.36
61.48
65.26
(grams) Si02
B (red)
C (gold)
D (blue)
F (yellow)
G (pink)
I (preen)
J (clear)
15
15
15
15
15
21 .
20.
18.
25.
23.
21.
21.
21.
24.
19.
20.
21.
9
7
5
2
1
4
6
03
17
49
65
05
A1203 Fe
3.74
5.2
6.2
3.1
3.3
4.5
4.3
5.38
3.30
6.38
5.04
4.97
4.
->
*
2.
1.
1.
3 .
2.
2.
3.
2.
3.
3.
2o3
i
87
65
62
80
58
42
07
07
50
27
71
Ti02 P
0.24 0
.30
.32
.17
.21
.25
.31
.25
.20
.25
.20
.54
205
.24
.10
.17
.09
.25
.06
.08
.35
.20
.52
.05
.13
Loss on
SrO MgO
0.31 1.04
.12 3.4
.22 1.25
.04 4.0
.10 0.72
.07 3.84
.15 1.29
.11 1.12
.08 1.39
.26 2.80
.11 4.25
.25 0.42
S03
2.18
2.16
7.0
2.3
2.35
2.5
2.4
1.75
1.80
2.70
2.28
2.27
Mn203
0.04
.28
.09
.12
.06
.05
.08
.03
.05
.07
.06
.04
Na20
0.64
.14
.07
.10
.13
.12
.65
.08
.20
.24
.16
.55
K20
0.165
.43
.45
.57
.245
.59
.05
.26
.32
.99
.87
.04
Li
(0.
(.
(.
(.
(.
20 Rb20
002)(0.001)
001) (.004)
005) (.007)
004) (.005)
012) (<.001)
Ignition
0.
1.
3.
1.
1.
0.
1.
1.
0.
1.
1.
75
61
25
16
68
95
0
13
99
81
70
20
-------
4. Refractories
Chemical Composition
(Nominal Weight Percent as the Oxide)
SRM
I03a
198
i»y
104
Type
Chrome refractory
Wt/Unit
(grams)
60
4S
^5
SiO,
46
2 54
AI.O,
2996
0 16
Afi
84
Total as
Ic.O,
066
1A
7 07
FeO
12.43
TiO,
0.22
.02
rw>
.03
SRM
Irtla
198
199
104
ZrO,
nni
< ni
ni
MnO
01 1
(MR
WIT
.43
P,0,
A AI
(Ml
nn
'.057
Cr,0,
1? fU«
0.026
CdO
A £Q
271
7 41
335
MgO
I O CA
n m
I]
85.67
L,,0
nnni
002
.001
Na,O
not?
01 S
.015
K,0
nnn
094
.015
E. Metals and Alloys
Numerous SRM's are available in this category. They
include steels, irons, high-temperature alloys, steel-
making alloys, aluminum-base alloys, cobalt-base alloys,
copper-base alloys, lead-base alloys, magnesium-base
alloys, selenium-base alloys, tin-base alloys, titanium-
base alloys, zinc-base alloys, and zirconium-base alloys.
High purity metals, including gold, platinum, and
zinc, available in wire, rod, and massive form, have been
certified for their trace-element contents and are recom-
mended especially for the development of new and improved
methods and for extension of sensitivity of detection of
trace constituents by chemical, optical emission, solid
mass spectrometry, and activation analysis. Microprobe
standards are also available in the form of iron-chromium-
nickel alloys, tungsten-molybdenum alloys, gold-silver
alloys, gold-copper alloys, and iron-silicon alloys.
These SRM's are certified for their major constituents and
are intended to calibrate quantitative electron microprobe
analytical techniques.
Because of the large number of SRM's classified under
this category, it is not feasible to list their properties
here. The catalogue available from the NBS office of
Standard Reference Materials should be consulted for
details.
186
-------
F. Metal-Organics
A scries of 24 organic materials with high metal
content are available as reference materials. These are
principally "soaps" of cyclohexanebutyric acid, supple-
mented by other types of compounds, such as chelates of
1-phenyl-l, 3-butane-dione. These materials are stable,
non-volatile, and oil-soluble, so they can be used to
prepare solutions in oil.
as follows:
The SRM's presently available are
SRM
I075a
lOSlb
I063a
I053a
1074a
107 8b
lOSSb
1080
1079b
IOS9b
1060a
106 Ic
I062a
1064
1065b
107la
I066a
1076
1077a
I069b
I070B
1057b
I052b
I073b
Conitini
Element
Al
Ba
B
Crt
Ca
Cr
Co
Cu
le
Pb
Li
Mg
Mn
»g
Ni
P
Si
K
Ag
Nd
Sr
Sn
V
Zn
ent Certified
(wt. percent)
81
28.7
14
24.8
12.5
9.6
148
16.5
10.3
36.7
4 1
6.5
138
16.2
13.9
95
14.1
101
42.6
12.0
20.7
230
13.0
167
Type
Aluminum 2-ethylhe\anoate
Ban urn cyclohexanebutyrate
Menthyl berate ;
Cadmium cyclohexanebutyrate
Calcium 2-ethylhexanoate
Tntf 1-phenyl-l. 3-butanediono)chromium(lll)
Cobalt cyclohexanebutyrate
Bi41-phenyH.3-butanediono)copper(ll)
Tns< 1-phenyl-l ,3-butanediono)iron(III)
Lead cyclohexanebutyrate
Lithium cyclohexanebutyrate
Magnesium cyclohexanebutyrate
Manganoui cyclohexanebutyrate
Men. uric cyclohexanebutyrate
Nickel cyclohexanebutyrate
Triphenyl phosphate
OclaphenyLyclotctrasilovane
Potassium erucate
Silver 2-ethylhexanoate
Sodium cyclohexanebutyiale
Stronoum cyclohexanebulyute
Dibutylnn bis(2-ethylhexanoale)
Bis( 1-phenyl-l, 3- butanediono)oxovanadium(IV)
Zinc cyclohexanebutyrate
3. SRM'S OF INDIRECT ENVIRONMENTAL INTEREST
The SRM's classified under this heading are of interest
in that their analysis simulates many of the problems
encountered in environmental samples. All of them have
been widely used by trace analysts so that their reliability
is well established. The use of such SRM's in the course
of an analytical program thus provides a means to correlate
analytical measurements with those obtained in other fields,
hence they serve as valuable reference materials where
direct interest materials are not available, and are
supplemental materials in other cases.
187
-------
A. Trace Elements in Glass
A series of four glasses containing a variety of trace
elements in the 0.02 to 500 ppm range have been prepared and
provide excellent reference material for determination of
trace-elements in refractory inorganic matrices. The
matrix is a soda-lime glass with the following nominal
composition: 72 percent Si02; 12 percent CaO; 14 percent
Na20; 2 percent A1203.
The material was prepared by addition of the trace
elements to the melt which was mixed, then extruded in the
form of a rod. The reference materials consist of wafers
sliced from the rod and can be obtained in two thicknesses -
1 mm, and 3 mm. Some 35 elements are certified or reported
in these glasses while 26 other elements are known to be
present.
The glasses are homogeneous in composition, from
wafer-to-wafer, but there is some radial segregation. The
certificate describes the limitations on their use.
SRM Trace Elements in Glass
SRM
mw
K09
mo
Kll
lil 2
HI 3
Iil4
fU5
Iil6
tilT
hi*
B19
Type - Matrix
Tran KlemcnlH in HUSH. Set . . .
Trnrr Momenta in HUBS, Sol . . .
1'ruc.e KlemenlB in Hunt. 5110 ppm .
Truer KlemenlB in iliiSH. 500 ppm . .
I'mi-i- Klemenls in HUSH. SO ppm
Tract' Kit-menu in China. 50 ppm . . .
Truce KlementH in Class. 1 ppm . . .
Trace Kle.me.nl9 in CliiHH. 1 ppm ....
Trui c Klemenls in Class, n 02 ppm .
Truce KlemenlH in Class, 0 12 ppm .
Trace Kleinents in Class Set
Truer Kli'mcnts in Clans. Set
Size
Wafers 3 mm Diumeier
Wafers 1 mm Diameter
Wafers 3 mm DIHWUT
Wafers 1 mm Diameter
Wafers .'1 mm Diameter
Wafers 1 mm Diameter
Wafers 3 nun Diameter
Wafers 1 mm Diameter
Wafer* 3 mm Diameter
Wnfers 1 mm Diameter
Wafers 3 nun Diameter
Wafers 1 mm Diameter
Unit of IMUC
Set 2 e»i:h614 and 8 16
N-t: 2 each B 15 and 6 17
fi Wafers
li Wafers
h Wafers
li Wafers
li Wnfers
ti Wafers
H Wafers
h Wafers
S-l: 1 each 610, li 12,
(>I4 and 816
Set: 1 each (ill, « 13.
HIS and K 17
Clement
Antimony. .
Barium .
Boron ....
Cadmium .
f'enum .
Chromium
Cobalt . . .
Copper
Dysprosium .
Krbium .
606
607
610-611
500 ppm
1351)
(444)
612-G13
50 ppm
id 11
(32)
(39)
( 'is "ii
(17 71
( '₯!»
614-615
1 ppm
f t (\t\\
(1 3))
(0 55)
(() 41)
07 i
134
616-617
0.02 ppm
in mn\
lu.u/o)
(0.20)
(0.65)
188
-------
SRM Trace Elements in Glass (contd)
Clement
Kurpoium ....
Gadolinium . . .
Gallium
OJold
Indium
Lunthiinum . . .
|,eiid
Manganese. . . .
Molybdenum. . .
Npodymium . .
Nickel
Potassium . . .
Silver . ...
Strontium. . . .
Thallium. . . .
Thorium . ...
Titanium . .
Uranium . . .
Ytterbium ....
606 607
!)
(4<» 11
425 7
(2541
5lr) 5
((> 1 8)
457 2
(437>
4ril 5
( 433)
612-013
SO ppm
(36)
(39)
fit
m
CWi
M«7
<39 rit
(3t>)
18 H
(64)
- - -
11 A
Cfi)
22 0
78 4
(157)
37 74
(50 1)
37 »
(49)
614-615
Ippm
(0 94)
nil
/ft C|
ift 7^1
It ^
/fi 00|
o 19
(1 41)
(I) Oil
.T)
ORSS
(0 59)
0 42
45 g
(0 2m)
0 748
(.1 1)
0823
t O A1\
616-617
0.02 ppm
m 9D
/n oc;\
Mil
1 ft^
(065)
29
in nqqo\
(0 02ti)
41 72
(00082)
00252
(2.5)
0.0721
In addition to thu 35 eli-im-ntn liNtrd abovr, ihc Chiss SKM'H cnntuin thi- fnllowniB 2B elrments: As. tie, Bi.
Cs. CI. H\ O.-. llf, UK. Li. l.u. MK. Nli. P. Pr. .Sr. ,S, Tn, TI-. Tli, Tm. Sn. W. V. Y. and /.r
B. Orchard Leaves
SRM 1571 Orchard Leaves was intended for use in the
calibration of apparatus and methods used in the analysis of
agricultural and other botanical materials for major, minor,
and trace elements. However, because of the variety of
elements certified, and the fact that it closely simulates
the kind of sample often obtained in environmental measure-
ments, such as those collected for particulate analysis,
it has been widely used for analytical methodology
investigations.
The elements listed below have been determined by at
least two analytical techniques and the uncertainties
represent those due to analytical measurement and homo-
geneity of a 250 mg sample.
189
-------
Element Content
A. Major Constituents Wt. Percent
Nitrogen 2.76 ± 0.05
Calcium 2.07 ± 0.03
Potassium 1.47 ± 0.03
B. Minor Constituents Wt. Percent
Magnesium 0.62 ± 0.02
Phosphorous 0.21 ± 0.01
C. Trace Constituents Ug/g
Iron 300 ± 20
Manganese 91 ± 4
Sodium 82 ± 6
Lead 45 ± 3
Boron 33 ± 3
Zinc 25 ± 3
Arsenic 14 ± 2
Copper 12 ± 1
Rubidium 12 ± 1
Nickel 1.3 ± 0.2
Mercury 0.155 ± 0.015
Cadmium 0.11 ± 0.02
Selenium 0.08 ± 0.01
Uranium 0.029 ± 0.005
In addition to the above elements, the following
elements have been determined but their content is not
certified because of minor analytical problems or because
they have been measured by only one technique: bismuth,
bromine, chlorine, chromium, cobalt, fluorine, lithium,
strontium, sulfur.
The analytical techniques used in the certification of
this material included: atomic absorption spectroscopy;
flame emission spectroscopy; isotope dilution mass-
spectrometry; neutron activation analysis; polarography;
optical emission spectroscopy; photon activation analysis;
nuclear track technique.
C. Bovine Liver
SRM 1577 Bovine Liver is the first animal tissue
material certified by NBS for its trace element content.
It is useful not only to those concerned with the effects
of trace elements from environmental pollution, but as a
190
-------
general trace element standard where a predominantly
organic matrix is present.
The material is certified for the following
elements:
L lenient Content
(Wt. Percent)
Nitrogen 10.6 ± 0.6
Potassium 0.97 ± 0.06
Sodium 0.243 ± 0.013
Cng/s)
Iron 270 ± 20
Copper 193 ± 10
Zinc 130 ± 10
Rubidium 18.3 ± 1.0
Manganese 10.3 ± 1.0
Selenium 1.1 ±0.1
Lead 0.34 ± 0.08
Cadmium 0.27 ±0.04
Mercury 0.016 ± 0.002
In addition to the above elements, the contents of the
following are reported but not certified because only one
technique was used in their determination: arsenic;
calcium; chlorine, cobalt; magnesium; molybdenum; silver;
strontium; thallium; uranium.
191
-------
SUPPLEMENTAL REFERENCES
Because of space limitations, the chapter references
have been limited to those directly concerned with the sub-
ject matter of this document. However, many additional
references were collected and reviewed and the decision for
rejection was often difficult. Accordingly, some of those
of considerable peripheral interest are given below to pro-
vide supplemental information of a general or specific
nature. The titles of the papers are descriptive of their
contents.
General
von Lehmden, I). J., R. II. Jungers, and R. E. Lee, Jr.,
Determination of trace elements in coal, fly ash, fuel oil,
and gasoline -- a preliminary comparison of selected
analytical techniques, Anal. Chem. 46, 239-245 (1974).
Machata, G., Trace analysis of metals in dusts and biological
material, Zbl. Arbeitsmed. 2_3(1), 4-6 (1973). In German.
(Air Pollution Abstr. 27629, June 1973).
Struempler, A. W., Adsorption characteristics of silver,
lead, cadmium, zinc and nickel on borosilicate glass, poly-
ethylene, and polypropylene container surfaces, Anal. Chem.
4^, 2251-4 (1973).
Yamagata, N., Reliability of sampling. In Japan Society of
Analytical Chemistry Symposium on Pollution and Analytical
Chemistry, 7th, Tokyo, Japan, March 16, 1973. Paper 4. In
Japanese. (Air Pollution Abstr. 28837, Aug. 1973).
Nuclear Methods .
Aras, N. K., W. H. Zoller, G. E. Gordon, and G. J. Lutz,
Instrumental photon activation analysis of atmospheric par-
ticulate material, Anal. Chem. ££, 1481-1490 (1973).
Dale, I. M., II. J. Duncan, and C. McDonald, Neutron activa-
tion analysis of atmospheric particulates. Radiochem.
Radioanalyt. Lett. L5, 77-86 (1973).
Dams, R., J. A. Robbins, K. A. Rahn, and J. W. Winchester,
Nondestructive neutron activation analysis of air pollution
particulates, Anal. Chem. 42, 861-867 (1970).
192
-------
Dams, R., K. A. Rahn, J. A. Robhins, G. I). Nifong, and
J. W. Winchester, Multi-element analysis of air pollution
particulates by nondestructive neutron activation, pp 509-
516. In "Proceedings of 2nd International Clean Air Congress,1
Washington, D.C., Dec. 6-11, 1970. Academic Press, N.Y. 1971.
Gordon, G. E., Instrumental activation analysis of atmos-
pheric pollutants and pollution source materials, pp 138-143.
"Proceedings of International Symposium on Identification
and Measurement of Environmental Pollutants," in B. Westley,
lid., National Research Council of Canada, Ottawa, Ont. 1971.
Gray, I)., D. M. McKown, M. Kay, M. I'.ichor, and .J. R. Vogt.,
Determination of trace element levels in atmospheric pollu-
tants by instrumental neutron activation analysis, IEEE
Trans. Nucl . Sci. 1_9, 194-198 (1972).
Kelly, .1. -J. , Neutron-activation analysis, pp 535-556. In
M. Zief, and R. Speights, lids., "Ultrapurity: Methods and
Techniques," Marcel Dekker, N.Y. 1972.
Kuykendall, W. li., .Jr., L. If. Fite, and R. E. Wainerdi,
Instrumental neutron activation analysis of air filter
samples, J. Radioanal. Chem. lj), 351-358 (1974).
Pillay, K. K. S. and C. C. Thomas, Jr., Determination of
the trace element levels in atmospheric pollutants by neutron
activation analysis, .J. Radioanal. Chem. 7_, 107-118 (1971).
Rahn, K. A., R. Dams, .J . A. Robbins, and J. W. Winchester,
Diurnal variations of aerosol trace clement concentrations
as determined by nondestructive neutron activation analysis,
Atnos. Environ. j>, 413-422 (J971).
Schramel, P., K. Samsahl, and J. Pavlu, Determination of 12
selected microelements in air particles by neutron activation
analysis, J. Radioanal. Chem. lj), 329-337 (1974).
Winchester, J. W., Application of neutron activation analysis
to the investigation of natural and pollution aerosols,
J. Radioanal. Chem. 1J9, 311-317 (1974).
X-Ray Fluorescence Methods
Birks, L. S. and J. V. Gilfrich, "Development of x-ray
fluorescence spectroscopy for elemental analysis of parti-
culate matter in the atmosphere and in source emissions.
Phase II, Evaluation of commercial multiple crystal spectro-
meter instruments." NRL Report 7617, EPA-650/12-73-006.
Environmental Protection Agency Interagency Agreement 690114,
Naval Research Laboratory, Washington, D.C., June 1973.
193
-------
Birks, L. S., J. V. Gilfrich, and P. G. Burkhalter, "Devel-
opment of x-ray fluorescence spectroscopy for elemental
analysis of particulate matter in the atmosphere and in
source emissions," NRL Report i:PA-R2-72-063. Naval Research
Laboratory, Washington, D.C., November 1972.
Cooper, J. A., Comparison of particle and photon excited
x-ray fluorescence applied to trace element measurements on
environmental samples, Nucl. Instrum. Meth. 106, 525-538
(1973).
Giauque, R. D., L. Y. Goda, and N. 1:. Brown, Characteriza-
tion of aerosols in California by x-ray induced x-ray
fluorescence analysis, linviron. Sci. Technol. £, 436-441
(1974).
Gilfrich, J. V., P'. G. Burkhalter, and L. S. Birks, X-ray
spectrometry for particulate air pollution - a quantitative
comparison of techniques, Anal. Chem. £5, 2002-2009 (1973).
Hammerle, R. II., R. II. Marsh, K. Rengan, R. D. Giauque, and
J. M. Jaklevic, Test of x-ray fluorescence spectrometry as
a method for analysis of the elemental composition of atmos-
pheric aerosols, Anal. Chem. £5, 1939-1940 (1973).
Mitsugi, H., N. Takata, M. Motoyama, M. Akamatsu, and
G. Hashizume, Determination of zinc and lead in suspended
particulates by fluorescent x-ray spectrometry, Japan Analyst
19, 1383-1388 (1970). In Japanese. (C.A. 74_, 45337J).
Mizohata, A. and T. Mamuro, F-lemental analysis of airborne
dust by energy-dispersive fluorescent x-ray spectrometry,
Annu. Rep. Radiat. Cent. Osaka Prefect. 15, 16-22 (1972).
See also 14_, 19-22 (1973). In Lnglish.
Rhodes, J. R., Energy-dispersive x-ray spectrometry for
multielement pollution analysis, Am. Lab. ^(7), 57-73 (1973).
Atomic Absorption Methods
Brodie, K. G. and J. P. Matousek. Determination of cadmium
in air by non-flame atomic absorption spectrometry, Anal.
Chin. Acta 6£, 200-202 (1974).
Kanno, S., Heavy metals (.atomic absorption spectrophotometry),
Japan Clin. 3_1 (6) , 1955-(«5, June 1973. In Japanese. (Air
Pollution Abstr. 30144, Oct. 1973).
-------
Lee, R. N., Trace metal analysis by atomic absorption spec-
trometry using a graphite furnace atomizer, in Pacific
Northwest Laboratory Annual Report for 1972 to the USAEC Div.
of Biomedical and I'.nvironmental Research, Vol. II: Physical
Sciences, Part I. Atmospheric Sciences, pp 85-87. Battelle
Memorial Inst., Richland, Wash., Pacific Northwest Labs.,
April 1973. (Mr Pollution Abstr. 34455, April 1974).
Matousek, J. P. and K. G. Brodie. Direct determination of
lead airborne particulates by nonflame atomic absorption,
Anal. Chem. 4_5, 1606-1609 (1973J.
Ranweiler, I.. P.. and J. L. Moyers, Atomic absorption proce-
dure for analysis of metals in atmospheric particulate
natter, Lnviron. Sci. Technol . 8, 152-156 n, 270-275 (1971).
Rokosz, A. and A. Grajpel, Emission spectrographic determina-
tion of non-homogeneity of laboratory samples of industrial
dusts, Chem. Anal. (Warsaw) 18(3), 593-598 (1973). In Polish.
(C.A. 7£, 139487p). ~
Sacks, R. D., and S. W. Brewer, Jr., Metals analysis in parti-
culate pollutants by emission spcctroscopy, Appl. Spectres.
Rev. 6_, 313-349 (1972).
195
-------
SugLmae, A., Rmission spectrographic determination of trace
elements in airborne particulate matter collected on silver
membrane filter, Appl. Spectry. 28^, 458-461 (1974).
lilectrochemical Methods
Colovos, G., G. S. Wilson, and J. Moyers, Determination of
trace amounts of zinc, cadmium, lead and copper in airborne
particulate matter by anodic stripping voltammetry, Anal.
Chim. Acta 6£, 457-464 (1973).
Ishii, T., Polarographic analysis of air pollutants (1),
analysis of inorganic materials, J. Pollution Control, £(6),
565-572 (June 1972). In Japanese. (Air Pollution-Abstr.
22395, Sept. 1972).
Matson, W. R., R. M. Griffin, and G. B. Schreiber, Rapid
subnanogram simultaneous analysis of Zn, Cd, Pb, Cu, Bi, and
Tl, pp 396-406. In D. Hemphill, Ed. "Trace Substances in
Environmental Health," Proc. 4th Conference, University of
Missouri, Columbia, Mo. 1971.
USCOMM-NBS-UC
196
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TECHNICAL REPORT DATA
(Plcaif read ImUr^etlont on the rtvent before completing)
1 REPORT NO
EPA-650/2-74-I25
3 RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE
Pollutant Analysis Cost Survey
5. REPORT DATE
December 1974
6. PERFORMING ORGANIZATION CODE
7. AUTHORIS)
Bernard Greifer and John K. Taylor
8. PERFORMING ORGANIZATION REPORT NO
. PERFORMING ORAANIZATION NAME AND ADDRESS
U.S. Department of Commerce
National Bureau of Standards
Washington, DC 20230
10 PROGRAM ELEMENT NO.
1AB013: RQAP 21ADD-BJ
11. CONTRACT/GRANT NO.
TAG 215
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 6/72-6/74
14. SPONSORING AGENCY CODE
8. SUPPLEMENTARY NOTES
6. ABSTRACT
The report summarizes various approaches to the chemical
analysis of heavy industry process materials and effluents for trace
element constituents that might contribute to environmental pollution.
It assesses the capabilities and costs of nuclear methods, spark source
mass spectrometry, x-rav fluorescence and electron and ion microprobe
spectrometry, atomic absorption spectrometry, absorption spectro-
photometry, atomic emission spectroscopy, voltammetry (polarography) and
potentiometry (ion-selective electrodes) for determining traces (less
than 100 ppm) of Hg, Be, Cd, As, V, Mn, Ni, Sb, Cr, Zn, Cu, Pb, Se,
B, F, Li, Ag, Sn, Fe, Sr, Na, K, Ca, Si, Mg, U, and Th in such matrices
as fly ash, coal, oil, ores, minerals, metals, alloys, organometallics,
incinerator particulates, slurry streams, and feeds to and from sedi-
mentation processes. The report includes a selected bibliography of
the current literature, and a review of the Standard Reference
Materials available for environmental analysis.
This report supersedes NBSIR 73-209, "Survey of Various
Approaches to the Chemical Analysis of Environmentally Important
Materials", of which it is a revision and extension.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Air Pollution
Water Pollution
Cost Effectiveness
Environmental Tests
Industrial Wastes
Emission Spectroscopy
Electron Probes
Polarography
Spectrophoto-
metry
X Ray Fluor-
escence
Air Pollution Control
Stationary Sources
Trace Elements
Particulates
Atomic Absorption
13B
14A
14B
20F
8 DISTRIBUTION STATEMENT
IB. SECURITY CLASS (ThilReport/
Unclassified
21. NO. OF PAGES
208
Unlimited
20. SECURITY CLASS (Thllpagt)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
197
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