Science of the Total Environment 336 (2005) 275 – 281

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Lead, cadmium, and zinc concentrations in plaster and mortar from

structures in Jasper and Newton Counties, Missouri
(Tri-State Mining District)
Phyllis M. Perry, Jeffrey W. Pavlik, Ralph W. Sheets, Richard N. Biagioni*
Chemistry Department, Southwest Missouri State University, 901 S. National Avenue, Springfield, MO 65804, United States
Received 8 February 2003; accepted 2 July 2004

Abstract

The primary goal of this study was to evaluate anecdotal evidence that within Jasper and Newton Counties, Missouri, two
counties within the Tri-State Mining District, granular mine tailings were commonly used in place of river sands in wall plasters
and mortar. Interior wall plaster and mortar samples from structures in this mining district were analyzed for lead, cadmium, and
zinc, and compared to samples from Springfield, MO (comparison site). The Jasper and Newton County samples showed
elevated concentrations of the three elements, consistent with the inclusion of mine tailings, with a number of samples
containing lead and cadmium at concentrations greater than EPA remediation targets for yard soil. X-ray diffraction studies
showed the presence of the zinc ore minerals, sphalerite and hemimorphite, in high level samples. Thin section optical studies
identified the major component of the aggregate as chert, a mineral abundant within the tailing piles. Because dust from
crumbling plaster and mortar could represent an avenue for significant heavy metal exposure to building occupants, we suggest
that there may be associated health consequences that should be further evaluated.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Lead; Cadmium; Zinc; Mining; Plaster

1. Introduction commenced in this area circa 1850 and continued

The Tri-State Mining District covers several
hundred square kilometers in southwestern Missouri,
southeastern Kansas, and northeastern Oklahoma.
Mining and processing of lead and zinc ores
* Corresponding author. Tel.: +1 417 836 4649; fax: +1 417
836 5507.
E-mail address: rnb266f@smsu.edu (R.N. Biagioni).
0048-9697/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2004.07.007
until the 1970s. The district’s lead and zinc production
ranked among the highest in the world. Mining and
ore processing produced approximately 500 million
tons of wastes, with a sizeable portion of that waste
remaining unsecured, estimated at 100 million tons in
1996 (EPA, 1996a).
The mineralogy of the region has been described in
numerous sources (Buckley and Buehler, 1905; For-
rester, 1948; McKnight et al., 1970). The principle zinc
276 P.M. Perry et al. / Science of the Total Environment 336 (2005) 275–281
ore of the region was sphalerite (cubic ZnS). Hemi-
morphite (Zn4Si 2O7(OH)2d H 2O) and smithsonite
(ZnCO3), though not of great economic importance,
were also commonly found in shallower mines above
the water table. Lead was present as galena (PbS) and
cerussite (PbCO3). Cadmium was present as an impurity
in sphalerite. The ore minerals were generally found as
inclusions in minerals such as chert (microcrystalline
SiO2 with water inclusions). Gallium was also present
at sufficient concentrations to allow its commercial
production as a byproduct of zinc refinement.
Much of the preliminary ore processing was carried
out at or near the mines. The wastes contain residual
metals, including lead, cadmium, and zinc. Because of
concerns about heavy metal contamination, especially
from lead, the US EPA designated several sites within
the Tri-State District as Superfund Sites: Cherokee
County (Cherokee County, KS, 1983), Tar Creek
(Ottawa County, OK, 1983), and the Oronogo-Duen-
weg Mining Belt (Jasper County, MO, 1990).
Of greatest concern are contamination of ground
water and exposure of residents, particularly children,
to heavily contaminated soil. A recent study (ATSDR,
1995) in Jasper County, MO, showed that nearly 14%
of children aged 6–71 months had blood lead levels
z10 Ag/dl, compared to no children with elevated
blood levels for children in a control group. Average
blood lead levels were also higher in youth and adults
in the study area compared to the control area. Blood
cadmium levels were not significantly different
between the study area and the control area. For the
study area, the factors most strongly correlated to
children’s blood lead levels included soil lead
concentrations and homes with lead water pipes.
Contaminated soil has been recognized as an impor-
tant avenue for lead exposure (ATSDR, 1992).
EPA initiated a number of remediation efforts that
have either been completed or are in progress, as
outlined in a series of EPA Records of Decision and
review reports (EPA, 1996a,b, 1997a,b, 1998, 2002).
Tailing piles have been removed in several areas. In
areas where private wells were contaminated, homes
were connected to city water supplies, provided with
point-of-use water purifiers, or supplied with bottled
water. Contaminated soil has been excavated from
residential yards, with a goal of reducing soil lead
concentrations to below 500 mg/kg and cadmium
concentrations to below 75 mg/kg.
Within the Tri-State Mining District, as with many
other mining areas, it was common to use mine
tailings for a wide variety of applications including
concrete aggregate, road construction, railroad ballast,
fill, landscaping, and sandblasting. Anecdotal evi-
dence suggested that granular tailings were used in
place of river sand in residential wall plaster, though
we are not aware of any documentation of this. We
initiated this study with the aim of determining
whether mine tailings are, in fact, commonly present
in wall plaster and masonry mortar found in home
interiors, and if so, if lead and cadmium are present at
levels high enough to present a potential health risk to
residents.
Most of the wall plasters evaluated in this study
appear quite distinct from modern gypsum plasters
that are light in color. Shortly before and after the turn
of the twentieth century, wall plaster and masonry
mortar were normally produced locally by combining
a cementing agent (lime, gypsum, or Portland cement)
with an aggregate, usually sand (Shivers, 1990).
Masonry mortars may be prepared in a similar
manner, but generally employ a coarser aggregate
and are harder. Wall plaster and masonry mortars
produced in this manner are compositionally similar
and differ primarily on their end uses. In this report,
we distinguish wall plasters from masonry mortar
because residents come into contact with wall plasters
to a much greater extent.
2. Methods
2.1. Samples
Fifty-three wall plaster samples and 29 masonry
mortar samples were collected from structures (pri-
marily residences, but also some public buildings) in
Jasper and Newton Counties, Missouri, including the
city of Joplin, Missouri, and a number of smaller
communities in the area. For comparison, an addi-
tional 24 plaster samples and seven masonry mortar
samples were collected in Springfield, Missouri,
where very little lead mining or processing was carried
out. Most of the wall plaster and mortar samples were
taken from abandoned buildings or from buildings
being razed. Samples from occupied structures were
obtained with permission of current residents.
 P.M. Perry et al. / Science of the Total Environment 336 (2005) 275–281
Fine gravel samples from three creeks in the Jasper
and Newton Counties study area (Turkey, Shoal, and
Hickory Creeks), and a sample from McDonald
County (Indian Creek), south of the study area, were
also collected.
2.2. Sample digestion
Prior to grinding, samples were dried in a 110 8C
oven, and the outermost layer was scraped off to
remove any surface contaminants. Plaster samples
were normally taken from the section facing the wall
interior. Care was taken to avoid inclusion of paint,
wall paper, lath, and other foreign matter.
Microwave digestion of samples was carried out
using a MARS 5 digestion unit (CEM, Matthews,
NC). Initial studies followed EPA Method 3051 (EPA,
1994), using 10-ml nitric acid and 2-ml HCl with 0.5-
g samples. For most of the measurements reported
here, digestions were carried out at atmospheric
pressure by microwave digestion, using 50-ml poly-
propylene sample tubes, with 5-ml nitric acid, 1-ml
hydrochloric acid, and 0.25-g samples. Temperature
was raised to 100 8C over a period of 10 min and then
maintained at that temperature for 30 min. Digests
were filtered to separate insoluble residue and were
diluted prior to analysis.
2.3. Stratigraphic evaluation
Five plaster samples of varying heavy metal
concentrations were selected to evaluate variations
of heavy metal content with depth. Any surface
coatings such as paint were removed. The samples
had surface areas of about 50 cm2. At five equally
spaced sites on each sample’s surface, subsamples
were collected at three depths (surface exposed to the
room, surface exposed to the wall cavity, and
midpoint). Each subsample was roughly cylindrical
with diameter of about 1 cm and a depth of 2 mm. The
subsamples were digested as described above.
2.4. Ore analysis
A sample of ore found on a tailings pile in
Duenweg, MO, was also evaluated. The ore sample
consisted primarily of a hard, white to grey material,
with smaller portions of a black rosin-like substance
277
wedged into crevasses. Both the black and lighter
portions were analyzed for metals. The black portion
was also analyzed by X-ray powder diffraction.
2.5. Metals analysis
A Varian Liberty 150AX Inductively Coupled
Plasma spectrophotometer system operating at
220.353 nm for lead, 228.802 nm for cadmium, and
206.200 nm for zinc, 317.933 nm for calcium, and
417.206 nm for gallium was used for analysis of
sample digests. Calibration standards contained 500
mg/l calcium.
2.6. X-ray diffraction studies
X-ray diffraction analysis was carried out using
Scintag XDS 2000 X-ray diffractometer operating
with a copper X-ray source (Ka wavelength 1.542 A).
Thirteen samples, including one control sample, were
finely ground, suspended in C2H2Br4 (density=3.0 g/
cm3), and centrifuged, leading to separation into two
distinct layers. The fraction more dense than C2H2Br4
was isolated and analyzed by X-ray powder diffrac-
tion over the range of 2H=208 to 1408. Major
components in the mixture were identified by
comparison to library spectra. After the X-ray
analysis, the powders were digested and analyzed
for their metal content.
2.7. Optical studies
Seventeen plaster samples, two mortar samples,
and gravel samples from the four creeks were
prepared as thin sections embedded in epoxy,
mounted on microscope slides, and ground to
approximately 0.1-mm thickness. The thin sections
were evaluated under a polarizing microscope for
particulate shape and birefringence. Digital images of
these slides were recorded.
3. Results
3.1. Method refinement
A preliminary survey showed that sample solutions
contained 300–2000 mg/l calcium and that calcium at
278 P.M. Perry et al. / Science of the Total Environment 336 (2005) 275–281

this concentration significantly (up to 30%) enhanced Table 2

sensitivity to lead, cadmium, and zinc. Calibration Number of masonry mortar samples with concentrations of zinc,
lead, and cadmium in specified ranges, from Jasper and Newton
standards were therefore prepared containing 500 mg/ Counties (Jsp/Nwt), MO (29 samples), and Springfield (Spfd), MO
l calcium, a concentration sufficient to compensate (7 samples)
adequately (F10%) for this matrix effect. In addition, Range (mg/kg) Zinc Lead Cadmium
results for samples digested using the atmospheric
Jsp/Nwt Spfd Jsp/Nwt Spfd Jsp/Nwt Spfd
pressure method were not significantly different from
N25,000 5
those carried out according to EPA 3051 (EPA, 1994), 10,000 – b25,000 8
so the more efficient atmospheric pressure digestion 2500 – b10,000 8 1 1
procedure was used for most samples. Using this 1000 – b2500 2 1 2
method, detection limits were approximately 10 mg/ 250 – b1000 1 2 8 2 1
kg for Pb, Cd, and Zn. Samples were visibly 100 – b250 0 0 10 0 8
25 – b100 3 2 3 2 11 1
heterogeneous; replicates from a particular plaster or 10 – b25 1 1 0 1 4 1
masonry mortar sample usually agreed to within 20%. b10 1 0 5 2 5 5

3.2. Wall plaster and masonry mortar analyses

for a number of masonry mortar samples from the
Observations for lead, cadmium, and zinc concen- mining district, but not from the control area.
trations in plaster and masonry mortar samples are In several cases, more than one sample of plaster
summarized in Tables 1 and 2. Several samples from and/or mortar was taken from the same structure. In
sites within the Tri-State Mining District show several instances, both plaster and mortar samples
elevated concentrations of the three metals, with taken from the same structure showed elevated
zincJleadNcadmium. Over 75% of these plaster concentrations of metals. In several other cases,
samples contained more than 1000 mg/kg Zn, with samples were taken from the same structure but from
more than 25% containing more than 10,000 mg/kg sections which appeared to have been constructed at
Zn. Lead and cadmium concentrations were also different periods. There was no systematic correlation
elevated, though not as much as the zinc concen- between the heavy metal concentrations observed for
trations. In contrast, plaster samples from Springfield, distinct sections of the same home.
MO, contained low concentrations of all three metals, River sand and gravel taken from the creeks in the
with the highest concentrations of Zn, Pb, and Cd study area were shown to contain on average 420 mg/
found to be 64, 13, and 2 mg/kg, respectively. kg Zn, 110 mg/kg Pb, and 1.4 mg/kg Cd. The zinc and
Likewise, high heavy metal contents were observed cadmium levels are substantially lower than the vast
majority of plaster samples from the mining district.
Table 1 The lead level is not high enough to have caused the
Number of plaster samples with concentrations of zinc, lead, and observed levels in the samples considering that
cadmium in specified ranges, from Jasper and Newton Counties combining the aggregate with the other components
(Jsp/Nwt), MO (53 samples), and Springfield (Spfd), MO (24 of wall plaster dilutes the metals.
samples)
Range (mg/kg) Zinc Lead Cadmium 3.3. Particulates
Jsp/Nwt Spfd Jsp/Nwt Spfd Jsp/Nwt Spfd
N25,000 4 Based on visual inspection and the microscope
10,000 – b25,000 10 images of the thin sections, particulates in the plaster
2500 – b10,000 27 2 and mortar samples could be classified as either sharp-
1000 – b2500 1 0
250 – b1000 4 19
edged or rounded-edged; a few samples contained no
100 – b250 0 7 8 distinct particulates. All of the samples with high
25 – b100 4 5 14 30 concentrations of lead and cadmium contained sharp-
10 – b25 2 11 7 2 3 edged particulates; all samples with rounded-edge
b10 1 8 4 22 12 24 particulates or no particulates contained low levels of
 P.M. Perry et al. / Science of the Total Environment 336 (2005) 275–281
these elements. Under polarized microscope, the
sharp-edged particulates appeared to be microcrystal-
line and showed little or no birefringence. The
appearance and behavior of these particulates were
the same as that of authentic chert samples. In
contrast, the rounded-edge particulates were mostly
single crystals that showed birefringence consistent
with larger crystals of quartz.
3.4. Stratigraphic studies
Two-sided t-tests (aV0.05) of the stratigraphic data
indicated no statistically significant differences in Pb,
Cd, or Zn concentrations between the surface exposed
to the room interior, the surface exposed to the wall
cavity, and sample core. In some cases, a thin
finishing layer (smooth, containing little or no
particulates) on the exposed surface was analyzed
separately, with concentrations significantly less than
those of the bulk sample.
3.5. X-ray studies
Preliminary X-ray diffraction studies on ground
wall plaster samples showed the bulk components of
the plaster including silica minerals (which would
include chert), calcite, dolomite, and gypsum, but did
not provide unambiguous identification of zinc, lead,
or cadmium ore minerals, which were expected to be
present at relatively low levels. Suspension of samples
in C2H2Br4 allowed partial separation of components
with densityb3.0 g/cm3 (silica, calcite, dolomite,
gypsum) from those with higher density, including
sphalerite, hemimorphite, and galena. X-ray analysis
of the higher density components showed the distinct
diffraction patterns for sphalerite (ZnS) and/or hemi-
morphite (Zn4Si2O7(OH)2d H2O) for those samples
with higher Zn concentrations. Lead ore minerals
were expected to be present at levels too low to be
detected by this method (10% by mass is typically the
minimum requirement), but galena was observed in
one sample. All samples also showed diffraction
patterns for lighter minerals, indicating that the
grinding and floatation process did not allow complete
physical separation of components.
The higher density fractions used for X-ray studies
were also evaluated for their heavy metal contents. In
each case, these fractions accounted for at least 50%
279
of the zinc, lead, and cadmium of the original
samples. The samples were all found to contain
gallium ranging from 0.25 to 12.5 mg/kg, with the
exception of the control sample, which contained 0.07
mg/kg gallium. The mean gallium level for samples
shown to have significant amounts of Pb and Zn was
2.8 mg/kg.
3.6. Evaluation of the ore sample
The black portion of the ore was shown to be
mostly sphalerite by X-ray analysis. It also was shown
to contain 0.6% mass cadmium and 110 mg/kg
gallium by ICP analysis. The white and grey portions
of the ore contained 30 mg/kg lead and minimal zinc
and cadmium.
4. Discussion
High concentrations of zinc, lead, and cadmium
were found in a number of samples in the district
where mining was carried out, but were not observed
for samples from the Springfield control sites. The
two most likely explanations for the high heavy
metals content of the plasters and mortars are: (1) the
metals were introduced as components of the plasters
or (2) the heavy metals represent atmospheric
deposition (dust or aerosols) resulting from smelting
operations in the area. The data presented strongly
support the first hypothesis and contradict the second.
The stratigraphic studies showed that the composi-
tions of the wall plaster samples were uniform with
depth, with no systematic differences in the heavy
metal concentrations when comparing surfaces
exposed to the room interior, wall cavity, or midpoint.
This is consistent with the heavy metals being
introduced as integral components of the plasters,
but incompatible with any plausible surface contam-
ination. In addition, the observation by X-ray dif-
fraction of two common zinc ore minerals, sphalerite
and hemimorphite, also precludes any surface depo-
sition mechanism.
The data also identify the aggregate present in the
high-heavy metals plasters and mortars as arising from
mine tailings rather than river sand. Mine tailings,
created by crushing ore, have sharp edges and contain
residual metals at elevated concentrations. In addition,
280 P.M. Perry et al. / Science of the Total Environment 336 (2005) 275–281
the microcrystalline composition of the sharp-edged
particles is consistent with chert, which was present in
abundance in the Tri-State ores. The observation by
X-ray diffraction of the zinc ores, sphalerite and
hemimorphite, and the elevated levels of gallium are
consistent with mine tailings. The correlation of high
metals contents to particulate shape is consistent with
the inclusion of granular tailings in place of river
sand. In contrast, sand and gravel taken from within or
near the study area showed relatively low levels of
heavy metals, which cannot account for the concen-
trations observed in plasters and mortars. In addition,
edges of river sand granules are rounded because of
weathering.
In the samples with higher levels of heavy metals,
the metals were almost always present in relative
concentrations ZnJPbNCd, but the ratio of the three
elements varied over a wide range. This variation is
consistent with mine tailings as the primary source of
heavy metals. Tailings in different areas are expected
to have a wide concentration range for residual metals
because of local variations in ore contents and
historical variations in mining and smelting processes,
and because weathering mobilizes the heavy metals.
The evidence presented here is fully consistent
with the hypothesis that mine tailings were used in
wall plaster and masonry mortar within the mining
district. We cannot make any estimate of the fraction
of structures containing tailings because samples were
collected based on accessibility to structures and do
not represent a systematic, randomized survey. How-
ever, we note that mine tailings represented a
convenient and inexpensive alternative to river sand,
so their widespread use in construction materials
would appear very plausible.
Elevated lead and cadmium were frequently
observed in the samples from the mining district,
and in several samples, concentrations were above
EPA target levels for soil excavation. Plaster and
masonry mortar in many of the older occupied
structures were visibly deteriorating, exposing occu-
pants to contaminated dust. Demolition of buildings
could also expose both workers and neighbors to dust
containing elevated metals concentrations. We have
neither the facilities nor expertise to determine the
health consequences of this exposure. However, we
note that leaded paint and lead plumbing are regularly
evaluated as possible contributors to lead exposure,
but this additional source, perhaps rare outside of
mining districts, is not. We suggest that the potential
contribution of dust from contaminated plasters and
masonry mortars to lead and cadmium exposure
should be further evaluated.
Acknowledgments
We would like to thank John Bailey (Joplin
Building Department), Mary Beth Houser (City of
Springfield), Tony Moehr (Jasper County Health
Department), and John Ford (Neosho Daily News),
who helped us identify sampling sites and procure
samples. We also thank Dr. Thomas Plymate and Dr.
Charles Rovey (Southwest Missouri State University
Department of Geography, Geology, and Planning) for
assistance with the X-ray diffraction and optical
studies. Funding was provided by Southwest Missouri
State University.
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