Executive
Summary.
We
have
investigated
potential
sources
of
lead
(Pb)
in
soils
near
the
formerly
operating
Exide
Technologies
secondary
lead
smelter
located
at
Laureldale,
PA.
The
specific
aim
herein
is
to
address
the
following
questions:
A)
is
there
evidence
of
significant
lead
accumulation
in
Reading-area
soils
as
a
result
of
contributions
from
Exides
historic
atmospheric
emissions
(i.e.,
stack
emissions
and
fugitive
dusts);
and
B)
are
soil
levels
exceeding
the
threshold
of
concern
(650
parts
per
million
lead,
abbreviated
herein
as
ppm
Pb)
identified
by
a
2000
EPA
Administrative
Order
on
Consent
with
the
company.
In
order
to
investigate
whether
Exide
is
a
major
contributing
source
of
Pb,
we
propose
the
hypothesis
that
emissions
from
secondary
lead
smelting
will
contribute
the
element
antimony
(chemical
symbol
Sb,
abbreviated
as
such
herein)
in
quantities
that
are
correlated,
and
proportional
to,
the
Pb
concentrations.
The
basis
of
this
hypothesis
is
that
antimony
is
present
in
the
feedstock
processed
at
secondary
lead
smelters,
the
majority
of
which
is
recycled
automotive
and
industrial
batteries;
lead-acid
battery
technology
long
used
Sb
as
an
alloying
agent
in
metal
components
such
as
posts,
grids,
cables,
and
terminals.
Accordingly,
if
Exide
is
a
significant
contributor,
we
expect
to
also
find
elevated
soil
Sb
concentrations
that
are
significantly
correlated
with
Pb
concentrations
in
Exide-
vicinity
soils.
Alternatively,
if
Exide
is
not
a
significant
contributor,
then
we
expect
to
find
an
absence
of
elevated
Sb
concentrations
even
when
soil
Pb
concentrations
are
elevated
as
a
result
of
other
anthropogenic
sources.
We
investigated
this
problem
and
the
hypothesis
stated
above,
through
a
study
conducted
in
2016
and
2017.
In
May
and
July
2016,
soil
samples
were
collected
as
30
cm,
5.2
cm
i.d.
soil
cores,
and/or
surface
composites
of
the
top
5
cm
of
the
soil
profile.
From
the
soil
cores,
we
removed
the
top
5
cm
of
material,
analyzed
this
portion,
while
examining
Pb
concentrations
at
>
5
cm
depth
from
a
limited
number
of
sites.
Soil
samples
were
collected
through
collaboration
of
the
following
individuals:
Michael
E.
Ketterer
(MSU
Denver),
Delilah
DeWilde
(MSU
Denver),
Karolina
Ryncarz
(MSU
Denver),
Nathan
Aist
(MSU
Denver),
Seth
Youtsey
(MSU
Denver),
Nicole
C.
Brambila
(Reading
Eagle
Company),
Mike
Urban
(Reading
Eagle
Company),
and
Jillian
Clemente
(Reading
Eagle
Company).
The
study
obtained
soil
samples
from
81
residential
locations
and
15
additional
non-residential
locations;
the
majority
of
these
locations
were
within
2
km
of
the
Exide
facility.
A
map
depicting
the
sampled
locations
is
depicted
in
Figure
1.
At
~
75%
of
the
locations,
single
grab
samples
were
collected
as
30
cm
depth,
5.2
cm
diameter
soil
cores
from
a
randomly
chosen
location
within
a
given
property.
Our
analytical
work
concentrated
on
this
0-5
cm
depth
interval
for
two
reasons:
A)
it
is
the
most
accessible
material
at
the
surface,
and
therefore,
the
material
most
relevant
to
human
exposure;
and
B)
if
an
atmospheric
lead
contamination
source
is
present,
the
enrichment
is
most
prominent
at
the
soil
surface.
For
a
subset
of
the
locations,
we
collected
duplicate
soil
cores
from
additional
locations
within
the
same
property,
and/or
composite
samples,
the
latter
consisting
of
multiple
0-
5
cm
depth
intervals
from
a
coring
device
that
were
then
combined
in
the
field.
Soil
samples
were
shipped
to
the
Chemistry
Department
and
were
processed
therein;
material
was
dried,
pulverized,
and
subjected
to
chemical
analyses
to
measure
the
elements
Pb
and
Sb.
Throughout
the
project,
samples
were
handled
following
chain-of-
custody
practices
to
preserve
the
integrity
of
the
samples.
Final
analytical
sub-samples
of
nominal
0.25
grams
were
taken;
sub-samples
were
dry-ashed
at
450o
C
for
2-3
hours
to
2
remove
organic
matter,
and
the
mineral
residues
were
dissolved
with
a
mixture
of
nitric
acid
and
hydrofluoric
acid,
followed
by
treatment
with
boric
acid.
The
vast
majority
of
the
samples
were
analyzed
for
both
Sb
and
Pb
by
inductively
coupled
plasma
mass
spectrometry;
for
a
subset
of
the
samples,
we
measured
Pb-only
using
the
technique
of
flame
atomic
absorption
spectrometry.
The
elements
lead
and
antimony
were
measured
and
reported
as
concentrations
in
parts
per
million
by
mass;
the
terms
ppm,
micrograms
per
gram,
and
the
abbreviation
g/g
are
all
synonymous,
and
we
use
ppm
herein.
The
uncertainties
in
all
measurements
are
conservatively
estimated
as
10%
relative,
signifying,
a
result
of
300
ppm
should
be
interpreted
as
300
30.
It
is
likely
that
many
of
the
residential
soil
sampling
locations
are
disturbed
and
do
not
contain
the
entire
deposited
inventory
of
anthropogenic
lead.
The
net
result
of
these
processes
is
that
lower
Pb
concentrations
are
found
than
would
be
otherwise
expected.
No
attempt
has
yet
been
made
to
investigate
soil
disturbances
via
measurements
of
137Cs
or
plutonium
as
indicators
of
soil
disturbance.
Concentrations
of
antimony
(Sb)
were
also
measured
in
the
soil
samples.
In
a
general
way,
these
indicate
significant
correlation
between
Sb
and
Pb,
which
is
3
consistent
with
a
secondary
lead
smelting
contribution
from
the
Exide
facility.
The
basis
for
this
association
is
that
secondary
lead
smelting
feed
contained
Sb
as
an
alloying
agent
mixed
with
Pb
metals
(e.g.,
battery
grids
and
terminals).
Soils
containing
>
1000
ppm
Pb,
obrtained
from
locations
close
to
Exide,
consistently
exhibited
elevated
Sb,
with
Sb/Pb
~
0.02
0.05.
Additional
data
points
from
residential
locations
>
5
miles
from
Exide,
especially
those
with
older
housing
and
close
to
vehicle
traffic,
would
be
ideally
needed
to
expand
upon
this
analysis,
and
to
better
delineate
contributions
from
Exide
vs.
other
human-derived
lead
sources.
Although
it
is
clear
that
Exide
is
a
contributing,
major
source
to
the
Pb
inventory
in
proximal
soils,
it
is
difficult
to
quantitatively
model
or
apportion
the
Exide-derived
contribution
to
the
soils
without
better
definition
of
two
items:
A)
the
expected
Sb/Pb
ratio
from
Exide
emissions;
and
B)
the
Sb/Pb
ratios
characteristic
of
lead-
contaminated
properties
from
the
Reading
vicinity,
but
from
more
distant
locations
(i.e.,
~
5
km
or
greater
distances)
unaffected
by
Exide
and
influenced
solely
by
non-
Exide
sources.
Figure
1.
Soil
collection
locations
for
the
2016
sampling
undertaken
by
MSU
Denver
and
the
Reading
Eagle
Company.
4
Introduction.
Many
studies
have
reported
elevated
concentrations
of
lead
(Pb)
in
soils
in
the
proximity
of
secondary
Pb
smelting
facilities.
These
facilities
recover
Pb
from
industrial
scrap,
using
thermal
and
chemical
processes;
the
most
important
stream
of
Pb-
bearing
scrap
is
automotive
and
industrial
lead-acid
batteries.
Several
workers
have
reported
Pb
contamination
in
the
proximity
of
presently
operating
or
former
lead
secondary
smelting
sites
(Kimbrough
et
al.,
1995;
Kimbrough
and
Suffet,
1996;
Amter
and
Eckel,
1996;
Kimbrough
and
Cardner,
1999;
Eckel
et
al.,
2002;
Machemer
et
al.,
2007).
The
2002
study
of
Eckel
et
al.
reported
the
use
of
the
element
antimony
(Sb)
as
a
pathfinder
element
for
contamination
emanating
from
secondary
lead
smelting.
The
latter
element
was
long
used
in
automotive
and
industrial
lead-acid
batteries
as
an
alloying
agent
in
Pb
metal,
to
render
the
Pb
components
harder
and
more
durable
with
respect
to
mechanical
integrity.
For
this
reason,
Eckel
et
al.
discussed
the
potential
use
of
Sb/Pb
ratios
as
fingerprints
of
secondary
lead
smelting
contamination,
and
the
use
of
this
ratio
as
a
means
of
discriminating
between
secondary
lead
smelting
contamination
vs.
other
common
anthropogenic
lead
sources
(e.g.,
paint,
historic
gasoline
emissions
from
tetraethyl
lead,
other
industrial
sources).
Eckel
et
al.
reported
a
Sb/Pb
range
of
0.0016
0.034
for
various
recognized
former
secondary
Pb
smelting
sites
throughout
the
US.
Following
this
same
reasoning,
Machemer
et
al.
(2007)
conducted
a
study
of
Sb
and
Pb
concentrations
in
the
proximity
of
a
Pb
battery
facility
located
at
Greer,
SC;
these
workers
found
a
clear
correlation
between
Sb
and
Pb
concentrations
with
a
Sb/Pb
ratio
on
the
order
of
~
0.01
as
shown
below
in
Figure
2:
Figure
2.
Relationship
between
Sb
and
Pb
concentrations
found
in
the
study
of
Machemer
et
al.
(2007)
in
soils
from
Greer,
SC,
from
locations
in
the
proximity
of
a
battery
manufacturing
facility.
Refer
to
Figure
5
of
Machemer
et
al.
(2007).
5
Machemer
et
al.
(2007)
concluded
that
the
lead
production
facility
exhibited
a
measurable
footprint
in
soils
in
its
immediate
proximity;
the
Sb
and
Pb
concentrations
were
relatively
well
correlated,
as
can
be
seen
by
the
green
data
points
(trailer
park
soil
litter)
in
Figure
2.
These
workers
also
found
that
soils
from
other,
more
distant
locations
adjacent
to
heavily
traveled
roads
did
not
exhibit
the
same
trend;
Sb
and
Pb
concentrations
were
relatively
uncorrelated,
and
Sb
concentrations
were
found
to
be
mainly
<
1
ppm
even
when
Pb
concentrations
are
elevated.
This
trend
can
be
seen
in
the
black
data
points
for
the
roadside
litter
soils.
In
this
study,
we
seek
to
investigate
the
Reading
vicinity,
to
investigate
whether
Exide
is
a
major
contributing
source
of
Pb
in
soils
near
the
plant.
Previous
studies
near
secondary
lead
smelting
facilities
indicate
a
relatively
intense
effect
but
within
a
very
limited
spatial
range
emanating
from
the
facility
(e.g.,
Eckel
et
al.,
2002;
Machemer
et
al.,
2007);
therefore,
we
envisioned
uncovering
similar
effects
in
the
immediate
vicinity
of
Exide.
This
facility
has
been
operating
since
the
1930s
and
the
proximal
area
has
received
cumulative
emissions
from
stacks
and
surface
level
fugitive
dusts.
During
the
previous
decade,
Exide,
under
US
EPAs
oversight,
remediated
220
properties
close
to
the
facility
that
exhibited
soil
Pb
concentrations
exceeding
an
action
level
of
650
ppm.
The
specific
aim
herein
is
to
address
the
following
questions:
A)
is
there
evidence
of
significant
lead
accumulation
in
Reading-area
soils
as
a
result
of
contributions
from
Exides
historic
atmospheric
emissions
(i.e.,
stack
emissions
and
fugitive
dusts);
and
B)
are
soil
levels
exceeding
the
threshold
of
concern
(650
parts
per
million
lead,
abbreviated
herein
as
ppm
Pb).
Sampling
Methods.
In
May
and
July
2016,
soil
samples
were
collected
as
30
cm,
5.2
cm
i.d.
soil
cores,
and/or
surface
composites
of
the
top
5
cm
of
the
soil
profile.
Throughout
the
project,
samples
were
handled
following
chain-of-custody
practices
to
preserve
the
integrity
of
the
samples.
Steel
tubing
(electrical
conduit,
purchased
at
home
renovation
stores,
5.2
cm
internal
diameter)
was
cut
into
40
cm
lengths;
these
tubes
were
driven
into
the
soil
using
a
3
lb
sledgehammer,
then
retracted;
the
top
of
the
soil
core
was
packed
with
paper
towel
to
maintain
its
integrity,
and
the
bottom
of
the
soil
core
was
taped
to
prevent
material
from
being
lost.
Soil
samples
were
collected
through
collaboration
of
the
following
individuals:
Michael
E.
Ketterer
(MSU
Denver),
Delilah
DeWilde
(MSU
Denver),
Karolina
Ryncarz
(MSU
Denver),
Nathan
Aist
(MSU
Denver),
Seth
Youtsey
(MSU
Denver),
Nicole
C.
Brambila
(Reading
Eagle
Company),
Mike
Urban
(Reading
Eagle
Company),
and
Jillian
Clemente
(Reading
Eagle
Company).
The
study
obtained
soil
samples
from
81
residential
locations
and
15
additional
non-residential
locations;
the
majority
of
these
locations
were
within
2
km
of
the
Exide
facility.
A
map
depicting
the
sampled
locations
is
depicted
in
Figure
1.
At
~
75%
of
the
locations,
single
grab
samples
were
collected
as
30
cm
depth,
5.2
cm
diameter
soil
cores
from
a
randomly
chosen
location
within
a
given
property.
Our
analytical
work
concentrated
on
this
0-5
cm
depth
interval
for
two
reasons:
A)
it
is
the
most
accessible
material
at
the
surface,
and
therefore,
the
material
most
relevant
to
human
exposure;
and
B)
if
an
atmospheric
lead
contamination
source
is
present,
the
enrichment
is
most
prominent
at
the
soil
surface.
For
a
subset
of
the
locations,
we
collected
duplicate
soil
cores
from
additional
locations
within
the
same
6
property,
and/or
composite
samples,
the
latter
consisting
of
multiple
0-5
cm
depth
intervals
from
a
coring
device
that
were
then
combined
in
the
field.
All
samples
received
a
code
name
of
RED-xxx,
where
RED
is
the
study
code,
and
xxx
is
an
integer
corresponding
to
the
sample
location
and
collection
order.
For
purposes
of
ensuring
the
confidentiality
of
the
participants
of
the
study,
and
protecting
their
interests
as
property
owners,
all
samples
will
be
referred
to
in
this
report
using
these
code
names,
and
no
residential
locations
will
be
described
by
street
address.
We
will
also
decline
to
identify
distance/direction
associated
with
individual
sampled
residential
locations
in
order
to
prevent
reverse
engineering
of
specific
addresses.
However,
non-residential
locations
will
be
identified
and
described
using
appropriate
information
to
reasonably
affix
their
geographic
locations.
Laboratory
Analyses.
We
removed
the
top
5
cm
of
material
by
cutting
the
entire
tube
and
soil
core
using
an
electric
reciprocating
saw,
being
careful
to
recover
and
weigh
the
entire
0-5
cm
core
interval.
In
selected
cores,
we
performed
further
sectioning
of
the
soil
into
5-
10
cm,
and
>
10
cm
intervals
in
order
to
examine
Pb
depth
profiles.
The
soil
intervals
were
oven-dried
at
105o
C
for
several
days
to
remove
moisture;
thereafter,
material
was
ground
to
~
1
mm
or
smaller
particle
size
using
a
large
porcelain
mortar/pestle.
The
partially
pulverized
material
was
sub-sampled
to
obtain
15-20
grams
of
material
that
was
additionally
ground
in
a
small
porcelain
mortar/pestle
to
produce
particles
of
<
0.1
mm
approximate
diameter;
this
finely
ground
material
was
subsequently
used
for
chemical
analysis.
From
the
finely
ground
material,
analytical
sub-samples
of
0.23
0.27
grams
were
weighed
into
2
mL
Pyrex
vials
with
an
analytical
balance
to
the
nearest
0.0001
grams;
the
material
was
dry-ashed
at
450o
C
for
2-3
hours
to
remove
organic
matter;
the
mineral
residues
were
transferred
quantitatively
to
50
mL
polypropylene
centrifuge
tubes.
Thereafter,
2.5
mL
of
concentrated
aqueous
nitric
acid
(70%
by
mass,
approximately
16
moles/liter)
and
1.5
mL
of
concentrated
aqueous
hydrofluoric
acid
(48%
by
mass,
approximately
29
moles/liter)
were
added
to
the
residue,
and
the
tubes
were
capped.
The
mixtures
were
heated
in
a
convection
oven
at
75-80o
C
for
16
hours;
after
opening,
de-ionized
water
was
added,
along
with
0.93
grams
of
boric
acid,
which
reacts
with
and
complexes
the
un-reacted
hydrofluoric
acid.
The
mixtures
were
diluted
to
50
mL
total
volume,
mixed
and
heated
briefly
in
a
microwave
oven
to
ensure
complete
dissolution
of
the
boric
acid
and
its
reaction
with
the
hydrofluoric
acid.
Inspection
of
the
solutions
indicated
that
the
dissolution
of
the
soil
was
essentially
complete;
in
some
cases,
<
1
mg
of
un-dissolved
visible
residue
was
apparent.
In
our
laboratorys
experience,
this
procedure
quantitatively
dissolves
most
soils
and
quantitatively
recovers
the
elements
Sb
and
Pb
from
a
variety
of
soil
types.
Quality
control
measures
in
the
dissolutions
consisted
of
the
preparation
of
blanks
(containing
the
acids
and
in
the
same
type
of
container,
but
no
soil),
duplicates
of
selected
samples,
and
the
preparation
of
a
control
sample
(NIST
1648,
Urban
Air
Particulate)
having
established
Sb
and
Pb
concentrations.
The
elements
Sb
and
Pb
were
measured
using
the
technique
of
inductively
coupled
plasma
mass
spectrometry
(ICPMS).
Sample
solutions
were
further
diluted
by
a
factor
of
50
(0.2
7
mL
of
the
original
digest
+
9.8
mL
of
1%
aqueous
nitric
acid).
The
diluted
samples
also
contained
10
g/L
of
the
elements
rhodium
(Rh)
and
iridium
(Ir)
as
internal
standards.
Matrix-matched
calibration
standards
were
prepared
that
contained
varying
concentrations
of
Sb
and
Pb
while
containing
the
same
10
g/L
of
Rh
and
Ir;
an
independent
calibration
verification
standard
was
also
prepared
that
contained
Sb
and
Pb
from
stock
solutions
obtained
from
different
commercial
suppliers.
Throughout
the
course
of
the
analytical
run
on
the
ICPMS
instrument,
one
of
the
calibration
standards
was
re-
analyzed
to
ensure
stability
of
the
calibration
curve.
A
Perkin-Elmer
ELAN
9000
ICPMS
instrument,
located
in
the
Chemistry
Department
at
MSU
Denver,
was
utilized
for
these
measurements.
The
ICPMS
procedures
are
similar
to
those
described
by
USEPA
in
Method
6020
for
ICPMS
analyses
of
environmental
soil,
water,
sediment
and
sludge
samples.
The
technique
of
flame
atomic
absorption
spectrometry
(FAAS)
was
used
to
measure
lead
in
selected
samples;
this
was
necessary
on
account
of
temporary
non-availability
of
the
ICPMS
instrument.
The
element
Sb
could
not
be
practicably
measured
using
FAAS,
however.
A
Thermo
flame
AAS
instrument,
also
located
in
the
Chemistry
Department
at
MSU
Denver
was
utilized.
In
the
flame
AAS
analysis;
the
50
mL
soil
digests
are
directly
analyzed
without
additional
dilution,
and
compared
vs.
a
calibration
curve
prepared
from
matrix
matched
solution
standards
of
0,
2,
5,
10,
and
20
mg/L
Pb.
A
few
samples
required
dilution
to
fall
within
the
linear
calibration
range.
For
both
the
ICPMS
and
FAAS
analyses,
the
solution
concentrations
determined
were
converted
into
soil
concentrations
using
the
analytical
sub-sample
masses
and
appropriate
volumetric
dilution
factors.
All
un-sectioned
soil
cores,
the
dried/ground
processed
soils,
and
all
solutions
prepared
from
the
samples,
have
been
archived
should
additional
study
or
questions
arise.
Results.
The
analysis
of
blanks
yielded
limits
of
detection
for
the
ICPMS
measurements
of
0.1
ppm
Sb
and
2
ppm
Pb;
using
flame
AAS,
the
Pb
detection
limit
was
30
ppm.
These
limits
of
detection
were
sufficiently
low
so
as
to
not
significantly
encumber
the
determination
of
either
Sb
or
Pb
in
the
levels
actually
found
in
the
unknown
soils.
The
duplicate
analysis
of
12
specific
samples,
conducted
using
separately
weighed/dissolved/analyzed
0.25
gram
soil
sub-samples,
indicated
excellent
agreement
among
these
duplicates,
as
shown
in
Table
1.
The
results
for
the
determination
of
Sb
and
Pb
in
NIST
1648
(Urban
Air
Particulate)
generally
indicate
good
agreement
between
the
found
vs.
referee
concentrations.
For
Sb,
a
concentration
of
36.6
ppm
Sb
was
found,
which
reflects
~
81%
recovery
vs.
the
non-
certified
concentration
of
45
ppm
Sb
reported
by
NIST.
For
Pb,
the
analysis
by
flame
AAS
reported
6750
ppm
Pb,
with
5970
ppm
Pb
being
found
by
the
ICPMS
technique;
these
compare
well
to
the
certified
Pb
concentration
of
6550
80
ppm.
Accordingly,
while
small
negative
biases
may
exist
in
the
Sb
concentrations,
the
reference
material
results
generally
indicate
that
the
concentrations
of
Pb
and
Sb
found
in
the
unknown
samples
may
be
reliably
used
as
a
single
batch
for
the
interpretations
presented
herein,
and
if
biases
exist,
they
are
relatively
small
and
likely
affect
all
of
the
unknown
samples
to
a
similar
extent.
Complete
depth
profiles
for
all
soil
core
intervals
(0-5
cm,
5-120
cm,
and
>
10
cm)
were
obtained
for
a
total
of
10
soil
cores;
these
results
are
given
in
Table
2.
The
depth
profiles
8
generally
indicate
that
concentrations
of
both
Sb
and
Pb
decrease
with
depth;
nevertheless,
elevated
concentrations
of
both
elements,
compared
to
the
Earths
crusts
concentrations
of
~
0.2-1.0
ppm
Sb
and
20-50
ppm
Pb,
are
both
evident
at
depths
of
up
to
30
cm.
The
elevation
at
the
surface
is
consistent
with
a
proximal
source
of
atmospherically
deposited
contamination,
and
this
surface
elevation
mirrors
what
has
been
found
near
other
secondary
lead
smelting
sites
(Kimbrough
et
al.,
1995;
Kimbrough
and
Suffet,
1996;
Amter
and
Eckel,
1996;
Kimbrough
and
Cardner,
1999;
Eckel
et
al.,
2002;
Machemer
et
al.,
2007).
In
Table
3,
results
for
Sb
and
Pb
concentrations
are
shown
for
all
of
the
study
locations.
All
of
these
results
refer
to
the
top
5
cm
soil
interval.
Most
samples
were
collected
as
cores
from
a
single,
randomly
selected
location
within
a
property;
others
are
surface
composites.
For
five
to
ten
individual
depth
intervals
of
the
top
5
cm
from
different
points
within
the
property
of
0-5
cm
were
obtained
with
a
5.2
mm
diameter
steel
tube,
and
these
intervals
were
combined
in
the
field.
Samples
are
designated
in
Table
3
as
either
30
cm
core
or
surf
comp
as
appropriate.
Residential
properties
are
not
identified
by
address;
non-
residential
locations
are
described
as
to
their
locations.
Note
that
all
samples
have
Pb
concentrations
reported;
in
some
cases,
results
for
Sb
are
not
given,
as
they
were
not
determined;
these
Pb
concentrations
were
measured
by
flame
AAS,
owing
to
the
unavailability
of
the
ICPMS
instrument
at
that
time.
Discussion.
As
previously
stated,
the
first
objective
was
to
compare
the
Pb
concentrations
encountered
vs.
the
650
ppm
threshold
previously
applied
in
remediation
efforts.
An
evaluation
of
the
results
shown
in
Table
3
indicates
that
the
overwhelming
majority
of
the
sampled
locations
exhibited
Pb
at
less
than
the
threshold
concentration
of
650
ppm.
The
average
Pb
concentration
of
all
samples
shown
in
Table
3
was
394
ppm,
with
a
standard
deviation
of
904
ppm.
The
median
concentration
was
181
ppm;
the
25th,
75th
and
90th
percentiles
of
Pb
concentrations
were
117,
274,
and
654
ppm,
respectively.
Only
10%
of
the
samples
(n=12)
exhibited
Pb
concentrations
exceeding
the
650
ppm
threshold;
moreover,
only
nine
of
these
samples
were
from
yards
of
residences,
with
the
other
three
being
obtained
at
non-residential,
wooded
locations.
The
nine
residential
samples
include
seven
unique
properties,
with
three
cores
having
been
obtained
from
one
specific
property.
Accordingly,
this
study
has
uncovered
only
seven
individual
residences
which
revealed
Pb
exceeding
650
ppm;
as
many
residences
were
collected
from
within
~
1
mile
of
the
Exide
location,
this
Pb
trend
suggests
the
absence
of
a
very
widespread,
pervasive
problem
with
elevated
soil
Pb
levels.
Nevertheless,
our
findings
indicate
the
need
for
further
study
and
possible
decisions
in
favor
of
remediation,
at
these
few
specific
residences.
It
also
must
be
noted,
however,
that
the
great
majority
of
the
samples
(n
=
108,
89%)
exhibited
>
100
ppm
Pb;
these
samples
all
contain
some
significant
levels
of
anthropogenic
lead
(likely
from
a
mixture
of
Exide
and
other
sources),
although
their
Pb
concentrations
do
not
indicate
severe
contamination.
We
emphasize
that
most
residences
were
sampled
by
collection
of
a
single
soil
core
from
a
single,
specific
randomly
selected
point
within
the
property;
this
indicates
the
presence
of
at
least
some
degree
of
anthropogenic
lead
contamination
within
the
sampled
portion
of
most
locations.
The
motivation
for
collecting
samples
in
this
manner
was
to
obtain
a
snapshot
of
a
large
number
of
residences
without
creating
an
enormous
sample
set
of
9
many
hundreds
or
thousands
of
field
samples.
We
caution
that
the
Pb
results
do
not
describe
an
average
result
for
the
sampled
property;
in
fact,
large
variations
in
lead
concentrations
within
a
single
residential
parcel
are
commonplace
in
human-impacted
environments.
Accordingly,
we
offer
the
opinion
that
additional
follow-up
sampling
is
warranted
to
investigate
the
spatial
distribution
of
lead,
and
more
closely
compare
the
found
concentrations
vs.
the
650
ppm
Pb
threshold,
to
ascertain
whether
contaminated
soil
should
be
removed
from
the
premises,
or
otherwise
abated,
to
prevent
human
contact
and
exposure.
Conversely,
even
when
residences
exhibit
<
650
ppm
Pb,
this
finding
does
not
imply
that
the
entire
property
is
clean,
and
properties
with
single-point
results
of
<
650
ppm
may
well
contain
other
specific
locations
within
the
property
with
soil
levels
exceeding
650
ppm.
The
ratios
(Sb/Pb)
were
evaluated
for
the
samples;
this
information
is
best
viewed
as
a
scatter
plot
of
ppm
Sb
vs.
ppm
Pb,
as
shown
in
the
results
of
Machemer
et
al.
(2007)
depicted
in
Figure
1.
The
results
of
the
present
Reading
study
are
given
in
Figures
3a
and
3b.
Our
results
bear
similarity
to
those
of
Machemer
et
al.
(2007);
it
appears
that
there
is
a
general
trend
of
increasing
Sb
concentrations
when
Pb
concentrations
are
elevated,
congruent
with
an
Exide
source
contribution.
The
Sb
elevation
is
especially
pronounced
for
the
six
samples
containing
>
1000
ppm
Pb
(Figure
3b).
It
is
noted
that
these
six
samples
exhibit
Sb
concentrations
ranging
from
33
to
197
ppm
Sb.
The
six
samples
with
Pb
>
1000
ppm
have
Sb/Pb
ratios
ranging
from
0.0197
to
0.0512;
these
ratios
are
similar
to
those
encountered
in
previous
studies
of
the
environs
of
secondary
lead
smelters
(Kimbrough
et
al.,
1995;
Kimbrough
and
Suffet,
1996;
Amter
and
Eckel,
1996;
Kimbrough
and
Cardner,
1999;
Eckel
et
al.,
2002;
Machemer
et
al.,
2007).
While
we
cannot
completely
rule
out
the
possibility
that
other,
non-Exide
sources
of
anthropogenic
Sb
are
contributing
Sb
inventory
to
the
samples,
the
gross
elevations
in
Sb
encountered
in
the
high-Pb
samples
appear
to
be
difficult
to
explain
by
sources
other
than
Exide.
A
fairly
comprehensive
discussion
of
the
geochemical
baseline
Sb
concentrations
in
the
Earths
surface
environment
is
given
in
Reimann
et
al.
(2010).
Table
1
of
the
Reimann
et
al.
(2010)
paper
quotes
0.3
ppm
as
an
average
concentration
of
Sb
in
the
upper
continental
crust;
an
average
coal
concentration
of
2
ppm
is
given
therein.
This
reference
also
reports
averages
and
statistics
for
a
large
number
of
other
published
studies
regarding
the
Sb
concentrations
in
surface
soils;
the
vast
majority
of
these
concentrations
are
<
1
ppm.
Nevertheless,
there
is
insufficient
information
from
our
present
studys
results
to
ascertain
the
fingerprint
of
Sb
concentrations
for
soils
having
elevated
Pb
arising
from
sources
besides
Exide.
We
have
sampled
a
cluster
of
several
residences
located
several
km
to
the
southwest
of
Exide
(refer
to
Figure
1).
A
good
case
in
point
is
Sample
Red-107,
which
exhibited
596
ppm
Pb
but
only
1.15
ppm
Sb.
The
Sb/Pb
ratio
herein
is
only
0.0019,
or
about
one
order
of
magnitude
smaller
than
encountered
from
the
proximal,
>
1000
ppm
Pb
sample
group
(Figure
3b).
Had
this
specific
sample
contained
a
significant
Exide
contribution
(which
it
apparently
does
not),
one
would
expect
the
Sb
concentration
therein
to
be
>
10
ppm.
10
We
find
that
additional
information
on
soil
Sb
and
Pb
concentrations
from
other
areas
of
Reading,
more
distant
from
Exide,
would
be
desirable
to
further
investigate
the
comparative
Sb/Pb
fingerprints
of
Exide-affected
vs.
other
anthropogenic
Pb-affected
soils.
It
is
plausible
to
envision
a
second
trend
line
on
Figures
3a
and
3b,
of
much
shallower
slope,
which
reflects
the
association
between
Sb
and
Pb
for
non-Exide
affected
(but
elevated
Pb)
soils
in
the
Reading
vicinity.
An
additional
limitation
of
this
study
is
that
we
lack
actual
samples
of
emissions
(air
filters,
air
pollution
control
baghouse
dust,
fugitive
dusts,
or
other
process
samples).
We
believe
it
would
be
appropriate
to
have
these
samples,
as
well
as
more-distant
Reading-area
samples,
in
order
to
construct
an
actual
apportionment
model
based
upon
Sb/Pb.
While
this
is
not
possible
at
present,
we
nevertheless
find
that
there
is
a
clear
pattern
of
elevated
Sb
while
Pb
is
elevated,
indicating
that
Exide
is
an
important
contributor
to
the
Pb
inventory
in
soils
obtained
proximal
to
the
facility.
The
vast
majority
(n=73,
90%)
of
the
residential
soil
sampling
locations
exhibited
lead
(Pb)
concentrations
of
less
than
650
ppm
in
the
0-5
cm
depth
interval.
Eight
residences
(10%
of
total
sampled)
exhibited
one
or
more
samples
exceeding
650
ppm
Pb
in
the
top
5
cm
of
the
soil
profile.
Only
one
residential
location
exhibited
soil
Pb
concentrations
>
1000
ppm
Pb
in
the
top
5
cm
of
soil.
11
expected.
No
attempt
has
yet
been
made
to
investigate
soil
disturbances
via
measurements
of
137Cs
or
plutonium
as
indicators
of
soil
disturbance.
Concentrations
of
antimony
(Sb)
were
also
measured
in
the
soil
samples.
In
a
general
way,
these
indicate
significant
correlation
between
Sb
and
Pb,
which
is
consistent
with
a
secondary
lead
smelting
contribution
from
the
Exide
facility.
The
basis
for
this
association
is
that
secondary
lead
smelting
feed
contained
Sb
as
an
alloying
agent
mixed
with
Pb
metals
(e.g.,
battery
grids
and
terminals).
Soils
containing
>
1000
ppm
Pb,
obrtained
from
locations
close
to
Exide,
consistently
exhibited
elevated
Sb,
with
Sb/Pb
~
0.02
0.05.
Additional
data
points
from
residential
locations
>
5
miles
from
Exide,
especially
those
with
older
housing
and
close
to
vehicle
traffic,
would
be
ideally
needed
to
expand
upon
this
analysis,
and
to
better
delineate
contributions
from
Exide
vs.
other
human-derived
lead
sources.
Although
it
is
clear
that
Exide
is
a
contributing,
major
source
to
the
Pb
inventory
in
proximal
soils,
it
is
difficult
to
quantitatively
model
or
apportion
the
Exide-derived
contribution
to
the
soils
without
better
definition
of
two
items:
A)
the
expected
Sb/Pb
ratio
from
Exide
emissions;
and
B)
the
Sb/Pb
ratios
characteristic
of
lead-
contaminated
properties
from
the
Reading
vicinity,
but
from
more
distant
locations
(i.e.,
~
5
km
or
greater
distances)
unaffected
by
Exide
and
influenced
solely
by
non-
Exide
sources.
Acknowledgments.
The
authors
would
like
to
sincerely
thank
Ms.
Nicole
C.
Brambila,
for
helping
formulate
the
concepts
and
objectives
for
this
study,
and
for
drawing
in
the
interest
and
support
of
other
staff
at
the
Reading
Eagle,
and
for
promoting
the
study
among
members
of
the
local
community.
We
are
appreciative
of
the
financial
support
from
the
Reading
Eagle
Company
for
the
field
work,
and
we
thank
the
MSU
Denver
Chemistry
Department
for
support
of
laboratory
expenses.
We
also
thank
the
many
residents
who
voluntarily
granted
access
to
their
properties
for
purposes
of
sample
collection,
and
we
thank
everyone
for
their
patience
in
awaiting
the
results
and
this
final
report.
12
Figure
3.
Bivariate
plot
of
Sb
vs.
Pb
concentrations
for
the
study
samples.
Figure
A
(upper):
samples
<
1000
ppm
Pb;
Figure
B
(lower):
all
samples
including
data
points
>
1000
ppm
Pb.
13
Literature
Cited
Amter,
S.;
Eckel,
W.P.
(1996)
Comment
on
off-site
forensic
determination
of
airborne
elemental
emissions:
a
case
study
at
two
secondary
lead
smelters.
Environmental
Science
and
Technology
30,
24172418.
Eckel,
W.P.;
Rabinowitz,
M.B.;
Foster,
G.D.
(2002)
Investigation
of
unrecognized
former
secondary
lead
smelting
sites:
confirmation
by
historical
sources
and
elemental
ratios
in
soil.
Environmental
Pollution
117,
273-279.
Kimbrough,
D.E.;
Steele,
N.;
Suffet,
I.H.
(1995)
Off-site
forensic
determination
of
airborne
elemental
emissions
by
multi-media
analysis:
a
case
study
at
two
secondary
lead
smelters.
Environmental
Science
and
Technology
29,
22172221.
Kimbrough,
D.E.;
Suffet,
I.H.
(1996)
Response
to
comment
on
off-site
forensic
determination
of
airborne
elemental
emissions
by
multi-
media
analysis:
a
case
study
at
two
secondary
lead
smelters.
Environmental
Science
and
Technology
30,
24192420.
Kimbrough,
D.E.;
Cardner,
N.H.
(1999)
Off-site
forensic
determination
of
waterborne
elemental
emissions:
a
case
study
at
a
secondary
lead
smelter.
Environmental
Pollution
106,
293298.
Machemer,
S.D.;
Hosick,
T.J.;
Ingamells,
R.L.
(2007)
Source
identification
of
lead
contamination
in
residential
and
undisturbed
soil
adjacent
to
a
battery
manufacturing
facility
(Part
1).
Environmental
Forensics
8,
77-95.
Reimann,
C.;
Matschullat,
J.;
Birke,
M.;
Salminen,
R.
(2010)
Antimony
in
the
environment:
lessons
from
geochemical
mapping.
Applied
Geochemistry
25,
175-198.
14
Table
1.
Results
for
the
duplicate
dissolution/analysis
of
12
randomly
selected
samples
15
Table
2.
Results
for
depth
profiles
of
Sb
and
Pb
in
10
selected
soil
cores
16
Table
3.
Results
for
soil
Sb
and
Pb
concentrations
in
the
study
samples.
17
Table
3.
Results
for
soil
Sb
and
Pb
concentrations
in
the
study
samples.
18
Table
3.
Results
for
soil
Sb
and
Pb
concentrations
in
the
study
samples.
19