Environ Geochem Health
DOI 10.1007/s10653-007-9094-0
ORIGINAL PAPER
Removal of contaminants in leachate from landfill by waste
steel scrap and converter slag
Byung-Taek Oh Æ Jai-Young Lee Æ Jeyong Yoon

Springer Science+Business Media B.V. 2007
Abstract This study may be the first investigation
to be performed into the potential benefits of
recycling industrial waste in controlling contaminants
in leachate. Batch reactors were used to evaluate the
efficacy of waste steel scrap and converter slag to
treat mixed contaminants using mimic leachate
solution. The waste steel scrap was prepared through
pre-treatment by an acid-washed step, which retained
both zero-valent iron site and iron oxide site.
Extensive trichloroethene (TCE) removal (95%)
occurred by acid-washed steel scrap within 48 h. In
addition, dehalogenation (Cl
production) was ob-
served to be above 7.5% of the added TCE on a molar
basis for 48 h. The waste steel scrap also removed
tetrachloroethylene (PCE) through the dehalogen-
ation process although to a lesser extent than TCE.
Heavy metals (Cr, Mn, Cu, Zn, As, Cd, and Pb) were
extensively removed by both acid-washed steel scrap
B.-T. Oh (&)
Department of Environmental Sciences and
Biotechnology, Hallym University, Chuncheon,
Gangwon-do 200-702, South Korea
e-mail: btoh@hallym.ac.kr
J.-Y. Lee (&)
Department of Environmental Engineering, University of
Seoul, Seoul 130-743, South Korea
e-mail: leejy@uos.ac.kr
J. Yoon
School of Chemical Engineering, Seoul National
University, Seoul 151-742, South Korea
and converter slag through the adsorption process.
Among salt ions (NH+4 , NO
3
3

3 , and PO4 ), PO4 was
removed by both waste steel scrap (100% within 8 h)
and converter slag (100% within 20 min), whereas
NO-3 and NH+4 were removed by waste steel scrap
(100% within 7 days) and converter slag (up to 50%
within 4 days) respectively. This work suggests that
permeable reactive barriers (PRBs) with waste steel
scrap and converter slag might be an effective
approach to intercepting mixed contaminants in
leachate from landfill.
Keywords TCE  PCE  Leachate  Steel scrap 
Heavy metals  Converter slag  Zero-valent iron
Introduction
Municipal solid waste landfills contain mainly a
mixture of various organic compounds, inorganic
salts, and heavy metals (Sandgren et al. 1996). The
decomposition of waste in the landfill may result in
producing environmentally harmful substances.
Landfill leachate treatment has received significant
attention in recent years since landfill leachate is a
frequent source of groundwater contamination
(USEPA 1988). Several in or ex situ physico-
chemical processes, such as solidification/
stabilization, slurry trench cut-off walls, and reactive
walls, have been introduced to manage leachate
123

contamination. However, many of these approaches
are not cost effective for treating large volumes of
contaminated groundwater. These problems have
been emphasized by the identification of chlorinated
solvents such as trichloroethylene (TCE) and tetra-
chloroethylene (PCE) in leachate-contaminated
groundwater (Chen and Zoltek 1995). In addition,
complete contaminants removal in leachate from
landfill is not always achieved, which can result from
the coexistence of contaminants.
Encouraging results in laboratory experiments
have stimulated a rapid increase in the use of zero-
valent iron (Fe0) as a reactive material to remove
chlorinated solvents from groundwater (Gerlach et al.
2000; Lampron et al. 2001). With a standard reduc-
tion potential (Eh8) of
409 mV (Weast 1978), Fe0
primarily acts as a strong reducing agent:
Fe0 ! Fe2þ + 2e
ð1Þ
Previous studies have shown that permeable
reactive barriers (PRBs) using Fe0 can remove
redox-sensitive groundwater contaminants (e.g., chlo-
rinated solvents and Cr(VI)) (Scherer et al. 2000;
Gandhi et al. 2002). One byproduct reported in PCE
and TCE reaction with Fe0 is acetylene. Cipollone
et al. (1995) have postulated that this reaction is
raised through the sequential hydrogenolysis
(replacement of a halogen (Cl
) by a hydrogen) of
PCE to TCE, dichloroethylenes (DCEs), and vinyl
chloride (VC), followed by VC dehydro-halogenation
to acetylene.
Industrial waste, such as fly ash, bottom ash, and
granulated slag of steel plans, have been studied as
possible cost-effective and convenient adsorbents for
the treatment of wastewater containing heavy metals
(Ortiz et al. 2001). Kwon and Kim (1999) reported
that converter slag has a higher capacity for pH
increase and removal of Fe, Al, and other heavy
metals in acid mine drainage than limestone. Con-
verter slag composed of magnetite (Fe3O4) has been
known to be suitable for use as a metal adsorber in
wastewater treatment.
The main objective of this study was to evaluate
the efficacy of waste steel scrap and converter slag to
treat mixed contaminants in leachate from landfill.
Emphasis was placed on determining whether waste
steel scrap is effective as both reducing agent and
heavy metal adsorber after pre-treatments. This waste
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Environ Geochem Health
steel scrap and converter slag are inexpensive and
abundant, and are, therefore, ideal for low-cost
leachate treatment from landfill.
Materials and methods
Converter slag (with a sieve size of 1.2–2 mm) as a
steel plant residue was obtained from a local steel
company in Korea. Waste steel scrap, which has a
surface area of 0.57–0.65 m2/g according to the
Brunauer-Emmett-Teller (BET) method (Alowitz and
Scherer 2002) and a sieve size of 7–10 mm, was
obtained from a local industrial complex dealing with
machine tools and was washed with organic solvent
while being treated with sonicator in order to remove
surface oil. Two different types of waste steel scrap,
then, were prepared through pre-treatment. One type
was physically scratched with sand paper to incur
rusting (RD). The other type was acid-washed with
2 N hydrochloric acid solution (AD) to have both
zero-valent iron site and oxide site during pre-
treatment. The granular zero-valent iron (FB;
1.0 mm diameter), which was commercially obtained
from Master Builder (Cleveland, OH, USA), was also
used to give a baseline to evaluate the efficacy of the
waste steel scrap.
Batch degradation assays were subsequently run to
separately test the reactivity of the prepared waste
steel scrap and converter slag towards TCE, PCE, ion
salts, and heavy metals, pollutants that are commonly
present in leachate from landfill. For this experiment,
three reactor sets were prepared in triplicate: chlori-
nated solvent (TCE and PCE at 10 and 100 mg/l), salt
ions (NH+4 , NO
3 , and PO4
3

at 10 mg/l each), and
heavy metals (Cr, Mn, Cu, Zn, As, Cd, Pb, and CN at
10 mg/l each). In order to investigate the reactivity of
the prepared steel scrap through pre-treatment, 5 g
each of RD, AD, and FB were added to 120-ml serum
bottles and 10 mg/l of TCE and PCE solutions were
filled without headspace to inhibit volatilization
respectively. In order to prove hydrogenolysis (Cl

production from chlorinated compounds) by the
prepared steel scrap, 100 mg/l of TCE and PCE
solutions were applied. The reactors were sealed with
Silicon septa and aluminum crimps. Reactors were
shaken on a reciprocating shaker (150 rpm, 258C) and
sampled after 4 and 48 h for each pollutant. For
analysis, the supernatant of each reactor was gently
Environ Geochem Health
transferred to 8.5-ml vial, with a silicon-lined cap
without headspace, wrapped with parafilm, and stored
at 48C until analyzed. In order to investigate the
ability of the prepared steel scrap to remove salt ions
and heavy metals, 5 g of RD, AD, FB, or converter
slag was added to 120-ml serum bottles containing
100 ml of de-ionized water amended with salt ions
(NH+4 , NO
3

3 , and PO4 at 10 mg/l each) and heavy
metals (Cr, Mn, Cu, Zn, As, Cd, Pb, and CN at
10 mg/l each). The reactors were sealed with silicon-
lined, gray-butyl septa, and aluminum crimps. Reac-
tors were shaken on a reciprocating shaker (150 rpm,
258C) and periodically sampled for each pollutant.
The samples were filtered with a 0.2-mm syringe filter
and stored at 48C until analyzed. Control reactors
were also prepared without reactive materials such as
RD, AD, FB, or converter slag.
Trichloroethylene (TCE) and PCE were quantified
using a Hewlett Packard gas chromatograph equipped
with an electron capture detector, a HP-VOC capil-
lary column (J&W Scientific, Folsom, CA, USA),
and Purge & Trap. The carrier gas was nitrogen at
2 ml/min, the detector temperature was 3008C, and
the inlet temperature was 2508C. The initial column
oven temperature was held at 458C for 2 min, then
increased 158C/min to 958C, held for 1 min, then
increased 108C/min to 2308C and held for 5 min.
Phosphate, ammonium ion, nitrate, and chloride
ion (from the dehalogenation of TCE and PCE) were
analyzed with a Dionex (Sunnyvale, CA, USA) DX-
120 ion chromatography (IC). Separation was
achieved with an IonPac CS14 cation column
(4 · 250 mm, Dionex) with 10 mM methansulfonic
acid and 0.3% acetonitrile eluent for ammonium ion.
Phosphate, nitrate, and chloride ion were measured
with an IonPac AS14 anion column (4 · 250 mm,
Dionex) with 8.0 mM Na2CO3 and 1.0 mM NaHCO3
eluent with conductivity detection. The eluent was
pumped at a rate of 1 ml/min. Cr, Mn, Cu, Zn, As,
Cd, and Pb were measured using inductively coupled
plasma atomic emission spectrometry (ICP-AES
7510; Shimadzu, Kyoto, Japan). This analysis was
conducted with 1.2 kW of RF power at a flow rate of
141 ml/min for coolant gas, 1.21 ml/min for plasma
gas, and 0.71 ml/min for carrier gas using argon. The
samples were injected at a rate of 1 ml/min. CN
concentration was separately determined using fully
automatic wet (water) chemical analyzer (AA3;
Bran-Luebbe, Norderstedt, Germany). Samples
containing CN were diluted to 1:20 (v:v) and added
to 50% Triton-X CN buffer to transform into
cyanogens chloride after reacting with chloramine
T. Cyanogens chloride resulted in forming a blue-
colored complex compound after reacting with pyr-
idine carboxylic acid. The complex compound was
distilled at 1458C and absorbance was measured at
630 nm. The concentrations of pollutants were
determined after peaks were identified by comparison
with retention times and quantified relative to
response factors of standard compounds.
Results and discussion
Reactivity of waste steel scrap for TCE and PCE
Previous studies have reported that zero-valent iron
can dechlorinate halogenated aliphatic organic com-
pounds in batch reactors. Gillham and O’Hannesin
(1994) suggested that metallic iron could be used to
remediate chlorinated solvents-contaminated ground-
water in the PRB system. Figure 1 corroborates these
previous findings and shows that chlorinated com-
pound, TCE, was effectively removed in batch
studies with the prepared steel scrap (RD, AD, and
FB) through pre-treatment.
In controls, there was more than a 10% TCE
concentration reduction in the 4-h reactors, but nearly
0% loss in the 48-h reactors. This discrepancy may
have resulted from experimental error such as the
presence of some head space in the 4-h reactors. This
10
0 hr
4 hr
TCE Conc. (ppm)
8 48 hr
6
4
2
0
Control RD AD FB
Fig. 1 Trichloroethylene (TCE) removal by two types of
waste steel scrap and granular zero-valent iron (initial
concentration: 10 mg/l). RD rusting, AD hydrochloric acid
solution, FB granular zero-valent iron
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discrepancy, although large, is still much less than the
losses due to the experimental conditions.
Extensive TCE removal occurred by RD (82.4%),
AD (94.5%), and FB (93%) for 48 h, demonstrating
that TCE removal was due to degradation by zero-
valent iron (Fig. 1). To investigate the activity of AD
to remove TCE, we also compared it with that of FB,
which has very large surface area. For reaction times
of 4 and 48 h, AD showed almost the same capability
to remove TCE with FB. In preliminary experiments,
waste steel scrap itself before the pre-treatment step
did not show any reactivity to contaminants including
TCE. Note that the waste steel scrap was reactive due
to pre-treatments such as sandpapered and acid-
washed steps, which resulted in the removal of
chlorinated compounds. Matheson and Tratnyek
(1994) observed that the reaction appeared to be
pseudo first order with regards to the contaminant
concentration. They also found that the products of
the reaction were chloride (Cl
), iron (Fe2+), and
non-chlorinated hydrocarbons as the final byproducts.
Similar results were obtained in our experiments, i.e.,
extensive dechlorination occurred by AD and FB for
48 h (Fig. 2). The value of the dechlorination extent
was approximately 7.5% (AD) and 11.5% (FB) of the
added TCE on a molar basis. AD, which originated
from waste steel scrap, exhibited extensive activity
for use as a reactive material in PRB, although
dechlorination of TCE by AD was less than that by
FB.
Tetrachloroethylene (PCE), which is a more
chlorinated compound than TCE, was removed by
RD, AD, and FB (Fig. 3). RD, AD, and FB removed
10
4 hr
48 hr
8
C l- C o n c . ( p p m )
6
4
2 2
0 0
Control RD AD FB
Fig. 2 Dechlorination of trichloroethylene by two types of
waste steel scrap and granular zero-valent iron (initial
concentration: 100 mg/l)
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Environ Geochem Health
PCE for a reaction time of 48 h by 39.9, 41.8, 67.6%
respectively, while untreated controls caused about
20% of volatilization loss. The extent of PCE
removal, however, was slightly less than that of
TCE, possibly due to the number of halogen (Cl
)
groups on organic compounds that were dehalogen-
ated by electrons originating from zero-valent iron.
The occurrence of dechlorination from PCE by the
waste steel scrap was also observed to a lesser extent
than that of TCE (Fig. 4), which was a tendency
consistent with the less PCE removal efficiency
observed. This result is supported by previous
studies. Arnold and Roberts (2000) suggested that
partially dechlorinated products are more reactive
than more highly chlorinated compounds due to the
rate-limiting step of dissociative electron transfer.
Removal of salt ions by waste steel scrap
The waste steel scrap prepared through pre-treatment
showed a high reactivity to remove salt ions. Among
the tested salt ions (NH+4 , NO
3
3

3 , and PO4 ), PO4 was
the most reactive by RD, AD, FB (100% within 8 h),
and converter slag (100% within 20 min), followed
by NO
+
3 (Fig. 5), while NH4 removal by converter
slag (50% within 4 days) alone was relatively slow
with no reactivity of waste steel scrap (RD and AD)
and FB (data not shown). The fast removal of PO3
4
by converter slag may be due to the formation of
precipitate after PO3
4 has reacted with metallic
cations (Al3+, Fe2+, Fe3+, Ca2+ etc.), which are
common components of converter slag in solution
(Oguz 2004). In removal of NO-3, the waste steel
10
0 hr
4 hr
PCE Conc. (ppm)
8 48 hr
6
4
Control RD AD FB
Fig. 3 Tetrachloroethylene removal by two types of waste
steel scrap and granular zero-valent iron (initial concentration:
10 mg/l)
Environ Geochem Health

6 reactivity was more effective than that of a previous

4 hr
batch study showing the reactivity of rusted iron to
5
48 hr remove NO-3 (Oh and Alvarez 2004). Under strong
reducing conditions, NO


Cl- Conc. (ppm)

4 3 is likely reduced to NO2 ,

+ +
NH3, and NH4 . Thus, NH4 removal by the waste steel
3 scrap was not further observed, even by FB, as
2
described above (data not shown).

1 Sorption of heavy metals

0
Control RD AD FB Heavy metals removal assays were also conducted in
additional batch reactors to investigate the ability of
Fig. 4 Dechlorination of tetrachloroethylene by two types of AD and converter slag to remove heavy metals.
waste steel scrap and granular zero-valent iron (initial
concentration: 100 mg/l)
Previous work by Ortiz et al. (2001) showed that
converter slag could be used as an adsorber material
to remove heavy metals in wastewater treatment.
12 Based on adsorption results, significant removal of
heavy metals (Cr, Mn, Cu, Zn, As, Cd, and Pb) by
10 AD and converter slag was observed (Table 1).
NO3 Conc. (ppm)

RD Interestingly, AD, which is known to be able to

8 AD
FB remove the chlorinated compounds (TCE and PCE)
6 Converter slag as described above, removed heavy metals except Mn
Control
to a great extent. The removal of heavy metals by AD
-

4
may be due to adsorption by iron oxide on the AD
2 surface that was formed through pre-treatment. This
hypothesis is supported by previous research (Wilkin
0
0 1 2 3 4 5 6 7 8
and McNeil 2003), suggesting that the rapid removal
Time (day) of heavy metals using granular zero-valent iron in
12
water contaminated by acid mine drainage is due to
adsorption onto the surface of iron metal or onto iron
10 corrosion products. Mn and Cd were almost com-
PO4 Conc. (ppm)

RD pletely removed in 20 min by converter slag. CN,

8 AD
FB
however, did not react as readily with converter slag
Converter slag as did AD, which removed up to 26.5% for 24 h.
6
Control
Among the mixed heavy metals, CN seems to be the
3-

4 most recalcitrant. Further experiments are needed to

determine whether the removal of mixed heavy
2 metals depends on pH and temperature.
0
0 1 2 3 4 5 6 7 8 9
Time (hour) Conclusions

Fig. 5 Removal of NO
3

3 and PO4 by two types of waste steel
scrap, granular zero-valent iron, and converter slag (initial
concentration: 10 mg/l each)
scrap indicated great activity, while no activity was
observed by converter slag, indicating that AD is the
effective reactive material to remove redox-sensitive
pollutants in leachate from landfill. The extent of AD
As machine tools and steel plant residues, waste steel
scrap and converter slag are abundant and can be
obtained at low cost. Laboratory experiments suggest
that waste steel scrap and converter slag can be used
as reactive materials in a PRB system to remove
mixed contaminants in leachate from landfill. This
approach may also be practical and effective for

123
 Environ Geochem Health

Table 1 Removal of heavy metals by AD and converter slag

Sample Heavy metals (mg/l)

Cr Mn Cu Zn As Cd Pb CN

Control 0h 6.7 6.5 10.2 9.6 9.1 9.4 7.9 8.3

24 h 6.5 6.5 10.1 9.6 9.0 9.4 8.4 8.4
AD 20 min 4.0 5.9 7.0 7.0 5.9 7.3 3.2 8.1
60 min 2.7 6.0 3.2 4.0 3.8 5.3 0.7 8.7
6h 0.2 7.3 0.2 0.5 0.2 3.3 ND 5.8
24 h 0.1 7.5 0.1 0.3 0.1 2.2 ND 6.1
Converter slag 20 min 4.1 0.1 0.1 0.3 1.6 0.1 2.0 9.8
60 min 4.6 0.1 0.2 0.4 1.3 0.1 1.6 11.2
6h 2.8 0.1 0.3 0.5 0.3 0.1 1.2 9.7
24 h 2.4 0.1 0.1 0.3 0.2 0.1 0.9 8.4
ND: not detected

treating other redox-sensitive groundwater pollutants,
such as nitroaromatic compounds, chlorinated sol-
vents, hexavalent uranium, and some pesticides.
Acknowledgements This work was funded by the Core
Environmental Technology Development Project for the Next
Generation (Project No. 042-041-004). The authors wish to
thank the National Instrumentation Center for Environmental
Management (NICEM) at Seoul National University for
valuable analytical assistance.
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