Toxicology Letters, 22 (1984) 301-306 301

Elsevier

TOXLett. 1270

BIOLOGICAL AVAILABILITY OF LEAD IN A PAINT AEROSOL

1. PHYSICAL AND CHEMICAL CHARACTERIZATION OF A LEAD
PAINT AEROSOL

(Lead; biovailability; paint; respirable; size distribution)

DAVID KALMAN, ROBERT SCHUMACHER, DAVID COVERT and DAVID L. EATON

Department of Environmental Health SC-34, University of Washington, Seattle, WA 98195 (U.S.A.)

(Received March 20th, 1984)
(Accepted March 27th, 1984)

SUMMARY

This study was conducted to determine the physical and chemical characteristics of an aerosol of lead-
based paint, generated in an industrial spray operation, that might influence the biological availability
of lead present in inhaled aerosols. Paint aerosols were collected, and mass-size distribution was deter-
mined using a portable cascade impactor under actual occupational conditions. Approx. 2% of the par-
ticulate mass collected was in the respirable range (less than 10 gm mean aerodynamic diameter),
although the maximum airborne concentration of lead was found to be 2-3 mg/m3. The lead concentra-
tion in a dried aerosol was very resistant to chemical digestion. Analysis by X-ray diffraction, atomic
absorption spectroscopy and inductively coupled plasma emission spectroscopy showed approx. 11%
lead by dry weight, although the wet weight concentration of lead reported by the manufacturer was
12.8%.

INTRODUCTION

Considerations in estimating bioavailability of lead pigments from paint aerosols

include both the solubility of the lead compound and the protection afforded by the
organic component of the paint as an impenetrable, inert envelope. The lack of ap-
preciation for the potentially important role of the paint residue in modifying lead
bioavailability is reflected by the fact that paints used in toxicological studies have
not generally been characterized for the nature of the organic component, even as
recently as 1978 [ 11. Previous evaluations of paint formulations for oral lead toxicity
have studied paints containing lead salts of fatty acids (lead octoate, lead
naphthenate) added as drying agents to oil-based paint. These lead compounds show

Abbreviations: GMMAD, geometric mass mean aerodynamic diameter.

0378-4274/84/$ 03.00 0 Elsevier Science Publishers B.V.

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higher biological availability than inorganic pigments [2], and their organic matrix
affords little or no resistance to digestion.
Little attention has been paid to modern plastic-based paint formulations as
sources of lead exposures. One study of plastic formulations containing lead com-
pounds of widely differing solubilities used as pigments, stabilizers or catalysts
detected no significant oral toxicity [3], but particle sizes were large (200-400 pm),
and formulations were quite different from spray paints. An in vitro study that
simulated gastric digestion of alkyl-resin paint did show only slight solubilization
[41.
The spray-painting operation of PACCAR, Inc. (Renton, WA) was identified as
a typical industrial setting where large volumes of lead-based paint are used routine-
ly. Previous industrial hygiene surveys found significant airborne lead concentra-
tions during spray operations, yet worker surveillance, including blood-lead values,
suggested that relatively little of this airborne lead was absorbed. Reasons for such
discrepancies between airborne lead concentrations and biological indices of lead ex-
posure include: (1) utilization of adequate protective equipment such as respirators;
and/or (2) physical characteristics of the lead aerosol which decrease the
bioavailability of inhaled and/or ingested lead paint aerosols.
We report here the physical and chemical characteristics of the lead paint aerosol
generated in this model paint-spraying operation.

METHODS

Paint supplied to PACCAR on a custom basis (from a major paint manufacturer)

was selected in consultation with PACCAR personnel as a representative polymer-
based lead pigment formulation.

Paint composition

Material safety data sheets supplied by the manufacturer indicated that the paint
contained 13.89% lead, 1.75% chromium (both on a wet-weight basis), and 60.0%
volatile solvents. The remainder consisted of presumably polymeric and inert
materials. The polymer was identified as ‘alkyd resin’. Based upon these values, we
estimated the dry weight as containing 34.7% lead and 4.4% chromium. The
manufacturer provided the following supplementary information: (1) the pigment
is PbCr04 and is present as 20% of the wet weight (12.8% lead); (2) no additional
lead is added except for 0.5% of a lead-drying agent (which the manufacturer would
not identify, but is probably lead naphthenate or lead octoate); and (3) the resin is
formed from hydrolyzed soya bean oil and phthalic anhydride.
Supplemental analyses were conducted on the paint samples, using a variety of
digestion methods and instrumental techniques, including X-ray fluorescence and
electron microprobe analysis of bulk paint and dried paint film. Quantitative deter-
 303

mination of lead in the dried aerosol by atomic absorption methods was hampered
by incomplete digestion and variable solubilizaton of the matrix. Among the
methods applied were: muffle furnace ashing [6] (900°C, 8 h), concentrated nitric
acid wet ashing [7], wet ashing in aqua regia [7], teflon bomb digestion with nitric
acid [8], and teflon bomb digestion followed by concentrated hydrochloric acid wet
ashing. Recovery experiments on lead acetate, lead oxide (Pb304) and lead chromate
were performed with many of these methods.
Final extracts were quantitated by atomic absorption and inductively coupled
plasma emission spectroscopic methods. All analyses were conducted using ultrex-
grade nitric acid and acid-rinsed borosilicate glassware. Laboratory blank analyses
were checked daily and with each batch of sample.

Aerosol collection and measurement

A cascade impactor (Sierra Series 260) was used for determination of particle
mass size distribution [9, lo]. The seven cascade impactor stages were preloaded
with weighed 18 mm (tare approx. 50 mg) uncoated glass cover slip collection
substrates. A flow rate of 3 l/min was chosen, based on preliminary tests, to yield
a particle size discrimination range that best included the mode of the paint
overspray particle distribution and the respirable range of particle sizes. Represen-
tative measurements were taken in the immediate vicinity of the painting stage,
within the confines of the spray booth, during actual routine painting. The impactor
was operated for 14 min. The impactor stages were reweighed to determine the col-
lected mass after the sample had sufficient time to dry and polymerize. The flow
rate was adjusted prior to sampling and was checked afterwards. Gravimetric deter-
minations of total particulate air concentrations within the spray booth area and in

70.
IO
\E 60,

! so-
B
H 40.

2 30.
F
4 20.

IO.
07 Ck?Q%l CSDOXI

I-O 2.0 3.0 5-O IO 20 30 50

Particle Diameter, Doa,pm

Fig. 1. Lead paint aerosol particle mass size distribution. Bracketed values indicate respirable mass frac-
tion within the size interval.
304

an area removed from the spraying operation were made over a 2-month period that
included the date of the size-distribution measurements.

RESULTS

Paint composition

The results of the analyses of bulk paint and dried aerosol are summarized in
Table I. Based on the degree of consumption of the bulk paint residue, the recovery
of model inorganic lead compounds, and the precision of replicate analyses, method
VI was selected as providing the best analytical results. In no case were lead concen-
trations as high as was reported by the manufacturer, although the lead: chromium
ratios measured agree with the manufacturer’s verbal data, within experimental
error.

Aerosol measurement

The results of aerosol mass size distribution measurements are shown in Fig. 1.
Fig. 1 presents the size distribution in finite differential form as the increment of
particle mass concentration per increment of logarithm of particle size sampled by
each impactor stage, A [m]i/ A log Dae;, where [m] = particle mass concentration of
ith increment and Dae = aerodynamic diameter. The distribution is seen to be mono-
modal with the particles narrowly distributed about a mode between 11 and 17 pm
aerodynamic diameter. The total mass concentration was 28 mg/m3.
If the particles are assumed to be distributed log-normally, a GMMAD of 14 pm
and a geometric strandard deviation of 1.2 are obtained. Approx. 20% of the par-

TABLE I

RECOVERY OF STANDARD LEAD COMPOUNDS AND LEAD CONTENT OF PAINT BY

DIGESTION METHODS

I II III IV V VI
Digestion method Muffle Aqua Nitric Hydro- Teflon Teflon
method furnace regia acid chloric bomb bomb
acid +conc. HCI
Undissolved yes no yes yes yes no
paint residue

Standard lead
recoveries (070)
PbCr04 93+2 93* 5 93 *2 96 k-5
Pb,04 94k2 90+ 10 92.0 + 0.4 92.0 + 0.4
Pb(OAc)z 91+ 4 99 -t3 99 *3

Dried paint assay <I 4+3 6+ 2 9.7kO.4 10.8rtO.5 10.8?0.6

(% bv weight1
 305

ticulate mass is less than 10 pm in aerodynamic diameter, and less than 3% of the
mass is below 10 pm in geometric diameter (assuming a particle density of 1.6).
The ACGIH-endorsed standard of respirability [1 l] was applied to this size
distribution by linear interpolation of size vs respirability increments. The mean %
respirability fractions for the mass-aerodynamic diameter intervals measured are in-
dicated in Fig. 1. Summation of these levels produces a respirable mass fraction of
the total size range sampled of 2%. This represents an upper limit of mass-fraction
respirable aerosol, as the contribution of particles of aerodynamic diameter 3 50
pm was neglected in these measurements. The total concentration of respirable par-
ticles was 0.69 mg/m3.
Total aerosol concentrations determined in ten or more separate measurements
were: plant background (no spray painting in operation): 0.4 -t 0.2 mg aerosol/m3;
areas remote from spray booth during spray painting: 1.9 + 0.4 mg aerosol/m3; per-
sonnel sampler worn by painter during spraying: 17 f 5 mg aerosol/m3; in spray
booth during painting: 26k7 mg aerosol/m3. Painting lasted for 15-20 min per
railcar for a total duration of 100 min per 8 h shift.

DISCUSSION

The paint composition data supplied by the paint manufacturer were internally
contradictory. The molar ratio of lead to chromium computed from the supplied
weight Vo levels for each element is 1:0.5 (Pb/Cr) rather than the 1:l ratio resulting
from pure PbCr04. In our own laboratory analysis of the dried paint, the Pb/Cr
ratio for two samples was found to be 1:0.43 and 1:0.52. These findings were consis-
tent with the manufacturer’s verbal report, but require that 50% of the lead be in
some form other than PbCr04.
The total lead concentration is also at variance with that stated by the manufac-
turer. Based on manufacturer’s data, the dried paint should contain up to 35% lead.
We have found a maximum of 11% lead in dried paint samples.
The resistance of the paint to chemical digestion rendered the analysis difficult
and may itself be an indication of the ability of this matrix to sequester the lead pig-
ment in a biological system.
While the maximum airborne particulate concentrations reached during spray
painting would indicate total airborne lead levels of 2-3 mg/m3, far in excess of the
current lead standard of 0.05 mg/m3, only about 2% (0.04-0.06 mg/m3) of the
paint aerosol, and consequently aerosol lead, found in this workplace would be
respirable according to the ACGIH criteria.

ACKNOWLEDGEMENTS

The authors wish to thank the following individuals for their assistance with the
design and execution of this project: Steven Cant, Washington State Department of
Labor and Industries; David Bissonnette, PACCAR, Inc.; and George McCaslin,
306

University of Washington Department of Environmental Health. This study was

supported by a contract with the State of Washington Department of Labor and
Industries.

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