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Simultaneous removal of As, Cd, Cr, Cu, Ni and Zn from
stormwater: Experimental comparison of 11 different
sorbents
Hu lya Genc--Fuhrman

, Peter S. Mikkelsen, Anna Ledin

Institute of Environment & Resources, Technical University of Denmark, Building 115, DK-2800 Kgs. Lyngby, Denmark
a r t i c l e i n f o
Article history:
Received 31 May 2006
Received in revised form
18 October 2006
Accepted 19 October 2006
Available online 14 December 2006
Keywords:
Heavy metals
Stormwater runoff
Secondary treatment
Sorption
Precipitation
Sorbents
A B S T R A C T
The potential of using alumina, activated bauxsol-coated sand (ABCS), bark, bauxsol-
coated sand (BCS), y ash (FA), granulated activated carbon (GAC), granulated ferric
hydroxide (GFH), iron oxide-coated sand (IOCS), natural zeolite (NZ), sand, and spinel
(MgAl
2
O
4
) as sorbents for removing heavy metals from stormwater are investigated in the
present study. The ability of the sorbents to remove a mixture of As, Cd, Cr, Cu, Ni and Zn
from synthetic stormwater samples were evaluated in batch tests at a starting pH of 6.5.
The metal speciation and saturation data is obtained using the PHREEQ-C geochemical
model and used to elucidate the sorption data. It is found that BCS, FA, and spinel have
signicantly higher afnity towards heavy metals mainly present as cationic or non-
charged species (i.e. Cd, Cu, Ni and Zn) compared to those present as anionic species (i.e. As
and Cr). However, IOCS, NZ and sand have higher afnity towards As and Cr, while alumina
has equally high afnity to all tested heavy metals. The Freundlich isotherm model is
found to t the data in many cases, but ill tted results are also observed, especially for FA,
BCS and GAC, possibly due to leaching of some metals from the sorbents (i.e. for FA) and
oversaturated conditions making precipitation the dominant removal mechanism over
sorption in batches with high heavy metal concentrations and pH. Calculated sorption
constants (i.e. K
d
) are used to compare the overall heavy metal removal efciency of the
sorbents, which in a decreasing order are found to be: alumina, BCS, GFH, FA, GAC, spinel,
ABCS, IOCS, NZ, bark, and sand. These ndings are signicant for future development of
secondary lters for removal of dissolved heavy metals from stormwater runoff under
realistic competitive conditions in terms of initial heavy metal concentrations, pH and
ionic strength.
& 2006 Elsevier Ltd. All rights reserved.
1. Introduction
Urban stormwater runoff, especially road runoff, is rich
in heavy metals that, unlike organic pollutants, are not
degradable in the environment. The major sources of
heavy metals in stormwater runoff are building materials
(e.g. Cu from roofs and Zn from galvanized steel), and
trafc-related sources such as brake linings (Cu, Ni, Cr, Zn,
Pb), tire wear (Zn), and autocatalysts (Pt, Pd, Rh). Due to
short term (e.g. acute toxicity) and long-term (e.g. carcinoge-
nity and reproducing damages) adverse effects of
heavy metals in the aquatic environment, treatment of
stormwater runoff containing heavy metals receives in-
creased attention.
ARTICLE IN PRESS
0043-1354/$ - see front matter & 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2006.10.024

Corresponding author. Tel.: +45 45 2516 11; fax: +45 4593 28 50.
E-mail address: hyg@er.dtu.dk (H. Genc--Fuhrman).
WAT E R R E S E A R C H 41 ( 2007) 591 602
Stormwater best management practices (BMPs) are widely
used for handling of stormwater. Although most of the BMPs
are constructed to control the water ow in order to alleviate
peak ows and avoid ooding, more attention has recently
been directed to construct BMPs that also remove pollutants.
The most common BMPs in Denmark are ponds, basins,
wetlands and swales. Of these, some are built to inltrate
stormwater, whereby pollutants are either accumulated in
the soil or transported to the groundwater. Others are built as
active scavengers for pollutants associated with particles. The
primary inadequacy of such systems is that the colloidal and
truly dissolved fractions cannot be removed via settling;
hence, there is a need for secondary treatment of stormwater,
after passing through a pond, basin or wetland. Filtration of
the stormwater, where both colloidal and truly dissolved
heavy metal fractions are primarily removed via sorption, is
one of the most promising technologies providing that
effective ltration media is used.
Although many studies of heavy metal removal from
stormwater using a variety of sorbents exist, they typically
only report removal percentages and do not document the
experimental conditions thus making the results impossible
to compare directly. Furthermore, the majority of previous
work on heavy metal removal using ltration/adsorption
deals with treatment in single heavy metal systems, and only
a few studies are carried out at realistic experimental
conditions in terms of stormwater (Liu et al., 2005; Pitcher
et al., 2004). However, it is important to understand and
quantify the heavy metal removal properties when they
coexist (Jang et al., 2005; Al-Asheh et al., 2000), and identical
experimental conditions are important when comparing
different sorbents. Consequently, the main objective of the
present study was to evaluate the efciency of 11 pre-selected
sorbents/ltration materials in batch tests under well-con-
trolled experimental conditions to identify those most
promising for potential use in secondary stormwater treat-
ment systems. Co-existence of the most important heavy
metals in realistic concentrations as well as initial pH and
ionic strength are prioritized properties in this study, whereas
other properties such as the content of organic matter and
colloids are included in a later study focusing only on the
most promising sorbents.
Although a wide range of sorbents are available as possible
ltration media the following 11 are selected based on a
literature survey: activated bauxsol-coated sand (ABCS),
alumina, bauxsol-coated sand (BCS), bark, y ash (FA),
granulated activated carbon (GAC), granulated ferric hydro-
xide (GFH), iron oxide-coated sand (IOCS), natural zeolite (NZ),
sand, and spinel (MgAl
2
O
4
). A mixture of As, Cd, Cr, Cu, Ni
and Zn is chosen, as dissolved fractions of these metals
reportedly pose environmental concerns (Makepeace et al.,
1995). Pb is excluded in this study, as Pb in stormwater is
primarily associated with suspended solids, which are
expected to be satisfactorily removed during pre-ltration
treatment (i.e. by settling). Furthermore, due to increasing
environmental concerns, Pb usage is decreased, which in turn
has signicantly reduced Pb concentrations in stormwater
(Furumai et al., 2002). Other metals such as Pt, Pd and Rh were
excluded as they are available in very low concentrations of
less concern.
Among the sorbents tested, alumina and IOCS are com-
monly used metal-oxide-based sorbents for heavy metal
removal from aqueous solutions (Baumgarten and Kirchhau-
sen-Du sing, 1997; Khaoidhiar et al., 2000). Similarly, BCS and
ABCS are previously tested as cost-effective sorbents espe-
cially for As (Genc- -Fuhrman et al., 2005). FA is an effective
heavy metal sorbent possibly due to its carbon, silica,
alumina and iron oxides content (Bailey et al., 1999). NZ is
widely available at low cost and has high ion exchange
capacity, thus it may have the potential to be used for
stormwater treatment (Pitcher et al., 2004). Activated carbon
(AC) and GAC are often employed for heavy metal removal
(Chen and Wang, 2000). On the other hand, GFH is effectively
used for arsenate removal (Sperlich et al., 2005) and included
here to observe whether the sorbent is capable of removing
other heavy metals. Bark is a by-product of the timber
industry and its high tannin content, especially polyhydroxy
polyphenol groups, gives bark an ion exchange ability (Bailey
et al., 1999). Moderate heavy metal removal using bark is
reported (Palma et al., 2003), and bark is suggested as a cost-
effective alternative to AC (Al-Asheh et al., 2000). Sand is also
included in the batch tests for two main reasons: rst, sand
ltration is commonly used for stormwater treatment (San-
salone, 1999), and the current study may provide data for
comparison; second, because IOCS, ABCS, and BCS are
prepared by coating a sorbent onto sand, having the removal
data for sand itself is useful for comparative purposes (i.e. to
see the effect of the coating). To the authors knowledge, no
study has yet been published using spinel for heavy metal
removal from water.
2. Materials and methods
2.1. Sorbents
The supplier information and physical characteristics of the
sorbents are provided in Table 1. Specic surface areas of the
samples were measured using the single-point-N
2
-BET meth-
od. Further details about the various sorbents, their physical
and chemical properties and preparation can be found from
the references cited in Table 1. Similar particle sizes of the
sorbent materials were used, as particle size may have an
effect on the removal (Smith, 1998). All sorbents were sieved
(or crushed if required) to the desired particle size (0.61mm)
and dried at 401C for 3 h without additional treatment before
being used in batch experiments, except for sand which was
rst acid washed for 24h using 10% HNO
3
. Alumina, bark, FA,
GAC, GFH, NZ, sand and spinel were commercially supplied,
while ABCS, BCS and IOCS were prepared in the laboratory.
BCS and ABCS were prepared from the alumina production
industry by-product red mud (Genc- -Fuhrman et al., 2005),
while IOCS was prepared in the laboratory by coating goethite
onto sand (Lo et al., 1997). FA is a waste incineration by-
product supplied from a municipal waste incineration plant
(MSWI) in Denmark. There are several NZs but here clinopti-
lolite, the most abundant naturally occurring zeolite, was
used.
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WAT E R R E S E AR C H 41 ( 2007) 591 602 592
2.2. Heavy metal concentrations
It is documented in the literature that the concentrations of
heavy metals in stormwater vary several orders of magnitude
(Makepeace et al., 1995; Walker et al., 1999). In this study, an
attempt was made to use realistic concentration ranges,
where the lowest values were below the Danish emission
limit values for discharge into fresh surface waters (DELV; see
Table 2) (DME, 1996); while, the highest values were signi-
cantly higher representing extreme conditions such as
snowmelt or rst ush concentrations after long dry weather
periods. The purpose was to evaluate and compare the
sorbents at both highly polluted and slightly polluted condi-
tions, since it is well known that some sorbents are effective
at rather high concentrations, but are less efcient and may
leach specic contaminants at low concentrations.
2.3. Batch experiments
Sorption experiments were carried out using synthetic
stormwater samples in 50mL conical PE batches at room
temperature (2271 1C). The required concentrations of As, Cd,
ARTICLE IN PRESS
Table 1 Overview and physical characteristics of the sorbents used in the study
Sorbent Supplier pH
pzc
a
Par. size, mm Surface area
b
, m
2
/g Literature
Alumina
c
Haldor Topse, Denmark 9.1
d
0.61.0 238.9 (Baumgarten and Kirchhausen-Du sing, 1997)
ABCS Prepared in the laboratory 8.3
e
00.5 42.2 (Genc--Fuhrman et al., 2005)
Bark Zugol, Sweden 0.61.0 0.32
f
(Vasconcelos and Bec-a, 1997)
BCS Prepared in the laboratory 8.3
e
00.5 4.6 (Genc--Fuhrman et al., 2005)
FA MSWI, Denmark 6.2 00.5 2.5 (Wang et al., 2004)
GAC Kemira, Denmark 6.1 0.61.0 784.5 (Marzal et al., 1996)
GFH IPS
g
, Germany 7.5-8 0.61.0 172.6 (Sperlich et al., 2005)
IOCS Prepared in the laboratory 9 0.61.0 1.5 (Lo et al., 1997)
NZ
h
Euremica, UK 5.6
i
01.0 24.2 (Matheickal and Yu, 1997)
Sand Dansand, Denmark 0.7 0.61.0 0.1 (Urbonas, 1999)
Spinel
c,j
Haldor Topse, Denmark 11
k
0.61.0 11.8
a
Point of zero charge.
b
BET-N
2
single point analysis.
c
Developed commercially as catalysts.
d
From (Stumm, 1992).
e
pHpzc of red mud (Apak et al., 1998).
f
From the cited literature.
g
Ingenieurgesellschaft Prof. Dr. Sieker MBH.
h
Clinoptilolite ((Ca, Na
2
, K
2
)
3
[Al
6
Si
30
O
72
].24H
2
0).
i
pHpzc is reported at the presence of cations (Feng et al., 2000).
j
MgAl
2
O
4
.
k
From (Anderson, 2005).
Table 2 Quantication limits, Danish emission limit values, runoff and initial concentrations in the batch experiments
(C
0
) of the heavy metals.
Heavy metals and concentrations (mg/L)
As Cd Cr Cu Ni Zn
Quantif. limit 1.0 0.05 0.5 1.0 0.5 1.0
DCR
a
1210 0.0513,730 12300 0.061410 149,000 0.722,000
ACR
b
1210 0.311 10230 6.5150 6150 16.6580
DELV
c
4 5 7 12 160 110
Batch 1 o1 0.1 o0.5 2.6 0.6 22.5
Batch 2 2.6 3.0 3.5 7.6 12.3 67.6
Batch 3 14 10.4 18 36.1 58.9 340
Batch 4 23 23.1 34.2 20.4 89.9 543
Batch 5 52 221 376 588 178 1350
Batch 6 128 160 212 246 545 3400
Batch 7 396 735 784 1250 2220 13,700
Batch 8 1000 2670 2830 1820 8640 52,300
a
Detected.
b
Average heavy metal concentration ranges reported in the literature for stormwater runoff (Makepeace, 1995).
c
Danish emission limit values (DELV) (DME, 1996).
WATER RESEARCH 41 ( 2007) 591 602 593
Cr, Cu, Ni and Zn were obtained by step-by-step diluting their
commercial stock solutions at 1000mg/L in HNO
3
to the
desired concentrations. The ionic strength of the water
samples was controlled using 0.01M NaCl, and all samples
had 0.003M NaHCO
3
to minimize the pH changes during
experiments. It was decided not to use a stronger buffer since
this would inuence the heavy metal speciation in a way not
realistic for stormwater. After preparing the solutions with
the required heavy metal concentrations, ionic strength, and
buffer; the pH was adjusted to 6.5 using strong acid or base
solutions to resemble the lowest realistic pH observed in
stormwater runoff. Afterwards, 50mL of the heavy metal
solutions with pH 6.5 were added to the PE asks with 1 g
sorbent to obtain a 20g/L sorbent dosage. Then, the solutions
and the sorbents were mixed by gently shaking the batches,
and the pH was re-measured and re-adjusted to 6.5 in each
batch within a few minutes. Following the pH adjustment the
batches were capped tightly and shaken for 48h. The pH
values were checked after the completion of the shaking time
to identify possible pH variations from the starting values.
The temporal evolution of the solution pH due to sorbent-
sorbate interactions was monitored in a separate set of
experiments for 48h. The used 48h shaking time and 20g/L
solid/solution ratio may overestimate the actual removal of
metals occurring in real ow-through stormwater lters but
were used here to compare the 11 sorbents under identical
conditions. It is noted that further studies on the effects of
sorption kinetics and lter surface loading are in progress.
Later, the batches were taken from the shaker and
centrifuged for 20min at 2000rpm (894g), and nally the
samples were carefully dispensed to 50mL PE sample cups,
acidied to pH 1.52 using strong HNO
3
and stored at 4 1C
until the heavy metal measurements.
Two sets of control batches were also run. The rst set
included 11 batches with different sorbents without any
heavy metal addition, following the same experimental
procedure as described previously to determine whether any
of the sorbents would release heavy metals. The second set of
control batches also followed the same experimental proce-
dure, but without adding any sorbents. This trial included 8
batches with the initial heavy metal concentrations given in
Table 2 in order to quantify any losses due to sorption to the
PE asks or additions due to contamination during the
handling of the samples. No signicant metal sorption on to
the ask walls was observed and all concentrations measured
from the second set of control experiments were within 75%
of the initial metal concentrations.
All chemicals used were reagent grade and used without
any further purication.
2.4. Heavy metal quantication
All the samples were sent to a certied commercial laboratory
(Analytica, Sweden) for quantication of heavy metal con-
centrations, where inductively coupled plasma atomic emis-
sion spectrometry (ICP-AES) or inductively coupled plasma
sector eld mass spectrometry (ICP-SFMS) was used, accord-
ing to USEPA Methods 200.7 (modied) and 200.8 (modied),
respectively. The methods quantication limits are given in
Table 2.
2.5. Heavy metal speciation calculations
Speciation calculations for the heavy metals were carried out
using a computer model, PHREEQ-C version 2 with a
thermodynamic database (i.e. LLNL.DAT) (Parkhurst and
Appelo, 1999), at a wide pH range employing the initial heavy
metal concentrations used in the experiments. The model
was also used for identication of oversaturated conditions of
any relevant metal mineral/salt during the experiments.
2.6. Analyzing sorption data
The solid phase heavy metal concentrations, q
e
(mg/g), were
determined for each sorbent by analyzing the corresponding
heavy metal concentration before and after the treatment
using the equation below:
q
e

C
0
C
e
X
, (1)
where C
0
and C
e
are the initial and equilibrium heavy metal
concentrations in the solution (mg/L), and X is the sorbent
dosage (g/L).
Freundlich isotherm,
log q
e
log K
1
n
log C
e
, (2)
where K is correlated with the quantity of sorbate associated
with the sorbent, and n is the Freundlich isotherm constant
related to the strength of the sorption, was used to investigate
the sorption data further.
The overall efciency of each sorbent in terms of heavy metal
removal was determined using sorption constants K
d
(L/g)
K
d

q
e
C
e
, (3)
where K
d
values were calculated corresponding to all the initial
concentrations used, and average K
d
values were calculated
and used to rank the sorbents for each metal.
3. Results
3.1. pH variations during the batch experiments
The pH increased with time for all sorbents except bark,
where the pH decreased (see Fig. 1). It was accentuated that
the pH increases were mainly due to dissolution of the
sorbent minerals in the process of shaking, while for bark the
observed pH decrease was primarily attributed to the release
of natural organic matter containing both acids and phenols
(conrmed by a yellow coloring of the samples during the
batch tests).
In most cases the pH increase was moderate, e.g. from pH
6.5 to 6.8 for ABSC, while for FA a major pH shift was observed
from pH 6.5 to 10.5. It is noted that the reason that the pH is
not changed signicantly for ABCS is that ABCS is prepared
from activated bauxsol (Genc--Fuhrman et al., 2004), which
was reuxed by HCl previously, and this process probably
already neutralized the surface. A nal pH of 7.7 was observed
in the NZ batches due to hydrolysis of zeolites as well as
cationic exchange. Similar results are reported elsewhere
with a remark that the pH increase is almost unavoidable
ARTICLE IN PRESS
WAT E R R E S E AR C H 41 ( 2007) 591 602 594
in a NZ heavy metal system (Ouki and Kavannagh, 1997;
Pitcher et al., 2004).
3.2. Heavy metal speciation and saturation conditions
The pH-dependent distributions between the dissolved metal
species (as calculated using PHREEQ-C) are presented in Fig. 2
for stormwater composition corresponding to batch 5 (Table
2). The results illustrate that both As and Cr are present as
anionic species; and the dominating As specie is HAsO
4
2
in
the pH range 6.510, while Cr is mainly present as CrO
4
2
at pH
values above 6.5. The other metals show somewhat more
complicated patterns, for example the most important Cd
species are CdCl
+
and Cd
2+
below pH 9.5, whereas Cd(CO
3
)
2
2
starts dominating above pH 10. The non-charged CuCO
3
is the
dominating Cu-specie in the pH range 6.59.0, while the
negatively charged species such as Cu(CO
3
)
2
2
and
CuCO
3
(OH)
2
2
dominate at higher pH values. The dominating
Ni-specie is Ni
2+
until about pH 9.5, succeeded by the
hydroxide species Ni(OH)
2
and Ni(OH)
3

at higher pH. Zinc is

mainly present as Zn
2+
below pH 8.5 and as Zn(OH)
2
at
pH49.0.
It is evident from the results presented in Table 3 that the
number of oversaturated minerals/salts is increasing with
increasing pH and increasing initial heavy metal concentra-
tion. Therefore, sorption may no longer be the primary
removal process in those batches, since precipitation of
minerals/salts on both the sorbents and the walls of the PE
asks may also occur.
3.3. Equilibrium concentrations and sorption isotherms
The results of simultaneous removal of Cd, Cu, Ni, and Zn
using the tested sorbents are presented in Fig. 3 on a double
logarithmic scale, while the results for As and Cr are
presented in Fig. 4 on a double or semi logarithmic scale. In
these gures, the equilibrium heavy metal concentrations (C
e
)
are depicted on the horizontal axis vs. the solid phase metal
concentrations (q
e
) on the vertical axis. As expected the
amount of heavy metal removed increased with increasing
initial heavy metal concentration in nearly all of the batches,
except a few cases where leaching was observed for As and Cr
(hence the semi-logarithmic depiction). Leaching of As was
observed when using bark, BCS, GAC, FA, NZ and sand, while
leaching of Cr was observed when using ABCS, BCS, FA and
spinel. It is highlighted that leaching of As and Cr was also
observed in the control batches involving sorbents but no
heavy metal addition. For example, 7, 114, 10 and 9 mg/L As
leaching was observed from Bauxsol, FA, GAC and NZ,
respectively. In the case of Cr, leaching was 137, 124, 40, 8
and 20mg/L from ABCS, FA, NZ, sand and spinel, respectively.
The calculated Freundlich isotherm parameters (K and n, cf.
Eq. (2)) are shown in Table 4. Although a high correlation was
observed in some cases, the r
2
values were low especially for
bark, BCS and FA. Fitting Langmuir isotherms to the data did
not improve the correlation. It is noted that here although
r
2
X0:5 signies a statistically signicant correlation, using
the estimated Freundlich isotherms for prediction is consid-
ered highly uncertain unless r
2
close to 1.0 is reached.
3.4. Sorbent ranking
The calculated average K
d
values for each batch are also given
in Table 4, while the overall results are presented in Fig. 5.
Each tested sorbent demonstrates different removal ef-
ciency for each heavy metal, for example, while IOCS
effectively retains As, it fails to repeat its performance for
Cd and Ni. Similarly, FA has very high afnity for Cd and Ni,
ARTICLE IN PRESS
Fig. 1 The variation of pH values as a function of time during the sorption experiments with starting pH of 6.5, initial As, Cd,
Cr, Cu, Ni and Zn concentrations of 1mg/L, sorbent dosage of 20g/L, ionic strength of 0.01M NaCl and 0.003M HCO
3

buffer.
WATER RESEARCH 41 ( 2007) 591 602 595
but it is ineffective for As and Cr (leaching). However, alumina
is consistently effective for all heavy metals tested. Conse-
quently, the overall heavy metal removal efciency of the
sorbents at the experimental conditions in a decreasing order
is, alumina4BCS4GFH4FA4GAC4spinel4ABCS4IOCS4
NZ4bark4sand.
4. Discussion
4.1. Alumina
At the experimental conditions used alumina is capable of
removing all heavy metals to concentrations below the DELV
except for the batches with the highest concentrations of Cd,
Cu and Zn. This high efciency is probably due to aluminas
high surface area (Table 1) and favorable heavy metal surface
interactions.
The dominant heavy metal species in the alumina system
(420% at pH 7.4, cf. Fig. 2) are HAsO
4
2
, CdCl
+
and Cd
2+
, CrO
4
2
,
CuCO
3
, Ni
2+
and Zn
2+
. The alumina surface is expected to be
positively charged at the experimental pH (note that the pH
pzc
of alumina is about 9, but decreases when forming hydro-
xides), which enhances electrostatic removal of the nega-
tively charged HAsO
4
2
and CrO
4
2
species. On the other hand,
alumina performed equally well for the heavy metal cation
species, which can be explained by other removal mechan-
isms like surface complexation (hydroxide groups), pore
ARTICLE IN PRESS
Fig. 2 Speciation of As, Cd, Cr, Cu, Ni and Zn in water obtained using the PHREEQ-C model with ionic strength of 0.01MNaCl,
0.003M NaHCO
3
buffer and heavy metal concentrations according to batch 5 (see Table 2).
WAT E R R E S E AR C H 41 ( 2007) 591 602 596
diffusion and specic adsorption. For batch numbers 58
precipitation of Cu, Cd and Zn minerals/salt may also be
counted as a relevant removal process (oversaturation, cf.
Table 3).
4.2. Activated bauxsol-coated sand and bauxsol-coated
sand
ABCS efciently retains As to values below the DELV
independent of the initial As concentration, and it is also
one of the most efcient sorbents for Cu. However, the
sorbent fails to remove Cr, Cd, Ni, and Zn as efciently as As
and Cu.
BCS performs better than ABCS for removing all metals
except for As. This can be explained by the negatively charged
BSC-surface at the experimental pH (8.6) compared to that of
ABCS (6.8). Consequently, the electrical attraction increases
the removal of positively charged metal ions. Furthermore,
the surface complexation between dissolved species and
oxide- and hydroxide groups on the surface will increase with
increasing pH. Oversaturation occurs only in batches 7 and 8
for ABSC (Table 3), thus sorption may be the dominant
mechanism for ABCS. On the other hand, for BCS it is
expected that e.g. Zn minerals/salts can precipitate in all
batches except for batch 1, and that Cd and Cu minerals/salts
may precipitate for batches 38. It can, therefore, be
suspected that precipitation and not sorption is the major
removal process for Zn, Cd, and Cu in the BCS batches.
4.3. Bark
Bark suffered from low heavy metal removal efciency (see
Fig. 5), and minor As and Cr leaching is observed especially at
low initial heavy metal concentrations (see Fig. 4). Further-
more, water discoloration is observed most likely due to the
release of organic acids and phenols. Among the metals,
especially Cu is known to form strong complexes with natural
organic acids, which can reduce the sorption (Du ker et al.,
1995; Dario and Ledin, 1997), and the low average K
d
observed
for Cu is, therefore, probably attributed to this phenomenon.
Considering the low afnity of the bark to the tested heavy
metals and the leaching of organic matter as well as As and
Cr, bark may be considered unsuitable as a secondary
treatment ltration media.
4.4. Fly ash
FA has high afnity for Ni, Zn, Cu and Cd, which at the high
pH during the experiments with FA mainly are present non-
charged or anionic species (i.e. Ni(OH)
2
, Zn(OH)
2
, Cd(CO
3
)
2
2
,
Cu(CO
3
)
2
2
). In addition, oversaturated conditions and conse-
quently precipitation of Cd, Cu, Ni and Zn minerals/salts (see
Table 3) will also contribute to the overall removal. The results
indicate that FA has low afnity to Cr and As species.
However, this is due to the considerable leaching from the
sorbent (see Fig. 4b). Despite the high removal efciency of FA
towards Cd, Cu, Ni and Zn, FA is unsuitable for secondary
treatment of stormwater due to the leaching of As and Cr and
the high efuent pH.
4.5. Granulated activated carbon
GAC is the most effective sorbent for Cr and it has moderate
to high efciency for Cd, Cu, Ni and Zn. On the other hand, it
has a signicantly lower efciency for As compared to that of
the other heavy metals (Fig. 5). Oversaturated conditions of
Zn-, Cd- and Cu- minerals/salts may also contribute to the
removal efciency in the GAC batches in the same manner as
in the BCS batches (Table 3).
4.6. Granulated ferric hydroxide
GFH was the third most effective sorbent when ranked
according to average K
d
values (Fig. 5). Previously GFH has
been advocated as a highly efcient sorbent especially for
arsenate removal (Sperlich et al., 2005), but here GFH
demonstrated moderate As removal efciency and is out-
performed by alumina, IOCS, ABCS, and spinel. This may be
ARTICLE IN PRESS
Table 3 Oversaturated heavy metal minerals/salts, e.g. SI40, where SI is dened as log(IAP/K
s
) in the batch experiments,
estimated by PHREEQ-C modelling with ionic strength of 0.01M NaCl and 0.03M NaHCO
3
buffer
pH Batch 1 Batch 2 Batch 3 Batch 4 Batch 5 Batch 6 Batch 7 Batch 8
5.8 (Bark) Zn, Cd, Cu
6.8 (ABCS) Zn, Cd, Cu Zn, Cd, Cu
7.2 (Sand) Cu, Cd, Zn Zn, Cd, Cu Zn, Cd, Cu
7.4 (Alumina) Cu, Cd Zn, Cd Zn, Cd, Cu Zn, Cd, Cu
7.5 (IOCS) Zn, Cd, Cu Zn, Cd, Cu Zn, Cu, Cd Zn, Cd, Cu
7.7 (NZ) Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu Zn
,
Cd, Cu
7.8 (GFH) Zn, Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu
8.6 (BCS, GAC) Zn Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu, As
8.7 (Spinel) Zn Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu Zn, Cd, Cu,
Ni
Zn, Cd, Cu, Ni, As
10.6 (FA) Cu Ni, Cd, Cu Zn, Ni, Cd,
Cu
Zn, Ni, Cd,
Cu
Zn, Ni, Cd,
Cu
Zn, Ni, Cd,
Cu
Zn, Ni, Cd,
Cu
Zn, Ni, Cd, Cu, As
WATER RESEARCH 41 ( 2007) 591 602 597
due to the pH differences, as the literature reports higher
arsenate removal efciencies using GFH at the pH values
below 7.5, e.g. below pH
pzc
(see Table 1) while the equilibrium
pH here was 7.8.
Despite its medium As removal efciency, GFH is the
second most effective sorbent for Cr and it is also effec-
tive for Cd, Ni and Zn. The dominant heavy metal species
at pH 7.8 are HAsO
4
2
, CdCl
+
and Cd
2+
, CrO
4
2
, CuCO
3
, Ni
2+
,
and Zn
2+
(Fig. 1). The pH is close to pH
pzc
, e.g. both posi-
tively and negatively charged groups are available at the
sorbent surface. This indicates that the electrostatic
attraction as well as surface complexation can be impor-
tant removal mechanisms. Moreover, the saturation calcula-
tions indicate that Cd, Cu and Zn could also be removed
due to precipitation of their minerals/salt in batches 58 (see
Table 3).
4.7. Iron oxide-coated sand
IOCS has moderate to poor heavy metal removal efciency
compared to that of the other sorbents, except from bark,
sand and NZ (Fig. 5). Interestingly, IOCS is the second most
ARTICLE IN PRESS
Fig. 3 Cd, Cu, Ni and Zn removal using (a) sorbents with high heavy metal removal efciency, (b) sorbents with moderate or
low heavy metal removal efciency; with starting pH of 6.5, sorbent dosage of 20g/L, ionic strength of 0.01M NaCl, and
0.003M NaHCO
3
buffer. DELV is Danish emission limit values for fresh surface waters.
WAT E R R E S E AR C H 41 ( 2007) 591 602 598
efcient sorbent for As following alumina, and according to
the results As is treated to below the DELVeven at the highest
initial As concentrations (see Fig. 4). The pH
pzc
of IOCS is 9
(Table 1), and thus the average surface charge is positive at
the experimental pH (7.5), which in turn attracts the
negatively charged anions like As and Cr. On the other
hand, IOCS has low afnity for Cu, Cd, Ni and Zn. This is
contradicting to previously reported results, where IOCS was
capable of effectively removing Cu, Cd, Ni and Pb from
wastewater (Lo et al., 1997). It is suggested that the observed
low sorption of these metals onto IOCS may be due to
differences in experimental conditions; here all heavy metal
co-existed whereas single heavy metal systems are typically
used in the literature, a relatively low sorbent dosage was
used (20g/L here compared with 200g/L in the literature), and
a comparably low but however realistic pH (7.5) was used, to
create a reasonable representation of a system with storm-
water and IOCS.
4.8. Natural zeolites
The afnity of NZ towards the heavy metals is Cu4Cd4Zn4
Ni4As4Cr (Table 4). As expected the removal efciency
towards the anionic species is lower compared to that of the
cationic and neutral species. This can be due to cation
exchange and electrostatic interactions, because the NZ has
a negative surface charge at pH 7.7 (pH
pzc
5.6; Table 1). It is
noted that the exchangeable ions in NZ predominantly are
Na
+
, Ca
2+
, and K
+
, and thus divalent Cd, Cu, Ni and Zn ions
are more favorably removed via cation exchange. Further-
more, a minor As leaching is observed in the control
experiments (i.e. 9mg/L) and at low initial As concentrations
(note that according to the supplier information NZ contains
5 mg/kg As).
4.9. Sand
The pertinent data indicates that the sand has a minor heavy
metal removal efciency compared to the other sorbents, and
the afnity of sand towards the heavy metals is Cr4As4
Cu4Cd Ni Zn (Fig. 5). Similarly, low heavy metal removal
using sand is also reported elsewhere (Sansalone, 1997). The
primary reason for this low sorption capacity is the low
surface area (see Table 1) and few sorption sites. It is
emphasized that the sand was merely included in this study
to be used for comparison with the other sorbents and the
obtained data suggests that the magnitude of the heavy metal
removal using sorbents prepared from coating a sorbent to
sand (i.e. IOCS, BCS, and ABCS) is signicantly greater than
that of sand itself.
4.10. Spinel (MgAl
2
O
4
)
Spinel has moderate to high heavy metal removal efciency,
and the overall evaluation shows that it is better than ABCS,
NZ, bark, IOCS and sand (see Fig. 5). The surface area of spinel
is relatively low (see Table 1), but it is expected to have very
high porosity, as the spinel used here is originally developed
as catalyst. Spinel has the highest pH
pzc
(about 11) of the
tested sorbents, and it could, therefore, be expected to
remove cationic species by electrostatic attraction at the
experimental conditions (pH 8.7; Table 4). On the other hand,
precipitation could for some metals (Zn, Cd, Cu) also
contribute to the removal.
ARTICLE IN PRESS
Fig. 4 As and Cr removal using (a) sorbents with high heavy metal removal efciency, (b) sorbents with moderate or low
heavy metal removal efciency; experimental condition were the same as in Fig. 3.
WATER RESEARCH 41 ( 2007) 591 602 599
4.11. Adsorption isotherms
Freundlich and Langmuir isotherms are commonly used in
the literature to study heavy metal sorption. Here, it was
observed that the Freundlich isotherm tted the data better
suggesting heterogeneous surface characteristics. When
evaluating FA, spinel, and BCS (sorbents with high end pH)
sorption isotherms gave lower r
2
values especially for Zn, Ni,
Cu and Cd (see Table 4). In these systems, precipitation may
play a role as removal mechanism besides adsorption, which
in turn may have decreased the capability of the Freundlich
isotherms to predict the removal.
Leaching of e.g. As from FA and bark could also provide
explanation on why the isotherm did not explain the data
very well.
5. Conclusions
In this study, 11 sorbents are examined in batch tests as
potential lter media for secondary treatment of stormwater.
The sorbents are tested in for the combined removal of As,
Cd, Cr, Cu, Ni and Zn removal from synthetic stormwater
samples at a starting pH of 6.5. However, the pH values are
changed to 5.8 (bark), 6.8 (ABCS), 7.2 (sand), 7.4 (alumina), 7.5
(IOCS), 7.7 (NZ), 7.8 (GFH), 8.6 (BCS, GAC), 8.7 (spinel) and 10.6
(FA) during the experiments, suggesting that in a secondary
stormwater treatment system with sufcient reaction time,
the pH of the discharged water is controlled by the sorbent
material rather than the inlet water composition.
It is found that the magnitude of the heavy metal removal
depends on the initial heavy metal concentration and varies
to a great extent among the sorbents. For example, while
sand and bark fail to remove all heavy metals to meet the
DELV; alumina, BCS, GFH and GAC can efciently remove the
heavy metals down to the DELV. The results from the present
study also show that the heavy metal speciation and the
surface charge are pH dependent, and that several possible
removal mechanisms interact in a complex manner.
The Freundlich isotherm is applied to the sorption data and
the constants K and n are presented. Although the isotherm
t the data in many cases, ill tted results are also observed
especially for FA, BCS and GAC possibly due to leaching of
some metals from the sorbents and oversaturated conditions
making precipitation the dominant removal mechanism over
sorption in batches with high heavy metal concentrations
and pH.
The sorbents are ranked using average K
d
values, and
it is found that when overall heavy metal removal is
considered alumina is the most effective followed by BCS,
GFH, FA, GAC, spinel, ABCS, IOCS, NZ, bark, and sand.
It is highlighted that despite the high afnity of FA, NZ
and bark to some heavy metals leaching of especially As and/
or Cr limits their usage. The current study provides important
new information on the efciency of a range of potential
sorbents in a multiple sorbate system using experimental
conditions, which resemble those of real life stormwater
runoff in terms of initial heavy metal concentration, pH, and
ionic strength.
ARTICLE IN PRESS
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WAT E R R E S E AR C H 41 ( 2007) 591 602 600
Acknowledgements
This work is funded by Danish Technical Research Council
(Grant no.: 26-03-0326). Laboratory technician Susanne Kruse
and the M.Sc. students Yushan Zhou and Peng Wu are
acknowledged for their contribution during the experiments.
Thanks are also to Haldor Topse A/S, Kemira Denmark and
Ingenieurgesellschaft Prof. Dr. Sieker MBH for supplying the
alumina, GAC, and GFH, respectively.
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