NBSIR 73-251

Analytical Methods for the

Detection of Toxic Elements in

Dry Paint Matrices--A Literature

Survey

Maya Paabo

Center for Building Technology

Institute for Applied Technology

National Bureau of Standards

Washington, D. C. 20234

July 1973

Final Report

Prepared for Office of Policy Development and Research

Department of Housing and Urban Development

Washington, D. C. 20410
1
NBSIR 73-251

ANALYTICAL METHODS FOR THE

DETECTION OF TOXIC ELEMENTS IN

DRY PAINT MATRICES--A LITERATURE

SURVEY

Maya Paabo

Center for Building Technology

Institute for Applied Technology

National Bureau of Standards

Washington, D. C. 20234

July 1973

Final Report

Prepared for Office of Policy Development and Research

Department of Housing and Urban Development

Washington, D. C. 20410

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

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director

Contents

Page

Abstract iv

1. Introduction 1

1.1. Purpose 1

1.2. Scope of the Literature Search 2

2. Analytical Methods 4

2.1. Sample Preparation .............. 4

2.2. Lead Determination ........ 6

2.2.1. Wet Chemical Methods ... 6

2.2.1.1. Spot Tests and Microchemical Tests . . 7 2.2.1.2. Gravimetry .............. 9

2.2.2. Spectrophotometric Methods . ..... 10

2.2.2.1. Colorimetry ....... 10

2.2.2.2. Atomic Absorption ...... .o. . 11

2.2.3. Electrochemical Methods ..... 14

2.2.3.1. Electrolytic Deposition ....... 14

2.2.3.2. Polarography .... 14

2.2.3.3. Anodic Stripping Voltammetry ..... 15

2.2.4. Neutron Activation Analysis 17

2.2.5. X-Ray Emission Analysis ....... 17

2.2.5.1. X-Ray Fluorescence .......... 18

2.2.5.2. Electron Microprobes ......... 21

2.3. Mercury Determination .. .............. . 22

2.3.1. Wet Chemical Methods-Spot Tests 22

2.3.2. Spectrophotometric Methods 23

2.3.2.1. Colorimetry ........ 23

2.3.2.2. Atomic Absorption .......... 24

i
Contents (cont.)

Page

2.3.3. Neutron Activation Analysis 24

2.3.4. X-Ray Emission Analysis 26

2.4. Arsenic Determination 26

2.4.1. Wet Chemical Methods-Spot Tests 26

2.4.2. Spectrophotometric Methods 27

2.4.2.1. Colorimetry 27

2.4.2.2. Atomic Absorption 27

2.4.3. Neutron Activation Analysis 28

2.4.4. X-Ray Emission Analysis 28

2.5. Cadmium Determination 29

2.5.1. Wet Chemical Methods-Spot Tests 29

2.5.2. Spectrophotometric Methods 29

2.5.2.1. Colorimetry 29

2.5.2.2. Atomic Absorption 29

2.5.3. Electrochemical Methods-Anodic Stripping

Voltammetry 30

2.6. Antimony Determination 30

2.6.1. Wet Chemical Methods-Spot Tests 30

2.6.2. Spectrophotometric Methods 31

2.6.2.1. Colorimetry 31

2.6.2.2. Atomic Absorption 31

2.6.3. Neutron Activation Analysis 32

2.7. Selenium Determination-Spectrophotometric Methods ... 33

2.7.1. Colorimetry 33

2.7.2. Atomic Absorption 33

ii
Contents (cont.)

Page

3. Summary and Conclusions 34

4. References 39

iii
Abstract

This report is a summary description of the chemical procedures

currently available for the analysis of selected toxic elements in

dried paint. The elements included in this report are lead, mercury,

cadmium, antimony, arsenic, and selenium. The literature search upon

which this report is based was directed primarily toward references

pertaining to the analysis of dried paint. A bibliography of 57

references to wet chemical analysis, colorimetry, atomic absorption

spectroscopy, electrochemistry, neutron activation analysis, and x-ray

emission analysis is presented.

Key Words: Analytical methods; antimony; arsenic; cadmium; lead:

mercury; review; selenium; toxic elements in paints.

iv
Analytical Methods for the Detection of Toxic Elements in

Dry Paint Matrices—A Literature Survey

1. Introduction

1.1. Purpose

The overall intent of the Lead-Based Paint Poisoning Program, as

undertaken by the National Bureau of Standards, under sponsorship of the

Department of Housing and Urban Development, is to determine the nature

and extent of the lead paint poisoning problem in the United States and

to recommend methods for its detection and elimination. A literature

survey, within the scope of this program, was conducted on analytical

methods for toxic elements in dry paints. The toxic elements selected

for study, in addition to lead (Pb) , were mercury (Hg) , arsenic (As),

cadmium (Cd) , antimony (Sb) , and selenium (Se) . It has been proposed

that paints and other surface-coating materials used for toys be considered hazardous substances if they contain more than 0.5% Pb or a

combined total of more than 0.05% Hg, As, Cd, Sb or Se on a dried weight

basis [l]"*". Many municipalities have already passed laws prohibiting the

sale and use of interior paints having a Pb content of more than 1% as

metal in total nonvolatile; and, since the passage of Public Law 91-695

(Lead Based Paint Poisoning Prevention Act) in January 1971, the detection

and control of the existing hazard from old lead-bearing paint has been

emphasized.

This has created a need for reliable analytical procedures for the

determination of Pb and the other five elements of interest in dry, aged

1 Figures in brackets indicate literature references at the end of this

paper.

1
paint. These procedures are needed in order to determine compliance

witli the abovementioned limits. Little information is present] y available on the relative merits of various methods of analysis of these six

elements as applied to aged paint. It is the purpose of this report to

review the literature and to establish the current state-of-the-art of

methods of chem.ical analysis for the six toxic elements pertaining to

aged paint.

1.2. Scope of the Literature Search

The literature on the analysis of toxic elements in dry paint

matrices is not numerous since most of the analytical determinations

have been applied to the analysis of liquid paints. An extensive '

literature reviev/ on Pb paint detection methods was made by Greifer [2]

in December, 1971. Because there has been an increased interest in the

subject since that time, the information contained in reference 2 has

been brought up to date and, in addition, the following abstracts

and journals were examined.

World Surface Coating Abstracts

National Paint and Coatings Association Abstract Review

Toxicity Bibliography

Activation Analysis Bibliography

Atomic Absorption Bibliography

Biological Aspects of Lead: An Annotated Bibliography

Environmental Research

Environmental Pollution

Environmental Letters

Archives of Environmental Health

2
To help assure a complete coverage of the literature, the manual

search was complemented by computer-assisted searches at four data banks:

MEDLINE and MEDLAR at the National Library of Medicine

TOXICON at the Oak Ridge Toxicology Information Response Center

NTIS of the Commerce Department

NASA Scientific and Technical Facility

The first two data banks are oriented toward medical literature, the

third data bank is concerned with research performed at all major

Departments and Agencies within the Federal Government as well as private

groups with Federal contracts, and the fourth data bank contains information of interest to the aeronautical and space sciences. The response

from the computer searches was scanty and did not add any useful citations to the manual coverage.

In order to obtain information on most current activities in the

field, personal contacts were made with staff members at NBS, universities, industrial laboratories and trade associations.

The information based on the abovementioned sources was used as

the basis for this report. This report includes a bibliography of 57

papers concerned with the analysis of toxic elements in dry paint matrices.

3
2. Analytical Methods

2.1. Sample Preparation

There are few analytical methods applicable to the analysis of

dried paints which are nondestructive and do not require any sample

pretreatment . Neutron activation analysis and x-ray fluorescence

spectroscopy are two major instrumental methods that can be used for

the determination of the metal content in paint samples as received.

However, in order to determine the metal content of paints by conventional procedures, such as wet chemical, spectrophotometric or electrochemical methods, the metals must be first converted into soluble forms.

One of the major problems encountered in dry paint analysis is the

quantitative separation of metals from the large masses of organic

paint matrices. The separation involves dry ashing either by heating

the sample or fusing it with a flux, at a temperature where the metal is

not lost by volatilization, and dissolution of the residue in acids; or,

wet oxidation of the organic matrix by various strong acids. As a rule,

mixtures of nitric, hydrochloric or perchloric acids have been used by ,

workers in the field to digest the paint matrix and to take up the

residue left over after dry ashing or fusion.

Few comparative studies have been made on methods used for the separation of Pb from the dry paint matrix. At NBS, during the course of an

experimental evaluation of analytical methods for determining Pb in

paint [3,4], several sample pretreatment steps were evaluated. For wet

ashing nitric and hydrochloric or mixtures of nitric, perchloric and hydrofluoric acids were used. Dry ashing at 500°C was followed with digestion

by nitric acid or a mixture of nitric and perchloric acids. *

4
The percent recovery of Pb was determined by Atomic Absorption (AA)

,

polarography or colorimetry. The most promising wet oxidation method was

the use of a mixture of nitric and perchloric acids since the insoluble

residue left behind, when dissolved in sulfuric acid and analyzed by

Anodic Stripping Voltammetry (ASV) , yielded a concentration of Pb <0.1

parts per million (ppm) . The dry ashing method at 450-550°C followed by

exhaustive extraction of the residue with hydrochloric, nitric, and hydrofluoric acids and with ammonium acetate solution was used for the certification of the Pb content in the powdered Pb-based paint Standard

Reference Material (SRM 1579) [5]. The eff iciency of the method was

checked with emission spectrographic analysis of the insoluble residues

to make sure that they did not contain significant quantities of Pb.

Westgate, et al [6], found wet ashing with Caro's acid (formed by

dropping concentrated hydrogen peroxide into concentrated sulfuric acid)

to be more efficient than dry ashing for destroying the organic matter

of paint for Pb determinations.

ASTM Committee DOl.21.03 is currently active in evaluating test

methods for the analysis of trace levels of heavy elements in paints [7].

In preliminary reports, they recommend the use of the dry-ashing method

for paints having a Pb content of 0.01-5.0%. The sample is heated to

500-525°C and the residues extracted with nitric acid and then with

ammonium acetate.

The other toxic elements, Hg, As, Cd, Sb and Se, are usually separated from the paint matrices by wet oxidat ion methods because of the

volatility of the elements and some of their salts or by fusion methods

5
followed by acid digestion of the solid formed with the flux.

No systematic studies for establishing the best ashing procedure involving these elements in dry paint matrices were found. Workers in

the field have either used the same wet ashing procedures as for Pb

or have used a dry fusion method.

Hoffmann preferred the use of the Schoeniger oxygen flask method for

igniting paint samples and converting the Hg present into mercuric nitrate

or by extraction with hot acetic acid to separate phenylraercuric compounds [8]. Digestion in hot sulfuric acid was found to be satisfactory

by Berger [9] for the dissolution of Hg from latex paints.

ASTM Committee DOl.21.03 [7] is considering recommending the wet oxidation method using sulfuric and nitric acids for paint samples containing the five elements. For best results the wet ashing is conducted under

reflux and the reaction is completed by the addition of nitric and perchloric acids. Studies were also made using the fusion method with the

sodium carbonate-borax flux for paint samples containing Cd and Sb to allow

solubilization of the elemental constituents. The results of these

studies will eventually appear as part of the official ASTM method for

determining the toxic elements in paint.

2.2. Lead Determination

2.2.1. Wet Chemical Methods

Wet chemical methods such as gravimetric and volumetric analysis or

spot tests were used exclusively for both the quantitative and qualitative

6
determinations of Pb in paints before modern instrumental methods became

popular, and even at present they are being used extensively despite

the complex chemical procedures often involved.

2.2.1.1. Spot and Microchemical Tests

Spot tests are the simplest qualitative methods for the chemical

determination of Pb in paint material. The dried paint may be tested

on location without any previous sample preparation by applying the test

solution to a scratch in the painted surface or to a loose paint chip.

This method has been applied most widely to the routine screening of Pb,

since it is specific, simple and inexpensive.

The most common reagent used is an alkaline solution of sodium sulfide, which precipitates Pb as a black sulfide [10,11,12]. Searle, et al

[10] was able to detect Pb concentrations as low as 0.1% by dipping the

paint chips into an aqueous solution 1% in sodium sulfide and sodium hydroxide and examining the black line visible in the layer containing Pb

paint. Sayre [11,12] estimated percent Pb semiquantitatively from 0.8

to 15% by comparing the shades of grays produced ia unknowns with the

gradations of gray in paints of known Pb content. Of the other metals

under consideration only Hg forms a black sulfide, but the quantity present

is usually so small that is does not cause significant interference.

Another way to estimate the Pb content of dried paint is to dissolve

the paint and to produce, with an appropriate reagent, a colored spot on

filter paper. This procedure permits a better visual comparison of colors

with spots obtained with standard solutions. Thioacetamide was

7
used by NBS for the semiquantitative determination of Pb between

0-5.77% [4]. The readings near the 1% level of Pb were variable because

of subjectivity in interpreting the resulting shades of color.

Westgate recommends the use of the potassium-copper-lead triple

nitrite or the lead iodide test for determining whether Pb is actually

present in significant quantities in dried paint flakes [6].

ASTM Committee DOl. 21.03 has proposed a method for determining

trace quantities of Pb in finishes [7]. They recommend dry-ashing the

sample, digesting the residue with hot sodium hydroxide solution and treating a drop of this mixture on filter paper with bromine water and benzidine. A blue color indicates the presence of at least 0.06% Pb.

A modification of the conventional spot tests on the filter paper

is the Weisz Ring Oven Technique, used by Locke and Riley for the qualitative analysis of paint pigments [13]. The paint chips are dissolved in

aqua regia and the residue taken up by acetic or nitric acid. Pb was identified by the appearance of a violet-red line when the filter paper, to

which Na-rhodizonate had been added, was fumed over concentrated HCl.

Instead of producing a colored reaction on the paint film or filter

paper, one can use the microchemical test; appearance of a colored

precipitate in solution as an indication of the presence of Pb. This

method requires the dissolution of the paint sample prior to analysis.

Pb can be detected by treating the resulting solution with the following

reagents: sulfuric acid, potassium iodide, mixture of sodium sulfide and

hydrogen sulfide, or potassium dichromate [14]. The British Standard

8
Institution has developed a procedure for precipitating lead iodide

for the detection of Pb in the range of 1.0 - 1.5% [15] . In the United

States, Kaplan and Shaull [16] have worked out empirical conditions for

practical screening purposes so that the lead iodide precipitate can be

used as a positive test to indicate the presence of 1% Pb or more.

2.2.1.2. Gravimetry

The only quantitative method involving wet-chemical procedures for the

determination of Pb in dried paints is the gravimetric method. Lead is

isolated as lead chromate and the weighed precipitate is used for calculating the Pb content. Searle, et al [10] used the method of Scott [17] for

determining Pb in samples containing approximately 2% Pb. The standard

deviation of 10 determinations of 0.5g samples was found to be 0.28%.

Westgate improved the standard chromate method by digesting dry paint

films containing about 1% Pb with Caro's acid [6]. A preliminary

titration for screening purposes on a portion of the Pb solution, using

ammonium molybdate solution as titrant and tannic acid as an indicator,

was used to indicate if the Pb level was below or above 1%. The

accurate gravimetric method based on lead chromate was used to determine

the exact Pb content.

The Westgate method, however, was found to be unsatisfactory by

an ASTM working group [18] which was set up to select a method for

determining Pb at the 1% level. The method was found to suffer from

poor reproducibility. They preferred the determination of Pb by

electrolytic deposition.

9
2.2.2. Spectrophotometric Methods

2.2.2.1. Colorimetry

In addition to characteristic, insoluble compounds, Pb also forms

colored complexes suitable for analytical purposes. Hoffmann studied

the feasibility of determining Pb colorimetrically as PbS in alkaline

solution by comparing visually the colors formed with those of standard

solutions or by determining the absorption at 390 nm [19,20], It is

not a quantitative method but allows an estimation of the Pb content to be

made at low concentrations, from 0.003 - 0.3%. A very accurate method for

the determination of Pb in paint employs the color of the Pb-dithizone

complex in chloroform near 510 nm. The reagent is capable of detecting

0.05 ppm Pb in solution. Since dithizone forms complexes with many

metals, the method requires extensive chemical manipulations to obtain

high selectivity. Barker, et al [21] used ammoniacal dithizone in the

presence of cyanide for the routine determination of Pb in paints which

were being used for school materials and toys. By comparing the colors

of the sample solutions with colors of standard solutions he was able

to readily detect 100 ppm Pb. An alkaline dithizone method was used by

Barltrop and Killala [22] for the analysis of paint samples in connection

with their study of lead poisoning in children. They followed the procedure of Browett and Moss [23] for the determination of the Pb content

in urine. A semi-automated analyzer was utilized to measure the color

of the chloroform extract at 505 nm. An extensive study of the application of the dithizone method to the analysis of dry paint was made

10
by NBS [3,4]. They used the ASTM E 35-63 method [24] for separating the

Pb complex in chloroform from interfering metals. This method utilizes

an ammonium citrate-cyanide solution as the masking agent. Photometric

measurements were made near 520 nm. The dithizone measurements had a

tendency to show a small positive error but the precision and accuracy

were thought to be adequate for the purpose of determining Pb in paint

at the 1% level.

2.2.2.2. Atomic Absorption

Although Atomic Absorption (AA) has found wide application for the

determination of Pb in various types of samples, it is only recently that

AA has been used for the analysis of Pb in dry paints and related materials. The principal advantages of this technique are its high sensitivity

and specificity. Quantitative analysis of any one metal can be made in

small amounts of material even in the presence of large amounts of other

substances. The detection limit for Pb is 1 ppm or less, depending on

experimental conditions. Unfortunately, most procedures require sample

pretreatment and almost no work has been done directly with solid samples.

In 1969 Searle [10] worked out a simple, rapid method for determining

Pb in paint scrapings by AA. After dry-ashing the sample the residue was

taken up with nitric acid. A dilute solution was aspirated into an airacetylene flame and the spectral line at 283.3 nm was used for analysis.

Standard lead nitrate solutions were used to calibrate the instrument.

The standard deviation by the AA procedure for 10 measurements, for

samples containing about 2% Pb, was 0.05%. A modification of Searle 's

11
method is presently being used by the Chicago Board of Health for the

determination of Pb in paint and plastic chips [25]. In England,

Hodson and Lord [26] used a method similar to Searle's for the routine

screening of toxic metals in paints on toys. The Sherwin-Williams

Research Center [27] analyzed 89 commercial paints for Pb by the AA

method. The detection limit was 0.0005%.

At the NBS, AA was among the methods evaluated for determining Pb in

paint [3,4] and was one of the methods used for certification of the

powdered Pb-based paint Standard Reference Material (SRM 1579) [5]. A

detailed method was developed for determining micro and/or macro amounts

of Pb in paint (0.5 to 100 ug of Pb/ml in final diultion) by measuring the

283.3 nm resonance line of the atomic vapor in a stoichiometric airacetylene flame [3]. The AA spectrophotometer was calibrated by means of

a standard lead nitrate solution prepared by dissolving high purity Pb

(NBS SRM-59e) in nitric acid. When the paint samples contained less than

0.005% Pb, an extraction with ammonium pyrrolidine dithiocarbamate in

acidic solution was recommended. In a comparison of four instrumental

mehtods for determining Pb in paint films [4], AA was found to be a method

of satisfactory precision (2-11%) for measuring paints containing up to

5.77% Pb. The major discrepancies were attributed to loss of lead during

various sample pretreatment steps. During the course of certification of

the powdered Pb-based paint reference material, the oxidation of the paint

matrix was accomplished by the dry ash method, and the standard deviation

of the AA analysis was 0.13% [5]. When the SRM paint material (containing

12
11.87% Pb) was analyzed by the AA method at seven different laboratories

using 9 different ashing procedures, the results varied from 1.57 to

13.52%, indicating the need for a standardized ashing procedure.

In order to avoid sample pretreatment , an AA method employing a

West type carbon rod flameless sample holder was evaluated at the NBS [3]

for the analysis of solid paint samples. Samples of paint chips were

either analyzed directly or mixed with graphite, but the lead content

could only be determined qualitatively. Work is underway to evaluate

the best procedure for the application of the flameless carbon rod

method to paint analysis. A rapid screening of pencil paint for Pb was

attempted by McDuffie [28], who sampled the paint directly by placing

the pencil in the edge of the AA burner flame. The AA response was

compared to the values obtained for Pb by digesting the paint with acid

solution and analyzing the solution by AA. A Pb content below 0.2%

could not be detected and the test was strictly qualitative.

An extensive study is being carried out by ASTM Committee DOl.21.03

[7], which has recommended the use of the AA method of analysis for

determining Pb in dry paints. Paints having a Pb content between 0.01

and 5.0% are to be analyzed by the method described in reference 3.

Paints having a Pb content between 0.0001 and 0.1% are to be analyzed

by the Delves cup method, which involves sampling the dried paint film

directly. The solid sample in a microsampling cup is ignited near the

AA flame and vaporized directly in the air-acetylene flame. During preliminary studies, 95% Pb recovery was obtained with paint spiked with

known amounts of a Pb drier, and a standard deviation of +0'002% between

duplicates was observed.

13
2.2.3. Electrochemical Methods

2.2.3.1. Electrolytic Deposition

Before the advent of AA, electrogravimetric analysis was thought to

be an excellent technique for the analysis of Pb in paint as compared to

spectroscopic, polarographic and colorimetric methods. A procedure for

determining Pb at the 1% level was developed by the ASTM working group

by comparing gravimetric, colorimetric and various electrolytic

methods [18]. The tentative method for determining low concentrations

of Pb in paint consisted of electrolytic deposition of Pb as the dioxide

on a platinum anode from a solution containing ammonium nitrate and

copper sulfate. It was later accepted as the official ASTM method

D 2088-68 [29]. The method is not free of interferences and carefully

controlled conditions must be maintained to prevent contamination or incomplete deposition. Manganese must be removed as a precipitate to prevent its deposition; and, to avoid incomplete deposition of Pb, any Hg

present must be removed by high temperatures during the ashing step. A

repeatability of 0.03% Pb can be expected by this method.

At NBS, electrolytic deposition was used as a check method for

the powdered Pb-based paint reference material [5]. The average result

of 11.92% compared favorably with the certified value of 11.87%.

2.2.3.2. Polarography

Even though no references were found to the previous use of this

electrochemical method for the analysis of Pb in a dry paint matrix,

polarography was included at NBS in the program of evaluation of

14
analytical methods for determining Pb in paints [3]. Polarography was

found to be a suitable method since the only experimental difficulties

encountered were during sample dissolution steps. Experimental details

were worked out for the use of a differential cathode ray polarograph [A].

Pb in an acidic solution containing ascorbic acid, was reduced with a

linear voltage sweep applied to the last few seconds of a growing

mercury drop. The peak current was measured on the cathode ray tube.

The method required the simultaneous analysis of a blank solution.

Standard solutions of Pb were needed for establishing the calibration

curve. A preliminary analysis of 23 samples containing 0 to 5.77% Pb

indicated that a precision better than 7% could be obtained. Thus,

polarography was chosen as one of the methods of analysis for certification of the Pb-based paint reference material [5], The average of

16 determinations was 11.93% Pb, with a standard deviation of 0.13% Pb.

The ease of applying polarography to the determination of Pb in

solutions was used also by Lukaszewski and Szymanowska [30] for determining whether paints used on ceramics contained Pb. They extracted Pb

from the paint with acetic acid and proceeded with the usual polarographic

procedure

2.2.3.3. Anodic Stripping Voltammetry

Anodic Stripping Voltammetry (ASV) is one of the most powerful

electrochemical approaches to trace analysis and is usually applied to

concentration ranges below those found for heavy metals in paint. Once

the sample has been brought into solution, the analysis can be carried

out very rapidly, and the basic sensitivity of the technique for lead is

approximately at the sub-nanogram level.

15
An electrochemical system and procedure for employing ASV for analysis of Pb in dried paint matrices has been developed by Mat son [31]. He

recommends the wet ashing procedure by nitric and sulfuric acids. Diluted

aliquots of the digest are run on the ASV system, plating at the composite

mercury-graphite electrode versus the silver /silver chloride reference

electrode at -0.8V for 5 minutes and stripping at 80 MV/sec. The concentration of Pb is determined by the standard addition method using lead

nitrate solution. Modifications to the procedure can be made to avoid

interferences, for example, from Ti02. The method can be used for

determining Pb in the range of 0.01 to 10% depending on the size of the

aliquot used for analysis.

A recent study by Schaplowski [32] concerning the potential hazard

of paint on pencils as a source of lead poisoning used the services

offered by Matson at the Environmental Sciences, Inc. Laboratory for

determining the lead content in paint by the ASV method. Analysis was performed in sodium acetate solutions at -1.1 Volts for 30 minutes with a sweep

rate of 55 MV/sec. The Pb content for four brands of pencils varied

from 0,03 to 12.5%. A similar technique has been used by the

New Orleans Department of Health to analyze paint samples for Pb [33].

An application of ASV was made by Lux, et al [34], for the investigation

of the age and place of origin of old paintings. Minute samples of

white lead from paintings were taken and Pb was determined at the levels

of 5 X 10 g and 3 x 10 g with standard deviations of +3.4 and 2.4%

respectively.

16
2.2.4. Neutron Activation Analysis

One of the two instrumental methods for the analysis of Pb in paint

that require no previous sample preparation is Neutron Activation Analysis

(NAA) . The method is potentially more sensitive, at least by an order of

magnitude, than either colorimetric or spectrographic methods.

Of the metals concerned, Pb has the lowest sensitivity for thermal

neutron reactions. It can be detected at the 1-3 ug level at a thermalneutron (n* ) flux of 10 n* cm sec for a 1 hour period [35], Since

the stable isotope of Pb, however, does not undergo reactions with

thermal neutrons that are useful for analytical purposes, Lutz investi252

gated the use of fast neutrons using Cf as the source [36]. The

induced nuclear reaction ^^^Pb(n,n') ^^^^pb vas followed by gamma

spectrometry with a Ge(Li) detector. Irradiation for 2 hours with the

252

600 ug Cf source and 100 minutes of counting with a 60 cc Ge(Li)

detector was required to detect 1% Pb in a 1.5 g paint sample. This

technique was also used to confirm the Pb content in the powdered leadbase paint Standard Reference Material (SRM 1579) [5]. The average value of

Pb for 4 samples was 11.1% as compared to the certified value of 11.87%.

2.2.5. X-Ray Emission Analysis

The second group of instrumental methods for the analysis of Pb in

paint that require no sample preparation involves the characterization

of x-ray emission lines. By measuring the radiation emitted between 0.1

and 5 nm, the technique is applicable for the determination of all

elements heavier than and including magnesium (atomic number 12)

.

17
2.2.5.1. X-Ray Fluorescence

With the development of high resulution solid state x-ray spectrometers, where the excitation source is a. primary x-ray, qualitative

analysis of metals in paint by x-ray fluorescence can be carried out on

a routine basis. McGinnes, et al [37] studied the quantitative aspect

of x-ray emission analysis by trying to overcome the complicating matrix

effect. He compared the intensities of spectra emitted by dry thin

films of paint of known and unknown composition and determined the

elemental concentrations of major pigment elements. The percentages

obtained for Pb in an alkyd resin agreed to within 6% with the values

determined by chemical analysis.

The use of radioisotope excitation sources has led to many practical

applications of x-ray emission analysis. For example, Pb in the pigment

of old paintings can be detected by interpreting the fluorescent x-ray

109

spectrum resulting from irradiation by a Cd source [38]. Development

of portable instruments consisting of a radioactive source and a solid

state detector have made possible the _in situ determination of Pb on

painted surfaces. Reece, et al [39] used portable x-ray fluorescence

analyzers containing a ^^Co source and Nal(Th) detector for in field

inspection during his study of elevated blood Pb levels in children in

2

the Cincinnati area. Pb contents ranging from 0.2 to 30.8 mg/cm were

reported in various interior and exterior paints. In antifouling marine

coatings, Pb was easily detected in the presence of large quantities of

cuprous oxide [40]. Laurer, et al [41,42] described the development of

such an instrument for the detection of Pb in wall paint. It utilized

18
"^Cd - Ag as the source of y-rays to stimulate the emission of the

Kg series x-rays of the Pb atoms, which were then detected by a solid

state Ge(Li) detector.

The instrumental response is directly related to the weight of Pb

2 per unit area; it was capable of detecting 0.26 mg of Pb/cm of paint

(approximately 3% by weight) in a 1 minute determination. The system

was calibrated by measuring sprayed paint samples of known composition

(2.5, 14 and 64 weight % Pb) or by comparing the instrument readings

to the results of chem.ical analysis of the paint samples. Of the

several available instruments, Berry [43] describes an x-ray fluorescence

analyzer designed to use a ^^Co x-ray source and Nal(Tl) detector. The

2 estimated detection limit is expected to be 0.5 mg Pb/cm of area. The

instrument was used to determine Pb in paint on various locations and the

results were compared with those of chemical analysis. The data indicated

that in no case was the chemically established Pb content underestimated

by using the radioisotope measurement. Barltrop, et al [44] describes an

instrument manufactured in England and its applicacion to the analysis

238

of paint films. The instrument contains a Pu source and a Nal

detector with Ga or Ge filters. The instrument was calibrated

by standard additions of a Pb compound to liquid samples

and by observing the count rates of dried films with a Pb content

between 1 and 31%. The accuracy of the readings was +0.2% in

the range of 0%-5% Pb. When, however, the results for comjnercial

paint films were correlated with chemical analyses using the 95% confidence limit the scatter of the data was too great to allow application

19
of this technique to Pb screening programs. The study of the masking

2 effect of overlying paintlayers indicated that a film of 77 mg/cm

(corresponding to about 9 thin layers) will cause a Pb content of 31%

to appear to be zero.

At NBS, in the course of evaluating laboratory procedures for

accurately determining Pb in dry paint, the x-ray fluorescence method

was also investigated [3]. In order to be able to use a single calibration curve, zinc oxide was added to all samples to reduce the differences caused by various paint matrices. A general purpose, single-channel

x-ray fluorescence spectrometer was used. The Pb content in unknowns

was estimated by comparing the Kg x-ray intensities to those of standard

samples containing known amounts of zinc oxide, titanium, dioxide and red

Pb oxide powders. The total analytical error was not expected to exceed

+10% for Pb at the 1% level. A study of 20 samples showed an average

negative error about 9% [4]. The method was used in testing the homogeneity of the powdered lead-based paint standard reference material,

SRM 1579 [5]. As an extention of the investigation mentioned above,

Rasberry [45] evaluated commercial portalbe x-ray fluorescence analyzers

to ascertain their detection limits and precision with which they can be

used for determining Pb on painted surfaces. The four design types

were classified as : (1) scintillation detector - balanced filter

energy discrimination, (2) noncooled detector - pulse height

analysis, (3) lithium-drifted germanium detector - pulse height

20
analysis, and (4) high purity germanium detector - pulse height analysis.

The analyzers were compared by determining the weight % of Pb in terms

2 of mg/cm on 27 samples coated with paints of known composition. The

2 amount of Pb added was varied between 0 and 6.6 mg/cm . Some of the

specimens had several overlayers of paint containing no lead in order

to simulate field conditions. Standard deviations for the four types of

analyzers for 14 of the specimens to which less than 1.00 mg/cm of Pb was

added were 0.46, 0.33, 0.15 and 0.21 mg/cm^ and the detection limits 0.9,

2

0.6, 0.3, and 0.4 mg/cm respectively. Tolerance limits for determining

2 1 mg/cm Pb for the four types were also calculated. It was concluded

2 that walls covered with paint containing Pb in excess of 1 mg/cm could

be identified, but the numerical values should be considered only semiquantitative since errors of 30% to 50% are not uncommon. Similar conclusions were arrived at by Challop and McCabe who commented on four

commercial instruments tested by the AEC Health and Safety Laboratory [46].

The statistical limits at the 90% confidence level for measuring painted

2 2 surfaces of Pb content 1 mg/cm or less varied from +0.41 mg/cm to

2 +1.0 mg/cm .

2.2.5.2. Electron Microprobe

A special case of x-ray emission analysis, when the excitation

source is an electron emitter, is electron probe microanalysis. It can

be used for a rapid qualitative or semiquantitative determination of the

elemental composition of each individual paint layer. Whiteley, et al [46]

illustrated the use of this method for determining the number, thickness

21
and composition of multiple coated substrates; Pb was detected among

other metals. Elzinga-Ter Haar [48], analyzing cross-sections of paint

samples from various objects of art, found Pb to be present in the range

of 20-44 wt %. The quantitation was made by comparing the count rates

with those of a reference standard.

2.3. Mercury Determination

I- 2.3.1. Wet Chemical Methods - Spot Tests

Fewer chemical methods have been developed for the determination of

Hg in dry paint matrices than for Pb. For purposes of the field detection

of HG in weathered paints, Vind and Drisko [49], after digesting the paint

in concentrated nitric acid, detected the presence or absence of Hg by using

cuprous iodide paper which develops an orange color vjith Hg. An alternative

method, based on the principle that mercuric salts catalyze the corrosion

of aluminum, was also used because of its relative simplicity even though

it was less sensitive than the cuprous iodide test. Both tests were considered reliable for the positive detection of Hg and negative results

obtained with paints specified to contain Hg were explained by the assumption that Hg biocides can be lost rather rapidly from exterior paints

during the weathering process.

Hg in dried paint chips has also been identified qualitatively with

the Weisz Ring Oven Technique by developing a violet-blue color on the

filter paper treated with nitric acid and an alcoholic solution of

diphenyl-carbazone [13].

22
2.3.2. Spectrophotometric Methods

2.3.2.1. Colorimetry

Two similar complexing reagents have been employed for the

colorimetric determination of Hg in dried paint. The colored complexes

of diphenylcarbazone with inorganic mercuric salts and phenylmercuric

compounds have been utilized by Hoffmann in a semiquantitative manner [8].

He isolated either the total mercuric compounds or the phenylmercuric

compounds by the Schoeniger oxygen flask method or by successive extractions with acetic acid and benzene respectively. The color formed by the

sample solution with diphenylcarbazone was matched with the color of

standard solutions. The detection limit for Hg by this method in a

100 mg paint film was approximately 0.04% as phenylmercuric compound.

When films containing between 0.04 and 0.3% Hg were analyzed, the

results for total Hg tended to be about 4% higher than theoretical

amounts, whereas the results for phenylmercuric compounds were considerably lower (25-50%) than theoretical amounts.

A quantitative method of high sensitivity and good accuracy for

assaying Hg in dry paint films was developed by Berger [9] using diphenylthiocarbazone (dithizone) as the complexing agent. The paint samples were

digested with sulfuric acid and the mercury extracted with a chloroform

solution containing dithizone. The mixed color method was used by making

spectrophotometric measurements at 475 nm for absorption of light by the

Hg complex and at 605 nm for excess dithizone in the solution. The experimental results for eight samples containing Hg at the 1% level were

within 0.2% of the theoretical amount with a standard deviation of 0.70%.

23
2.3.2.2. Atomic Absorption

Although several techniques have been developed for determining Hg

by AA and have been applied successfully for the analysis of many

different types of materials, the method has not found wide application

so far for the analysis of Hg in dry paint matrices.

A flameless AA method, following wet oxidation of dry paint films,

was used by the Sherwin-Williams Research Center for* the survey of a

series of commercial paints [27]. The experimental procedure of Hatch

and Ott was followed [49], which employed sodium chloride-hydroxylamine

sulfate medium to reduce the mercury to its elemental state and measured

the absorption of the 253.7 nm line of atomic Hg vapor. The detection

limit for Hg in the paint samples was 0.00005%.

ASTM Committee DOl.21.03 is considering adopting AA as a standard

method for determining low levels of Hg in dry paint matrices [7]. The

use of stannous chloride for the chemical generation of monatomic Hg

vapor is preferred instead of the use of the air-acetylene flame. The

details of the wet oxidation steps and the following analysis by AA are

being assessed by several laboratories before acceptance of the method,

v • • r:f . 2.3.3. Neutron Activation Analysis

The nondestructive feature of activation analysis, along with the

high sensitivity and the very small sample size required, have prompted

the use of NAA in the forensic sciences where characterization of paint

samples is being used in the course of crime detection. Elem_ents at

trace levels can be detected with a flux of thermal neutrons when

24
a nuclear reaction of sufficient cross section occurs. The nuclear

reaction of "^^^HgCn, y) ''^^^* ''^^^^Hg has been used as an analytical indi-

-3

cator in paint analysis. Hg can be detected at the 1 - 3 x 10 ug level

13 -2 -1

at a thermal-neutron flux of 10 n' cm sec for a 1 hour period [35].

Snow, et al studied the qualitative and quantitative significance

of various elements found in black paints [51]. By irradiating 78

different paint films with a thermal-neutron flux of approximately

13 —2 —1

10 n* cm sec and by measuring the gamma-ray emission with a Nal(Tl)

detector, they were able to detect Hg at the 2.6 ppm level (avg. dev.

7.7%). In a separate study Snow and Washington [52], comparing 300

samples of various colored paints, detected Hg at the same level with the

same precision. Schlesinger, et al [53] also reported on the effective

application of NAA for the comparison of 155 different paint samples

from motor vehicles, interior and exterior walls, woodwork and other

sources. The samples were irradiated at a thermal neutron flux of

12 ^ -2 -1

1.8 - 2.8 X 10 n' cm sec and Nal(Tl) was used as the detector.

Among 19 elements detected, Hg was measured at the 51 ppm level.

Another interesting application of NAA has been the investigation of

old paintings with respect to their age and origin. Minute samples of

pigment from Flemish-Dutch and Venetian paintings were subjected to NAA

13 -2 -1

by Lux, et al [34]. By irradiating the samples at 2 x 10 n' cm sec

and using Ge(Li) as the detector, Hg (in this case the nuclear reaction

202 , 203 ^ of Hg(n,Y) Hg) was detected at 0.5-5 ppm, depending on the sample

size.

25
2.3.4. X-Ray Emission Analysis

The only reported case of analysis of Hg in dry paints by X-Pay

fluorescence has been in a study of antifouling coatings. Hg was

detected below the 0.05% level in the presence of large quantities of

cuprous oxide [40]

.

2.4. Arsenic Determination

2.4.1. Wet Chemical Methods - Spot Tests

The most popular method for determining As in trace quantities in

various materials has been the Gutzeit method or some modification of it.

The method is very sensitive and can be used for determining As at the ug

level. It requires rendering the sample soluble before arsine can form a

colored compound with mercuric chloride. The maior interference is caused

by the presence of Sb, and separation of As by distillation is required.

Barker [21] employed the Gutzeit method for the routine determination

of As in paints used for toys and school materials. From the colored

stains formed, he was able to detect the presence of As in the samples

at a concentration as low as 20 ppm. The Gutzeit stain method was also

used [27] in a survey of paints for their heavy metal content. The

detection limit was 0.0001%. For the qualitative analysis of paint

chips using the Weisz Ring Oven Technique, Locke and Riley included

the Gutzeit test for the detection of As when As and Sb would likely

not be present together [13].

26
2.4.2. Spectrophotometric Methods

2.4.2.1. Colorimetry

A characteristic soluble complex of As was employed by Hodson and

Lord [26] in their screening procedure for the determination of toxic

elements in toys. The As contained in the dry paint film on toys was

determined colorimetrically by a dry fusion of the sample with sodium

carbonate, dissolving the ash in a mixture of nitric and hydrochloric

acids, and measuring the colored comples formed with silver diethyldithiocarbamate at 522 nm. The concentration of arsenous oxide was

estimated with the help of a standard curve. The method was adequate

for the determination of As at the 250 ppm level.

2.4.2.2. Atomic Absorption

Conventional AA has not been applied to the analysis of small

amounts of As found in paint matrices. The detection limit for As

using an air-acetylene flame is about 1 ug/ml and the resonance lines

for As are in the low wavelength region where acetylene flame absorption

occurs. ASTM Committee DOl.21.03 [7] is considering the use of an

argon-hydrogen flame and the 193.7 nm spectral line for the determination of As at low concentrations in paint matrices. The details of

the sample pretreatment and the m.easurement technique will have to be

worked out and assessed.

27
2. A. 3. Neutron Activation Analysis

The principal instruinental method used for deteririning As in paint

matrices that does not require any sample pretreatm.ent is I^eutron Activation Analysis (N^A) . The high sensitivity of the method is especially

applicable for the determination of As at trace quantities. The nuclear

75 76 reaction of interest is As(n,Y) As and its detection limit at a 13 ~2 1 ""A thermal-neutron flux of 10 n* cm sec for 1 hour is 1-3 x 10 ug [35].

Schlesinger, et al [53] irradiated 155 paint samples with a thermal

12 -2 -1

neutron flux of 1.8 - 2.8 x 10 n* cm sec and detected As in the

concentration range of 6.3 to 42 ppm among a total of 19 elements.

Substituting a Kal(Tl) detector with a Ge(Li) detector improved the

resolution of As and Sb peaks [54]. Snow and Washington [52], in their

survey of 300 paint samples, detected As at the 72 ppm level with a

standard deviation of 5.5% when samples were irradiated with a thermal

13 -2 -1

neutron flux of about 10 n' cm sec and the y-^ay emission was

measured with the Nal(Tl) detector.

2.4.4. X-Ray Emission Analysis

The second instrumental method used for As analysis in dry paint

matrices that does not require sam^ple pretreatment is x-ray fluorescence.

Driscoll and Freiman [40] report that the detection of As in antifouling

coatings is easily accomplished at the 0.02% level.

28
2.5. Cadimium Determination

2.5.1. Wet Chemical Methods - Spot Tests

The only reference found for a wet chemical method for determining

Cd in dry paint is by Locke and Riley [13], who detected Cd qualitatively in paint chips by the Weisz Ring Oven Technique. VJhen the

dissolved sample, on filter paper, is treated with ferrous dipyridyl-iodide

reagent the formation of an intense red color stain indicates the

presence of Cd.

2.5.2. Spectrophotometric Methods

2.5.2.1. Colorimetry

The high selectivity of dithizcne for the characterization of

metals has been found useful for the determination of the metal contents

of paints. In addition to the detection of Pb, Barker [21] used the

dithizcne reaction for detecting Cd in paint on toys and school materials. In order to separate Cd from Pb with sufficient selectivity, Cd

was extracted from, an alkaline solution in the presence of tartrate

as the masking agent. The intensity of the dithizone complex with Cd

was compared with that of the blank and standard solution. Cd at a

concentration of 100 ppm was easily detected by this technique.

2.5.2.2. Atomic Absorption

Even though AA is the most commonly used method for determining Cd

in many types of materials because of its extreme sensitivity and

freedom of interference effects, it has not found wide application for

determining the metal in dry paint matrices. Fodson and Lord [26] used

the AA m.ethod for screening paints for their Cd content. Cd was

29
detected by using an air-acetylene flame and by measuring the absorption

of the 228.9 nm resonance line. A sensitivity of 0.02 ug/m] was observed. When 89 paint samples were surveyed for their metal contents, es

sentially by the same method used at the Sherwin-Williams Research Center

Cd was detected between 0.002% and 0.004% in three samples [27]. The

detection limit was 0.0006% if a sufficient quantity of sample was available. AST^T Committee DOl. 21.03 [7] is also considering the recom.-

mendation of the method for determining Cd in dry paint films following

the wet ashing procedure. The method is being tested on two samples

containing 98 and 179 ppm Cd.

2.5.3. Electrochemical Methods - Anodic Stripping Voltammetry

The use of electrochemical methods has found little application

for the characterization of Cd in dry paint films. Matson [31],

during the ASV analysis of paint for Pb, sim.ultaneously determined

the amount of Cd present in the sam.ple extract.

2.6. Antimony Determination

2.6.1. Wet Chemical Methods - Spot Tests

Sb has been identified qualitatively in dry paint chips by the

Weisz Ring Oven Technique. Locke and Riley [13] detected Sb after an

extensive separation scheme, when potassium iodide and Rhodamine B

solutions were added to the filter paper containing the dissolved paint

sample. Sb was identified by the blue-violet stain developed on the

filter paper. A blank should be run for comparison.

30
2.6.2. Spectrophotometrlc Methods

2.6.2.1. Colorimetry

The presence of trace amounts of Sb in dry paints has been estimated

colorimetrically by Barker [21] using the color reaction with iodide in

the presence of sodium hypophosphite. The quantity of Sb could be

estimated at the ppm level when the color developed after a specific

time period was compared with solutions containing known amounts of Sb

.

A more quantitative colorimetric method was used by Hodson [26], who

determined the concentration of Sb in paint samples by the brilliant

green method. The optical density at 640 nm of the sam.ple solutions

was compared with a reagent blank. The sensitivity of the method permitted an estimation of the Sb concentration at the ug/ml level with

the aid of a calibration curve.

2.6.2.2. Atomic Absorption

An entirely satisfactory AA method of analysis for determining Sb

in dry paints has not yet been developed. AA was used at the SherwinWilliams Research Center [27] for the analysis of a series of dry paint

samples. The air-acetylene flame and the absorption of the 231.1 nm

resonance line were utilized. The Sb content detected varied between

0.001 and 1.95%. In samples which were dry ashed and only the acid

soluble Sb was determined, the highest concentration of Sb detected

was 0.02%, with a detection limit of 0.001%. In samples which were

ashed by the fusion method and the total amount of Sb was determ-ined,

31
the concentration of Sb varied between 1.12% and 1.95% with an undetermined detection limit. ASTM Committee DOl.21.03 [7] is considering

the use of AA following a wet oxidation procedure as an approved method

for determining Sb in paints. Test samples containing 99 ppm to 2A7 ppm

Sb are being analyzed using the air-acetylene flame and the absorption

of the 231.1 and 217.6 nm resonance lines. Diffeifent ashing methods are

being evaluated at the same time. It is expected that at a later date

ASTM will publish the optimum method. ,

2.6.3. Neutron Activation Analysis

The third method employed for the analysis of Sb in paints is NAA.

121 122

The nuclear reaction of analytical interest is Sb(n,y) Sb with a -4

limit of detection of about 4-9 x 10 ug at a thermal-neutron flux of

13 -2 -1

10 n' cm sec for a 1 hour maximum. Snow, et al [51,52] detected

Sb in dry paints at 52 ppm with an average deviation of 4.4% by

irradiating the film.s with a thermal neutron flux of approximately

13 -2 -1

10 n* cm sec and measuring the y-vay emission with a Nal(Tl)

detector. Schlesinger [53,54]^ during the analysis of 155 different

paints, detected Sb at 3.4 ppm to 126 ppm when the films were irradiated

12 -2 -1

with a neutron flux of 1.8 - 2.8 x 10 n* cm sec and a Mal(Tl)

detector was used. Lux [34,35], during the study of old paintings, also

detected Sb in pigment samples. The detection limit for Sb was

10"^ yg.

32
2.6.2. Spectrophotometric Methods

2.6.2.1. Colorimetry

The presence of trace amounts of Sb in dry paints has been estimated

colorimetrically by Barker [21] using the color reaction with iodide in

the presence of sodium hypophosphite . The quantity of Sb could be

estimated at the ppm level when the color developed after a specific

time period was compared with solutions containing known amounts of Sb.

A more quantitative colorimetric method was used by Hodson [26], who

determined the concentration of Sb in paint samples by the brilliant

green method. The optical density at 6An nm of the sample solutions

was compared with a reagent blank. The sensitivity of the method permitted an estimation of the Sb concentration at the ug/ml level with

the aid of a calibration curve.

2.6.2.2. Atomic Absorption

An entirely satisfactory AA method of analysis for determining Sb

in dry paints has not yet been developed. AA was used at the SherwinWilliams Research Center [27] for the analysis of a series of dry paint

samples. The air-acetylene flame and the absorption of the 231.1 nm

resonance line were utilized. The Sb content detected varied between

0.001 and 1.95%. In samples which were dry ashed and only the acid

soluble Sb was determined, the highest concentration of Sb detected

was 0.02%, with a detection limit of 0.001%. In samples which were

ashed by the fusion method and the total amount of Sb was determined.

31
the concentration of Sb varied between 1.12% and 1.95% with an undetermined detection liinit. ASTM Committee DOl.21.03 [7] is considering

the use of AA following a wet oxidation procedure as an approved method

for determining Sb in paints. Test samples containing 99 ppm to 247 ppm

Sb are being analyzed using the air-acetylene flame and the absorption

of the 231.1 and 217.6 nm resonance lines. Different ashing methods are

being evaluated at the same time. It is expected that at a later date

ASTM will publish the optimum method.

. 2.6.3. Neutron Activation Analysis

The third method employed for the analysis of Sb in paints is NAA.

121 122 The nuclear reaction of analytical interest is Sb(n,Y) Sb with a -4

limit of detection of about 4-9 x 10 ug at a thermal-neutron flux of

13 -2 -1

10 n' cm sec for a 1 hour maximum. Snow, et al [51,52] detected

Sb in dry paints at 52 ppm with an average deviation of 4.4% by

irradiating the film.s with a thermal neutron flux of approximately

13 -2 -1

10 n* cm sec and measuring the y-ray emission with a Nal(Tl)

detector. Schlesinger [53,54]^ during the analysis of 155 different

paints, detected Sb at 3.4 ppm to 126 ppm when the films were irradiated

12 -2 -1

with a neutron flux of 1.8 - 2.8 x 10 n* cm sec and a Nal(Tl)

detector was used. Lux [34,35], during the study of old paintings, also

detected Sb in pigment samples. The detection limit for Sb was

32
2.7. Selenium Determination - Spectrophotometry

2.7.1. Colorimetry

A quantitative method for determining small amounts of Se in dry

paint films has been the codeine sulfate reaction. VThen codeine is added

to a solution of Se in concentrated sulfuric acid a characteristic bluish

color is produced. An adaptation of the technique developed for biological samples [56,57] was used to survey commercial paints for the Se

content [27]. Concentrations detected varied between 0.0014% and 0.0322%

with a detection limit of 0.0010%.

No references to the AA analyses of Se in dry paint were found.

ASTM Committee DOl.21.03 [7] is considering an AA method for the

determination of Se by using an air-acetylene flame and the absorption of the 196.0 nm resonance line. No experimental data are yet

available.

2.7.2. Atomic Absorption

33
3. Summary and Conclusions

This report was written for the purpose of reviewing various

analytical approaches that have heen used for the detection and measurement of toxic elements in dry paint matrices. The numerous methods

described have been arranged according to each element of interest and

are sununarized in table I. The majority, about forty, of the published

methods refer to the analysis of Pb in dry paint and many of these are

only qualitative or semi-quantitative. There are relatively few

references to the other five elements.

A major problem in the analysis of all the elements is the separation of the elements from the organic paint matrices with which they

are associated. The ashing and digestion steps seem to be sources of

considerable error as compared to the subsequent instrumiental determinations. It is obvious that the poor precision of several methods can be

traced to incomplete oxidation or losses sustained during the oxidation

processes. There is a definite need for a proven, reliable oxidation

procedure for each element under consideration. In addition to dry

ashing at a high temperature or wet ashing with strong mineral acids,

the use of atomic oxygen for the low temperature ashing of the organic

paint matrix should also be considered.

Of the wet chemical methods described, the spot test offers the

greatest number of advantages for a rapid qualitative field determination. A practical semi-quantitative field test has been worked out for

Pb determination only, utilizing the black sulfide precipitate formation

on a paint chip. A second simple procedure for paint samples for Pb

34
Table I

Analytical Methods Employed for the Analysis of Dry Paint Matrices

21? Hg As Sb Sg

Spot Test X X X X X

Gravimetry x

Colorimetry x x x x x x

Atomic Absorption x x (x)® x x (x)

Electrolytic Deposition x

Polarography x

Anodic Stripping x (x)

Voltairanetry

Neutron Activation x x x x Analysis

X-Ray Fluorescence x x x

Electron Microprobe x

a - Parenthesis indicate tentative method.

35
involves the iodide precipitate formation, this time from a solution

containing the paint extract. Other elements can also be identified by

colored spot formations and the technique has been used for all the

elements except Se. However, since the other elements are present in

trace quantities as compared to Pb, the procedures invplved are either

too complex or the reactions are not specific for the determination of

several elements simultaneously. The Weisz Ring Oven Technique offers

the simplest technique for the extraction of the metals from the paint

and separation of the metals before the final identification is made.

Colorimetry is the only method that has been applied to the determination of all the six elements in dry paint, but the method usually requires extensive chemical manipulations that have to be carried out

in a laboratory if the results are to be quantitative. The sensitive

dithizone reaction seems to be the best choice for the determination

of Pb, Hg and Cd; As and Se each require a different complexing agent.

The wet chemical methods are being replaced preferentially by a

variety of instrumental methods, AA being the most promising one.

With proper care as to sam.ple pretreatment , all the elem.ents concerned

can be determined by AA, using the air-acetylene flame for five elements

and either a flameless or cold vapor technique for Hg analysis. In

order to eliminate the losses encountered during sample pretreatment

steps and to avoid the problems associated with flame absorption or

emission interferences when the elements are present in low concentration

in the sample, there has been increased emphasis on the development of

36
flameless solid sampling techniques. A modification of the sampling

boat, the Delves cup method, has been recommended for Pb analysis at

concentrations below 0.1%; direct sampling of paint by the flame has

been attempted; and the West type carbon rod flameless sample holder for

solid samples is being evaluated. Hopefully these attempts will result

in an accurate AA method of analysis for solid paint samples that can

be used to replace the conventional procedure of aspirating an aqueous

solution into the flame.

Electrochemical methods have been applied to the analysis of Pb

only, although polarography and ASV are both suitable for Cd determination.

Another instrumental method of great sensitivity that has been

employed for aged paint analysis is NAA. Pb is the least sensitive

metal and the method has been used mostly for the detection of Hg, As,

and Sb in trace quantities. The method has found only limited application for the analysis of dry house paints since few laboratories

have intense neutron sources available.

Currently the most popular nondestructive screening method for in

situ measurement is x-ray fluorescence. The method has been applied

mainly for Pb determination; and in one reported case also for the

detection of Hg and As. X-ray fluorescence could be used for determ.ining

the other five elements with the required sensitivity if the elements

were first concentrated by proper chemical means. Several commercial

instruments developed for the determination of Pb in painted surfaces

have been evaluated extensively. At the present state of development,

37
portable x-ray fluorescence analyzers yield only semi-quantitative data.

The presence of Pb is determined in units of mass per surface area which

can only be converted into a weight fraction if the exact composition

of the paint is known. An accepted convention that 1% Pb in a layer of

paint gives a reading of 0.08 mg/cm is often used fo'r interpreting

experimental results. The x-ray fluorescence technique must be developed

further before an accurate determination of Pb in dry paints is possible.

A closely related method, electron probe microanalysis, has also

been applied to the detection of Pb on a few occasions. The ability of

this method to simultaneously determine the elemental distribution and

the thickness of paint films should make it useful in surface coating

analyses.

In terms of future work, emphasis should be placed on the development of sampling techniques and detection methods for toxic elements in

dry paint matrices, specially for Cd and Se. Reliable chemical analyses

are essential for the fundamental understanding of the hazards posed by

the toxic elements present in paints and for the protection of the

public against such hazards.

38
4. References

[1] Federal Register 36., No. 211, p. 20985, (November 1971).

[2] Greifer, B. , Report on Literature Review, . Surveys , and Conferences

Lead Paint Poisoning Hazard Detection Methods, NBS Report No. 10649,

(December 1971)

.

[3] Greifer, B., Experimental Evaluation of Analytical Methods for

Determining Lead in Paint and Building Materials, NBS Report 10674,

(January 1972).

[4] Greifer, B. , Rasberry, S. D. , Rains, T. C, Maienthal, F. J., and

Deardorff, E. R. , Comparison of Laboratory Methods for Determining

Lead in Dried Paint Films, NBS Report No. 10966, (January 1973).

[5] Greifer, B., Maienthal, E. J., Rains, T. C, and Rasberry, S. D.,

Development of NBS Standard Reference Material: No. 1579

Powdered Lead-Based Paint, NBS Special Publication No. 260-45,

(March 1973).

[6] Westgate, M. W., Shurts, R. B. , and Adams, E. F., Determination of

Lead in Paints at the One Percent Level, National Paint, Varnish

and Lacquer Association, Circular No. 773, (May 1956).

[7] Private Communication, ASTM Committee D 01.21.03.

[8] Hoffmann, E. , Determination of Phenylmercuric Compounds and Total

Mercury in Paints, Zeitschrift fuer Analytische Chemie, 182 , p. 193, (1961).

[9] Berger, H. W. , The Determination of Mercury in Latex Paints and

Paint Films Containing Mercury Fungicides, Journal of Paint

Technology, 38.> P- 371, (1966).

[10] Searle, B., Chan, W. , Jensen, C, and Davidow, B., Determination

of the Lead in Paint Scrapings by Atomic Absorption, Atomic

Absorption Newsletter, 8^, p. 126, (1969).

[11] Sayre, J. W. , A Spot Test for Detecting Lead in Paint, Pediatrics,

46, p. 783, (1970).

[12] Sayre, J. W. , Spot Test for Lead in Paint (Continued), Pediatrics,

48, p. 330, (1971).

[13] Locke, D. C. , and Riley, 0. H. , Chemical Analysis of Paint Samples

Using the Weisz Ring Oven Technique, Studies in Conservation, 15 , p. 94, (1970).

39
Le Giorgis, G. , Analysis of Paints Containing Lead, Ind. Vernice,

Milan 16, p. 64 (1962), Analytical Abstracts No. 2806, (1963).

British Standards Institution, Permissible Limit of Lead in LowLead Paints and Similar Materials, BS 4310:1968.

Kaplan, E. , and Shaull, R. S., Determination of Lead in Paint

Scrapings as an Aid in the Control of Lead Paint Poisoning in

Young Children, American Journal of Public Health, 51^, p. 65, (1961).

Scott, W. W. , Standard Methods of Chemical Analysis , Editor N. H.

Furman, 5th Ediction, Vol. 2, y. 1859, (D. Van Nostrand, New York,

New York, 1939)

.

Determination of Lead at the One Percent Level, National Paint,

Varnish and Lacquer Association, Technical Bulletin No. 21,

(May 1962).

Hoffmann, E. , Analytical Method for Determining Lead in a Paint Film,

The Australian Paint Journal, 4_, p. 23, (1960).

Hoffmann, E. Determination of Small Quantities of Lead in Paint

(Minimum 0.003%), Zeitschrift fuer Analytische Chemie, 208, p. 423,

(1965)

.

Barker, J. H. , Chapman, W. B., and Harrison, A. J., Toxic Metals

in School Materials and Toys, Journal of the Association of Public

Analysts, 2, p. 89, (1964).

Barltrop, D., and Killala, N. J. P., Factors Influencing Exposure

of Children to Lead, Archives of Diseases of Childhood, 44_, p. 476,

(1969) .

Browett, E. V., and Moss, R., Manual and Semi-Automatic Methods for

the Determination of the Lead Content of Urine, Analyst (London),

90, p. 715, (1965).

Lead by the Dithizone (Photometric) Method, E 35-63, ASTM Book of

Standards, pt. 32, p. 282, (1973).

Chicago Board of Health, Private Communication.

Hodson, T. , and Lord, D. W. , A routine Screening Procedure for Determining Toxic Metals in Toys, Journal of Association of Public

Analysts, 9, p. 60, (1971).

Scott, R. W. , Sherwin-Williams Research Center, Private Communication.

McDuffie, B., Rapid Screening of Pencil Paint for Lead by a Combustion-Atomic Absorption Technique, Analytical Chemistry, 44 , p. 1551, (1972).

40
[29] Determination of Low Concentrations of Lead in Paint, ASTM D2088-68,

ASTM Book of Standards, pt. 21, p. 385, (1972).

[30] Lukaszewski, Z., and Szymanowska, H., Application of Polarography

in Determining Lead Extracted from Paints Used on Ceramics,

Chemia Analityczna, (Warsaw), 17_, p. 387, (1972).

[31] Matson, W. R. , Environmental Sciences Associates, Inc., Private

Communication.

[32] Schaplowski, A. F., Lead in Paint on Pencils, HSMHA Health Reports,

Public Health Service, U.S. Department of Health, Education and

Welfare, 86, p. 961, (1971).

[33] City of New Orleans Department of Health, Private Communication.

[34] Lux, F., Braunstein, L., and Strauss, R. , Modern Trends in Activation Analysis, NBS Spec. Publ 312, Vol. 1, pp. 216-225, (1968).

[35] Guinn, V. P., Trace Characterization, NBS Monogr. 100, p. 339,

(1967).

[36] Lutz, G. J., NBS, Personal Communication.

[37] McGinness, J. D., Scott, R. W. , and Moretensen, J. S., X-Ray

Emission Analysis of Paints by a Thin Film Method, Analytical

Chemistry, 41, p. 1858, (1969).

[38] Frankel, R. S., and Aitken, D. W. , Energy-Dispersive X-Ray

Emission Spectroscopy, Applied Spectroscopy, 24_, p. 557, (1970).

[39] Reece, R. M. , Reed, A. J., Clark, C. S., Angoff, R., Casey, K. R.

,

Challop, R. S., and McCabe, E. A., Elevated Blood Lead Levels and

the In Situ Analysis of Wall Paint by X-Ray Fluorescence, American

Journal of Diseases of Children, 124 , p. 500, (1970).

[40] Driscoll, C. and Freiman, A., X-Ray Fluorescence Spectrometry in

Antifouling Coating Systems, Journal of Paint Technology, 42,

p. 521, (1970).

[41] Laurer, G. R. , Kneip, T. J., and Albert, R. E. , X-Ray Fluorescence:

Detection of Lead in Wall Paint, Science, 172 , p. 466, (1971).

[42] Laurer, G. R. and Berry, P. F., Nuclear Instruments in the Fight

Against Lead Poisoning, Isotopes and Radiation Technology, 9,

p. 275, (1972).

[43] Berry, P. F. , Texas Nuclear X-Ray Fluorescence Analyzer for Lead,

Isotopes and Radiation Technology, 9_, p. 272, (1972).

41
[44] Barltrop, D., Harford, C. L., and Killala, N. J. P., The Determination of Lead in Paint Films with a Portable Isotope Fluorescence

Analyzer, Bulletin of Environmental Contamination and Toxicology,

6, p. 502, (1971).

[45] Rasberry, S. D., Investigation of Portable X-Ray Fluorescence

Analyzers for Determining Lead on Paint Surfaces, Applied

Spectroscopy, 27^, p. 102, (1973).

[46] Challop, R. S., and McCabe, E., Detection of Childhood Lead

Poisoning: New Techniques in Microblood and Wall Lead Analysis,

American Public Health Association, 99th Meeting, (October 13, 1971).

[47] Whiteley, P., Fletcher, K. E. , and Rothwell, G. W. , Electron Probe

Analysis in the Investigation of Surface Coatings Problems, Journal

of Oil and Colour Chemist's Association, _52, p. 410, (1969).

[48] Elzinga-Ter Haar, G. , On the Use of the Electron Microprobe in

Analysis of Cross-Sections of Paint Samples, Studies in Conservation, 16, p. 41, (1971).

[49] Vind, H. P. and Drisko, R. W. , Field Identification of Weathered

Paints, Naval Civil Engineering Laboratory, Port Hueneme, Calif.,

Technical Report R766, (April 1972).

[50] Hatch, W. R. and Ott, W. L. , Determination of Sub-Microgram

Quantities of Mercury by Atomic Absorption Spectrophotometry,

Analytical Chemistry, 4_0, p. 2085, (1968).

[51] Snow, K. B., Hoffmann, C. M. , Brunella, R. L., and Pro, M. J.,

Comparison of Paints by Neutron Activation Analysis, International

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[52] Snow, K. B. , and Washington, W. D., Comparison of Paints by Neutron

Activation Aanlysis, II. Colored Paints, Journal of Association of

Official Analytical Chemists, 54, p. 917, (1971).

[53] Schlesinger, H. L., Lukens, H. R., Bryan, D. E., Guinn, V. P., and

Hacklemann, P. P., Forensic Neutron Activation Analysis of Paint,

Atomic Energy Commission Report GA 10142, (1970).

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Hacklemann, R. P., Forensic Neutron Activation Aanalysis of Paint,

Isotopes and Radiation Technology, 9^, p. 269, (1972).

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of the "Alte Pinakothek" in Munich, Zeitschrift fuer Analytische

Chemie, 221, p. 235, (1966).

42
[56] Davidson, J., The Quantitative Adaptation of the Codeine Test to

the Colorimetric Determination of Selenium in Plant Materials,

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p. 450, (1939).

[57] Gortner, R. A., and Lewis, H. B., Quantitative Determination of

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Analytical Edition, 11, p. 198, (1939).

43
FORM NBS-114A (1.711

II <: nrPT of CDMM \ Pfll^I lf"A'rU1M dl} if W l^t^i*'^' MO 9 P.nu'r Ai~ r-r^ a c inn BIBLIOGRAPHIC DATA NBSIR 73-2S1

SHKET

3« F^ccipicnt S- Accession No*

4. Tl fLK AN'U SUb l l I Lt Analytical Methods for the Detection of Toxic Elenents in

Dry Paint Matrices—A Literature Survey

5a i^ublic^cion Ustc

6. Performing Organization Code

7. AUIIIOR(S)

Maya Paabo

8. Performing Organization

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU 01- STANDARDS v DEPARTMENT OF COMMERCE

WASfllNG'I ON, D.C. 20234

10• w. riujLLi/ P rrt ior r/TajasK/ cl-/ U»vorK nrl' WnLJnnit Mr. ino. 460R400

11. Contract/Grant No. IAA-H-34-71

12, Sponsoring Organization Name and Address

Office of Policy Development and Research

Department of Housing and Urban Development

Washington, D.C. 20410

13, Type of Report & Period Covere dFinal

14, Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSi RACT (A 200-wurd or less factual summary of most significant information. If document intludes a significant

bibliogr J:,'~>hy or literature survey, mention it here.)

This report is a summary description of the chemical procedures currently

available for jhe analysis of selected toxic elements in dried paint. The

elements included In this report are lead, mercury, cadmium, antimony, arsenic,

and selenium. The 1. •"erafur.. search upon which this report is based was directed primarily toward references pertaining to the analysis of dried paint.

A bibliography of 57 references to vjet chemical analysis, colorimetry, atomic

absroption spectroscopy, elecr.rochemistry, neutron activation analysis, and

x-ray emission analysis is presented. ^

17. KEY WORDS (Alphabetical order, separated by semicolons)

Analytical methods; antimony; arsenic; cadmium; lead; mercury; review; selenium;

toxic elements in naints

18. AVAILABILITY SI ATEMENT

[X~] UNLIMITED.

for OFFICIAL DISTRIIUITION. DO NOT RELEASE

TO NTIS.

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