NBSIR 73-209

Survey of Various Approaches to the

Chemical Analysis of Environmentally

Important Materials

Bernard Greifer and John K. Taylor

National Bureau of Standards

Department of Commerce

Washington. D. C. 20234

July 1973

Final Report

Prepared for The Environmental Protection Agency

Office of Research and Monitoring

Research Triangle Park, North Carolina 27711
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NBSIR 73-209

SURVEY OF VARIOUS APPROACHES TO THE

CHEMICAL ANALYSIS OF ENVIRONMENTALLY

IMPORTANT MATERIALS

Bernard Greifer and John K. Taylor

National Bureau of Standards

Department of Commerce

Washington, D. C. 20234

July 1973

Final Report

Prepared for The Environmental Protection Agency

Office of Research and Monitoring

Research Triangle Park, North Carolina 27711

U. S. DEPARTMENT OF COMMERCE, Frederick B. Dent, Secretary

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts. Director
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SURVEY OF VARIOUS APPROACHES TO THE CHEMICAL ANALYSIS

OF ENVIRONMENTALLY IMPORTANT MATERIALS

Bernard Greifer and John K. Taylor, Editors

Report to

Office of Research and f^onitoring

The Environmental Protection Agency

Research Triangle Park, N. C. 27711

NBS - EPA - I AG 0215 (D)

Analytical Chemistry Division

Institute for Materials Research

U. S. Department of Commerce

National Bureau of Standards

Washington, D. C. 20234
TABLE OF CONTENTS

PAGE

INTRODUCTION 2 by Bernard Greifer

1. REPORT FORMAT 2 A. Scope of Report 3

B. Organization of Rep'ort 5 2. TRACE ANALYSIS OF REAL SAMPLES 8

A. Materials Balances 8

B. Matrices of Interest^ 10

C. Sampling . . . ^ . .12

D. Choice of Analytical Method 14

3. REFERENCES. ...... ........ .16

NUCLEAR METHODS 17

by Donald A. Becker

1. INTRODUCTION 17

2. NUCLEAR METHODS 17

A. Activation Spectrometry 17

B. Neutron Activation Analysis 18

C. Fast Neutron Activation Analysis 18

D. Charged Particle Activation Analysis 19

E. Photon Activation Analysis 19

F. Nuclear Track Technique 20

G. Isotope Dilution Analysis 20

3. ANALYTICAL APPLICATION TO SPECIFIC MATERIALS. . . .21

A. Fly Ash 22

B. Coal 22

. C. Oil 23

P. Ores and Minerals 23

E.. Metals and Alloys 24

F. Organom.etallics 25

G. Incinerator Particulates 25

H. Slurry Streams, Feeds to/from Flotation . . . .25

Processes, and Sediments in Flotation

Processes

4. RESULTS AND DISCUSSION 26

5 . REFERENCES 33

ii
TABLE OF CONTENTS (Continued)

PAGE

SPARK SOURCE MASS SPECTROMETRY 4 3

by Paul J. Paulsen

1. INTRODUCTION 43

A. Interferences 45

B. Sample Requirements 46

C. Sensitivity 46

2. PRECISION OF MEASUREMENTS BY SSMS. 4 7 3. ACCURACY OF ANALYSIS BY SSMS 4 7 A. No Standards Used; Concentrations Estimated. . .48

B. Analysis Using Standard Reference Materials. . .49

(SRM' s)

C. Analysis Using Synthetic Standards 50

D. Analysis Using Stable Isotope Dilution 51

4. PROCEDURE FOR ANALYSIS OF MATERIALS 5 2 A. Group I Matrices 53

B. Group II Matrices 54

C. Group III Matrices (metals and alloys) 55

5. ANALYSIS BY ISOTOPE DILUTION .56

6. ELEMENT COVERAGE OF SSMS ANALYSIS 59

7. COST (TIME) OF ANALYSIS BY SSMS 60

8. CONCLUSION 62

9. REFERENCES 66

X-RAY FLUORESCENCE AND ELECTRON MICROPROBE METHODS 71

by Stanely D. Rasberry and Kurt F. J. Heinrich

1. X-RAY FLUORESCENCE 71

A. Application to Matrices of Environmental . . . .78

Interest

1. Fly Ash and Incinerator Particulates . . . .78

2. Coal 79

3. Oil 79

4. Ores, Minerals and Cement 80

5. Metals and Alloys 81

6. Organometallics 81

7. Slurry Streams, and Feeds and Sediments in. .82

Flotation Processes

8. Slags and Glass 82

iii
TABLE OF CONTENTS (Continued)

. PAGE

X-RAY FLUORESCENCE AND ELECTRON MICROPROBE METHODS (Continued)

2. ELECTRON PROBE MICROANALYSIS 83

• 3. REFERENCES 95

ATOMIC ABSORPTION SPECTROMETRY . .107

by Theodore C. Rains

1 . INTRODUCTION 107

.2.,, INSTRUMENTATION AND TECHNIQUE 108

A. Interferences , 110

S. SAMPLE REQUIREMENTS Ill

A. Sampling 112

B. Sample Preparation .112

4. APPLICATION TO MATERIALS OF ENVIRONMENTAL INTEREST. .115

5. "RESULTS AND CONCLUSIONS 116

A. Tabulated Information ..... 116

B. Costs , 117

C. Conclusions 117

6. REFERENCES 125

ABSORPTION SPECTROPHOTOMETRY 131

by R. W. Burke

1. INTRODUCTION , , 131

2. ANALYSIS OF SPECIFIC MATERIALS 132

3. CONCLUSIONS 134

4. REFERENCES. 138

ATOMIC EMISSION SPECTROSCOPY 144

by Danold W. Golightly

1. INTRODUCTION. , 144

A. Optical Emission Sources 144

B. Chemical Preconcentr at ion .149

2. APPLICATION TO MATERIALS OF ENVIRONMENTAL INTEREST. .149

A. Group 1 - Streams to and from Air Scrubbers . . .150

B. Group 2 - Metals and Alloys (Fe, Al , Cu, Pb, Zn).150

iv
TABLE OF CONTENTS (Continued)

PAGE

ATOMIC EMISSION SPECTROSCOPY (Continued)

C. Group 3 - Ores, Minerals, and Sediments from. . 152

Coal Flotation Processes

D. Group 4 - Coal, Feeds to Coal Flotation .... 153

Processes, Organometallics (formed by Combustion

Processes)

E. Group 5 - Fly Ash and Incinerator Particles . . 153

3. COST (TIME) OF ANALYSIS 153

A. Survey Analyses 153

B. Quantitative Analyses 155

4. REFERENCES 162

VOLTAMMETRY (POLAROGRAPHY) 173

by E. June Maienthal

1. INTRODUCTION 173

A. Background. 174

2. APPLICATIONS TO ENVIRONMENTAL ANALYSIS 177

3. CONCLUSIONS 185

4. REFERENCES , 193

5. BIBLIOGRAPHY 195

A. Fly Ash, Coal, Oil, Organometallics, 195

Incinerator Particulates and Minerals

B. Metals, Alloys, and Ores 200

C. Slurry Streams, Feeds to and from Flotation . . 210

Processes, Sediments in Flotation Processes,

and Water (general)

POTENTIOMETRY ( ION- SELECTIVE ELECTRODES) 215

by Richard A. Durst

1. INTRODUCTION , 215

A. General Considerations 215

2. APPLICATIONS 218

A. Cadmium 218

B. Calcium , . 219

V
TABLE OF CONTENTS (Continued)

PAGE

POTENTIOMETRY ( ION- SELECTIVE ELECTRODES) (Continued)

C . Copper 219

D. Cyanide 219

E. Fluoride 220

:

' F . Lead ,,..,...,220

G. Silver/sulfide 220

H . Sodium 221

I . Potassium 221

3. DISCUSSION 221

4. REFERENCES ..... 224

vi
LIST OF TABLES

NUCLEAR METHODS

1. Trace Elements in Environmental Materials 31

2. Element Index to References Nuclear Methods 32

SPARK SOURCE MASS SPECTROMETRY

1. Simultaneous Determination of Twenty-seven Elements. 64

by Spark-Source Mass Spectrometry in Typical Coal

and Fly Ash Samples

2. Subject Index to References 65

X-RAY FLUORESCENCE AND ELECTRON MICROPROBE

1. Analysis of Fly Ash and Incinerator Particulates . . 87

by X-Ray Fluorescence

2. Analysis of Coal by X-Ray Fluorescence 88

3. Analysis of Oil and Organometal 1 ics by X-Ray .... 89

Fluorescence

4. Analysis of Ores, Minerals and Cements by X-Ray. . . 90

Fluorescence

5. Analysis of Metals and Alloys by X-Ray Fluorescence. 91

6. Analysis of Slurry Streams, Feeds and Sediments by . 92

X-Ray Fluorescence

7. Analysis of Slags and Glasses by X-Ray Fluorescence. 93

8. Analysis of Particulates by the Electron Probe ... 94

Microanaly zer

ATOMIC ABSORPTION SPECTROMETRY

1. Analysis of Metals and Alloys by Atomic Absorption .119

Spectrometry - Flame Method

2. Analysis of Fly Ash, Ores and Minerals by Atomic . .120

Absorption Spectrometry - Flame Methods

3. Analysis of Fly Ash, Ores, Minerals, Metals and. . .121

Alloys by Atomic Absorption Spectrometry - NonFlame Methods

4. Analysis of Slurry Streams and Process Streams by. .122

Atomic Absorption Spectrometry - Flame Methods

5. Analysis of Coal, Oil, Organometal 1 ic s by Atomic . .123

Absorption Spectrometry - Flame Methods

6. Analysis of Coal, Oil and Organometallics by . . . .124

Atomic Absorption Spectrometry - Non-Flame Methods

ABSORPTION SPECTROPHOTOMETRY

1. Analysis of Coal, Oil, Organometallics, Metals, and. 136

Alloys by Absorption Spectrophotometry

2. Analysis of Fly Ash, Ores, Minerals, Incinerator . .137

Particulates, Slurry Streams, Process Feeds by

Absorption Spectrophotometry

vii
LIST OF TABLES (Continued)

PAGE

ATOMIC EMISSION SPECTROSCOPY

'

1. Summary of Spectrographic and Spec tromet r ic .... 156

Detection Limits

2. Summary o£ Spectrographic and Spectrometr ic .... 157

Analysis of Various Materials

3. Index to Emission Spectroscopy References ..... 158

4. Estimates of Time Required for Several Types. . . . 159

of Spectrographic and Spectrometr ic Analyses

VOLTAMMETRY (POLAROGRAPHY)

1, Analysis of Fly Ash, Coal, Oil, Organometall ics , . . 187

Incinerator Particulates, and Minerals by

Polarography

2, Analysis of Ores, Metals, and Alloys by Polarography 188

3. Analysis of Slurry Streams, Sediments, Process . . 189

Feeds, and Water by Polarography

4, Element Index to References for Table 1 190

5. Element Index to References for Table 2 ..... . 191

6. Element Index to References for Table 3 ..... . 192

viii
LIST OF FIGURES

PAGE

INTRODUCTION

1. Applications of trace element analysis to 9

monitoring materials, process streams, and

effluents of a typical industrial process

X-RAY FLUORESCENCE AND ELECTRON MICROPROBE

1. X-ray fluorescence analyzer

2. X-ray fluorescence spectra of liquid paints .... 75

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

3. Calibration curve for determination of lead in. . . 76

dry paint powder, following preparation by

dilution with a common matrix (ZnO) ; obtained

using the same conditions as given in Figure 2

ix

SURVEY OF VARIOUS APPROACHES TO THE CHEMICAL ANALYSIS

OF ENVIRONMENTALLY IMPORTANT MATERIALS

ABSTRACT

Various approaches to the chemical analysis o£ heavy

industry process materials and effluents for trace element

constituents that might contribute to environmental pollution are summarized.

The capabilities and costs of nuclear methods, spark

source mass spectrometry, x-ray fluorescence and electron

microprobe spectrometry, atomic absorption spectrometry,

absorption spectrophotometry, atomic emission spectroscopy,

voltammetry (po larography) and potent iometry ( ion- select ive

electrodes) for determining traces (less than 100 parts

per million) of 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 such matrices as fly

ash, coal, oil, ores, minerals, metals, alloys, organometallics, incinerator particulates, slurry streams, and

feeds to and from sedimentation processes have been

assessed.

The report includes a critically selected bibliography

of the current literature.

Key words: Air pollution; atomic absorption; electron

microprobe; emission spectroscopy; environmental analysis; industrial effluents; ionselective electrodes; nuclear activation

analysis; particulate analysis; polarography

spark source mass spectrometry; spectrophotometry; trace elements; water pollution; x-ray

fluorescence.

1
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 tlie 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 programs

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

liave been relatively unexplored. These trace elements may

be a source of valuable byproducts that could be recoA^ered,

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

2
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.

T]ie 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.

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 nay be considered

as major or minor constituents according to their relative

concentrations in the matrix materials, but m.ost of the

3
attention will be directed tox'/ard elements present at or

below the 100 ppm (100 yg/g) level.

The analytical methods included in this reviev; embrace

nuclear methods, mass spectrom.etr ic methods, x-ray, optical,

and electrome tr ic methods of analysis, specifically:

1. Nuclear methods

2. Spark source mass spectrometry

3. X-ray fluorescence and electron microprobe spectrometry

4. Atom.ic absorption spectrometry

5. Absorption spectrophotometry

6. Atomlc omlsslon spectroscopy

^ 7. Voltammetry (polarography) and pot ent iomet ry (ionselective 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- di lut ion 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, v;et 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

:

4
1. Instrumentation requirement

2. Detection limit

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 application.

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 connectin

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 determinations 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 comm.on 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

information and the references.

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 sequentially,

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

tlie two extremes of low-cost multi-element survey methods

and high-cost s ingle -element determinations. Also, the

6
cost per sample for large numbers of routine determinations

can be expected to be less than indicated in the tables.

Accordingly, the tabulated values should be considered

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 provided

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.

Tlie tabulated information and supporting references

are presented without judgments as to the relative merits

of the various analytical instruments and procedures. Decisions regarding the suitability of alternative methods

for trace element determinations should be based on experiences

with real samples.

7
2. TRACE ANALYSIS OF REAL SAI-4PLES

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 flov/ diagram showing

the different chemical analyses that m.ight 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 intermediates are analyzed as products. The effluent gases,

solids, and liquids are analyzed before being recycled,

recovered as byproducts, 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.

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 environm.ent (i.e. contamination) . Many engineers would be pleased with a product

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.

8
RAW MATERIALS

Ores

Concentrates

Scrap metal

Fuel (coal)

Chemicals

Catalysts

Solvents

|analysis|~*-

INDUSTRIAL

PROCESS

Smelting

Refining

Etc .

'ANALYSIS

PRODUCTS

Metals

Chemicals

Acids

Plastics

ANALYSIS

EFFLUENTS

GASES SOLIDS LIQUIDS

Furnace gas Fly ash Slurry streams

Metal vapors Coal ash Coagulates

Sulfur dioxide S lags Sediments

Nitrogen oxides Oxide dusts

Metal particles

RECYCLE- ANALYSIS RECOVERYWASTES

Permissible levels

Figure 1. Applications of trace element analysis to monitoring materials,

process streams, and effluents of a typical industrial process.

9
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 tlie analyses in the final products, or waste products,

or emissions. Accurate measurements are best ensured when

dependable, evaluated metliods 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:

10
1. Rax; 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.

4. Process waste waters including coagulates, sediments,

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.

T]ie 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 engineer

ing specialists to assure that the samples are representative

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

11
C . Sampling

One of the most important considerations in chemical

analysis is the assurance that the sam.ples 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 laboratory. If these are not tlie same composition

as the slags, sediments, process stream.s, etc. which they

purport to represent, 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 Fiost of the time. The

trace element com.pos it ions m.ay 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 tliat 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

12
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 changes with time or some process variable, (3)

sample alteration 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 engineering 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,

wlien are the best times to sample, hovi 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 be of importance

in many cases to a proper interpretation of the analytical

data. The name of the person taking the sample, and reference

13
to tlie notebook or log sheet should also be indicated. All o these natters assume special importance when legal considerations liiay be involved.

The analytical chemist ordinarly requires only a part

of the sample collected. In this event it is imperative

that tlie portion used for analysis be representative of

the sample submitted to the laboratory. Trained analytical

chemists are axvare of such m.atters, but the availability

of analytical instruments that can be used by laymen prompts

this note of caution. Even 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 authentication which might be needed at a later

date. In some cases a bank of analyzed samples m.ay 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

knowledgeab ly and are free from losses or outside contamination.

D . Choice of Analytical Method

Although the performance parameters which com.prise the

bulk of the tabulated information seem to provide a basis

for comparison of the relative merits of the alternative

14
methods of analysis, it is possible that such a comparison

hiight 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 procedure

or the extent to v;hich the samples reflect the actual bulk

matrix compositions, and so on.

The "best" methods of analysis v/ill 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

15
through volume analyses or considered a worthwhile investment in improved technological capability, before such new

methods are adopted. The value o£ 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, H. R., Sampling and

Analyzing Trace Quantities, Chem. Engineering 7J_, 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) ,

16
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. However, 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 differentiation 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 radioisotope

resulting from an irradiation process. A brief description of

the more important methods presently in use folloivis.

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 radio17
activity is observed. This radioactivity is usually detected

and quantitated using a high resolution lithium-drifted

germanium semiconductor detector [GeCLi)] for greatest

specificity. In this technique, each radioisotope may be

uniquely identified through the observation of a.) its gammaray 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.

B. NAA - Neutron Activation Analysis

' This method is similar to the previous technique, except

that a radiochemical separation can be employed after irradiation, but before measuring the radioactivity. This separation,

if done competently, can remove all or most of the interfering

radioactivities while retaining all or a knovm 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 precision and accuracy

with this technique.

C . FNAA - Fast Neutron Activation Analysis

This is another method of activation analysis in which

18
fast neutrons are used as the irradiation source. This fast

neutron source could be a Cockcrof t-Walton neutron generator

producing 14 MeV neutrons, another type of particle accelerator

used for generating fast neutrons, or a radioisotope source

such as californium- 2 52 , 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 microns

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.

E. 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,

19
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 system for counting, and can also have a radiochemical separation step included in the analysis. Two

of the important disadvantages, hoivever, 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 bombardment. 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 substoichiometr ic 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

2 0
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

a/ 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, organometallics, incinerator particulates, slurry streams, feeds

to/from flotation processes, and sediments in flotation

processes has been investigated. It does not seem to be

feasible 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

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 dissolution of the sample after irradiation, with an appropriate

— This is not to be confused with Isotope Dilution Mass

Spectrometry which uses enriched stable isotopes as

tracers, rather than radioactive isotopes.

21
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 activation 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-destruct ively , 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 has 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

22
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 demonstrated

several times, notably the determination of 13 trace elements

by AS in crude petroleum (81), and the systematic determination

of 11 trace elements in crude oils, distillation fractions,

asphalts, etc., by NAA with radiochemical separations (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. Additional 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

23
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 o£ 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.

E . Metals and Alloys

.. Much analytical data has been published on the activation

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, antimoy)

or fission under neutron irradiation (such as uranium or

24
thorium) are much more difficult to analyze for trace

element concentrations.

F . Organometall ics

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.

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 publications

are available which specifically treat this material.

H. Slurry Streams, Feeds to/from Flotation Processes, and

Sediments in Flotation Processes

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).

25
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 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 elsev/here.

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 radioactivities 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)

26
normal contamination problems no longer exist. In fact, v;hen

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, (preconcentrat ion , dissolution,

etc.) should be kept to a minimum.

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 sensitivity 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 5x10 n. cm sec . 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 detection limit can often be

27
exceeded when specialized counting equipment is used. For

instance, even though the listed detection limit for sodium in

3 6 Table 1 is 10' yg, as little as 4x10' yg o£ sodium has been

determined with a precision of better than ±10 percent, using a 3-Y-Y sum-coincidence spectrometer (36,101).

.. In column 7, the estimated SAMPLE SIZE (grams) has been

listed. This sample size is very flexible for neutron activation 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.

28
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.

In column 10, the SELECTIVITY has been evaluated on the

basis o£ ease o£ determination by the primary nuclear

analytical method. In the case o£ 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 radiochemical 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 individual

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

29
involved. These areas have been discussed extensively in

the literature and so will not be further discussed here

(106,10 7,108). It is sufficient to say that the uncertainties

involved are well understood, so that \srith these techniques

levels of accuracy and precision of ±5 percent are possible

in many cases, and ±25 percent in almost all cases, in

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.

30
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a31
Table 2 Element Index to References

Nuclear Methods

Element References

Mercury 9, 16, 47 , 67 , 68 , 69 , 81

Beryl 1 ium 20,22,23,24,48,70

Cadmium 17,26,29,67,71

Arsenic 29,30,57,67,75,76,81

Vanadium 29,46,57,58,80

Manganese . y 3,14,29,65,76

Nickel 31,45,77,81

Ant imony 7,28,29,76,81

Chromium 15,27,29,32,59,66,77,81

Z inc 9,14,27,29,32,60,61,65,67,76

Copper 8,13,14,18,27,29,62,65,76,77

Lead 42,48

Selenium 44,63,67,81,82

Boron 24 , 34 , 48

Fluorine 24,33,48

T,J_i 1-i. 1Lx- h1 X i-I- um^^ill 38 48 64 74

Silver 1,2,29,37,77,83,84

Tin 29305681

X 1 Ull in 14 40 66 76 77 81

Strontium 29,41,54,55

Sodium 19,29,36,65

Potassium 25,27,29,85

Calcium 6,29,39

Silicon 52,53,77,78

Magnesium 29,43,78

Uranium 4,5,25,34,35,50, 51, 74, 79,81

Thorium 25,49,50,72,73,74

32
REFERENCES

1. Adam, F . ; Hoste, J.; Speecke, A., Detection of Silver in

Lead by Neutron Activation Analysis, Talanta 1_0, 1243

(1963)

2. Nakai, T.; Yajima, S.; Okada, M., Activation Analysis by

Short-Lived Nuclides. IV. Determination o£ Silver by

Silver-110, Nippon Kagaku Zasshi 8j^, 1422 (1960).

3. Bouten, P., Hoste, 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 Quantities 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, G. J., Beamer, W, H., Determination of Trace

Impurities in Magnesium by Activation Analysis, Anal.

Chem. 24-, 181 2 (1952).

7. Tejam, B. M., Haldar, B. C, N-Benzoyl -N-Phynylhydroxyl

amine as a Subs toichiometr ic Extractant in Activation

Analysis, IV. Determination of Antimony, Radiochem.

Radioanal. Lett. 9, 189 (1972).

8. Miloslov, Krivanek, Frantisek, K., Substoichiometr ic

Determination of Copper in High-Purity Metals by Activation 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 8, 296 (1961).

10. Ibid, A New Principle of Activation Analysis Separations,

10, 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 Subs toichiometric Isotope Dilution, Analyst

95, 393 (1970).

33
13. Ruzicka, J. Stary, J. Isotope Dilut ion 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. 3_0, 1785

, , (1958)

.

15 . . Fasalo, G. B., Malvano, R., Solvent Extraction of Cr^^

.• with Tr ibenzylamine , Anal. Chim. Acta 2_9, 569 (1963).

16. V/estermark, T., Activation Analysis of Mercury, Intern.

J. Appl. Radiation Isotopes 9^, 11 (1960).

17. Ricci, E., Mackintosh, . W. D., Neutron Activation Method

for the Determination of Traces of Cadmium in Aluminum,

Anal. Chem. 3^, 230 (1961).

18 . . Chinagl ia , B., The Determination of Some Elements in

Aluminum by Non-Destructive Radioac tivation Analysis,

Energia Nucl. 8, 571 (1961).

19. Plumb, R. C., Measuring Trace Elements, Nucleonics

14 , 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. Aidankin, B. C, etc., A Method for Beryllium in Ores

by Means of Pho toneutrons , AEC-TR-4498, 99-105 (1961).

22. Mezhiborskaya, K, B., Radioac tivation Determination of

Beryllium, Atomic Energy, USSR 6, 416 (1959).

23. Guinn, V. P., Lukens, H. R. , The Photoneutron Determination of Beryllium and Deuterium, Trans. Amer . Nucl.

Soc. 9, 106 (1966).

24. Ricci, E., Hahn, R. L., Sensitivities for Activation

Analysis of 15 Light Elements with 18 MeV Helium-3

Particles, Anal. Chem. 39_, 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).

34
26. Lieberman, K. W., Kramer, H. H., Cadmium Determination

in Biological Tissue by Neutron Activation Analysis,"

Anal. Chem. 42^, 266 (1970).

27. Vasiler, I. Y., Razumana, G. N. , Determination of Trace

Impurities in Indium Antimonide by a Neutron Activation

Method, Radiokhimiya U, 573 (1969).

28. Adams, F., Hoste, J., Activation Analysis of Antimony

by Sum-Coincidence Spectrometry, Nucleonics 2_2, 5 5 (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, P., Hoste, J., Determination of

Impurities in Ti and Ti Dioxide by Neutron Activation

Analysis. I. Simultaneous Determination of 16 Trace

Elements, Anal. Chim. Acta 4_6, 165 (1969).

31. Neeb, 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

35, 141 (1966).

33. Wilkniss, P. E., The Determination of F, CI, Br, and I in a Single Sample by Photon Activation Analysis,

Radiochim. Acta. U, 138 (June 1969).

34. Carpenter, B. S., Determination of Trace Concentrations

of Boron and Uranium in Glass by the Nuclear Track Technique, Anal. Chem. 44-, 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. 44, 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 Analysis, Talanta 4, 51 (1960)

35
38. Wiernik, M. , Amiel, S., Activation Analysis of Lithium

by Means of ^Li 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 Analysis 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. 3, 1020 (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. (19 71)

.

43. Smathers , J. B., Duffey, D., Derivative Neutron Activation Determination of Magnesium, Nucl. Appl. Technol .

7_, 84 (1969).

44. Nadkarni , R. A., Haldar, B. C, Subs t oi chiometr i c Determination of Selenium by Neutron Activation Analysis,

Radiochem. Radioanal. Letters 7_, 305 (1971).

45. Ibid, Subst iochiometric 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 Analysis, Anal. Chem. U, 113 (1970).

47. Gillette, R. K., Investigations into the Determination

of Mercury in Copper, Mound Laboratory Report No. MLM1772 (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_6 , 81 (1965).

50. Amiel, S. Analytical Applications of Delayed Neutron

Emission in Fissionable Elements, Anal. Chem. _34_,

1683 (1962).

36
51. Campbell, F. T. and Steele, E. L., Uranium Assay by

Nondestructive Neutron Activation Analysis, Radiochem.

Radioanal. Letters U, 245 (19 72).

52. Nadkarni, R. A., and Haldar, B. C., Determination of

Silicon, Phosphorus and Sulfur in Alloy Steel by Neutron

Activation Analysis, Anal. Chim. Acta ' 4_2_ 279 (1968).

53. Vogt, vT. R. and Ehmann , W. D., Silicon Abundances in

Stony Meteorites by Fast Neutron Activation Analysis,-

Geochim. Cosmochim. Acta 29, 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. H. , and Meinke, W. W., Radiochemical Separation of Strontium by Amalgam Exchange, Talanta 10_

737 (1963).

56. Hamaguchi, H., et al.. Determination of Trace Quantities of Tin by Neutron Activation Analysis, Anal.

Chim. Acta 30_, 335 (1964).

57. Fukai, R. , and Meinke, W, -V., Activation Analysis

of Vanadium, Arsenic, Molybdenum, Tungsten, Rhenium,

and Gold in Marine Organisms, Limnology and Oceanography 7_, 186 (1962) .

58. Das, H. A., et al.. Routine Determination of Vanadium

in Silicate Rocks by Neutron Activation Analysis,

Radiochem. Radioanal. Letters 4, 307 (1970).

59. Brunfelt, 0., and Steinnes , E., Determination of

Chromium in Rocks bv 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. 36_, 1594 (1964).

62. Grimanis , A. P., Rapid Determination of Copper in

Plants by Neut rcn Activation Analysis, Talanta 15, 279

(1968).

37
63. LaFleur, P. D., "Activation Analysis Section: Summary

:>

. of Activities, July 1968 to June 1969," NBS Tech. Note

508 (1970)

.

6-4,. : Smith, G. W. , et al . , The Neutron Activation Determination 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. 1_5 , 642 (1972).

68. Rook, H. L., LaFleur, P. D., and Gills, T. E., Mercury

in Coal: A New Standard Reference Material, Environmental Letters 2_, 195 (1972).

69. Kennedy, E. 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 Radioact ivation Method for the

Determination of Beryllium in Minerals , Raw Materials

and in Hydr ome tal lurgi cal Products, J. Anal. Chem. USSR

15_, 323 (1960).

71. Bilefield, L. I., Determination of Cadmium in Rocks

by Neutron Activation Analysis, Analyst 8^, 386 (1961).

72. Leddicotte, G. -V., Mahlman, H. A., Determination of

Microgram and Submicrogram Quantities of Thorium by

Neutron Activation Analysis, "Intern. Conf. Peaceful

Uses of At. Energy," 8^, 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).

38
74. Amiel, S., New Methods of Rad io - Ac t ivat ion Analysis

Based on Delayed Neutron Emission and Secondary Reactions,

"Utilization of Research Reactors," Vol. 3, 307-14, Vienna

lAEC, London (1962).

75. Saskoloka, H,, Rowinska, L. The Search for Internal

Isotopic Tracers in Metallurgical Materials. I. Determination of In, W, As, Au , Sc, Re, Ir, and Ca by the

Neutron Activation Method, J. 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.

Anal. Chem. 38^, 813 (1966).

77. Leddicotte, G. W. et al., The Determination of Trace

Elements in Reactor "^laterials by the Method of Neutron

\ctivation Analysis , TID- 7555 , 192 - 21 5 (1958).

78. Lobanov, E. M., Mingalier, G. G., Rapid Neutron Activation Determination of Si, Al , Ba and '^In in Synthetic

'^Kicas , Akt ivat s ionny i i Analiz Elementiogo Sastava

Geologicheskikh Obekter, 77-83, Tashkent (1967).

79. DeLange, P. W., et al . , Critical Evaluation of Spiking

of Low Grade Ore Samoles in Activation Analysis for

Gold and Uranium, Talanfa 15, 1488 (1968).

80. Wahl , IV. H., Molinski, V. J., Rapid Radiochemical

Separation Procedures for Activation Analysis Indicators,

"^roc., Inter. Conf. Modern Trends in Act. Anal."

44, College Station, Texas (1965).

81. Shah, K. R., Filby, R. H., Holler, W. A., Determination of Trace Elements in Petroleum, by Neutron Activation Analysis. II. Determination of Sc, Cr, Fe, Co,

Ni, Zn, As, Se, Sb , Eu , Au , Hg and U, J. Radioanal.

Chem. 6, 413 (1970).

82. Pillay, K. K. S., Thomas, C. C, Neutron Activation

Analysis of the Selenium Content of Fossil Fuels,

Nucl. Aopl. Technol. 7, 478-(1969).

83. Turkstra, J., Pretorius , P. J., Nondestructive Determination of Platinum Metals in Ores, Matte and Lead

Assay Beads by Reactor Activation Analysis and High

Resolution Gamma Suect rometrv , Anal. Chem. 4_2, 835

(1970).

39
84. j\Iorris, D. F. C, Killick, R. A., The Determination

of Silver in Galena and Blende by Radioact ivation Analysis, Anal. Chim. Acta. 20, 587 (1959).

85. Sorin, M., Popescn, G., Determination of Potassium in

Geological Samples Using Neutron Activation Analysis,

Ann. Soc. Geol. Belg. 94^, 132 (1971).

86. Samsahl, K., Brune , D. and Wester, P. 0., Simultaneous

Determination of 30 Trace Elements in Cancerous and

Non-Cancerous Human Tissue Samples by Neutron Activation

Analysis, Internat. J, Apul . Rad . Isotopes 16_, 273

(1965). ' •

87. Nadkarni, R. E., and Ehmann, W. D., Determination of

Trace Elements in Biological Standard Kale by Neutron

Activation Analysis, J. Radioanal . Chem. 3_, 175

(1969) .

88. Colombo, U. P., et al . , Systematic Neutron Activation

Technique for the Determination of Trace Metals in

Petroleum, Anal. Chem. 36_, 802 (1964).

89. 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 Act. Anal.," NBS Spec. Publ. 312, Vol. I,

p. 93 (19 69) .;

90. Internat. Atomic Energy Agency, 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).

91. Internat. Atomic Energy Agency, "Nuclear Activation

Techniques in the Life Sciences," Proceedings of a Symposium, .Amsterdam, May 1967 , IAEA, Vienna (1967).

92. DeVoe, J. R., Editor, "Modern Trends in Activation

Analysis. Chapter 2. Biomedical Applications," Proceedings of the 1968 International Conference on

Modern Trends in Activation Analysis, NBS Spec. Publ.

312 , Vol. 1, D 98- 212 (1969) .

93. Ibid, "Chapter 4. Geochemical and Cosmochemical Applications," pp 288-413.

94. Brunfelt, A. 0., and Steinnes, E., "Activation Analysis

in Geochemistry and Cosmochemis t ry

, " Univers i tet s forloget

,

Oslo (19 72) . 40
95. Allen, R. 0., et 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. Guinn, V. P., et al.. The Trace Element Characterization of Crude Oils and Fuel Oils Via Instrumental

Neutron Activation Analysis, "Proc., Nuclear Tech. in

Environmental Pollution," Salzburg, p. 347, IAEA, Vienna

(1971).

98. Malvano , R., Neutron Activation Analysis in Metallurgy,

Atompraxis Ij^, 309 (1965) .

99. Albert, P., ApDlication of Radioelements to Investigating the Purification of ^!etals 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 P-ublishers) pp 1- 51 (1965).

100. Bunshah, R. F., editor, "Modern Analytical Techniques 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 , "Act ivation Analysis Section:

Summary of Activities, July 1968 to June 1969."

NBS Tech. Note 508, p 76 (1970).

102. DeVoe, 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 Internat.

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).

~"

41
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 Meutron

Activation Analysis, Anal. Chim. Acta. 38, 333

(1967) .

107. DeVoe, J. R., Editor, "Proceedings, 1968 International Conf. vfodern 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).

42
CHAPTER 3

SPARK SOURCE mSS SPECTROMETRY

Paul J. Paulsen

1. INTRODUCTION

In spark source mass spectrome tr ic (SSMS) analysis,

samples are introduced as solid "electrodes" into the

source chamber which is evacuated to a pressure of

- 7 - 8 1x10 to 1x10 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 elem.ents 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 decrease in abundance with each increasing charge

(i.e. Fe "'"> Fe"*" ^> Fe"*" , e tc . ) . 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 sim.ultaneous ly

detects all elements from Li (mass 7) to U (mass 258) on

each exposure. By making a graded series of exposures

43
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 sequentially across the ion multiplier (by changing

tlie 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 m.g 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)

.

44
A. Interferences

Although the SSMS can potentially detect all

elements, there will be interferences present v;hich 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.) liaving 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 minim.ize 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 interferences (at what concentration levels), however from

previous experience we know it will be only a small

percentage of the possible elements. In a recent publication in American Laboratory, R. Broivn [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.

45
B. Sample Requirements

The spark source requires conducting or semiconducting samples for sparking which are stable under the

- 7 - 8

10 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 insulating solids by

SSMS, however it is important to note that any sample

manipulation will result in some degree of contamination 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 '^^lOO mesh size and be well

mixed in order to meet this homogeneity requirement.

C. Sens it ivity

Modern spark source instruments can obtain 1 ppb

detection limits with 1 hour of sample sparking at "^2000

mo. s s resolution

niass -^ using photographic detection. If

the instrument has electrical detect ion, 0 . 1 ppm detection

limits are obtained when scanning the entire mass range in

"v^lO minutes. Detection limits at the ppb level are

obtained from electrical detection when using the peak

46
switching mode (1 to 30 sec integration o£ each peak)

however this mode only allows examination of a limited

number o£ elements in each sample (10 to 20 elements)

Both modes o£ 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 "^±3

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 given precisions of ±10 to 30 percent [2] and in

the peak switch mode of electronic detection, precisions

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 depend on the availability of a suitable reference standard with the same composition

(same basic matrix) . With a good reference standard the

47
obtainable accuracies can equal the precision values

just mentioned. The following is a general outline of

different approaches to the standard's 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 calculated 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 . 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.

48
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 are 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

photographic 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 concentrations the uncertainties in the

certified standard may be a significant source of error.

49
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 having elements chemically combined in the

same way as they are in the sample. Thus^ '^'"*^^3 ^'^^ K2Cr20y) 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 AI2O2 matrix. It could serve quite

adequately, however, for determining Cr in water solutions which were prepared for sparking by evaporation

with graphite powder, mixing, and pressing into electrodes.

50
D. Analysis Using Stable Isotope Dilution

Isotope dilution analysis with the SSMS can provide

an absolute method o£ 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 concentration: (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 preconcentration.

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

51
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 absolute 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.

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

52
(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 Matrices

The SSMS has about the same sensitivity for organic

compounds as it does for inorganic elements. The "v^ZOOO

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 would 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

53
desired, a wet ash procedure would be better. Both oils

and organometallics can be handled by wet ashing, possibly

in sealed tubes or bombs.

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 require 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 phys ical -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 duplicated with a synthetic mixture.

54
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 comparison 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 processing 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

55
to combine with anions to form ionized molecular

species in the spark source.

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:

56
1. It applies only to elements with two or

more isotopes and cannot be used for gases.

2. The requirement o£ 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 solution as a minimum treatment.

3. Measurement of an isotope ratio by SSMS

- 8 - 6 requires about 10 to 10 grams of an element for

consumption in the sparked volume (<10 mg)

.

4. Item 3 plus problems of interferences in

essence require a preconcentrat ion step for any

isotope dilution analysis of elements below a few

hundred ppm. The preconcentrat ion 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 procedures such as electrodeposition

anion or cation exchange and solvent extraction

have been used in our laboratory for preconcentrat ion

Generally the last step has been electrodeposition

onto pure gold wires for sparking. Preconcentrat ion

of water and acids [11] is obtained simply by

evaporation onto the gold wires used for sparking.

57
5. Analysis by isotope dilution requires that

the measured altered ratio be significantly different

from both the natural and "spike" isotopic ratios.

A photoplate 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 specifications for trace elements (e.g., pollution s tandards I I )

.

58
In this situation, the sample would be spiked with

the exact amount of spike isotope that gives an altered

isotope ratio of 1 at the critical specified concentration. 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 concentrations are close to meeting or failing specifications 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].

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.

59
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

for this report could be determined for each sample;

however, the specific elements would not be known until

the samples were run . In 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 Mg . ) 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 dilution . One-gram samples would give analyses down to

'vO.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

60

J
examples will be given which represent extremes for

cost, coverage and accuracy; (a) an all inclusive

survey analysis with estimations o£ concentrations

(factor of 3 to 10) and (b) isotope dilution analysis

of a limited number of multi - is otope 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

.

a. Sample preparation '^^l hour or less .

b. SSMS instrument and photoplate development

'^'l hour.

c. Photoplate interpretation '^^l hour.

TOTAL Two to four samples tested for '^^60 elements

per man day - results ±3 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, preconcentration 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.

61
8. CONCLUSION

There are two types of applications where the SSMS

can be clearly superior to any other single analytical

method.

M, 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 information 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 environmental 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 plate interpretation would identify

all elements which grossly pass or fail. Only

elements near the critical concentrations would require

the more precise densitometry data, and these results

6 2
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 50 ml samples.

63
Table 1

Simultaneous Determination of Twenty-seven Elements

by Spark-Source Mass SpectrometrVg^in

Typical Coal and Fly Ash Samples^ J Matrix

Element Coal ( 1 ) Fly Ash ( 1

)

(ppm) (ppm)

Hg 0.08 <0 .01

Be 1.2 8.0

Cd 0.19 0.70

As 0 . 30 22

V . .12 50

Mn ' - 30 400

Ni ' 2.7 50

Sb 0.14 4.5

Cr 4.5 110

Zn ;. - 10 2 60

Cu 2 5 200

Pb 3.9 60

Se - 0.32 0 . 30

B 42 2 30

F . 5.7 150

Li -- 42

Ag ' ; 0.2 2 0.50

Sn ,0.83 60

Fe 160 0 Major

Sr 100 2000

Na 5000 Maj or

K 410 7000

Ca 4000 Major

Si Maj or Maj or

Mg 4500 Major

U 1.9 30

Th 4.5 40

(a) ^ *In addition to the above elements of interest,

reference (1) lists values for 34-38 additional

elements.

64
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

I I , 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

I II o Analysis Using Synthetic Reference Standard

6, 7, 17, 25, 26, 28, 32, 35, 36, 37, 38, 41, 48

IVo 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, Organometallics 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

Xo Analysis Using Electronic Detection

1, 2, 5, 20, 22, 30, 31, 36, 37, 45, 49, 51, 52

65
References

[1] Brown, R. , Jacobs, M„ L., and Taylor, H. E., A Survey of

the Most Recent Applications of Spark Source Mass

Spectrometry, American Laboratory, 4_, 29 (1972).

[2] Bingham, R, A. and Elliott, R. M., Accuracy of Analysis

by Electrical Detection in Spark Source Mass Spectrometry,

Analo Chem., £3, 43 (1971).

[3] Halliday, J. S., Swift, P., Wolstenholme , W. A.,

"Quantitative Analysis by Spark Source Mass Spectrometry",

Adv. in Mass Spectrom. , 3, Int. Petrol, London, 143 (1966).

[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,

25-2 9 September 1967.

[5] Evans, C. A., Jr., Guidoboni, R. J.,, and Leipziger, F. Do,

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_8, 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. Jo, 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., 4]^, 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 Techniqueo, Anal,

Chem., 42, 673 (1970).

66
[11] Kuehner, E. C, Alvarez, R. , Paulsen, Po J., and Murphy,

T. J., Production and Analysis of Special High-Purity

Acids Purified by Sub-Boiling Distillation, Analo Chem.

,

44, 2050 (1972).

[12] Kessler, T. , Sharkey, A. G., Jr., and Friedel, R. A.,

Spark-Source Mass Spectrometer Investigation 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. Jo, Mass Spectrographic Detection of Impurities

in Liquids, J. Appl. Phys., 32, 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. H., Sto John, L. E., Jr., and

Lisk, Do J. , Determination of Fluorine and Bromine in

Halogenated Herbicide Residues in Soil by Spark Source

Mass Spectrometry, Anal. Chem., 4_4 , 1069 (1972) »

[18] Franklin, J. Co, 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-7405o

[19] Leipziger, F. D., Isotope Dilution Analyses by Spark

Source Mass Spectrography, Anal. Chem., 3_7 , 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, Oo 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).

67
[22] Brown, R. and Vossen, P. G. T., Spark Source Mass

Spec trometric Survey Analysis of Air Pollution Particles,

Anal. Chem., 42^, 1820 (1970).

[23] Jones, R, M. , Kuhn, W. F,, and Varsel, C, Spark Source

Mass Spectrographic Analysis of Tobacco Ash, Anal.

Chem. , £0, 10 (1968)

.

[24] Harrison, W. W. , Clemena, G. G., and Magee, C. W.

,

Forensic Applications of Spark Source Mass Spectrometry,

J. of the AOAC, _54, 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, 1666 (1969).

[26] Harrison, Wo Wo and Clemena, G. G., Factors Affecting the

Use of External Standards for Spark Source Mass

Spectrometry, Anal. Chem., 4£, 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 , So S. C. , Gutenmann, W. H., and Lisk, D. J.,

Determination of Mercury in Apples by Spark Source Mass

. Spectrometry, Anal. Chem,, £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., 42^, 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., 310 (1970).

[32] Taylor, S. R. , Geochemical Application of Spark Source

Mass Spec trography- I I . Photoplate Data Processing,

Geochim. Cosmochim. Acta, 3_5, 1187 (1971).

[33] Morrison, G. H. and Rothenberg, A. M, , Homogenization of

Nonconducting Samples for Spark Source Mass Spectrometric

Analysis, Anal. Chem., 4_4 , 515 (1972).

[34] Taylor, S. R. , Muir, P., and Kaye, M. , Trace Element

Chemistry of Apollo 16 Lunar Soil from Fra Mauro, Geochim.

Cosmochim. Acta, 35, 975 (1971).

68
[35] Taylor, S. R. , Geochemical Analysis by Spark Source Mass

Spectrography , Geochim. Cosmochim. Acta, 2_9, 1243 (1965) .

[36] Conzemius, R„ J. and Svec, H. J., An Electrical Detection

System for a Spark-Source Mass Spectrograph, Talanta,

1_6, 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 Spec trographic Determination

of Impurities in Liquids, Mass Spectroscopy, 1_6, 241 (1968) ,

[39] Chastagner, P. and Tiffany, B., Analysis of Curium and

Californium by Single-Exposure Spark Source Mass

Spectrometry, Int. Jo 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,

Analo Chem., £1, 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., 4_0, 869 (1968).

[42] Chastagner, P., Analysis of Microsamples by SingleExposure Spark Source Mass Spectrometry, Anal. Chem.,

4]^, 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. Ko , Alvarez, R. , Paulsen, P. J., Paulson,

R. A., Rains, T. C, and Rook, H. L. Interaction of

Nitrilotriacet ic 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, TexaSo

[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.

69
[47] Morrison, G, H. , Kashuba, A. T., and Rothenberg, A. M,

,

Elemental Abundances in Lunar Materials by Spark Source

Mass Spectroscopy, 18th Annual Confo 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 o£ Lunar Materials by Probe

Technique, 18th Annual Con£. 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, Mo 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

of Some Biological Materials, 13th Annual Conf. on Mass

Spectrometry and Allied Topics, May 16-21, 1965,

St. Louis, Missouri.

70
CHAPTER 4

X-RAY FLUORESCENCE AND ELECTRON MICROPROBE METHODS

Stanley D. Rasberry and Kurt F. J. Heinrich

1. X-RAY FLUORESCENCE

X-ray fluorescence analysis is noted for its applicability

to a diversity of sample types and it has gained extensive

industrial use for monitoring the composition of both rav^r 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 particulates, liquids, slurries, filtrates, powders,

metals and other sample types. The applications of x-ray

fluorescence analysis are being described 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

categorize 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 subsequent decay from excited state coupled with electron- atom,

recombination. The energy transfer, in both excitation and

emission (decay) is dependent upon the atomic number (element)

of the atom involved in the interaction. That is, an emitted

71
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 quantitation

depends in part on measuring the rate (intensity) at which

x-rays of a given energy are emitted.

The apparatus necessary to 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 wavelengths.

Another possible choice for excitation is the use of radioisotopes; here too, filters can be used. Outside the precise

definition of fluorescent spectroscopy, excitation can also

be effected by bombarding the specimen with electrons (10-

100 keV) , protons (1-200 MeV) , or a variety of ions.

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 changing

or equipment for direct examination of continually flowing

liquid, slurry or powder streams.

72
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 resolved

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 beamto-crystal angle. The dispersion characteristics 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 detectors, gas-filled proportional detectors and gas-flow proportional 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

73
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 have

a large number of possible variations. This, together with the

wide variety of excitation and detection possibilities, causes

the number of permutations of instrument configurations to be

large. One of the most generally effective arrangements for

quantitative elemental analysis is shown in Figure 1. This

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)

74
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 the x-ray spectra of two

samples of liquid paint. The spectrum 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.

II -1-71 LIQUID PAINT

iio-

- 3

0.01% S&,Cd,Sr« At 0.05% Hfl 1.0% Pb

0.06% Sb.Cd.Sr a A« 0.3%

1.0% Pb.

PbL^

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.

75
Quantitative determination of elements v,'hich 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 prepared,

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.

eooi 1 r- 1 1 r

LEAD AOOEO (WEIGHT %)

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.

76
Usually, x-ray fluorescence analysis can be performed

directly on a sample with little or no preliminary treatment;

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 preconcentrat ion 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 precision 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 simultaneous

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, automation is economically attractive owing

77
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 concentration, 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.

A. Application to Matrices of Environmental Interest

1. Fly Ash and Incinerator Particulates . (References 7-19)

Methods for the x-ray fluorescence analysis of fly ash and

incinerator particulates were not actively researched until

about five years ago. Since that time, extensive work has

78
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 determining

one element should not exceed $1.00. Lower concentrations 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 particulate 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 interelement correction

procedure. Kiss was able to accurately determine 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

79
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 determinations using ion exchange

preconcentration . The method is finding increased use

(including work at NBS) in monitoring wear metals in

engine and gearcase oils.

4. Ores, Minerals and Cement . (References 38-54) X-ray

fluorescence analysis has found wide industrial acceptance in

these areas over the past twenty years. This is especially

true in the cement industry, where tens 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 Flanagan (44) and

Campbell and Thatcher 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.

8 0
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

of 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 treatment. 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. Organome tallies , (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

81
metallo-organic compounds primarily to be used for the calibration o£ spectrochemical equipment used in the determination

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; corrections are

required. Sampling is also an important aspect of the problem.

Standardization is difficult, because to simulate the material

under analysis requires flowing a 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.

82
Slags are usually treated with preparation techniques 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

Electron probe microanalysis has been available, with

commercially 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 Refs. 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 ym. 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 single-bent crystal spectrometers.

The instrument at NBS has three such spectrometers, sc that

83
three elements can be measured simultaneously. The wavelength

o 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 thus provides for a rapid means for qualitative

and semiquantitative analysis, which is particularly useful

in the analysis of small particles.

.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 ym.

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-part iculates 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

84
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-particulates can

be isolated, mounted and restrained. Quantitative analysis

of metals requires a flat polish, equivalent to that obtained

with 1/4-ijm diamond polishing compound. Non- conduct ive

specimens are given a sub-ym coating of a conductor (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 v/ith x-ray fluorescence, the instrument operators may be non-degreed technicians, but supervision should be in the hands of a graduate

chemist, or equivalent.

85
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 knowledg

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.

86
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References

Bo oks Related to X-ray Fluorescence Analysis

1. H. A. Liebhafsky, H. G. Pfeiffer, E. H. Winslow and

P. D. Zemany, "X-ray Absorption and Emission in

Analytical Chemistry," Wiley, New York (1960).

2. L. S. Birks, "X-ray Spect rochemical Analysis," 2nd

Ed., Interscience , New York (1969).

3. R. Jenkins and J. L. De Vries , "Practical X-ray

Spectrometry," Springer -Ver lag , New York (1969).

4. E. P. Bertin, "Principles and Practice of X-ray

Spectrochemical Analysis," Plenum, New York (1970).

5. R. 0. Miiller, trans, by K. Keil, "Spectrochemical

Analysis by X-ray Fluorescence," Plenum, New York

(1972).

6. K. F. J. Heinrich, 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.

Fly Ash and Incinerator Particulates

7. S. C. Goadby and J. F. Stephens, "Determination of

Sulphur in Fly-ash by X-ray Emission Spectroscopy,"

Fuel 46_, 19 (1967) .

8. J. Leroux and M. Mahmud, "Flexibility of X-ray Emission

Spectrography as Adapted to Microanalysis of Air

Pollutants," J. Air. Poll. Control Assoc. 20, 402

(1970) .

9. C. H. 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. Goulding and J. M, Jaklevic, "Trace Element

Analysis by X-ray Fluorescence," Lawrence Berkeley

Laboratory, Report UCRL-20625 (May 1971).

95
11. D. A. Landis , F. S. Goulding and B. V. Jarrett, "Some

Aspects of X-ray Fluorescence Spectrometers for Trace

Element Analysis," 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 Semiconductor Detector X-ray Spectrometers," Lawrence

Berkeley Laboratory, Report LBL-647 (July 1972).

14. J. C. Wagner, E. H. Bicknese and F. R. Bryan, "X-ray

Determination of Zinc in Basic-Oxygen Flue Dust and

Bias t-Furnace Sinter," Appl. Spectrosc. 2J^, 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. H. R. Bowman, J. G. Conway and F. Asaro, "Atmospheric

Lead and Bromine Concentration in Berkeley, Calif.

(1963-1970)," Envir. Sci . and Tech. 6 , 5 58 (197 2).

o o 17. P. Greenfelt, A. Akerstrom and C. Brosset, "Determination of Filter -Collected Airborne Matter by

X-ray Fluorescence," Atmos . Envir. 5^, 1 (1971).

18. C. L. Luke, "Determination of Traces of Lithium,

Beryllium or Phosphorus by X-ray Analysis," Anal.

Chim. Acta 45_, 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).

96
22. E. Davidson, A. W. Gilkerson and S. G. Shequen, "X-ray

Fluorescence Analysis with a New High Speed Multichannel Instrument," Reprint from Applied Research

Laboratories, Sunland, Calif. (1965).

23. C. H. Anderson and R. E. Jones, "Determination of

Inorganic Constituents of Coal' by X-ray Fluorescence,"

Reprint from Applied Research Laboratories, Sunland,

Calif. (1968).

Oil

24. E. L. Gunn, "Problems of Direct Determination of Trace

Nickel in Oil by X-ray Emission Spec trography ,

AnaI.*Chem. 36_, 2086 (1964).

25. E. L. Gunn, "Absorption Effects in X-ray Fluorescence

Measurement of Elements in Oil," Advan. in X-ray

Anal . 6 , 403 (1963)

26. C. C. Hale and W. H. King, Jr., "Direct Nickel Determinations in Petroleum Oils by X-ray at the 0.1-P.P.M.

Level," Anal. Chem. 33_, 74 (1961).

27. C. W. Dwiggins , Jr. and H. N. Dunning, "Quantitative

Determination of Nickel in Oils by X-ray Spectrography," Anal. Chem. 3^, 1040 (1959).

28. C. W. Dwiggins, Jr. and H. N. Dunning, "Quantitative

Determination of Traces of Vanadium, Iron, and Nickel

in Oils by X-ray Spectr ography , " Anal. Chem. 32^, 1137

(1960) .

29. C. C. Kang, E. W. Keel and E. Solomon, "Determination

of Traces of Vanadium, Iron, and Nickel in Petroleum

Oils by X-ray Emission Spec trography , " Anal. Chem. 32 , 221 (1960).

30. J. G. Bergmann, C. H. Ehrhardt, 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). —

97
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 Spectr ographic

Method for the Determination of Vanadium and

Nickel in Residual Fuels and Charging Stocks,"

Anal. Chem. 2_7, 1880 (1955).

34. L. S. Birks, E. J. Brooks, H. Friedman and R. M. Roe,

"X-ray Fluorescence 7\nalysis of Ethyl Fluid in

- Aviation Gasoline," Anal. Chem. 22^, 1258 (1950).

35. J. L. Caley, "The Use of X-ray Emission Spect rography

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. D. Jovanovic, "Development of an X-ray Emission Spectrography Method for the Determination of Molybdenum

. in Oils," Anal. Chem. 42, 775 (1970).

Ores , Minerals and Cement

38. H. J. Rose and R. Brown, "X-ray Fluorescence Analysis

of Niobat e -Tantalat e Ore Concentrates ," Advan . in

X-ray Analysis 598 (1964).

39. A. P. Langheinrich , J. W. Forster and T. A. Linn, Jr.,

"Energy Dispersion X-ray (EDX) Analysis in the NonFerrous 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

Quantometer 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.

24-. 427 (1970).

98
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, "Suggested Method for Spect r ochemi cal 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, "Nonproportional, Non-linear Results from X-ray Emission

Techniques Involving Moder at e - Dilution Rock Fusion,"

Geochim. et Cosmochim. Acta 30^, 745 (1966) .

46. K. Norrish and J. T. Hutton, "An Accurate X-ray Spectrograph 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 Si 1 ica -Alumina Catalysts," Anal. Chem. 3^, 357 (1967).

48. B. L. Bean, "A Method of Producing Sturdy Specimens of

Pressed Powders for Use in X-ray Spectrochemical

Analysis," Appl. Spectrosc. 2_0, 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 Spectrochemical 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 Spect rography , " U.S. Bur. of Mines Rept. of

Investigation 5416 (1958)

53. D. 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).

99
54. D. F. Sermin, "The Application of the ARL X-ray Quantometer 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 L. Silverman, "Determination of Iron,

Chromium and Nickel by Fluorescent X-ray Analysis,"

Anal. Chem. 3j., 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. 2S_, 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 Intereleraent Effects,"

Appl. Spectrosc. 2l_, 324 (1967).

61. S. D. Rasberry, H. J. Caul and A. Yezer, "X-ray Fluorescence Analysis of Silver Dental Alloys with Correction for a Line Interference," Spectrochim. Acta

23B, 345 (1968) .

62. A. Chow and F. E. Beamish, "Determination of Gold by

.

, X-ray Fluorescence Methods," Talanta 1^, 539 (1966).

63. K. Hirokawa, "Determination of Impurities in Some NonFerrous Metals by Fluorescent X-ray Spectroscopy,"

Science Repts . of the Res. Inst. Tohaku Univ. A- 13 , 263 (1961). English.

64. W. M. MacNevin and E. A. Hakkila, "Fluorescent X-ray

Spectroscopic Estimations of Palladium, Platinum,

Rhodium and Iridium," Anal. Chem. 29, 1019 (1957).

100
65. L. S. Birks and E. J. Brooks, "Ha fnium - Z ir conium and

Tantalum-Columbium Systems," Anal. Chem. 1017

(1950)

66. W. J. Campbell and H. E. Marr III, "Identification and

Analyses of Copper-Base Alloys by Fluorescent X-ray

Spect rography , " U.S. Bur. of Mines Rept. of Investigation 7635 (1972)

67. A. Carnevale and A. J. Lincoln, "An X-ray Fluorescent

Method for the Determination of Copper in SilverCopper 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. 3_3, 1343

(1961) .

69. R. Alvarez and R. Flitsch, "Accuracy of Solution X-ray

Spectromet ric Analysis of Copper-Base Alloys," NBS

Misc . Publ . 260-5 (1965) .

70. R. E. Michaelis, R. Alvarez and B. A. Kilday, "Determination 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. 16, 136 (1962).

72. R. W. Taylor, "X-ray Spectr ochemical Determination of

Niobium and Tantalum in High-Alloy and Stainless

Steel," Dev. in Appl. Spectrosc. 4, 65 (1964).

73. G. E. Hicho, H. Yakowitz, S. D. Rasberry and R. E.

Michaelis, "A Standard Reference Material Containing

Nominally Four Percent Austenite," Adv. in X-ray

Anal . U_, 78 (1971) .

74. S, D. Rasberry, "Application of Computers in Electron

Probe and X-ray Fluorescence Analysis," Adv. in

X-ray Anal. 1S_, 56 (197 2).

75. L. Backerud, "Determination of Copper in Complex

Brasses by X-ray Fluorescence Spectroscopy,"

Appl. Spectrosc. 21_, 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) .

101
77. D. F. Sermin, "The Application o£ 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).

Or ganometal 1 ics (Also see papers in section: Oil)

80. S. A. Bartkiewicz and E. A. Hammatt, "X-ray Fluorescence 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 Fluorescence," Analyst 92_, 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 , 16 71 (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. 2_2 , 99 (1968).

84. A. H. Smallbone and E. 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 E. Davidson, "On Stream Analysis

of Solutions," Reprint from Applied Research Labor-

\ atories, Sunland, Calif. (1972).

102
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. 2_2 , 415 (1968).

90. K. J. Garska, "Microgram Determination of Chlorides by

Deposition as Silver Chloride and X-ray Fluorescence,"

Anal. Chem. 40^, 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. 3_5 , 368 (1963).

92. H. 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 ixK Natural

Waters by X-ray Fluorescence Spectrometry after Concentration by Evaporation," Dachan Hwabak Hwoejee 1

, 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 1_3^, 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 Quantometer to the Analysis of Glass

Powders," Reprint from Applied Research Laboratories,

Sunland, Calif. (1969).

97. E. W. Orrell, "Ceramic Analysis by X-ray Fluorescence - the Non- Automatic Spectrometer," Br. Ceram. Res. Ass.

Spec. Pub. 50, 70 (1966).

103
98. R. S. Lowe, "Ceramic Analysis by X-ray Fluorescence - the Automatic Instrument," Br. Ceram. Res. Ass. Spec.

Pub . 50^, 79 (1966) .

99. F. H. Dorr, "Rontgenf luores zenzanaly tische Methoden

fur die Glasanaly se ," Glastechn. Ber . 34, 175 (1961).

100. D. 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 Electron Probe Microanaly zer , " J. of the Iron and Steel

Inst. 18_3, 42 (1956) .

104. R. J. Bird, "Electron Probe Micro -analys is in a Petroleum

Research Laboratory," Inst. Petroleum 4_8 , 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 Mi croanaly zer , " 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 Electron Microprobe," J. Inst. Met. 91, 66 (1962).

109. R. Castaing, J. Philibert and C. Crussard, "Electron

Probe Microanaly zer and its Application to Ferrous

Metallurgy," J. of Metals 9, 389 (1957).

104
110. D. B. Clayton, T. B. Smith and J. R. Brown, "The

Application of Electron probe Microanalysis to the

Study of Microsegregat ion in Low Alloy Steel,"

J. Inst. Met. 90, 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. Macros, "Application of Electron Probe Microanalysis to Cu-Zn Diffusion," Thesis (MIT) 1958).

113. D. A. Melford and P. Duncumb, "The Met allographic

Application of X-ray Scanning Microanalysis," Metallurgia 5^, 159 (1958)

114. D. 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 Microanaly zer , " Geochim. et

Cosmochim. Acta 14_, 114 (1958).

117. K. F. J. Heinrich, "Identification of Inclusions

with the Electron Probe Microanaly zer , " 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. 2_2, 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 Microanalysis," NBS Spec. Pub. 298_, Washington, D. C.

(Oct. 1968).

122. L. S. Birks, "Electron Probe Microanalysis," 2nd Ed.,

Wiley, New York (1971)

105
Supplemental References

123. H. E. Bumstead, "Application o£ the X-ray Spectrometer

to the Needs of the Industrial Hygiene. Laboratory,"

Indust. Hygiene J., p. 392 (1964.

124. J. W. Cares, "The Quantitative Determination of Airborne

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," Environ. Sci. and Tech.

6, 922 (1972).

126. C. L. Luke, et al., "X-ray Spec trometr ic Analysis of Air

Pollution Dust," Environ. 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. 6_, 1121

(1972)

.

128. V. E. Cosslett, New York Academy of Science Annals

97, 464-481 (1962).

106
CHAPTER 5

ATOMIC ABSORPTION SPECTROMETRY

Theodore C. Rains

1. INTRODUCTION

Atomic absorption spectrometry. CAAS) has been demonstrated

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 unkown concentration is determined by comparison v/ith absorbance measurements 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.

107
2. INSTRIBIENTATION 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, hollovj-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 tlie 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, nonf lame 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 flame methods in greater sensitivity, lower detection

limits, and the ability to accomodate very small samples

(0.5 to 50 yl) . The main factors in the production of

atomic vapor are (a) efficiency of atomization, (b) length

of flame or nonf lame cell, [c) oxidant-fuel used to produce

atomic vapor, and (d) position within atomic vapor in which

absorption measurements are made.

108
Requirements for the wavelength selector may vary considerably 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 backgound 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 X for the de termiination

of nickel, iron and cobalt. If background radiation is

emitted by the primary source of radiation, a narrov/ band

pass in the selector will minimize its effect. There are

some special instances v/here 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 v/ith

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 m.ultiplier 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 lO"^ yg/ml.

With non-flame methods such as the carbon rod atomizer, the

detection limits for 33 of these elements have been extended

109
to an absolute value of 10" to 10~ 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.

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 interference occurs when the analyte is ionized in the flame

causing a reduction in signal strength. Mutual or interelement 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.

110
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 hightemperature flame usually introduces another type of interference 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 interference 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 1 iquid- 1 iquid extraction is used

to remove the interferent; this has an added effect of

increasing the sensitivity of the analysis by preconcentrating the analyte.

3. SMPLE REQUIREMENTS

The kinds of samples suitable for analysis by atomic

absorption spectrometry cover a wide range. The analyte

111
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) procedures for obtaining samples in solution, and (c) methods

of separation or preconcentrat ion , if required. The nature

of the sample matrix (e.g. coal, fly ash, ores, minerals,

metals, etc.) governs the choice of sampling, dissolution,

and preconcentrat ion 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 introduce

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 determinations.

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

112
to work well for all jnatrices, 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, agricultural, metallurgical, mining, geochenical , 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 liolds 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 witli 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 combinations 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

113
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.

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 Preconcentrat ion

Separation or preconcentrat ion 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 preconcentration step for one or several elements. The methods of

separation and preconcentration are liquid- liquid extraction,

ion exhange 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

(diphenyl thiocarbazone) , cupferron, and several dithiocarbamate derivatives, particularly diethylammonium diethyldithiocarbamate and ammonium pyrrolidine dithiocarbamate (7)

,

114
The chelates formed are extracted into a water - immiscible,

nonaqueous solvent such as methyl isobutyl ketone (MIBK)

After removal of the aqueous phase, the met al -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 ENVIROWIENTAL INTEREST

Atomic absorption spectrometry has been compared v.'ith

other spectrochemical m.ethods (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; cl inical - air, blood, tissue and hair,

urine and bone; industrial - cement, chemicals, coal, gasoline

and liquid fuels, lubricating oils, pharmaceuticals, and

polymers; nutr it ional - beverages, fats and foodstuff;

metallurgical - iron and steel, ferrous and non-ferrous alloys

115
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 respectively. 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 determinations . Column 10 in Tables 1-6 is an element index to the

references, and provides entry to additional information

116
on individual elements in specific matrices. No literature

was available on the 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 elem.ent

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

determined in the same solution is increased. Atomic

absorption spectrometry appears to be capable of providing

an analytical capability which can meet the financial

requirements of most industrial and municipal laboratories.

C . Conclus ions

Atomic absorption spectrometry is a versatile analytical

tool which can be used to determine 25 Qf 27 elements of

interest present in macro or trace concentrations as constituents in environmentally significant matrices. Its high

117
specificity, moderate instrument and labor requirements,

and simple operating procedure inake it eminently suited

for routine trace element determinations at a reasonable

cos t

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References

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Spectroscopy," Volume 1, Society for Analytical

Chemistry, London, 1972.

2. Winefordner, J. D. and Vickers, T. J., Flame Spectrometry,

Anal. Chem. 4_4, 150R (1972).

3. Slavin, W. , "Atomic Absorption Spectroscopy," Interscience, New York, 1968.

4. David, D. J., The Application of Atomic Absorption to

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5. Dean, J. A., and Rains, T. C. , Editors, "Flame Emission

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6. Slavin, W. , Atomic-Absorption Spectroscopy-Cr itical

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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, American 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. 47-6 9.

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

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125
13. Manning, D. C. , A High Sensitivity Arsenic-Selenium

Sampling System for Atomic Absorption Spectroscopy,

At. Abs. Newsl. 1£, 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. ]_1_, 37 (1972).

15. Pollock, E. N., and West, S. J., The Determination of

Antimony at Submicrogram Levels by Atomic Absorption

Spectrophotometry, At. Abs. Newsl. lAy 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. 8^, 3 (1969) .

18. O'Gorman, J. V., Suhr, N. H., and Walker, P. L., Jr.,

The Determination of Mercury in Some American Coals,

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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_5 , 660 (1971).

20. Oliver, M. , The Determination of Trace Metals in Polymers

by Atomic Absorption Spectrophotometry, At. Abs. Newsl.

10_, 12 (1971).

21. Barnett, W. B., Hahn, H. L., and Peterson, G. F., The

Rapid Determination of Several Elements in a Single

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At. Abs, Newsl. 10_, 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. 10_, 73 (1971).

24. Price, J. P., Utilization of Atomic Absorption

Spectroscopy in the Synthetic Fiber Industry, At. Abs.

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126
25. Stresko, V., and Martiny, E., Determination of Antimony

in Geological Materials by Atomic Absorption Spectrometry,

At. Abs. Newsl. U, 4 (1972).

26. Sighinolfi, G. P., Determination of Beryllium in

Standard Rock Samples by Flameless Atomic Absorption

Spectroscopy, At. Abs. Newsl. 11, 96 (1972).

27. Fleming, H. D., Some Applications of Atomic Absorption

Spectroscopy in Metallurgical Laboratories, Atomic

Absorption Spectroscopy Symposium, May, 1970, Melbourne,

Australia (Published by Varian Techtron Pty. Ltd.,

Austral is )

28. Sanders, J. B., Application to the Analysis of

Petroleum Products, ibid.

29. Dagnall, R. M., and V/est, T. S., Observations on the

Atomic Absorption Spectroscopy of Lead in Aqueous

Solutions in Organic Extracts and In Gasoline, Talanta 1

, 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. 5_3, 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. , Application of Atomic Absorption Spectroscopy to Trace

Analyses of Petroleum, Microchem. J. 1_0, 148 (1966).

33. Moffith, A. E., Quinn, P. M. , and Limtiaco, L. P.,

Applications of Atomic Absorption Spectrophotometry

in Occupational Health Studies, Amer. Lab., p. 8

' (August 1971)

34. Kahn, H. L., Graphite Furnace Applications in Atomic

Absorption, Amer. Lab., p. 35 (August 1971).

35. Bazliov, A. S., Zherebenko, A. V., and Koko, P. A.,

Atomic Absorption Analysis of Polymetallic Ores,

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36. Amos, M. D. , Nonflame Atomization in AAS - A Current

Review, Amer. Lab., p. 57 (August 1972).

127
37. Rains, C, and Menis, 0., Determination of Submicrogram 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. 25^, 313 [1971).

39. Gandrud, B. W. , and Skogerboe, R. K. , Investigation

of the Hollow Cathode Discharge as an Atomic Absorption

Medium, Appl. Spectrosc. 2_5, 243 (1971).

40. Goleb, J. A,, The Determination of Mercury in Small

Terrestrial and Nonterrestr ial 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. 4, 749 (1970).

42. Prey, V., Teichmann, H. , and Bickler, D., Die

Bestimmung von Silicium in Organischen Verbindungen

mit Hilfe der Atomarabsorpt ion , 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 9_7, 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 Energy, 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.

128
47. Kirkbright, G. F., Sargent, H. , 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. £, 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 Longo, S. L.,

Ion Exchange Separation of Traces of Tin, Cadmium, and

Zinc From Copper and their Determination by Atomic

Absorption Spectrophotometry, At. Abs. Newsl. 8_, 102

(1969) .

51. Thompson, R. J., Morgan, G. B. , and Purdue, L. J.,

Analysis of Selected Elements- in Atmospheric Particulate

Matter by Atomic Absorption, At. Abs. Nev/sl. 9, 53

(1970) .

52. Kalb, G. W. , The Determination of Mercury in V/ater and

Sediment Samples by Flameless Atomic Absorption, At.

Abs. Newsl. 9, 84 (1970).

53. Manning, D. C, Non-Flame Methods for Mercury Determination by Atom.ic Absorption - A Review, At. Abs.

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54. Nakahara, T., Munemori, M., and Muska, S., De term.ination

of Selenium in Sulfur by Atomic Absorption Spectrophotometry, Anal. Chim. Acta _50, 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 Spectrophotometry, Anal. Chim. Acta 29, 202 (1963).

129
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, , Determination of Zinc in Food, Urine, Air, and Dust by Atomic

Absorption, Amer. Ind. Hygiene Assoc. J. 2_9, 469 (1968).

60. Kirkbright, G. F., The Application of Non-flame Cells

in Atomic-absorption and Atomic-fluorescence

Spectroscopy, Analyst 96_, 609 (1971).

61. Burke, K. E., Non-Aqueous Atomic Absorption Spectroscopy

Determination of Microgram Quantities of Antimony,

Bismuth, Lead, and Tin in Aluminum, Iron, and NickelBase 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. , Determination of Microamounts of Cadmium, and Zinc in Copper,

Nickel, Aluminum and Uranium Metals by Solvent

Extraction - Atomic Absorption Spectrophotometry,

Japan Analyst 20_, 1137 (1971).

63. Hwang, J. Y. , Trace Metals in Atmospheric Particulates

and Atomic Absorption Spectroscopy, Anal. Chem. 44 , No. 14, 20A (1972).

64. Obermiller, E. L., and Freedman, R. W. , Rapid Determination of Calcium, Magnesium, Sodium, Potassium and

Iron in Coal Ash by Atomic Absorption Spectrophotometry, Fuel 44_, 199 (1965).

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25A (1964).

130
CHAPTER 6

ABSORPTION SPECTROPHOTOMETRY

R. W. Burke

1. INTRODUCTION

For the past forty years j absorption spectrophotometry

has played a major role in the analysis of important industrial and research materials. Numerous factors have been

responsible for the popularity of this technique. Foremost

among these are: (1) its modest apparatus requirements, (2)

the possibility of its use by skilled technicians, (3) its

good sensitivity and (4) its high accuracy.

Several points 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 spectrophoto

metry is, for all practical purposes, a wet-chemical technique

Samples must therefore always 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 procedure. This deficiency,

however, is common to all wet-chemical techniques and is best

overcome by the analyst's experience. A second drawback of

absorption spectrophotometry is that it is primarily a single

element technique. Consequently, it is not suited for quick,

survey-type, analyses. Finally, the technique is generally

131
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 stength. 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 spec trophotometr ic method becomes essentially

an absolute one. This is often not the case with more

sophisticated instrumental 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

compounds which are readily available commercially.

: 2,. ANALYSIS OF SPECIFIC MATERIALS

Tables 1 and 2 summarize the relevant information on

the possible spec trophotometr ic determination of some twentyone elements in fly ash, incinerator particulates, 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

132
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 spectrophotometric 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 procedures 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 spectrophotometry.

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 determination. These costs can undoubtedly be substantially

133
reduced, perhaps even tenfold, by determining several

elements on the same sample and/or by determining the same

element simultaneously in a number o£ samples of similar

material.

As already mentioned, one of the advantages of absorption 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, spectrophotometric instrumentation is quite rugged with downtime

perhaps averaging no more than 1 percent.

... 3.. CONCLUSIONS

The primary purpose of this chapter has been the

delineation of state-of - the-rart procedures for the spectrophotometric determination of some twenty-one elements in fly

ash, incinerator particulates, coal, oil, ores, minerals,

metals, alloys, organome tallies , slurry streams and flotation

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 measurement

should be scarcely affected by the nature of the matrix being

analyzed, provided adequate dissolution procedures are used.

In all of the methods referred to above, solvent

extraction has invariably been the method of choice when

134
separations are necessary. This method is the most widelyused 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 development 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.

135
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References

1. Committee Report, The Determination of Small Amounts of

Mercury in Organic Matter, Analyst 9_0 , 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 9£, 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., "Colorime trie 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.> (1965).

8. Sandell, E. B. , "Colorime trie 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, Spectrophotometry, 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 96_, 398 (1971)

11. Stary, J., Systematic Study of the Solvent Extraction

of Metal Oxinates, Anal. Chim. Acta 28_, 132 (1963).

12. Motojima, K. , Hashitani, H. , and Imanashi, T.

,

Spectrophotometric Determination of Microgram Quantities

of Manganese in Uranium and Aluminum with 8-Hydroxyquinaldine. Anal. Chem. 34, 571 (1962).

138
13. Sandell, E. B,, "Colorimetric Determination of Traces

of Metals," 3rd ed. , pp. 606-620, Interscience , New

York, 1959.

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

Spec trophotome trie Determination of Cobalt, Nickel and

Copper with 2 , 3 -Quinoxal inedi thiol , Talanta 17_, 255

(1970)

16. Burke, R. W. , and Menis, 0., Extraction-Spectrophotometric

Determination of Antimony as a Ternary Complex, Anal.

Chem. 38_, 1719 (1966).

17. Fogg, A. G. , Jillings, J., Marriott, D. R. , and Burns,

D. T., A Critical Study of Brilliant Green as a Spectrophotome tr ic Reagent: The Determination of

Antimony, Analyst 94_, 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 8_, 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- I I

Spectrophotometric Determination of Copper as Rose

Bengal Bi sphenanthrol inium 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. Hoste, J., and Gillis, J., Spectrophotometric Determination of Traces of Selenium with Diaminobenzidine

Anal. Chim. Acta 12_, 158 (1955).

25. Cheng, K. , Determination of Traces of Selenium, Anal.

Chem. 28, 1738 (1956).

139
26. Kawashima, T. , and Tanaka, M. , Determination of

Submicrogram Amounts of Selenium(IV) by Means of the

Catalytic Reduction of 1 , 4, 6, 11 -Te traazanaphthacene

,

, Anal. Chim. Acta 40_, 137 (1968).

27. Spicer, G. S., and Strickland, J. D. H. , The Determination of Microgram and Sub-microgram Amounts of Boron,

Anal. Chim. Acta 18_, 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 6_0 , 139 (1972).

32. Babko, A. K. , and Marchenko, P. V., Photometric Determination of Boron in Steel, Zavod. Lab. 26^, 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).

34o Belcher, R. , Leonard, M. A., and West, T. S., A New

Spot Test for the Detection of Fluoride Ion, Talanta 2_,

92 (1959).

35. Bartkiewicz, S. A., and Robinson, J. W. , Rapid Method

for the Determination of Fluoride in Liquids, Anal. Chim

Acta 22_, 427 (1960) .

36. Belcher, R. , and West, T. S., A Study of the Cerium(III)

Alizarin Complexan-Fluor ide 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) .

140
38. El-Ghamry, M. T. , and Frei, R. W. , Spect ropho tome trie

Determination of Trace Amounts of Silver(T}, 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., She st idesyatnaya , N. L., and Zimomrya,

G. G. , Extraction of Tin(II) as its Compound with

Brilliant Green, Zh. Anal. Khim. 26_, 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.

3]^, 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. E., and Siitonen, S., The

Photometric Determination of Silicon as a-Sil icomolybdic

Acid, Anal. Chim. Acta 2£, 78 (1959).

46. Halasz, A., Pungor, E., Properties and Analytical

Applications of the Heteropolymolybdates of Phosphorus,

Arsenic, Silicon and Germanium, Talanta 1_8 , 557 (1971).

47. Stary, J., and Hladky, E., Systematic Study of the

Solvent Extraction of Metal 3-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 IonAssociation Complexes Directly in the Organic Phase,

Talanta 17 , 240 (1970)

141
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., "Color imetric Determination of Traces

of Metals," 3rd ed, , pp. 844-851, Interscience , New

. . York, 1959.

Coal

lA. Abernethy, R. P., and Gibson, F. H. , Color imetric 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. 239, 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. 38, 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, 42^, 301 (1970).

4B. Lambdin, C. E. , and Taylor, W. D. , Determination of

Trace Copper in Petroleum Middle Distillates with

Cuprizone, Anal. Chem. 40_, 2196 (1968).

5B. 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. 39, 251 (1967).

142
Particulates

IC. Sommer, L. , and Kuban, V., Spect rophotometric Determination o£ Beryllium with Chrome Azurol S, Analo Chim,

Acta 44 , 333 (1969)

2C. Stara, V., and Stary, J., Spectrophotome trie Determination o£ Traces of Arsenic, Talanta 17_, 341 (1970).

3C. Dickey, D. W. , Wiersma, J. H, , Barnekow, R. G. , Jr.,

and Lott , P. F, , Determination of Selenium by the

Ring Oven Technique, Mikrochim. Acta 605 (1969),

143
CHAPTER 7

ATOMIC EMISSION SPECTROSCOPY

Danold W. Golightly

1. INTRODUCTION

Atomic emission spectra of the elements have long provided

a powerful means for multi-element, chemical trace analysis.

The capabilities of optical emission spectrome trie analysis

have improved v/ith the increasing demands of our developing

technological age and the growing awareness of the contribution of trace concentrations of many elements to environ^

mental 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 (IR8R) on tlie subject. However, neither state-of-the-art nor

details of techniques are simple to elucidate concisely.

This chapter summarizes the most recent teclmiques for OES

analysis for 27 elements in the matrices: fly ash, coal, oil,

ores, minerals, metals, alloys, organometal lies , incinerator

particles, slurry streams, and feeds and sedim.ents in flotation

processes.

A. Optical Emission Sources

The basic sensitivity (change in analyte signal per unit

change in analyte concentration) of optical emission

144
spectrometry is a complex function of analyte element, sample

matrix, emission source, detector(s), and spectrometer optics.

Thus, elements that have lovi excitation potentials for

resonance lines and little tendency to form stable or nonvolatile 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

Tlie 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-volatile matrix) are listed

in Table 1, column 1 (1). Spectroscopic buffers that control

volatilization of solid compounds and stabilize excitation

conditions in the arc plasm.a enable considerable improvement

in spectrographic detectability. 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.

145
Further improvements in detectability of the elements

in spectra from 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

detectability 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-quantities

of analytes with 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 v;ith coefficients of variation of about 6 percent.

Sparks and AC Arcs

Discharges cliaracteri zed 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 and 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).

146
Dilute solutions are particularly amenable to analysis

by the copper-spark or graphite- spark technique. This method

was first described by Gerlach and Riedl (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 matrix material

in the residue is detrimental to detectability and precision,

however, chemical separations, such as extraction, ion exchang

or electrodeposit ion , 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.

147
Hollow Cathode

Mention also must be made of the hollow- cathode discharge.

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 elect rodeposi ted 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 oxideacetylene, oxygen-acetylene, oxygen-hydrogen, etc. Some

detection limits from oxygen - ace tylene flam.es (24) are

surveyed in Table 1, column 8.

From among the various micro-wave discharges, capacitativecoupled and inductively coupled flame-like plasmas, the

induction-coupled argon plasma appears to be a source that

148
provides stable, bright spectra and thus, good detectability

for many elements. Table 1, column 9 summarizes detection

limits from this source (25, 26).

B . Chemical Preconcentration

The key to OES analysis of many elements approaching

part-per-billion concentrations is preconcentration (or

enrichment) of impurities. General methodology and precautions have been described by Thiers (27), Minczewski (28),

Mizuike (29) , and Lighty and Currier (30)

.

The techniques of most importance to removal of impurities

from a matrix and concentration are liquid- liquid extraction,

ion-exchange and electrodepos ition . 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, Jackv/erth et al. have described DTPA complex

exchange reactions (30a) , coprecipi tat ion 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 dissolution of matrices (30d) as sample manipulations preceding

spectrochemical analysis.

2. APPLICATION TO MATEPJALS OF ENVIRONMENTAL INTEREST

The twelve matrices, subjects of this report, can be

separated into five groups for discussion. These groups,

which assemble similar matrices, are:

149
A. Group 1 - Streams to and from Air Scrubbers

The liquids and solids collected in v;et scrubbers can be

analyzed by techniques long established by Kopp and Kroner

(31a, 31b, 32a, 33a, p. 1010). Kopp and Kroner analyzed for

Ag, Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Mo, Mn, Ni, P,

Pb, Sr, V, and Zn in preconcentrated water samples by the

rotating-disk high-voltage spark method. Concentrations

from 0.01 to 100 yg/ml were determined on a direct-reading

spectrometer. A volume of water evaporated (8 to 10 hrs)

to 5 ml contained 20g of total solids/liter; the major

portions of solids were salts of Ca , K, Mg, and Na. Concentration 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 (31c, 31d)

,

for spectrome tr ic water analysis should be directly applicable

to analysis of water from wet scrubbers.

Haffty (32b) has described a residue method capable of

detecting almost 60 elements in the ng/ml range. The technique

lias been applied to analysis of water sediments. Barnett

(33a, p. 1001) has described a residue method for 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 spec trome tri c analysis of the metals Al , Cu,

Fe, Pb and Zn are detailed in the ASTM Methods for Emission

150
Spectrochemical Analysis (33a). Only metal constituents

important to bulk metallurgical properties of these alloys

arp of concern in the ASTM m.ethods. 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, et al . (33b) have developed a chemical

preconcentrat ion technique that enables emission spectrochemical

analysis to be carried out for parts-per-million of Ag, As,

Au, Bi, Cd, Ge, In, Mo, Pb, Sn and Tl in alloys of Al , Cr, Co,

Fe, Ni and Ti. Killeen (33c) has used a dc-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 preconcentration methods, defined by the specific problem, will be

required.

Elwell and Scholes (35), Dozinel (36), Tolle (36a) and

Publicover (36b) provide further information on spectrometric

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

151
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), Schoenfeld (51),

de Villiers et al . (52) and in ores by DeMontleau (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 spect rogr aphy with a plasma-arc

source.

152
D. Group 4 - Coal, Feeds to Coal Flotation Processes,

Qrganometallics (formed by 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).

E. 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 hydrofluoric

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

153
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) 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 sam.ple 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.

154
B . Quantitative Analyses

Quantitative analysis provides concentration information

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 microphotometry 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 quantitative measurements. These differences are reflected in the estimated

times (costs) for quantitative analyses summarized in Table 4.

155
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Column in Spec tr ographic and Spectrometr ic

Table 1 Emission Sources References

1 DC Arc in Air 1

2 DC Arc, Li Salt Buffer 2

3 DC Arc, Controlled Atmosphere 3,4,5,6,7

4 DC Arc, Reduced Pressure Argon 8

5 Spark, Porous Cup Rotating Disk . 10,11,12,13

6 Spark, Copper and Graphite 15,16,17,18

7 - Hollow Cathode 23

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9 Argon Induction-Coupled Plasma 25

Column in Spec tr ographic and Spec trome trie

Table 2 Analysis of Various Materials References

1 Water, Rotating Disk Method 32a

2 Water, Residue Method 32b, 33a

3 Aluminum, Spark Emission 33a, 33b

4 Coal Ash 4 5

5 Copper, Globular Arc 36b

6 Minerals and Phosphate Rocks 48

7 Minerals and Powders 52

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159
Optical Emission Spectrometry General References

IB. Morrison, G. H. , Ed., "Trace Analysis," Wiley Interscience

,

New York, 1965.

2B. Call, J. P., Ed., "Trace Analysis of Semiconductor

Materials," Pergamon-Macmillan.j New York, 1964.

3B , Harvey, C. E., "Semiquantitative Spectrochemistry,"

Applied Research Laboratories, Glendale, Galif, 1964.

4B . A.S.T.M., "Methods for Emission Spectrochemical Analysis,"

Committee E-2 on Emission Spectroscopy, 6th Ed.,

American Society for Testing and Materials, Philadelphia,

Pa. , 1971.

5B. Pinta, M. , "Detection and Determination of Trace

Elements; Absorption Spectrophotometry, Emissioi)

Spectroscopy, Polarography , " Davey, New York, 1966.

6B. Meinke, W. W. , and Scribner, B. F., Eds., "Trace

Characterization, Chemical and Physical," Nat. Bur.

of Stand. , Monogr. 100, U.S. Govt. Printing Office,

Washington, D.C., 1967.

160
Optical Emission Spectrometry Reviews

IR. Dekalb, E. L., Kniseley, R. X., and Fassel, V. A.,

Optical Emission Spectroscopy as an .Analytical Tool,

Ann. N. Y. Acad. Sci. 137, 255 (1966).

2R. Barnes, R. M. , Emission Spectrometry, Anal. Chem. 44_ (5),

122R-150R (1972).

3R. Winefordner, J. D. , and Vickers, T. J., Flame Spectrometry,

Anal. Chem. 44_ (5), 150R-182R (1972).

4R. Margoshes, M. , Emission Spectrom.etry , Anal. Chem. 4_2 (5),

398R-417R (1970).

SR. Winefordner, J. D. , and Vickers, T. J., Flame Spectrometry,

Anal. Chem. £2 (5), 206R-251R (1970).

6R. Margoshes, M. , and Scribner, B. F., Emission

Spectrometry, .^al. Chem. £0 (5), 225R-246R (1968).

7R. Scribner, B. F. , and Margoshes, M. , Emission

Spectrometry, Anal. Chem. 56_ (5 ), 52 9R-345R (1964).

SR. Xorris, J. A., ASTM Symp. Spec. Anal. Trace Elements.

American Society for Testing and Materials, Philadelphia,

Pa., 1958.

161
References

1. Ahrens , L. H., and Taylor, S. R. , "Spectrochemical

Analysis, A Treatise on the d-c Arc Analysis of

Geological and Related Materials," 2nd Ed., p. 181,

Addison-Wesley , Reading, Mass., 1961.

2. Harvey, C. E., "Semiquantitative Spectrochemistry,"

Applied Research Laboratories, Glendale , Calif., 1964.

3. Morrison, G. H. , Rupp , R. L., and Klecak, G. L.,

Spectrographic Analysis of High Purity Silicon Carbide,

Anal. Chem. 32, 933-935 (1960).

4. ASTM Comm.ittee E-2 on Emission Spectroscopy. Methods

for Emission Spectrochemical Analysis, 4th Ed.,

American Society for Testing and Materials, Philadelphia,

Pa. , 1964.

5. Mittledorf, A. J., The Spex Speaker ^(4), Spex

Industries, Inc., Metuchen, N. J., 1962.

6. -. Morrison, G. H. , and Rupp, R. L., In "Silicon Carbide,"

Edited by J. R. O'Connor and J. Smiiltens, p. 2 27 , Pergamon Press, Oxford, 1960.

7. Rupp, R. L. , Klecak, G. L., and Morrison, G. H., Spectrographic Analysis of High Purity Nickel, Anal. Chem. 3 2

,

931 (1960).

162
8. Gordon, W. A., and Chapman, G. B., Quantitative DirectCurrent Arc Analysis of Random Compositions of Microgram

Residues in Silver Chloride Common Matrix, Spectrochim.

Acta 25B , 123-137 (1970)

9. Hambidge, K. M. , Use of Static Argon Atmosphere in

Emission Spec t rochemical Determination of Chromium in

Biological Materials, Anal. Chem. 103-107 (1971).

10. Baer, W. K. , and Hodge, E. S., The Spectrochemical

Analysis of Solutions, A Comparison of Five Techniques.

Appl. Spectrosc. 1_4 , 141-146 (1960),

11. Feldman, C, Direct Spectrochemical Analysis of

Solutions, Anal. Chem. 2A, 1041 (1949).

12. Feldman, J., Conference on Analytical Chemistry and

Applied Spectroscopy, Pittsburgh, Pa., March 1963.

I3a. Wilska, S., Sensitivity of Direct Spectral Analysis

of Solutions, Acta Chem. Scand. S, 890-897 (1951).

13b. Wilska, S., Quantitative Spectral Analysis of Trace

Elements in Water, Acta Chem. Scand. 5_, 1368-74 (1951).

14. Gerlach, W. , and Riedl , E., Spectroanalyt ical Studies.

XIII. The Spectroscopic Test of Purity in the New

Primary Radium Standard, Z. Anorg. Chem. 221 , 103-108

(1934).

163
15. Fred, M. , Nachtrieb, N. H. , and Tomkins, F. S.,

Spect rochemical Analysis by the Copper Spark Method,

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• York, 1950.

17. Morris, J. M. , and Pink, F. X., Symposium on Spectrochemical Analysis for Trace Elements, ASTM Special

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18. Feldman, C, Rare Earths Microanalysis, In Encyclopedia

of Spectroscopy, Edited by G. L. Clark, pp. 275-277,

Reinhold, New York, 1960.

19. Duffendack, 0. S., and Thompson, K. B., Developments

in the Quantitative Analysis of Solutions by Spectroscopic

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(1936).

20. Duffendack, 0. S., Analysis of Caustic Liquors for

Traces of Impurities, Ind. Eng. Chem. , Anal. Ed. 1

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, 161-164 (1938) .

21. Hess, T. M. , Owens, J. S., and Reinhardt, L. G.

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Analysis of Organic Materials for Traces of Metallic

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164
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Pervunina, R. I., Shilina, A. T., Tr. Inst. Eksp.

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22a. Pfeilsticker , K. , Intermittent Arc with h.f. Excitation,

Z. Elektrchem. 4_3 , 717-721 (1937).

22b. Pf eilst icher , K. , Experiments with the Self- Igniting

Interrupted Arc, Z. Metallkunde 3£, 211-14 (1938).

23. Korovin, Y. I., On the Increase of Sensitivity of

Determinations by Means of a Hollow Cathode Discharge,

Zh. Analit. Khim. 16_, 494 (1960).

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Applicable to Spec trographic Analysis for the Halogens

and Gases, J. Opt. Soc. Am. 37_, 93-98 (1947).

23b. Adams, K. B., and Burns, K. , Westinghouse Corp. Research

Memo 6-94602-9-M37 (1957).

23c. Thornton, K. , The Use of a High Temperature Hollow

Cathode Lamp for the Spect rographic Analysis of

Steels, High Temperature Alloys, and Related Materials

for Trace Elements, Analyst 9£, 958-967 (1969).

23d. Ropert, M. E., Use of a Luminescence Discharge Source

for Non-Conducting Materials in Spectrographic

Analysis, Compt. Rend. 271, 992-994 (1970).

24. Fassel, V. A., and Golightly, D. W. , Detection Limits

of Elements in the Spectra of Premixed, Oxyacetylene

Flames, Anal. Chem. 39 , 466-476 (1967)..

165
25. Dickenson, G. , and Fassel, V. A., Emission Spectrometric Detection of the Elements of the Nanogram per

Milliliter Level Using Induction-Coupled Plasma

•

, Excitation, Anal. Chem. 41, 1021 (1969).

26. Fassel, V. A., Electrical Flame Spectroscopy, Plenary

lecture presented at XVI Colloquium Spectroscopicum

Internationale, Heidelberg, Germany, Oct. 1971.

27. Thiers, R. E., Separation, Concentration and Contamination,

in "Trace Analysis," Edited by J. H. Yoe and H. J. Koch,

Jr., Wiley, New York, 1957.

28. Minczewski, J., Preconcentrat ion in' Trace Analysis, in Nat.

Bur. Stand., Monogr. 100, U.S. Govt. Printing Office,

Washington, D.C., 580 pages (April, 1967).

29. Mizuike,- A., Separations and Preconcentrat ions , Chapter

4 in Trace Analysis, Edited by G. II. Morrison, WileyInterscience , New York, 1965.

30. Eighty, P. E., and Currier, E. W. , Emission Spectroscopy,

Chapter 2 in "Trace Analysis of Semiconductor Materials,"

Edited by J. P. Call, Macmillan Co., Nev; York, 1964.

30a. Jackwerth, E., and Graffmann, G. , Fine KomplexAus tauclireaktion zur Indirekten Photome tris chen und

Atoms absorptions - Spektrometr is chen Bestimmung von

Spurene lementen , Z. Anal. Chem. 2 5 7 , 265-268 (1971).

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30b. Jackwerth, E., Lohmar, J., and Schwark, G., Anreicherung

und Spektrochemische Bestimmung von Spurenelementen

in Reinsten Thai liumpr aparaten , Z. Anal. Chem. 25 7 , 101-106 (1971).

30c. Jackwerth, E., Doring, E., Lohmar, J,, and Schwark, d .

Spurenanreicherung Durch Partielles Losender Matrix,

Z. Anal. Chem. 260, 177-184 (1972).

30d. Jackwerth, E., and Kulok, A., Versuche zur Anreicherung von

Edelmetal Ispuren in Reinstquecksilbar Durch Partielles

Losen der Matrix, Z. Anal. Chem. 25 7 , 28-33 (1971).

31a. Kopp , J. F., and Kroner, R. C, A Direct - Reading

Spectrochemical Procedure for the Measurement of 19

Minor Elements in Natural IVater, Appl. Spectrosc. 1_9 (5)

155-159 (1965).

31b. Kopp, J. F., and Kroner, R. C, Tracing Water Pollution

with an Emission Spectrograph, J. Water Pollution

Control Federation 39, 1659-1668 (1967).

31c. Pforr, G., and Aribat, 0., Spectrographic Analysis of

Solids and Viscous Solutions Using a Plasma Source,

Z. Chem. 1_0 , 78 - 79 (19 70).

31d. Sakai , S., Determination of Metallic Ingredients of

Waste Water by Rotating Disk Solution Excitation,

Bunko Kenkyu 13, 94-102 (1965).

167
32a. Kopp , J. F. , and Kroner, R. C, A Five Year Summary o£

Trace Metals in Rivers and Lakes of the United States,

Oct. 1, 1962; Sept. 30, 1967; U. S. Dept. o£ Interior,

Federal Water Control Administration, Cincinnati,

Ohio, 1967.

32b. Haffty, J., Residue Method for Common Minor Elements,

U. S. Dept. 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 Spect rochemical

Analysis, Sixth Ed., American Society for Testing and

Materials, Philadelphia, Pa., 1971.

33b. Balfour, B. E., Jukes, D. , and Thornton, K. , A Spectrochemical Method for the Determination of Trace Impurities

in Metallurgical Materials, Appl. Spectrosc. 2_0, 168-171

(1966) .

33c. Killeen, 0. P., Spect rographic 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., Spectrochemical Analysis of Trace Impurities in Copper Using

Copper Fluoride as a Carrier-Distillation Agent, Appl.

Spectrosc. 22, 268-271 (1968).

168
35. Elwell, 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 Alloys, "(English translation by G. R. Andraso,

Pittsburgh, Pa.), Charles Dozinel, Brussels, 1960.

36a. Tolle, H. , Spect rographic Determination of Trace

Impurities in Pure Copper Using a Globule Arc in

Oxygen, Z. Analyt. Chem. 24i0, 162-170 (1968).

36b. Publicover, W. E., Spectrochemical Analysis of OxygenFree Electrolyt ically 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. Atwell, M. G., and Golden, G. S., The Emission

Spectrographic Carrier-Distillation Determination of

Traces of Lead, Bismuth and Tin in Nickel-Base Alloys,

Appl. Spectrosc. 24-, 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. 37, 379-389 (1946).

169
38a. Shapiro, L., Developments in Applied Spectroscopy

_8, 143-157 C1970).

39. Mittledorf, A. J., Emission Spectrochemical Methods,

Chapter 6 in "Trace Analysis," Ed. by G. H. Morrison,

Wiley- Interscience , New York, 1967.

I40. Collins, A. C, Emission Spect rome t ri c Determination

of Barium, Boron, Iron, Manganese, and Strontium in

Oilfield Waters Using a Plasma Arc, Appl. Spectr. 2

1

, 16-19 (1967).

41a. Abernethy, R. F., lirgun, S., Eriedel, R. A., McCartney,

J. T., and Wender, I., Coal and Coke, in Encyclopedia

of Industrial Chemical Analysis, V.IO, Ed. by F. D.

Snell and L. S. Ettre, pp. 209-262, Wiley- Interscience

,

New York, 1971.

41b. Abernetliy, 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. Sharkey, A. G., Shultz, J. L., and Friedel, R. A.,

Advances in Coal Spectrometry - Mass Spectrometry,

: U. S. Bur. Mines Kept. Invest. 6318 (1963).

43. Gibson, F, H., and Ode, W. H., Applications of Rapid

Methods for Analyzing Coal Ash and Related Materials,

RI 6036, U. S. Bur. Mines, 1962.

170
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. Ecrement, F. , Dosage Elem, Etat Traces Roches Autres

Subst. Miner. Natur., Actes Colloq. , 173-85 (1968);

C. A. 75, 83749y (1971).

47. Govindaraju, K. , Dosage Elem. Etat Traces Roches

Autres Subst. Miner. Natur. , Actes Colloq. , 133-44

(1968); C. A. 75_, 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. 2^, 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. Transfer 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).

171
Schoenfeld, I., Spect rochemical Determination o£ Fluorine

in Standard Rocks, Appl. Spectrosc. 24_, 359-361 (1970).

de Villiers, D. B., van Wamelen, D. , and Strasheim, A.,

Semiquantitative Procedure for the Simultaneous

Spectrographic Determination of Thirty Elements in Powder

Samples, Appl. Spectrosc. 20_, 298-301 (1966).

de Montleau, Ph., Spectrographic Analysis with the Tape

Machine, Method. Phys. Anal. 6, 162-166 (1970).

172
CHAPTER 8

VOLTAMMETRY (POLAROGRAPHY)

E. June Maienthal

1. INTRODUCTION

Voltammetry (polarography) is a well known analytical

technique that has considerable potential for environmental

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 vo 1 1 amme t ry

Attractive features of voltammetry include high

sensitivity, good selectivity, moderate cost of instrumentation, and the ability to determine several constituents

in the same solution. Modern instrumentation has

improved polarography with respect to sensitivity,

selectivity, 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 pretreatment

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.

173
A . Background

With a conventional d.c. pen-recording polarograph

and a dropping mercury electrode, solutions containing

as little as 1 yg/ml (0.01 millimolar) can be analyzed.

Accuracies o£ 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 wave 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

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.

174
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. Electrodes 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 interfering ion or ions in the

second cell.

175
The best polarographic precision obtainable, so far, can

be achieved by using the second cell in the comparative

mode o£ 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 constituents on

micro amounts of sample.

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 mercurygraphite, glassy carbon, etc. Cathodic stripping, which

is the reverse of the procedure described above, can

be used for determination of anions.

176
2. APPLICATIONS TO ENVIRONMENTAL ANALYSIS

Voltammetr ic 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 overs implication , as any one

of the matrices may require some individual consideration.

These groupings have been based, not necessarily on

the similarities of the matrix, but rather on the complexity

of sample dissolution and of other chemical pre treatments

which may be necessary before the instrumental measurement.

Fly ash, coal, oil, organometallics , incinerator particulates,

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 with 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

177
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, 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 constituent, 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, hov;ever, 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

178
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 classification 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

polarographically at -0.63V in a supporting

electrolyte containing ammonium hydroxide and potassium

chloride. Other workers (6) have used an ammonium

179
chloride - ammonium hydroxide or a 30 percent ammonium acetate

supporting electrolyte, and have also determined copper

and zinc at the same time.

Landry (7) determined lead and zinc in the atm.osphere

using cadmium and manganese as internal standards,

in an ammonium chloride-ammonium hydroxide supporting

electrolyte. Earlier workers (8) determined lead in

O.IN KCl by addition o£ a known amount o£ 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 o£ air

using a supporting electrolyte of potassium nitrate,

glycine and nitric acid at a pH o£ 3.

Tetraethyl lead in air was determined by Khlopin

(10) a£ter absorption o£ about 0.5 cubic meter o£ air

in castor oil containing a saturated solution o£ 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 £or the determination o£ zinc,

lead, copper, cadmium, manganese, and bismuth in air.

He reports that all six elements may be determined

simultaneously

.

180
Urone 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 yg/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 tr iethanolaminesodium hydroxide supporting electrolyte (13) Pines

(14) used a similar supporting electrolyte and determined

amounts down to 20 yg of manganese in air with coefficients

of variation of 8.5 percent. For 500-800 yg of manganese^

the coefficient of variation was 2.5 percent.

Babina (15) determined titanium in air after absorption

in 0.5 M sulfuric acid or collection on a PVC filter. Potassium

oxalate was used as a supporting electrolyte and the

pH of the solution was adjusted to 3 - 3.5 with potassium

hydroxide. Errors of ± 6 percent were obtained, and

more than 50 yg/ml of iron and 1 yg/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

Particulates collected in laboratory air, suburban

air, rural air, and industrial air have been analyzed

181

I
at the National Bureau of Standards by cathode ray polarography 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 cyclohexanebutyrates

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 determinations

were at the major constituent level, hence the determinations

required only a few mg. of Scimple. 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 wear and predicting 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 v;ith 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 botanical 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).

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

183
of corrosion products is another one o£ NBS experiences

that has applications of environmental interest.

Complete compositional analyses have been made

on samples as small as 90 yg in the case of thin films

composed of antimony-bismuth, lead-tin-tellurium, nickelchromium-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 doim 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 aiuminum directly, with

no separations, in amounts ranging from 0.6 to 200 ppb.

184
3. CONCLUSIONS

The examples discussed here demonstrate the applicability

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 instrumentation discussions for pure solutions,

because a realistic evaluation has been made on the

basis of problems 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

equipment should be required other than that present

in an ordinary chemical analytical laboratory.

185
A technician, well-trained in analytical manipulations,

should be capable of performing most of the analyses,

provided a detailed procedure is available. A competent

electroanalyt ical chemist should be available for consultation.

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Table 4. Element Index to References

Fly Ash, Coal, Oil, Organometallics

,

Incinerator Particulates and Minerals by Polarography

Element

Determined

Mercury

Beryl 1 ium

Cadmium

Arsenic

Vanadium

Manganese

Nickel

Antimony

Chromium

Zinc

Copper

Lead

Selenium

Boron

Fluorine

Lithium - Silver

Tin

I ron

Strontium

Sodium

Potassium

Calcium

Sil icon

Magnesium

Uranium

Thorium

Reviews

References

2,3,6,7,11,12,13,16,25,29,30,32,42,164

2,17

40

2,17,25,30,32,34,35,36,43

13, 13a, 18, 164

3,17

15, 32, 36, 46b, 46c

2 , 3, 11-14, 17, 25, 29, 30, 31 , 32, 41- 44 , 46c, 164

2, 3, 8-14, 16, 25, 30, 42, 46b, 46c, 164

2, 3, 12, 13a, 16, 17, 20-32, 42, 46b, 164

33

37,46b

2, 13a, 17, 18, 36, 46b, 164

1

1

19

37a, 38

45,46,46a

190
Table 5. Element Index to References

Ores, Metals, and Alloys by Polarography

Element

Determined

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

Thallium

Tellurium

Reviews

References

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

47,53,69,7 0,78,82,90,94,99,119

70,75

51,5 5,62,66,7 5,7 7,78,8 0,86,92,98-100,103,104

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

48,53,56-59,62,67,69,7 0,73,74,7 6-78,84,8 6,87,92-94,

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

49,65,85,122,126,127

52,62,63,64,69,70,106

101,102,131,132

191
Table 6. Element Index to References

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

Fluorine

Lithium

Silver

Tin

Iron

Stront ium

Sodium

Potassium

Calcium

Silicon

Magnesium

Uranium

Thorium

Bismuth

Reviews

References

147,151,154,155,162,163,165,167,181-184

142-145

162,178

147,153,169

154-156,162,167,169,178

141

178

140,147,151,153-155,158.162,165,167,168

179-185

139,147-149,151-158,162,166,167,182-184

139,14 7,151,155,157,159,160,163,165-168

182-184

171

137

140,165

139,147,162,185

135,136,137

135,136

135,136,138,178

135,136,178

172-177

146

170,186,187
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,

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,

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193
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.

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194
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,

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41. Takazawa, F. , and Sherman, G. D. , Polarographic determination of zinc in soil, J. Assoc. Official Agr . Chem.,

30, 182-6 (1947)

.

42. Cohen, E., Determination of micro amounts of heavy

metals in air by anodic -s tripping voltammetry, (Zn,

Cu, Pb, Cd) , Bull. Soc. Chim. Fr., 1972, 416-9.

198
43. Jones, G. B.. The p olarographic determination of zinc

and manganese in plant and animal tissues and soils.

Anal. Chim. Acta, 11_, 88-97 (1954).

44. Kogan, I. B., Po larographic determination o£ zinc oxide

in the atmosphere, Zavod. Lab., 16^, 932 -4 (1950).

45. Pignataro, N., Polarographic analysis in mineralogy.

Rend. Soc . Mineral. Ital., 71_, 71-96 (1947).

46. Sinyakova, S. T., Polarographic analysis o£ mineral

raw materials, Trudy Komissii Anal. Khim., Otdel. Khim

Nauk, Akad. Nauk S.S.S.R., 2, 133-56 (1949).

46a. West, P. W. , and Hale, C. H., Application of polarography

in the petroleum industry, Petroleum Refiner, 29_f 109-11

(1950).

46b. Korshunov, I. A., and Shchennikova , M. K., Polarographic

determination of metals in used lubricating oils (Cr,

Fe, Sn, Pb, Cu) , Zavod. Lab., 13_, 682-6 (1947).

46c. Korshunov, I. A., Sazanova, L. N., and Protsenko, R. V.,

Use of polarographic method in analysis of ash components

of coal (Cu, Zn, Cr) , Zavod. Lab., 13, 301-3 (1947).

199
B. Metals, Alloys, and Ores

Cadmium

47. Temmerman, E., and Verbeek, F., The determination of

traces o£ Sb , Sn, and As in Cd by pulse polarography

,

Anal. Chim. Acta, 43_, 263-72 (1968).

48. Temmerman, E., and Verbeek, F. , Determination o£ traces

of Bi, Cu, and Pb in Cd by pulse polarography, J. Electro-

. anal. Chem., 12, 158-165 (1966).

49. Temmerman, E., and Verbeek, F., The determination of

traces of Tl in Cd by pulse polarography, J. Electroanal.

Chem. , 19 , 423-9 (1968)

.

Cobalt

50. Lagrou, A., and Verbeek, F., The determination of traces

of nickel in Co by pulse polarography, J. Electroanal.

Chem. , 19 , 125-9 (1968)

.

51. Lagrou, A., and Verbeek, F., The determination of traces

of Zn and Mn in Co by pulse polarography,, J. Electroanal. Chem., 19, 413-21 (1968).

Copper, Copper Base, Brass and Bronze

52. Cathro , K. J., Polarographic determination of arsenic and

tellurium in copper, Aust. J. Appl. Sci., 9^, 255-264 (1958).

53. Eve, A. J., and Verdier, E. T., Polarographic determination of traces of bismuth, iron, lead, antimony, nickel,

cobalt and manganese in refined copper. Anal. Chem.,

2_8 , 537-8 (1956) .

54. Fleury, M. , and Capelle, R. , Polarographic determination

of cadmium in bronze, Chim. Anal., 45_, 193-8 (1963).

55. Maienthal , E. J., and Taylor, J. K., Improvement of

polarographic precision (Cu and Zn in Brass and Bronze) , Microchimo Acta, 1967, 939.

200
56. Milner, G. W. C, Polarographic determination of lead

in brasses and bronzes. Analyst, 7_0, 250-3 (1945).

57. Spalenka, M. , Polarographic determination o£ lead and

cadmium in copper and its alloys, Me tallwirtschaft

2_3 , 341-3 (1944).

58. Fleury, M. , and Capelle, R. , Polarographic determination of lead and cadmium in copper - aluminum alloys,

Chim. Anal., 45^, 117-123 (1963).

59. Capaccioli, T., Sbrolli, W. , and Vercellone, A., Rapid

polarographic analysis of lead and copper in commercial

brass, Ann. Chim., Roma, 4£, 1125-1142 (1959).

60. Milner, G. W. C., Polarographic determination of nickel

in copper-base alloys. Analyst, 70^, 468- 74 (1945).

61. Zopatti, L. P., and Comwell, J. C, Determination of

Se in Cu by cathode ray polarography , in press.

62. Ripen, R. , and Pop, G., Ascorbic acid in polarographic

analysis, (Se , Fe , Pb , Zn, Cd, in Cu and anodic mud

during Cu electrolysis), Rev. Chim., 1£, 411-12 (1963).

63. Maienthal , E. J., and Taylor, J. K., Determination of

tellurium by cathode-ray polarography (in brass and

cast iron), Anal. Chem., 3_7 , 1516 (1965).

64. Bykov, I. E., and Gorshkova, L. S., Polarographic determination of tellurium in copper alloys, Zavod. Lab.,

2_5 , 674- 76 (1959) .

65. Gertseva, N. S., Polarographic determination of Tl in

presence of Cu without their preliminary separation,

Teoriya i Praktika Polyarograf. Analiza, Akad. Nauk

Moldavsk, SSR, Materialy Pervogo Vses. Soveshch., 1962 , 222-9 .

66. Milner, G. W. C, Applications of the polarograph to

metallurgical analysis. II. Polarographic methods for the

determination of zinc in copper-base alloys, Metallurgia,

35, 265-7 (1947)

201
67. Toropova, V. F. , Polarographic determination o£ lead

in lead bronzes, J. Applied Chem. , 18, 177-80 (1945).

Ga Arsenide

68. Jennings, V. J., Determination of some trace impurities

in gallium arsenide by square-wave polarography , (Bi,

Cu, In, Cd) , Analyst, 87, 548-557 (1962).

Steels , Alloys

69, Maienthal , E. J., "Determination of trace elements in

steels, alloys, and other metals by cathode ray

polarography" (Al , Pb , Bi , Te , Sb , Sn , Ti , Cu , Fe , and

Cd) , talk presented at the Oct. 8-13, 1972, meeting

of the Electrochemical Society in Miami Beach, Florida.

70. Maienthal, E. J., Analysis of Sb-Bi, Cu-Ni-Cr-Al, and

Pb-Sn-Te thin films, Polarographic Analysis, 29, NBS

Tech. Note 455, Taylor, J. K., ed. , (1968).

71. Yana, M., Mochizuki, H., Kajiyama, R. , and Koyama, Y.,

Polarographic determination of arsenic in iron and steel,

Japan Analyst, ^, 160-3 (1956).

72. Dolezal, J., and Novak, J., Rapid methods for analysis

of metals and mineral raw materials, (Cu and Bi) , Collect.

Czechoslov. Chem. Communs . , 24^, 51 (1959).

73. Scholes , P. H., An evaluation of the formate buffer

method for the simultaneous determination of Cu and Pb

in steel. Analyst, 86, 116-24 (1961).

202
74. Tajima, N., and Kurobe, M. , Determination of traces

of copper and lead in cast iron and pig iron, Japan

Analyst, 9, 801-6 (1960).

75. Stabryn, J., Polarographic determination of copper,

zinc and chromium in cast-iron turnings, Hutn. listy,

15^, 302 (1960).

76. Nadezhina, L. S., and Razumova, V. P., Polarographic

determination of small amounts of lead in pure metals

and ferrous alloys, Zhur. Anal. Khim. , 12_, 731- 5 (1957).

77. Goto, H. , and Namiki , M. , Simultaneous determination of

Pb and Zn in iron, steel and iron ores, by D. C. polarography, Sci . Dept., RITU, 1_9 , 245- 53 (1967).

78. Yakovlev, P. Ya., Malinina, R. D. , Razumova, G. P., and

Dymova, M. S., Use of polarography in the analysis of

ferrous metals (Sn, Pb , Cd, Cu , Sb , Bi, Ni , Co, Zn, and

W) , Teoriya i Praktika Polyarograf. Analiza, Akad. Nauk

Moldavsk, SSR, Materialy Pervoga Vses. Soveshch, 1962 , 198-202

79. Scholes , P. H., The determination of tin in pure iron,

mild steel and certain low-alloy steels by cathode ray

polarography, Analyst, £6, 392-9 (1961).

80. Maekawa, S., Yoneyama, Y., and Fujimori, E., Determination of trace elements in iron and steel. I. Determination of zinc in iron and mild steel by dithizone extraction

followed by polarography, Japan Analyst, 9_, 244-7 (1960).

Pb and Pb-Base Alloys

81. Athavale, V. T., Dhaneshwann, R. G., Nehta, M. M. , and

Sundaresam, M. , Polarographic determination of antimony

in refined lead, Analyst, 86_, 399-401 (1961).

82. Kraus , R. , and Novak, J. V., Polarographic determination

of Sb in hard Pb , Die Chemie, 56, 302-3 (1943).

203
83. Goto, H., and Ikeda, S., Pol arogr aphi c determination of

As in Pb , Sci . Rep. Res. Inst. Tohoku Univ., 9_, 91-6

- (1957)

.

84. Gertseva, N. S., Polarographic determination of bismuth, copper and lead when present together, Trudy

Inst. Metallurg, Akad. Nauk, SSSR, 1957, 238-240.

85. Maienthal , E. J., Bismuth, In, Tl, and Cd in Pb-base

alloys, Polarographic Analysis, 11, NBS Tech. Note

273 (1965)

.

86. Burlacu, G. , Bot, 0., and Antonescu, I., Polarographic

determination of copper, lead, cadmium and zinc in lead

concentrates. Stud. Cercet. Stiint. Chim., Cluj , 7,

17-23 (1956).

87. Zagorski, Z., Polarographic determination of oxidised

lead in metallic lead, Chem. Anal., Warsaw, 1^, 80-90

(1956) .

88. Zagorski, Z., and Kempinski, K., Concentration of Ag

traces in Pb by coprecipi tation , Chem. Anal., £, 423

(1959) .

89. Shinagawa, M. , Murata, T., and Yoshida, T., Polarographic

determination of tin in lead-base alloy containing

antimony, Japan Analyst, 6_, 215-9 (1957).

90. Kovalenko, P. N., and Lektorskaya, N. A., Polarographic

determination of tin and antimony in metallic lead,

Zavod. Lab., 16, 924-9 (1950).

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., 1_3, 569- 71 (1947).

92. Yakovlev, P. Ya., Razumova, G. P., and Malinina, R. D.

,

Polarographic determination of impurities in nickel-based

alloys by co -precipi tat ion with methyl violet, (Bi, Pb , Cd,

Zn) , Zavod. Lab., 25, 1039-41 (1959).

204
93. Mukhina, Z. S., Tikhonova, A. A., and Zhemchuzhnay a

,

I. A., Determination of traces of lead, bismuth, tin

and cadmium in nickel-base alloys, Zavod. Lab., 2 2 , 535-7 (1956)

Ores

94. Morris, A. G. C, Determination of traces of antimony,

copper and lead in ferromanganese with a cathode-ray

polarograph. Analyst, _87 , 478- 84 (1962).

95. Cerny, A., Indirect polarographic and comp lexeme trie

determination of very small amounts of arsenic in

iron and ores, Hutn. Listy, 13^, 715-6 (1958).

96.. Oshman, V. A., and Chistyakova, A. P., Polarographic

determination of cadmium in an acid sulphate - iodide

supporting electrolyte, Zavod. Lab., 2J7 , 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, 195 8 , 21-4.

205
Scholes , P. H., Cathode-ray polarography : typical

applications to metallurgical analysis, R. § D. , 1962 , 38-41.

Odone , G. , and Picasso, G. , Polarographic analysis of

traces o£ metals in iron ores, (Cu, Pb , Zn , Ni , and Sn)

,

Chim. e Ind. , 42, 598-605 (1960).

Semerano, G. , and Gagliardo, E., Polarographic determination o£ iron, lead, and zinc in some zinc ores, Anal.

Chim. Acta, 4, 422-7 (1950).

Zelenina, T. P., Polarographic determination o£ lead in

chromite ores, Sb . Trud. Vses. Nauch . - Iss led . Corn.

-Metaluurg. Inst. Tsvet. Met., 1962 , 335- 8.

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. Gos . Nauch.

Issled. Inst. Tsvet. Met., 1962 , 669- 75.

Alimarin, I. P., Ivanov-Emin, B. N., and Pevzner, S. M.

,

Trudy Vsesoyuz. Kinferentsii Anal. Khim. , 2, 471-92

(1943)

.

Krai, S., and Rett, V., Rapid polarographic determination of tin in f errotungs ten , metallic tungsten and

tungsten ores, Hutn. Listy, 15_, 638-9 (1960).

Shinagawa, M. , Murata, T., and Okashita, H., Polarographic

analysis of uranium. Separation of concomitant ions with

anion- exchange resin, Japan Analyst, 8^, 356-61 (1959).

Krai, S., and Kysil, B., Polarographic determination of

very small amounts of zinc in ferromanganese and in

manganese ores containing cobalt, Hutn. Listy, 1_3, 716-7

(1958)

.

Vesela, M. , Polarographic determination Zn in Mn , ferromanganese and Mn ores, Hutn. Listy, 1_5^, 805-6 (1960).

Ringbom, A., and Torn, L., Polarographic determination

of small quantities of zinc in materials rich in iron,

Finska Kemis ts amfunde ts Medd. , 56, 12-7 (1947).

206
113. Cooper, W. C, and Mattern, P. J., Polarographic determination of small amounts of metals in iron pyrites,

(Zn, Cu, Ni) , Anal. Chem. , 24, 572-6 (1952).

Te and Te Concentrate

114. Pats, R. G. , and Semochkina, T. V., Polarographic determination of lead and copper in tellurium and tellurium

concentrate, Zavod. Lab., 28, 800-1 (1962).

Sn an d White Metal Alloys

115. Itsuki, K., and Kaji, T., Determination of copper and

lead in crude tin by alternating current polarography

,

Japan Analyst, 8, 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 determination 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)

TiO.

119. Lagrou, A., Vanhees , J., and Verbeek, F. , Determination

of traces of Sb , Cu, and Pb in TiO^ by pulse polarography,

Z. anal. Chemie., 224, 310-17 (1967).

U

120. Saito, K., and Takeuchi, T., Determination of trace impurities in metallic uranium. XIV. Determination of

lead by alternating- current polarography, Japan Analyst, —10, 152-6 (1961).^ 207
Zn and Zn base Alloys

121. Gajan, R. J., and Geehan, D. M. , Rapid determination

o£ aluminum, iron, copper, cadmium and lead in zincbase 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 o£ one another,

Metall u. Erz, 39, 184-7 (1942).

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 determination 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., 40_, 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, 2 5B , 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).

208
Reviews

130. Rooney, R. C, Polarographic determination of trace

elements in Fe , J. Polarographic Soc, 1958 , 21-4 .

131. Scholes , P. H., Cathode-ray pol arogr aphy : typical

applications to metallurgical analysis, R. 5 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) .

209
C . Slurry Streams, Feeds to and from Flotation Processes,

S^ediments in Flotation Processes, and Water (generalTT

133. Proszt, J., and Gyorbiro, K. , Po larographic testing of

drinking and usable water. I. Determination of hardness

and alkali-metal content. (K, Na, Ca, and Mg) , Chen. Anal.

. Warsaw, 1 , 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, 1_5 , 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. E., 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. , 24, 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., Fedoseeva, 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., 2

5

, 1748-51 (1970).

140. Whitnack, G. C, 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., Polarography of arsenic in the mineral

waters of La Bourboule, Bull, Soc . Chim. Biol., 36 , 695-703 (1954).

142. Rozanski, L., Indirect polarographic determination of

arsenate in mineral waters, Chemia Analit., 16, 793-799

(1971). ~~

210
143. Davidyuk, L. A., New polarographic determination of As

in natural H^O, Dopov. kad. Nauk Ukr. RSR, (1966), 90.

144. Mal'kov, E. M., and Fedoseeva, A. G., Determination o£

nanogram amounts of bismuth [in natural water] by anodic

stripping [from a mercury-graphite electrode], Zavod.

Lab. , 36^, 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 imDOsed voltage, Chim. Analyt.,

53, 176-182 (1971).

146. 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_6, 69-74 (1941).

148. Reznikov, A. A., Polarographic determination of small

quantities of copper, bismuth, lead) cadmium, and zinc

in natural waters, Trudy Vsesovuz. Konferentsii Anal.

Khim., 2, 573-84 (1943).

149. Sinko, I., and Dolezal, J., Simultaneous determination

of copper, cadmium, lead and zinc in water by anodicstripping polarography, J. Electroanal. Chem., 25,

299-306 (1970).

150. Chizhevskaya , M. S., The polarographic determination of

copper in industrial effluent waters, Sb. Nauch. Rabot,

Molotov Med. Inst., Molotov, 1955 , 79-8 2.

151. Whitnack, G. C,, Applications of cathode-ray polarography

in the field of oceanography. (Cu, Co, Zn, Mn,

J. Electroanal. Chem., 2_, 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 po laro graDhv , 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 concentrations [in trade wastes] (Cu, Pb, Ni, Zn, and Cd)

,

Anal. Chem., 34, 213-6 (1962).

211
154. Canals, E., Marignan, R. , and Cordier, S. , Po larographic

analysis of thermal waters. I. Construction of a laboratory polarimeter (Cu Ni and Co), Trav. Soc. Pharm.

Montpellier, 8, 57-60 (1948).

155. Porter, J. D., Ullman, W. W. , Sanderson, IV. W. , Purdue

Univ., Eng. Bull., Ext. Ser., 1959, 587. (Publ. 1960)

(Cu, Zn, Cd, Pd, 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. , 8_, 221-4 (1963) .

158. Kuroda, K., Lead content of the hot springs of Japan,

Bull. Chem. Soc. Japan, 1_5, 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, F., and Pohl, F. A., Automated

analysis of very pure water (Al , Bi, Cd, Co, Fe, Ga, In,

Ni, Pb, V, Zn, Zr) , Z. Anal. Chem., 222, 210 (1966).

162. Kovalenko, P. N., Polarographic determination of small

amounts of lead and cadmium in copper electrolytes (rapid

method), Uch. Zap. Rostov, na Don Univ., 4JL, 123-134

(1958).

163. Wahlin, E., Polarographic determination of traces of

metals in organic material. Determination of Pb , Cu,

Cd, Ni, Zn and Fe, Acta Chem. Scand., 7_, 956-68 (1953).

164. Visintin, B., Monteriolo, S., and Giuseppi, S. A.,

Polarographic determination of lead, cadmium, tin and

zinc in water, Ann. Idrol., 1_, 212-21 (1963).

165. Mal'kov, E. M., Fedoseeva, A. G., Slastenova, 0. A., and

Stromberg, A. G., Determination of traces of lead and

copper [in natural waters and effluents] by anodicstripping polarography on a mercury graphite electrode,

Zavod. Lab., 36, 1439-41 (1970).

212
166. Weiss, D., and Fidler, J., Osci 1 lopolarogrpahic determination of low concentrations of heavv metals in mine waters,

(Pb, Cu, Ni, Cd, and Zn) , Rudy, 1_2 , 204 (1 964).

167. Popova, T. P., Po larographic 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^O), Gidrofiz. i. Gidrokhim. Issled., Akad . Nauk Ukr,

SSR, (1965) 133.

169. Smith, J. D., and Redm.ond, J. D., Anodic - stripping

voltammetry applied to trace metals in sea water (17 ions)

J. Electroanal. Chem., 33_, 169- 7 5 (1971).

170. Cervenka, A., and Korbova^ M., Folarographic determination

of selenium in water, Chem. Listy, 4_9 , 1158-61 (1955).

171. Antal, P., Sources of error in the polarographic determination of microgram amounts of uranium (after enrichment of

solid samples and water), Mikrochim. Acta, 2_, 235-44

(1961) .

172. Spivakovski, V. B. , Zim.ina, 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. D., 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., J. Electroanal. Chem., 2, 25-38 (1961).

177. Hetman, J. S., Application of polarography to analysis of

sew|ge a^d industrial wastes (V, Cr, Ni/Co, Ca, Mg, S",

SO^ ,S0^ , and CN"), Proc. Effl. and Water Treatment Conv.

(1960) 60.

213
178. Kuroda, K. , Zinc content of the Hot Springs of Japan,

Bull. Chem. Soc. Japan, 15_, 88-92 (1940).

179. Macchi, G., Determination of ionic zinc in sea water by

anodic- stripp ing voltammetry with use of ordinary capillary

electrodes, J. Electroanal. Chem., £, 290-98 (1965).

180. Ariel, M. , and Eisner, U., Trace analysis by A.S.V.

I, Trace metals in Dead Sea brine 1. Zn and Cd,

J« Electroanal. Chem., 5_, 362 (1963).

181. Whitnack, G. C., and Sasselli, R., Application of anodicstripping voltammetry to the determination of some trace

elements in sea water (Zn, Cd, Pb and Cu) , Anal. Chim.

Acta, 47_, 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, H. E., Matson, W. R., and Mancy, K. H., Tracemetal characterization in aquatic environments by anodic

stripping voltammetry, (Zn, Cd, Pb, Cu) , J. Water Pollut.

Contr. Fed., 42_, 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. Maienthal, E. J., and Taylor, J. K., Electrochemical

techniques in water analysis, in Water and Water Pollution

Handbook, 4^, 1751 Lili 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, CI, 0,

Bi, 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).

214
CHAPTER 9

POTENTIOMETRY (ION-SELECTIVE ELECTRODES)

Richard A. Durst

1. INTRODUCTION

Ion- select ive electrodes, when applicable, provide

one of the simplest analytical metliods for measurement

of the concentration of dissolved substances. Modern electronic potentiometers provide essentially direct readout

in concentration units, independent of operator skill

or judgment. V/hen the substance of interest is already

dissolved, it may be monitored automatically and continuously.

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 informtation on these and

related matters will be found in the general references

(1, 2).

A. Gener al Cons ider at ions

Applicability to most of the sample matrices under

consideration requires a pretreatment procedure involving

sample dissolution and masking of interferences to provide

215
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 pre treatment . Ion-selective

electrodes are logarithmic sensors (emf output is

proportional to the logarithm of the concentration)

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.

Tills problem can be overcome 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 conditions, an imprecision of

approximately 1-5 percent is normal, while in plant or

remote monitoring situations, 5-10 percent imprecision may

be expected. Using titration procedures, v;hich 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.

216
Manpower skills required to make electrode measurements

are minimal once the analytical procedures are developed,

liowever, sample preparation and pretreatment may be

highly complex and require a technician trained in

cliemical manipulations such as wet ashing, separations,

and dilution.

At the present time, there are over two dozen

different kinds of commercially available ion- select ive

electrodes. Of these, almost half are suitable for

the determination of elements of interest in this survey.

Tlie cost of these sensors range from $150 to $300 , depending on type (i.e., solid-state, liquid ion-exchange,

combination, etc.). Portable, battery-operated meters

are available in the $300 to $500 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 glassvvrare are usually

trivial expenses. Thus, an ion- selective electrode

measurement system, can be acquired for as little as

$500, or more typically, $1,000 to $2,000.

Analysis costs will depend on the number of samples

to be analyzed, the pretreatment involved which depends

on the matrix of the sam.ple, and the accuracy and precision

217
desired which determine the particular electrode procedure

to be used, i.e., direct measurement, titration, addition

technique, etc. In general, automated procedures can

be developed based on electrode sensors.

2. APPLICATIONS

Ion-selective electrodes have not yet found extensive

use in the analysis of the process materials surveyed

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 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: 10'"'"M to IO'^'m (10 ppb) . pH range of operation: 1-14.

interferences: Ag , Hg , and Cu

++ 1 + + + 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) .

218
B. Calcium range: IM to 10 ^1 (0.4 ppm) . pH 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 range: IM to lO'^M (6 ppb)

pH range: 0-14.

interferences: Ag"*" § Hg"^"*" must be absent;

Fe"*"'"'' must be less than 1/10 Cu^"*" level.

Applications include monitoring plating and

etching baths for printed circuit manufacture, oil

refining processes, industrial and mining waste waters,

and determining copper in ores, minerals and alloys (7, 8).

D. Cyanide range: 10"^M to 10"^?I (0.03 ppm) . pK range: 0-14.

interferences: sulfide ion must be absent;

iodide should not exceed the cyanide level

To prolong electrode life, an operating

- 3 - 5 range of 10 M to 10 M CN is recommended

Applications include monitoring industrial metal

extractions and certain petrochemical processes,

determination of cyanide in plating baths, rinse

tanks, and metal finishing solutions (9).

219
E. Fluoride range: IM to 10 M (0.02 ppm)

.

pH range: 0-9^

interferences: hydroxide ion is the only

significant interference: OH concentration must not exceed F level, i.e.,

pOH>pF.

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: 10 ""'"M to 10 '^M (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 electroplating baths, petroleum products, and non-ferrous alloys (22).

G. Silver/sulf ide range: IM to 10 '''m 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).

220
H. Sodium range: IM to lO'^^M (0.02 ppm)

pH range: 3 - 12.

interferences: the most serious interference is Ag^ to which the electrode

4 + is 10 times more sensitive; H is also

a serious interference but easily controlled by pH buffering; Li"*^, K^, and

NH^ 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: IM to 10 (0.4 ppm).

pH range: 2-11.

interferences: major interference from

Cs"*" and Rb"^; minor interference from

NH^, Na"^, Ag"^, and Li"*".

Applications include monitoring potassium in industrial

process streams and in biological fluids (29, 30).

3. DISCUSSION

Ion-selective electrodes can be used to determine

specific elements precisely and at very low levels if the

matrices can be suitably modified or degraded to provide

the elements as ions in solution. For most of the

matrices under consideration in this survey, such a conversion can be carried out by chemical m.eans, e.g.,

wet ashing with acids. This chemical pretreatment

221
is time-consuming and often requires considerable skill

but in many cases can be automated if large numbers

of samples 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

potent iometry or one of the single -increment techniques,

imprecisions of 1 percent to 10 percent can be achieved

by most electrodes, if interferences are properly masked,

from concentrated solutions to the 1 ppm level. At

the sub-ppm level, precision will degrade due to variable

blanks, poor ionic buffering, and slower electrode

response. Direct potent iometry or addition methods

are rapid, requiring only 1 to 5 minutes and are easily

portable for field use. For higher precision, o.l

percent to 1 percent, titrations or multiple -addition

techniques can be used with a concomitant increase

in experimental 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 considerations. With miniaturized electrodes,

lower sample volume limits of iPl to lOyl are feasible.

- 5 - 9 For a 10 M solution, only about one nanogram (10 g) of

sample element is required. The feasibility of such

222
microdeterminations has been reported, e.g., 0.4 ng of

fluoride (lOwl) was determined with an accuracy and prec

sion of about 1 percent using a fluoride electrode (31).

223
REFERENCES

(1) Durst, R. A., Editor, "Ion-Selective Electrodes," NBS Spec. Publ.

314, U.S. Govt. Printing Office, Washington, 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. W. , Alkaline Pulping Liquor

Analysis, TAPPI 53, 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, E. D., and Wallace, R. M. , Cupric-Selective Electrode

with Copper (II) - EDTA for End Point Detection in Chelometric

Titrations of Metal Ions, Anal. Chem. 41, 2072 (1969).

(8) Frant, M. S. Applications of Specific Ion Electrodes to

Electroplating Analyses, Plating, 686, (1971)

(9) Frant, M. S., et 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. £0, 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. H. , et al.. The Potentiomet ric Determination of Fluorine

in Nuclear Fuel Reprocessing Solutions, Anal. Chim. Acta

45, 233 (1969).

(13) Edmond, C. R. , Direct Determination of Fluoride in Phosphate

Rock Samples Using the Specific Ion Electrode, Anal. Chem.

41, 1327 (1969).

224
(14) Guth, J. L., and Wey, R. , A Rapid Determination of Fluoride in

Minerals and Rocks, Bull. Soc. Franc. Mineral. Crist. 9_2, 105

(1969) .

(15) Collis, D. E., and Diggens, A. A., The Use o£ a Fluoride Responsive Electrode for "On-Line" Analysis of Fluoridated Water

Supplies, Water Treatment and Examin. 18_, 192 (1969).

(16) Pavel, J., et al . , Microdetermination of Fluorine in Organic

Compounds by Direct Measurement with a Fluoride Electrode,

Microchem. J. 1_5 , 192 (1970).

(17) Younghans, R. S., and McMullen, T. B., Fluoride Concentrations

Found in NASN Samples of Suspended Particles, Fluoride 3_» 1^3

(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 £,

5 (1971).

(20) Rinaldo, P., and xMontesi, P., Instrumental Techniques for Titration

of Fluoride in Cryolite and Aluminum Fluoride, La Chemica

e L'Industria 5_3, 26 (1971).

(21) Svoboda, K., and Ixfeld, H., Sampling and Automatic Analysis

of Gas Forming Fluoride Emission, Staub -Reinhal t 3^, 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. 41, 2038 (1969).

(25) Brunow, G. , et al.. Reactions of Sulfur during Sulfate Pulping,

Acta Chem. Scand. 26^, 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 54, 2051 (1971).

(27) Webber, H. M. , and Wilson, A. L., The Determination of Sodium in

High Purity Water with Sodium Responsive Glass Electrodes,

Analyst 94-, 209 (1969) . 225
(28) Eckfeldt, E. L., and Proctor, W. E., Low Level Sodium Ion

Measurement with the Glass Electrode, Anal Chem 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_0, 931 (1968).

226
FORM NBS-H4A (1-711 U.S. DEPT. OF COMM. 1. PL' HI. iC .A HON OR RlvPORT NO. 2. Cov'z Acccs-jion

BIBLIOGRAPHIC DATA NBSIR 73-209

3. Recipient's Accession No.

4. TITLE AND SUBTl I'LE Survey of Various Approaches to the Chemical

Analysis of Environmentally Important Materials

5. Publication Date

6. Performing Organization Code

7. AUTHOR(S)

Bernard Greifer and John K. Taylor, Editors

8. Performing Organization

INJDoiK 1 J L. \J J

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No. 3105440

11. Contract/Grant No. NBS-EPA-IAG 0215(D)

12. Sponsoring Organization Name and Address

The Environmental Protection Agency

Research Triangle Park, North Carolina 27711

IJ. 1 ype or Keport oi Heriod

Covered

Final

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSTRACT (A 200-word or 1 ess factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.) Various approaches to the chemical analysis of heavy industry process materials and effluents for trace element constituents that might

contribute to environmental pollution are summarized.

The capabilities and costs of nuclear methods, spark source mass

spectrometry, x-ray fluorescence and electron microprobe spec trom.etry

atomic absorption spectrometry, absorption spectrophotometry, atomic

emission spectroscopy, voltammetry (polarography) and potent iometry

(ion-selective electrodes) for determining traces (less than 100 parts

per million) of 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 such

matrices as fly ash, coal, oil, ores, minerals, metals, alloys,

organometallics , incinerator particulates, slurry streams, and feeds to

and from sedimentation processes have been assessed.

The report includes a critically selected bibliography of the

current literature.

17,

17. KEY WORDS: Air pollution; atomic absorption; electron microprobe;

-emission spec troscopy ; envi rnnment a 1 3 ti a 1 y s i s ; industrial effluents;

KEY \;OKUS (.'Mphabetical order, .separated by s enucolons) ^ q _ 5 g | g ^ eleCtTOdeS;

vation analysis; particulate analysis; polarography;

nuclear acti

spark source mass

t^nprtrnTTietrv : .snec troDhotometrv : trace elements: Kater DOl lution;

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