Chemosphere 44 (2001) 997±1009

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Loading estimates of lead, copper, cadmium, and zinc in urban

runo€ from speci®c sources
Allen P. Davis *, Mohammad Shokouhian, Shubei Ni
Environmental Engineering Program, Department of Civil and Environmental Engineering, University of Maryland, College Park,
MD 20742, USA
Received 13 June 2000; received in revised form 29 September 2000; accepted 29 September 2000

Abstract

Urban stormwater runo€ is being recognized as a substantial source of pollutants to receiving waters. A number of
investigators have found signi®cant levels of metals in runo€ from urban areas, especially in highway runo€. As an
initiatory study, this work estimates lead, copper, cadmium, and zinc loadings from various sources in a developed area
utilizing information available in the literature, in conjunction with controlled experimental and sampling investiga-
tions. Speci®c sources examined include building siding and roofs; automobile brakes, tires, and oil leakage; and wet
and dry atmospheric deposition. Important sources identi®ed are building siding for all four metals, vehicle brake
emissions for copper and tire wear for zinc. Atmospheric deposition is an important source for cadmium, copper, and
lead. Loadings and source distributions depend on building and automobile density assumptions and the type of
materials present in the area examined. Identi®ed important sources are targeted for future comprehensive mechanistic
studies. Improved information on the metal release and distributions from the speci®c sources, along with detailed
characterization of watershed areas will allow re®nements in the predictions. Ó 2001 Elsevier Science Ltd. All rights
reserved.

Keywords: Runo€; Stormwater; Loadings; Metals; Lead; Copper; Cadmium; Zinc

1. Introduction technologies to minimize pollutant input to receiving

As point source inputs of pollutants continue to be
addressed, the fraction of the pollutant burden to local
waterways contributed by non-point sources becomes
increasingly important. Less is known about non-point
sources and control is much more dicult. Urban
stormwater runo€ is being recognized as a major
source of pollutants to receiving waters and a number
of recent investigations have evaluated stormwater
runo€ quality characteristics and best management
*
Corresponding author. Tel.: +1-301-405-1958; fax: +1-301-
405-2585.
E-mail address: apdavis@eng.umd.edu (A.P. Davis).
waters.
Heavy metals are of particular interest in stormwater
runo€ due to their toxicity, ubiquitousness, and the fact
that metals cannot be chemically transformed or de-
stroyed. A number of investigators have found various
levels of metals in runo€ from urban areas and in
highway runo€ (Wu et al., 1996, 1998; Sansalone and
Buchberger, 1997; Barrett et al., 1998). Generally levels
follow the order: Zn 20±5000 lg=l† > Cu  Pb
5±200 lg=l† > Cd < 12 lg=l†. The sources of metals
in urban stormwater runo€ are numerous and the metal
release mechanisms are complex. Metal ¯uxes depend on
land use characteristics, speci®c materials and compo-
nents employed within the drainage area, hydrometeo-
rological e€ects, and others. It is expected that major

0045-6535/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 0 ) 0 0 5 6 1 - 0
998 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009
contributors of metals in non-industrial areas are auto-
mobiles and structures that use metallic constituents in
various components.
The goals of this work are to estimate metal load-
ings from individual components of automobiles and
buildings utilizing information available in the litera-
ture, in conjunction with controlled experimental and
sampling investigations. Speci®cally, sampling has been
initiated on automobile brake areas and building siding
and roofs. Controlled laboratory studies have been
completed on automobile tire shavings and used vehicle
motor oil. With this information on speci®c metal
levels produced from these sources, assumptions of
building and automobile densities and characteristics
for a typical developed residential area are employed to
produce an estimate of the pollutant loading for each
source. Dominant sources are identi®ed. These results
are compared with published estimates of metal load-
ings for residential land use areas. This study is de-
signed as a preliminary investigation to identify
important sources of metals from a broad array of
possible inputs. These principal sources should be tar-
geted for fundamental mechanistic investigations of
metal origin and release. Knowledge of the sources of
these pollutants allows decisions to be made targeting
metal reduction plans and evaluating changes in pol-
lutant loading due to modi®cations in development and
land use.
2. Experimental methodology
All labware was soaked in HCl bath for at least 24 h
and rinsed thoroughly with de-ionized water to prevent
metal contamination. The water used for sampling and
laboratory studies was a synthetic rain water, unless
otherwise speci®ed. The synthetic rain water contained
23 lM NaCl (Baker), 18 lM HNO3 (EM Science), and
18 lM H2 SO4 (Baker) and was based on the chemical
makeup of rainfall in Maryland (Maxwell and Mahn,
1987). De-ionized water was from a Hydro-Service re-
verse osmosis/ion exchange apparatus, Model LPRO-20.
Synthetic rain water was prepared in bulk volume in a
20-l plastic container. After preparation, the pH of the
solution ranged from 4.2 to 4.4.
2.1. Automobile and building sampling
Plastic spray bottles (400 ml) ®lled with the synthetic
rain water were used to collect samples. Usually 120 to
160 ml of synthetic rain water was sprayed at a medium
intensity (spray diameter ˆ 7 to 10 cm at a spray dis-
tance of 30 to 40 cm) on automobile front wheels or
building walls and then collected using sheets of alumi-
num foil. The collected water was transferred from the
foil to a 125-ml acid-washed polyethylene sample bottle.
The surface area of the wash part was determined,
ranging from 180 to 300 cm2 . All samples were brought
to the University of Maryland, Environmental Engi-
neering Laboratory for analysis.
2.2. Used engine oil sampling
Used engine oil was obtained from 13 automobile
repair shops near the University of Maryland campus.
In each case, 5 ml of oil was mixed with synthetic rain
water in 125-ml plastic bottles to produce a total volume
of 100 ml for the oil/water mixture. The sample bottles
were shaken at a medium speed for 24 h. After shaking,
samples were placed in the refrigerator, which helped to
separate the water from the oil phase. After chilling, the
water was carefully separated from the oil, collected in a
clean plastic bottle, and acidi®ed. In addition, a single
virgin automobile motor oil was purchased and evalu-
ated in the same manner.
2.3. Tire sampling
Automobile tires were also obtained from repair
shops near the University of Maryland campus. All
dirt and sand were removed from the tire surfaces,
they were washed with hot water and soap, and air
dried at room temperature. The clean tread surface of
each tire was abraded using a steel brush. The small
particles of tire (tire powder) were collected on clean
white paper.
Samples of 100 mg tire powder were placed in 125-ml
plastic bottles and 100 ml of synthetic rain water was
added. The sample bottles were shaken for 24 h. After
shaking, the tire powder/water mixture was ®ltered using
a syringe ®lter holder with a 0.2 lm Gelman Supor
Modi®ed Polysulfone ®ltration membrane, discarding
the ®rst few ml of ®ltrate. The ®ltrate was then acidi®ed
with HNO3 to pH < 2 and stored at 4°C.
2.4. Roof rain water sampling
Only in the case of roof sampling was runo€ from an
actual rain event was employed. Just before the start of
a rain event, a plastic bag with a drawstring was placed
at the exit point of a roof downspout. Approximately
500±1000 ml of ®rst ¯ush rain was collected in a few
minutes.
Along with the roof samples, a rain water blank was
also taken. To collect the blank, a pan covered with an
identical plastic bag was placed in an open area at the
beginning of the rain event and the rain was collected for
approximately 20 min. The collected roof rain water
samples and the blank were transferred to 125-ml plastic
bottles and transported to the laboratory. The samples
were acidi®ed and stored.
 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009
2.5. Instrumentation and analytical procedure
Metals standards were prepared with HNO3 (EM
Science, reagent grade) from a 1000 mg/l solution of lead
as Pb NO3 †2 , a 0.1 M copper solution as Cu NO3 †2 , a
1000 mg/l solution of cadmium as CdCl2 and a 100 mg/l
solution of zinc as ZnCl2 (all from VWR). A Varian
Techtron Model 61 AA-5 atomic absorption spectro-
photometer equipped with a graphite furnace (GFAAS)
and a chart recorder were used for approximately the
initial 25% of the metals analysis work. With the Varian
GFAAS, standards and samples were pipetted manually
with a 10 ll Eppendorf pipette into the graphite furnace.
The measured sample absorbances were employed with
linear calibration curves to calculate the metal concen-
trations in the samples. The practical quantitation limits
were found to be 1 lg/l for Pb and Cu, and 0.2 lg/l for Cd.
In the later portion of the study, a Perkin-Elmer
Model 5100 ZL atomic absorption spectrophotometer
with autosampler was used for all metal analyses. The
quantitation limits (QL) for lead, copper, cadmium, and
zinc were 1, 1, 0.2, and 0.3 lg/l and the linear ranges for
these metals were 0±50, 0±50, 0±5, and 0±2.5 lg/l, re-
spectively. Most of the zinc samples had concentrations
high enough for measurement using ¯ame AAS. If the
sample metal concentration exceeded the highest stan-
dard concentration, the sample was diluted with de-
ionized water. For sample metal concentrations below
the quantitation limits, the concentrations greater than
the quantitation limit in that data set were ®tted using a
log distribution. Values for the concentrations less than
the QL were predicted using the ®tted distribution
(Helsel, 1990); statistical analyses were then completed
on the entire data set.
2.6. QA/QC
Standard practices for the handling of trace metal
samples were implemented. This included the soaking of
all plastic sample bottles in HCl for >24 h, followed by
thorough rinse in de-ionized water. Field blanks were
collected with each sampling excursion. These blanks
were obtained by spraying the synthetic runo€ onto bare
foil, and otherwise carrying these samples completely
through the sampling procedure, including transporta-
tion and storage of samples, acidi®cation, and analysis
of metals. In all cases, concentrations of lead, copper,
cadmium, and zinc detected in the ®eld blanks were
below the respective quantitation limits. Trace metal
grade HNO3 was used for sample acidi®cation to
pH < 2 and all samples were stored at 4°C. GFAAS
analyses followed instrument manufacturer's recom-
mendations and ultrapure Ar was used for the inert
carrier gas. All metal standards were synthesized from
dilution of commercial standards, prepared using Stan-
dard Methods (APHA, 1985). Only linear calibrations
999
meeting preset criteria were accepted. Usually r2 values
for linear calibrations were greater than 0.99; in no case
was the r2 < 0:96. Analytical reproducibility was
checked using duplicate or triplicate analysis of each
sample.
A study of multiple washings of the same building
area allowed an estimate of the reproducibility of mea-
surements. A single area was washed using the synthetic
runo€ 12 consecutive times. All samples were collected,
handled, and analyzed as previously described. Initially,
metal concentrations declined as they were washed o€
the wall. This was also seen in our lead washing study
(Davis and Burns, 1999). However, relatively constant
concentrations were found after the initial removal of
metals. Therefore, considering the last six samples as
being constant, the results found metal concentrations
as (mean  S.D., range): Pb (51  15, 37±76 lg/l), Cu
(18  3:3, 12±20 lg/l), Cd (1:2  0:1, 1.0±1.2 lg/l), and
Zn (1600  230, 1200±1800 lg/l) suggesting good preci-
sion and reproducibility of results.
3. Results and discussion
3.1. Sampling results
It should be stressed that in all cases, the sampling
results do not represent the total amounts of metals that
may be present on the target areas, but only represent
metals washed/extracted by the synthetic rain water
wash under the speci®c conditions employed. A more
vigorous mechanical agitation or chemical digestion
process would likely produce higher metal levels.
3.1.1. Building siding samples
Table 1 displays summary information on metal
values from building siding, presented as metal removed
per wall surface area for six siding materials. Among the
di€erent types of building materials, the highest lead
concentrations were found from brick and painted wood
buildings; consequently, sampling from these siding
types was emphasized. The lowest lead concentrations
were found from unpainted wood, metal, and vinyl
siding, although fewer samples were taken from these
materials.
The highest lead levels were found from painted
wood (mean 520 lg=m2 , median 110 lg=m2 ) and likely
result from releases of lead from lead paint (Sutton et al.,
1995; Davis and Burns, 1999). Painted wood structures
have higher lead concentrations than those not painted.
Decades ago, lead-based paint was commonly used for
painting building exteriors and trim. The most common
form of lead used in paints was basic lead carbonate
(Pb3 CO3 †2 OH†2 ). This lead compound is weathered
over time and lead can be released from the paint, either
in particulate form, or through dissolution mechanisms
1000 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009

Table 1
Results of building siding sampling for metals
Metal concentration (lg=m2 ) Samples < QL
Geometric mean Median Mean Min. Max.
Brick: 30 samples
Lead 94 76 300 7 4500 0
Copper 25 23 47 6 280 0
Cadmium 0.6 0.4 1.4 <0.2 6.8 6
Zinc 630 720 2100 26 23 000 0
Painted wood: 13 samples
Lead 73 110 520 <1 3000 2
Copper 28 34 80 <1 280 2
Cadmium 1.4 1.7 3.4 <0.2 15 3
Zinc 1400 1600 2800 36 8400 0
Concrete: seven samples
Lead 14 20 26 <1 89 1
Copper 12 16 35 <1 170 1
Cadmium <0.2 <0.2 0.3 <0.2 0.6 3
Zinc 900 1400 1200 220 1900 0
Metal: four samples
Lead 2.7 4.0 9.8 <1 31 1
Copper <1 <1 1.6 <1 4.6 3
Cadmium 0.3 0.3 0.4 <0.2 1.1 1
Zinc 170 120 690 26 2500 0
Unpainted wood: three samples
Lead 9.0 8.9 93 <1 270 1
Copper 31 23 120 4 320 0
Cadmium 0.5 0.7 0.6 <0.2 0.9 1
Zinc 200 200 330 56 730 0
Vinyl: three samples
Lead 11 7.6 11 7.6 17 0
Copper 11 7.6 16 4.3 35 0
Cadmium 0.3 0.4 0.4 <0.2 0.5 1
Zinc 52 66 60 24 91 0
All siding: 60 samples
Lead 45 50 270 <1 4500 5
Copper 18 19 51 <1 320 6
Cadmium 0.6 0.4 1.5 <0.1 15 15
Zinc 590 820 1900 24 23 000 0

(Barnes and Davis, 1996). Details on lead release in
runo€ from painted structures have recently been pre-
sented by Davis and Burns (1999).
Copper concentrations from brick (47 lg=m2 , mean;
23 lg=m2 , median) and wood (80 lg=m2 ; 34 lg=m2 )
were higher than from concrete, metal, and vinyl
building sidings (1:6±35 lg=m2 ; < 1±16 lg=m2 ). Paint
does not seem to be a major factor in producing high
copper concentrations. Values for unpainted wood sid-
ing were not signi®cantly di€erent from copper levels
from painted materials. A possible source would be
copper used as a wood preservative. Overall, copper
concentrations from buildings were equal to or lower
than that of lead.
Zinc was found at levels one or two orders of mag-
nitude higher than the other three metals examined from
all types of siding. The highest levels were from brick,
concrete, and painted wood structures with typical val-
ues near 1000 lg=l. Sampling results of all siding types
show low cadmium concentrations, in many instances
below the quantitation limit (<0:2 lg=m2 ).
Overall results from Table 1 clearly indicate the
higher metal levels resulting from brick and painted
wood buildings. Also, the clear di€erences among dif-
ferent types of buildings suggest that the building ma-
terial itself is the metal source, and not that the buildings
are collecting atmospheric emissions. It can be suggested
that deposited metals are responsible for the lower
 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009
concentrations from metal and vinyl sidings. Addition-
ally, the metal levels found from all buildings follow the
trend: Zn > Pb > Cu > Cd, mirroring the trend noted
in actual stormwater runo€ measurements, as discussed
above.
3.1.2. Roof samples
Totally, 38 roof runo€ samples, divided into three
di€erent building types, plus 4 blanks (rainfall only)
were collected. A summary of the sample results from
the capture of ®rst-¯ush runo€ from roofs during actual
rain events is presented in Table 2. The results are
summarized as the di€erence between the roof sample
and the corresponding blank. One blank sample showed
relatively high levels of metals ± 6 lg=l Pb, 18 lg=l Cu,
and 130 lg=l Zn. The three other rain water blanks for
di€erent rain events showed zinc levels that were much
lower. A test of metal leaching from the plastic bag used
to collect the rain water blanks indicated that the addi-
tion of synthetic rain water and subsequent shaking
produced levels of all metals less than quantitation
limits. The reason that the one sample was particularly
high in metals is not known.
The quality of runo€ from roof catchments varied
considerably. Zinc concentrations were high (>100 lg=l)
in most samples with several greater than 1000 lg=l.
With the exception of zinc, metal levels from residential
roofs were small. However, all metal levels from com-
mercial and institutional buildings were signi®cantly
larger than those from residences. For lead and zinc, this
di€erence was approximately an order of magnitude.
With cadmium, the increase was less; copper levels were
two or more orders of magnitude greater than in the
residential sampling. Yaziz et al. (1989) found Pb and
Zn concentrations in runo€ from tile roofs to range from
102±271 and 49±193 lg=l, respectively; Zn levels similar,
but Pb levels higher than those documented in the cur-
rent study.
In some cases, the type of roof was known. Gener-
ally, ®berglass and asphalt roof catchments demon-
strated better runo€ quality than those constructed
using slate tile, rubber, and galvanized metal, in terms of
lead and copper levels. Not surprisingly, the highest zinc
concentration (7600 lg=l) resulted from a galvanized
Table 2
Net metal concentrations from roof sampling
Roof runo€ sampling
Residential: 13 samples Commercial: 13 samples
Median (lg/l) Mean (lg/l) Median (lg/l)
Lead 2 1.5 12
Copper 7 7.5 29
Cadmium 0.1 0.12 0.7
Zinc 110 100 760
1001
metal roof sample. Both zinc and copper are commonly
used in materials in roof areas. Zinc is easily corroded
and the appearance of zinc in the roof runo€ is not
unexpected. Copper is more noble, but will weather
nonetheless. Copper sheeting is common in ¯ashing and
other trim in roof areas, and rain gutters. Its prevalence
in commercial/institutional buildings likely produces the
high copper levels found from roofs of these structures.
3.1.3. Automobile brakes
An estimate for copper release from automobile
brake abrasion has been given as 1.5 mg/km-vehicle
(Malmqvist, 1983). Linking this with an estimate that
5% of brake particles are copper (Hewitt and Rashed,
1990) produces a discharge estimate of 75 lg Cu/km-
vehicle. Brake pad material can contain copper, zinc,
and brass (which contains several percent lead), con-
tributing other metals to the environment during brake
wear. Since estimates for the other metals were not
available, releases of lead, cadmium, and zinc were es-
timated by normalizing concentrations found to those
for copper during the sampling of automobile front
wheels. Obviously, the static testing will not collect all
brake material released during automobile use, but
metal ratios from the accumulated brake dust can be
employed to construct useful estimates for these num-
bers. When obtaining samples, it was noticed that front
wheels usually had brown or gray dust accumulated on
the metallic components of front wheels, while back
wheels were generally cleaner. Fifty-four samples were
analyzed, with metal levels ranging over about 1.5 or-
ders of magnitude. Results of the sampling program are
summarized in Table 3. In all cases, a distribution of
metal concentrations was found. Zinc was found at
higher levels than copper, with a ratio of 1.18 for the
population means, producing an estimated zinc contri-
bution of 89 lg=km-vehicle. Lead and cadmium were
found at lower levels with ratios to the copper mean of
0.04 and 0.0066, respectively, resulting in estimated
loadings of 3 and 0:5 lg=km-vehicle.
3.1.4. Tire samples
Results were obtained from four di€erent brands of
automobile tires. In one tire, 65 lg=g lead and 17 lg=g
Institutional: 12 samples
Mean (lg/l) Median (lg/l) Mean (lg/l)
62 64 64
200 2100 5000
1.3 0.4 0.6
1100 460 1100
1002 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009
Table 3
Metal concentrations from automobile front brake areas and used oil extraction
Metal concentration (lg=l)
Geometric mean Median
Brakes: 54 samples
Lead 5.9 7 11
Copper 37 26
Cadmium 0.3 0.2
Zinc 160 150
Used oil: 13 samples (lg=l-oil)
Lead 270 400
Copper 770 1400
Cadmium 20 20
Zinc 9  104 1:6  105
a
Value for copper estimated from Malmqvist (1983) and Hewitt and Rashed (1990). Other metals estimated from ratios to copper.
copper were detected. Lower lead, copper, and cadmium
concentrations were generally found in the remaining
tire samples; the mean metal levels found were
17 lg=g Pb, 5 lg=g Cu, and 1 lg=g Cd. However, zinc
was found at greater than 1000 lg=g in all four tire
samples, with a mean value of 3400 lg=g. Zinc is added
to automobile tires as a ®ller, which is released by tire
wear and subsequent water contact. For comparison,
mean levels in 29 tire samples as found by Sadiq et al.
(1989) for Pb and Cu were 57 and 7 lg=g, respectively.
The metal levels of Sadiq et al. result from nitric/per-
chloric acid digestion at 120°C. These values should
represent total metals present in the tire matrix. Thus,
these lead and copper values are generally higher than in
the present study, which employed the less aggressive
synthetic rain water.
3.1.5. Engine oil samples
Summary results for the water/oil mixtures converted
to metal mass per liter of oil are also shown in Table 3.
Again, the metal concentrations varied signi®cantly.
Zinc is the heavy metal of most concern in the engine oil.
The zinc concentration was always greater than the
other metals, and was usually signi®cantly greater. A
zinc concentration as high as 1:9  105 lg=l-oil was
found in the water extract of one used engine oil. The
mean zinc concentration for the 13 used engine oils was
1:25  105 lg=l-oil, with a median value of 1:6  105 .
Concentrations of the other metals were two or more
orders of magnitude lower.
One virgin oil was also investigated, which contained
1:8  105 lg=l-oil. The high zinc concentration appar-
ently results from the use of zinc additives in formulat-
ing the oil to provide wear protection for the engine.
These components also act as antioxidants for the oil in
the combustion chamber. Some lead was also found in
the virgin oil (460 lg=l-oil), but negligible amounts of
copper and cadmium (<10 and <4 lg=l -oil, respec-
tively). These limited results suggest that at least Cu and
Metal:Cu lg=km-vehiclea Samples < QL
Mean (mean)
0.04 3 1
280 1 75 0
1.9 0.0066 0.5 5
330 1.18 89 0
1100
2100
100
1:25  105
Cd are accumulated in the oil during use. For compar-
ison, Chen et al. (1994) studied one type of engine oil,
new and used, and evaluated water-soluble metals. Their
results indicated no detectable concentrations for lead,
cadmium, and copper in the water-soluble fractions of
new engine oil. In the used oil, cadmium was not found;
unspeci®ed lead concentrations were detected. Copper
was detected at unspeci®ed ``low'' concentrations. The
average zinc concentration was 21 900 lg=l-oil for new
oil and 45 500 lg=l-oil for used oil.
3.2. Estimates of metal annual loadings
In order to utilize the metal levels determined from
the sampling in annual loading estimates, a number of
assumptions are necessary to characterize building and
vehicle densities and relationships to other parameters.
Typical and reasonable values are employed for dem-
onstration purposes. These densities can be appropri-
ately modi®ed as more accurate estimates become
available or if speci®c information for a developed area
is given. The loading estimate is made for a low density
residential area with an assumed density of 5 houses per
hectare. For calculation of metals from these homes,
assumptions for size are necessary, along with rainfall
event estimates; necessary information includes exterior
wall and roof area per house, number of rainfall events
per year (60) (Urbonas, 1999), and total rainfall per
year. Mean metal values for brick buildings and resi-
dential roofs are utilized. Loadings for siding must be
handled di€erently from roofs because the source data
were collected using di€erent techniques.
For these surfaces, simplifying assumptions are em-
ployed. These include the fact that all vertical walls are
assumed to be washed evenly in each storm. Also, ``®rst
¯ush'' considerations were not included. In the former
case, walls that are not washed during an event may
continue to accumulate metal and at some point, will be
washed; annually, the loading is the same as a continu-
 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009
ous wash. Further research is necessary to understand
these accumulation and washo€ mechanisms better.
The metal loadings from automobiles require an as-
sumption for vehicles per household (2) and the distance
driven per year (24 000 km). Finally, tire wear/km and
oil leaked/km assumptions are necessary. All assump-
tions are summarized in Table 4. A value of 48 l-oil/ha-
yr corresponds to 43 kg oil/km2 -cm rainfall, somewhat
higher than the value for oil and grease calculated by
Stenstrom et al. (1984) for residential areas, but much
lower than the value for parking properties. With oil,
only rainwater-extractable metals are employed. It is
assumed that not all oil will be mobilized during a rain
event and that a portion of the oil will partition with
sediments and not enter the runo€ stream.
The density assumptions are combined with the en-
vironmental sampling data of Tables 1±3 to produce the
annual loading calculations of Table 5. Mean values are
employed from the sampling results. The mean value
must be used to calculate total loadings appropriately
(Parkhurst, 1998) and in cases where the mean is sig-
ni®cantly greater than the median, a few sources con-
tribute the majority of the metal load. To these speci®c
building and automobile loadings are included ``back-
ground'' rainfall metal levels from Chesapeake Bay wet
deposition estimates (Scudlark et al., 1994). Finally,
values for metals in dry atmospheric deposition, esti-
mated to occur uniformly over the area, are added based
on Chesapeake Bay studies by Wu et al. (1994).
3.2.1. Lead
A total annual loading of 0.069 kg Pb/ha-yr is esti-
mated from the sources of lead. Most of the lead results
from building walls, making up 79% of the total. The
sampling program found high levels of lead on brick
walls. Wet deposition, at 10%, was the second largest
source of lead.
Estimates of yearly pollutant loadings resulting from
di€erent land use, for utilization in GIS analyses have
been published by Wong et al. (1997). These loadings
were calculated from stormwater monitoring data in the
Santa Monica Bay (CA) watershed. The annual loading
for lead presented by Wong et al. (1997) for a low
density residential area is presented in Table 5 for
Table 4
Assumptions used to estimate total annual metal loadings from various sourcesa
Source Assumptions
Siding 600 m2 /house
Roof 100 m2 /house
Brakes 2 autos/house 24 000 km/auto-yr
Tires 240 000 km/ha-yr 0.05 g/km/tire
Oil 240 000 km/ha-yr 0.2 l-oil/1000 km
a
Residential density is 5 houses/ha.
1003
comparison. Only 11% of the Wong et al. value of 0.6
kg/ha-yr is accounted for here by the speci®c sources.
Both values are much less than the 1.5 kg/ha-yr found by
Bryan (1972) from a North Carolina residential area
when leaded gasoline was used.
3.2.2. Copper
The largest contributor to the calculated copper
loading of 0.038 kg/ha-yr was brake emissions from
automobiles, at 47%, followed by building siding at
21%. This loading represents 15% of the annual loading
of 0.2 kg/ha-yr suggested by Wong et al. (1997).
3.2.3. Cadmium
Little cadmium was found from any of the sources
evaluated. The estimated annual loading was 0.0012 kg/
ha-yr. The largest contributor was wet deposition, at
41%, followed by building walls (21%) and dry deposi-
tion (19%). No annual loading for comparison is avail-
able, but to produce an average runo€ concentration of
1 lg/l in 90 cm/yr rainfall, 70% runo€, a loading of
0.0063 kg/ha-yr is required, equal to ®ve times the value
calculated.
3.2.4. Zinc
The largest metal loading was found for zinc at 0.646
kg/ha-yr. This represents 108% of the 0.6 kg/ha-yr
loading estimated for zinc by Wong et al. (1997).
However, this latter value may be a low estimate as it
corresponds to a runo€ concentration of approximately
95 lg/l, which is quite low as compared with stormwater
values recently measured. The largest contributor was
runo€ from the brick walls, at 58%, followed by tire
wear at 25%. Four of the ®ve sources evaluated gave
signi®cant contributions to zinc levels, with only oil
being small, at 1%.
3.2.5. Speci®c sources
The distribution of total metals among the seven
sources examined is shown in Fig. 1. The most signi®-
cant overall contributor of metals was building siding,
which was the highest source for lead and zinc, and the
second largest for copper and cadmium. Atmospheric
deposition was very important in the cadmium loading
Result
60 rainfall events/yr 180 000 m2 /ha-yr
0.9 m rain/yr 450 000 l/ha-yr
240 000 km/ha-yr
4 tires 48 000 g tire/ha-yr
48 l-oil/ha-yr
 1004

Table 5
Metal loadings in urban stormwater runo€
Lead Copper Cadmium Zinc
Unit Loading % of Unit Loading % of Unit Loading % of Unit Loading % of
value (kg/ha-yr) Total value (kg/ha-yr) Total value (kg/ha-yr) Total value (kg/ha-yr) Total
Buildings
Siding 180 000 m2 /ha-yr 300 lg/m2 0.054 79 47 lg/m2 0.0085 22 1.4 lg/m2 0.0003 21 2100 lg/m2 0.378 58
5
Roof 450 000 l/ha-yr 1.5 lg/l 0.007 1 7.5 lg/l 0.0034 9 0.12 lg/l 5  10 5 100 lg/l 0.045 7
Total 0.055 80 0.0118 31 0.0003 26 0.423 65

Autos
Brakes 240 000 km/ha-yr 3 lg/km 0.0007 1 75 lg/km 0.018 47 0.5 lg/km 0.0001 10 88 lg/km 0.021 3
5
Tires 48 000 g tire/ha-yr 17 lg/g 0.0008 1 5 lg/g 0.0002 0.6 1 lg=g 5  10 4 3400 lg/g 0.163 25
5 6
Oil leakage 48 l-oil/ha-yr 1100 lg/l 5  10 <0.1 2100 lg/l 0.0001 0.3 100 lg/l 5  10 0.4 1:25  105 mg/l 0.006 1
Total 0.0016 2 0.0183 48 0.0002 15 0.19 29

Total buildings and autos 0.0563 82 0.0302 79 0.0005 41 0.0613 95

Wet depositiona 0.0056 8 0.0026 7 0.00048 41 0.013 2

Dry deposiotionb 0.0069 10 0.0055 14 0.00022 19 0.020 3
A.P. Davis et al. / Chemosphere 44 (2001) 997±1009

Total 0.069 0.038 0.0012 0.646

Value from Wong et al. (1997) 0.6 0.2 ) 0.6

% of Value from Wong et al. 11% 19% ) 108%
(1997)
a
From Scudlark et al. (1994).
b
From Wu et al. (1994).
 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009 1005

Fig. 1. Estimated contributions of various sources of metals in urban residential stormwater runo€. Brick buildings. Total metal
loadings: Pb ˆ 0:069 kg=ha-yr, Cu ˆ 0:038 kg=ha-yr, Cd ˆ 0:0012 kg=ha-yr, Zn ˆ 0:646 kg=ha-yr.

and to a lesser extent for copper and lead. Brake emis-
sions were signi®cant for copper and tire wear only for
zinc. Oil leakage contributed less than 1% of the total for
all four metals. This agrees with the 4 mg/l values for oil
and grease noted in residential stormwater runo€
(Stenstrom et al., 1984), which corresponds to <1 lg=l
Zn at 1:25  105 lg Zn/l-oil. Metals from oil should only
be of concern should illicit disposal of large volumes
occur. Roof runo€ was also small compared with other
sources.
Since the annual loadings calculations are based on
an idealized watershed area, an analysis was preformed
to evaluate how the previous conclusions would be
modi®ed if some characteristic of the input was changed.
The ®rst situation evaluated is the assumption of hous-
ing density. Doubling this value to 10 units per ha
doubles the metal input from siding and roofs. Also,
since automobile density is linked directly to housing
density, values for brakes, tires, and oil are doubled as
well. Wet and dry deposition are not a€ected. Results
are presented in Table 6.
The total loadings for Pb, Cu, and Zn were essentially
doubled, bringing Pb and Cu loadings closer to the es-
timates by Wong et al. (1997). However, the distributions
among sources were not signi®cantly a€ected and the
dominant category did not change for any of these three
metals. Since depositions were the dominant sources for
Cd, doubling the housing density slightly a€ected the
distribution of this metal. Building siding became the
dominant source, at 30% of total. Wet deposition fol-
lowed at 29%, which was followed by brakes at 14%.
A second scenario doubled only the automobile
density, which corresponded to a doubling of the auto-
mobile mileage traveled in the drainage area. Accord-
ingly, metal loadings from brakes, tires, and oil were
doubled. Pb, which did not have these three sources as
major contributors, saw negligible impact from this
modi®cation. With copper, this doubling just strength-
ened the dominance of brakes as a source of the metal.
Brakes increase to the third most dominant Cd source
(18%), behind wet deposition (36%) and siding (29%).
Tires became a major source of Zn (39%), just below
siding at 45%.
The ®nal scenario tested was to double atmospheric
deposition. Zinc and lead source distributions were not
signi®cantly impacted by this modi®cation. Dry depo-
 1006

Table 6
E€ects of watershed density assumptions on metal loadings
EMC Building Roof Brakes Tires Oil Wet deposition Dry deposition Total
lg=l†a Ldgb b b b b b b
% of Ldg % of Ldg % of Ldg % of Ldg % of Ldg % of Ldg % of Loading
Total Total Total Total Total Total Total (kg/ha-yr)
Standard
5
Lead 7.7 0.054 79 0.007 1 0.0007 1 0.0008 1 5  10 <1 0.0056 8 0.0069 10 0.069
Copper 4.2 0.0085 22 0.0034 9 0.018 47 0.0002 0.6 0.0001 0.3 0.0026 7 0.0055 14 0.038
5 5 6
Cadmium 0.13 0.0003 21 5  10 5 0.0001 10 5  10 4 5  10 0.4 0.00048 41 0.00022 19 0.0012
Zinc 72 0.378 58 0.045 7 0.021 3 0.163 25 0.006 1 0.013 2 0.020 3 0.646

2x Housing density
Lead 14 0.108 87 0.014 1 0.0014 1 0.0016 1 0.0001 <1 0.0056 4 0.0069 6 0.125
Copper 7.6 0.0169 25 0.0068 10 0.036 53 0.0005 0.7 0.0002 0.3 0.0026 4 0.0055 8 0.0685
5
Cadmium 0.19 0.0005 30 0.0001 7 0.0002 14 0.0001 6 1  10 0.6 0.00048 29 0.00022 13 0.0017
Zinc 140 0.756 60 0.09 7 0.042 3 0.326 26 0.012 1 0.013 1 0.020 2 1.26

2x Auto density
Lead 7.8 0.054 77 0.0007 1 0.0014 2 0.0016 2 0.0001 <1 0.0056 8 0.0069 10 0.0703
Copper 6.2 0.0085 15 0.0034 6 0.036 64 0.0005 0.9 0.0002 0.4 0.0026 5 0.0055 10 0.0566
5 5
Cadmium 0.15 0.0003 19 5  10 4 0.0002 18 0.0001 7 1  10 0.7 0.00048 36 0.00022 16 0.00135
Zinc 93 0.378 45 0.045 5 0.042 5 0.326 39 0.012 1 0.013 2 0.020 2 0.837
A.P. Davis et al. / Chemosphere 44 (2001) 997±1009

2x Atmospheric deposition
5
Lead 9.0 0.054 66 0.007 1 0.0007 1 0.0008 1 5  10 <1 0.0112 14 0.0138 17 0.0813
Copper 5.2 0.0085 18 0.0034 7 0.018 39 0.0002 0.5 0.0001 0.2 0.0052 11 0.011 24 0.0464
5 5 6
Cadmium 0.21 0.0003 13 5  10 3 0.0001 6 5  10 3 5  10 0.3 0.001 51 0.00044 23 0.00188
Zinc 75 0.378 56 0.045 7 0.021 3 0.163 24 0.006 1 0.026 4 0.040 6 0.679
a
Event mean concentration at 90 cm/yr total precipitation.
b
Loading (kg/hr-yr).
 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009 1007

sition increased to the second greatest source of copper.
Since deposition was the dominant Cd source under the
baseline conditions, the doubling reinforced the impor-
tance of these sources. The total Cd loading increased by
more than 50% to 0.0019 kg/ha-yr and 74% of the Cd
loading was attributed to deposition.
Overall, these changes did not alter the major con-
clusions discussed previously. In all scenarios, buildings
are the major sources of lead and zinc, and brake
emissions is the major source of copper. Atmospheric
wet deposition remains the dominant source of Cd, ex-
cept when housing density is doubled, where siding be-
comes just slightly higher. Absolute loading values are
impacted and become closer to the published values for
urban areas at higher housing densities.
This analysis leads to two conclusions. First, the
source results are not particularly sensitive to the as-
sumptions made. A 100% variation in any of the sources
would not impact the conclusions. Second, the same
basic conclusions drawn based on the simple model
drainage area can also be used for other, somewhat
di€erent watersheds. The analysis is not particularly
sensitive to the housing density of the watershed.
3.2.6. Alternate land uses
Two variations related to the land use and building
characteristics were also investigated. In the ®rst case,
the dominant building type was changed from brick to
vinyl. In the sampling study, the metal levels from vinyl
siding were found to be considerably lower than from
the brick. Metal distributions are graphically presented
in Fig. 2. This modi®cation produces profound changes
in the loadings and source distribution for most of the
metals. The total lead and zinc loadings are drastically
reduced, falling to 0.017 and 0.28 kg/ha-yr, respectively,
with the respective contributions from siding decreasing
from 79% to 12% and from 58% to 4%. The dominant
sources shifted to dry and wet deposition for lead and
tire wear for zinc. Less-drastic reductions were found in
copper and cadmium since siding was not such an im-
portant source. The percentages of the other ®ve sources
increased accordingly.
In the second analysis, the building density was
doubled and the roof concentrations were selected from
the commercial sampling data set (Table 2) in order to
simulate a commercial land use. The metal levels from
commercial roofs were much higher than from residences.

Fig. 2. Estimated contributions of various sources of metals in urban residential stormwater runo€. Vinyl buildings. Total metal
loadings: Pb ˆ 0:017 kg=ha-yr, Cu ˆ 0:033 kg=ha-yr, Cd ˆ 0:0010 kg=ha-yr, Zn ˆ 0:279 kg=ha-yr.
1008 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009

Fig. 3. Estimated contributions of various sources of metals in urban commercial stormwater runo€. Total metal loadings:
Pb ˆ 0:180 kg=ha-yr, Cu ˆ 0:243 kg=ha-yr, Cd ˆ 0:0022 kg=ha-yr, Zn ˆ 2:16 kg=ha-yr.

Naturally, the yearly loadings were signi®cantly in-
creased (lead, 0.18; copper, 0.24; cadmium, 0.0022; and
zinc, 2.2 kg/ha-yr). This change made a substantial im-
pact on the source distribution for all metals ± especially
with copper, where the roof percentage went from 9% to
74% (Fig. 3). The other metals also saw major increases
from roof runo€ (lead: from 1% to 31%, cadmium: from
5% to 29%, zinc: from 7% to 46%).
In all of these estimates, any attenuation of metals
during overland travel is neglected. However, in a steady
state, any attenuated metals may also be a metal source
to the runo€. Additionally, the importance of roadways
on the metal estimates should be noted. This analysis
assumes that all vehicle travel is done throughout the
area of residence, or that travel outside the area is
matched by non-resident travel inside. The location of a
major trac thoroughfare with non-resident trac
would signi®cantly increase vehicle metal loadings.
Concurrently, the presence of only low trac density
residential streets would produce lower loadings, domi-
nated by resident vehicle travel outside the resident area.
The results presented and described depend on the
various values and assumptions employed in the ana-
lyses. For several of the parameters used from the
sampling program, sample populations were low and
mean values can be biased by one large or small value.
With a larger database and more focused mechanistic
studies, information on metal distributions can be em-
ployed to re®ne the results presented here, increasing the
utility and con®dence of the output. The work by Davis
and Burns (1999) represents one attempt in this direc-
tion. In many cases, rather than deterministic values,
stochastically distributed inputs could be employed to
produce distributed ranges of loadings from various
sources. Obviously, mechanisms of metal release,
transport, and fate will depend on a number of factors,
including hydrometeorological considerations.
4. Summary and conclusions
Sources of lead, copper, cadmium, and zinc in urban
stormwater runo€ have been quantitatively evaluated.
Sources examined included building siding and roofs;
automobile brakes, tires, and oil leakage; and wet and
dry deposition. A controlled sampling program, along
 A.P. Davis et al. / Chemosphere 44 (2001) 997±1009
with assumptions on residence and automobile densities
and use allow the estimation of annual loadings for each
metal from each source. Important sources identi®ed are
building siding for all four metals, vehicle brake emis-
sions for copper and tire wear for zinc. Atmospheric
deposition is also important for cadmium, copper, and
lead. Future research should target these sources to
advance the mechanistic understanding of each metal
source contribution. Loadings and source distributions
depend on density assumptions and the type of materials
present in the area examined. This work was designed as
an introductory study to estimate metal loadings. Im-
proved information on the metal release and distribu-
tions from speci®c sources with focused subsequent
research, along with detailed characterization of drain-
age areas will allow re®nements in the predictions.
Once signi®cant sources of metals are identi®ed and
con®rmed, reducing these inputs to receiving waters
must be addressed. Public education can play an im-
portant role in this endeavor. Reducing metal inputs
from vehicle and building materials may require modi-
®cations or elimination of metal parts. The removal of
lead paint may have a signi®cant impact on lead in ur-
ban runo€ (Davis and Burns, 1999). The alternative is to
design and install stormwater treatment systems that
address metal pollution. With detailed information on
pollutants from various sources, environmental impacts
of land development can be more accurately quanti®ed,
decisions on the needs of stormwater treatment can be
made, and pollutant loadings entering receiving waters
can be estimated.
Acknowledgements
This work was supported by the Department of En-
vironmental Resources of the Prince George's County
(Maryland) Government, under the guidance of Dr.
Mow-Soung Cheng, and by the National Science
Foundation Young Investigator Award, BCS-9358209.
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