Waste Management 24 (2004) 945955

www.elsevier.com/locate/wasman

Leaching assessment of road materials containing primary lead

and zinc slags
a,*
R. Barna , P. Moszkowicz b, C. Gervais b

a
Ecole des Mines dAlbi, Campus Jarlard, 18013 Albi Cedex 9, France
b
LAEPSI, Institut Natonal des Sciences Appliquees Lyon, 69621 Villeurbanne Cedex, France

Accepted 29 July 2004

Abstract

Characterisation of the leaching behaviour of waste-containing materials is a crucial step in the environmental assessment for
reuse scenarios. In our research we applied the multi-step European methodology ENV 12-920 to the leaching assessment of road
materials containing metallurgical slag. A Zn slag from an imperial smelting furnace (ISF) and a Pb slag from a lead blast furnace
(LBF) are investigated. The two slags contain up to 11.2wt% of lead and 3.5wt% of zinc and were introduced as a partial substitute
for sand in two road materials, namely sand-cement and sand-bitumen. At the laboratory scale, a leaching assessment was per-
formed rst through batch equilibrium leaching tests. Second, the release rate of the contaminants was evaluated using saturated
leaching tests on monolithic material. Third, laboratory tests were conducted on monolithic samples under intermittent wetting con-
ditions. Pilot-scale tests were conducted for eld testing of intermittent wetting conditions. The results show that the release of Pb
and Zn from the materials in a saturated scenario was controlled by the pH of the leachates. For the intermittent wetting conditions,
an additional factor, blocking of the pores by precipitation during the drying phase is proposed. Pilot-scale leaching behaviour only
partially matched with the laboratory-scale test results: new mass transfer mechanisms and adapted laboratory leaching tests are
discussed.

2004 Elsevier Ltd. All rights reserved.

1. Introduction nant release for specic chemical conditions, and

Increasing interest in the use of waste materials in
roads has led to a need for improved knowledge of the
long-term behaviour and eco-compatability of waste
materials in roads. The European Committee for Stand-
ardisation (CEN, 1997) has developed a four step meth-
odology to assess leaching behaviour that is designed to
take into account both material properties and specic
applications. The methodology provides advice on the
use of specic leaching tests, selected with consideration
for the application to be assessed.
Equilibrium leaching tests, which typically are con-
ducted on crushed materials, aim to measure contami-
*
Corresponding author. Tel.: +33 5 63 493134; fax: +33 5 63
493243.
E-mail address: radu.barna@enstimac.fr (R. Barna).
typically evaluate the eect of pH. Mass-transfer leach-
ing tests, carried out on monolithic or granular materi-
als, aim to determine pollutant release rates by
accounting for both chemical and physical properties
of the wastes and waste materials. Typically, the release
of inorganic contaminants from monolithic waste mate-
rials is evaluated by tank leaching of continuously
water-saturated material with periodic leachant renewal
(Kosson et al., 1996a; Cote et al., 1986).
However, materials in many eld or management sce-
narios cannot be assumed to be continuously wetted.
Rather they experience cyclic wetting and drying under
varied environmental conditions (e.g., variable relative
humidity, temperature, atmospheric CO2) (van der Sloot
et al., 1997). Moisture loss during storage may be ex-
pected to inuence precipitation and redistribution of

0956-053X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2004.07.014
946 R. Barna et al. / Waste Management 24 (2004) 945955
the contaminants within the pore structure. Another
potential consequence of storage for alkaline cement-
based materials is the carbonation reaction between
portlandite and carbon dioxide from the atmosphere
(Lange et al., 1997; Macias et al., 1997). Only recently
has research been conducted to assess how the phenom-
ena of drying and carbonation inuence the release of
inorganic contaminants from Portland cement-based
materials during cyclic wetting and storage (Garrabants,
2003; Gervais et al., 1994, 1999b; Sanchez et al., 2003).
Thus, estimates based on a continuously saturated ma-
trix cannot adequately simulate eld conditions unless
adjusted to account for cyclic periods of leaching and
non-leaching.
In the current diusion-based approach, this has
been attempted by multiplying the contaminant release
rate estimated under continuously saturated conditions
by a wetting frequency term, which is related to the
fraction of the total assessment interval that the matrix
is saturated (Kosson et al., 1996b). This approach as-
sumes that there are no signicant changes to the chem-
ical or physical composition of the solid matrix under
variable wetting conditions. Therefore, specic tests
have been developed to examine the eects of intermit-
tent wetting on the release of inorganic contaminants
from waste.
For this research, the environmental assessment of
slag-containing roading materials was undertaken rst
through batch equilibrium leaching tests, which were
used to determine: (i) the acid neutralisation capacity
of the material, and (ii) the solubilisation of Pb and
Zn as a function of pH. The release rate of the contam-
inants from the roading materials was evaluated using
mass-transfer leaching tests on monolithic material for
both saturated conditions and for conditions allowing
for wetting and drying cycles. In addition, eld tests
were conducted.
Fig. 1. Pilot scale test sections for control and ISF slag-containing sand-cements and sand-bitumens.
Table 1
Sand-cements and sand-bitumens composition
Components (wt%) SCcont SCisf
Calcareous sand 06 mm 94.5 46.5
Slags ISF/LBF 47
Binding material
5.5 5.5
2. Methodology, materials and methods
The methodology used is based on the European
standard ENV 12-920 (CEN, 1997), for which four
experimental steps have to be carried out to determine
the leaching behaviour of a material in a specied sce-
nario. The application of the standard to this investiga-
tion is described in the following four steps.
2.1. Description and characterisation of the wastes and
waste materials
Two primary smelting slags, generated from the
processing of lead and zinc ores, were studied. As lead
and zinc ores are often mixed, the production of primary
lead leads to the production of some primary zinc and
vice versa. Therefore, the slags contain both lead and
zinc but in dierent amounts. Our research uses a slag
produced in the smelting of zinc using an imperical
smelting furnace, termed the ISF slag, and a slag pro-
duced in the smelting of lead using a lead blast furnace,
termed the LBF slag. Both slags, provided by Metaleu-
rop Nord SA, France, were characterised physically and
chemically. The slag oxide composition was measured
by X-ray uorescence (XRF). Data on slag density
and particle size distribution are reported by Gervais
et al. (1994).
The slags were used as a substitute for 50% of the
weight of sand in two road materials: sand-cement
(SC) and sand-bitumen (SB). Both sand-cement and
sand-bitumen, as shown in Fig. 1, constitute the base
layer of the road, just below the surface layer and above
the foundation layer. The level of substitution was cho-
sen from results obtained during a preliminary study.
Colas SA manufactured both types of SC and SB mate-
rials, whose content is detailed in Table 1. For SC, the
water/binding material ratio was 1.5. Three sand-
SClbf Components (wt%) SBcont SBisf SBlbf
46.5 Calcareous sand 04 mm 70 47 47
Calcareous sand 13 mm 30
47 Calcareous ller 3 3
Slags ISF /LBF 50 50
5.5 Bitumen 20/30 4.5 4.5 4.5
 R. Barna et al. / Waste Management 24 (2004) 945955
Table 2
Main oxide composition of the raw materials (acid digestion coupled with ICP analysis)
Oxide (wt%) SiO2 Al2O3 Fe2O3
Ligex 2R 30.95 8.9 1.8
Calcareous sand and ller 35.3 0.2 1.1
cements were prepared, a control sand-cement (SCcont),
a sand-cement containing ISF slag (SCisf), and one with
LBF slag (SClbf). The oxide composition of the road
materials used (binding material, sand and ller) is given
in Table 2. Sand-cements were cast as cylinders of 9.5
cm diameter and 30 cm height, cured for 28 days in a
humidity-saturated atmosphere and then stored indoors
for 4 months before testing.
A control sand-bitumen (SBcont), a sand-bitumen
containing ISF slag (SBisf), and a sand-bitumen con-
taining LBF slag (SBlbf) were prepared. Mixing rates
for the sand-bitumens are given in Table 1, and are ex-
pressed with bitumen provided in excess of 100% for
the sand/slag required. Because the slag does not contain
enough ne particles, calcareous ller (<1 mm) was
added to the sand-bitumenslag mixtures (Table 1).
Sand-bitumens were cast as blocks of 10 25 35 cm
from which cylinders of 8 cm diameter were cut for
the leaching tests (Gervais, 1999).
The total lead and zinc contents in the materials were
measured by inductively coupled plasma (ICP) analysis
for the sand-cements and by X-ray uorescence for the
sand-bitumens after acid digestion (NF X 31-151; AF-
NOR, 1993). For the materials prepared with ISF slags,
the permeability to water was measured and the porosity
was determined by mercury porosimetry (Gervais,
1999). The sand-bitumen samples had to be frozen be-
fore being crushed down to 300 lm to prevent binding
of the particles by overheating of the bitumen (Gervais,
1999).
2.1.1. Measurement of acid neutralisation capacity and
constituent solubilisation as a function of pH
The proposed standard test TC 292 (CEN, 2001a,b) is
used to test the pH-dependent solubilisation of the ma-
jor metallic pollutants under steady-state conditions.
The applied protocol, modied from the acid neutralisa-
tion capacity test (Center, 1991; Stegemann and Shi,
1997), aims to measure matrix alkalinity and constituent
solubilisation as a function of pH. The test consists of a
series of extractions with solutions of varying concentra-
tions of acid or base at a liquidsolid ratio of 10 ml/g.
Table 3
Main oxide composition and pollutant content of ISF and LBF slags (acid digestion coupled with ICP analysis)
Slags FeO CaO SiO2
ISF 33.7 18.1 21.9
LBF 33.4 20.0 23
947
MnO CaO MgO K2O Na2O P2O5
0.2 49.5 6.84 0.87 0.86 0.08
36.4 0.2 1.5 1.2
Aliquotes of nely crushed material (<300 lm) are con-
tacted either with nitric acid or sodium hydroxide solu-
tions of varying concentrations. After a contact time of
48 h under agitation, the leachates are ltered through
0.45 lm pore size polypropylene membranes, the pH
of each ltrate measured and the composition analysed
on an ICP-AES with a quantication limit of 10 lg/l.
The same laboratory protocol for the leachate sampling
and analysis is applied for all the reported experiments.
2.1.2. Qualitative assessment of slag matrix alteration and
of the pollutants xation in the wastes matrix in various
chemical environments
The release of lead and zinc from slag depends on the
size of slag particles and how the slag reacts with alka-
line water from sand-cement mixes. Slag tends to be
glassy, and its solubilisation is not dependant on pH
for pHs between 4 and 9, but is known to be increased
in alkaline environments (Chou and Wollast, 1985; Bra-
dy and Walther, 1989). To evaluate the release rate for
the slag, a single extraction test was conducted on sam-
ples prepared by mixing uncrushed slag with solutions
simulating the pore water solution of sand-cement and
sand-bitumen. The simulated pore water of sand-cement
has a composition of 1 g/l Ca(OH)2, 2.2 g/l NaOH and
1.6 g/l KOH and pH around 13 (Gervais, 1999), while
the one for sand-bitumen was demineralised water.
The liquid/solid ratio was 10 ml/g and the contact time
72 h. The alteration of the slag was evaluated by meas-
uring the release of silica and of the two contaminants of
interest, lead and zinc.
2.2. Description of the scenarios
The leaching behaviour of the sand-cements and
sand-bitumens was evaluated for two scenarios: rst,
under saturated conditions, in which the material was
continuously in contact with water, and secondly, under
intermittent wetting conditions, in which the material, ex-
posed to rain, sun, wind, experiences cyclic wetting and
drying under variable environmental conditions. The
materials were tested for all scenarios at the laboratory
Al2O3 Zn Pb S As
10.4 6.92 0.69 1.58 0.15
1.89 11.2 3.5 0.7 0.1
948 R. Barna et al. / Waste Management 24 (2004) 945955
scale. Field verications were restricted to the ISF slag.
Authorisation from the French Environmental Admin-
istration for eld testing of the LBF slag was not
obtained.
2.3. Leaching behaviour at laboratory scale: parametric
tests
Both continuous tank leaching (without a draining
and drying period) and intermittent tank leaching
(leaching with periods of draining and drying) were car-
ried out to assess the leaching behaviour of the materials
in, respectively, saturated and intermittent wetting condi-
tions. Table 4 summarises the number of cycles and the
leaching period duration for each material/leaching test
combination. The material samples, pasted in cylindrical
leaching vessels, were contacted with the leachant only
on the upper side, which had a diameter of 95 mm for
the sand-cements and 80 mm for the sand-bitumens.
The sand-cement samples were cut (dry concrete cutting
equipment, diamond disk) just before the beginning of
the leaching tests to ensure that the surface contacted
by the leachant was not carbonated. The drawback of
this preparation is that slags contained in the materials
were cut increasing the likelihood for leaching compared
to eld situations. During leaching intervals, material
samples were contacted with a volume of leachant
(demineralised water and synthetic pore water) at a liq-
uidsolid ratio of 2 ml of leachant per cm2 of exposed
surface. The test temperature was 23 2 C, and no stir-
ring of the leachant occurred during the leaching inter-
val. At the end of each leaching interval, eluates were
mixed, sampled and analysed.
The continuous leaching schedule consisted of unin-
terrupted leaching of the monolithic sample with lea-
chant exchange at designated intervals following a
progression typical of tank leaching tests (i.e., 8, 16 h,
1, 2, 3 days, 1, 3 weeks and 1 month up to a cumulative
time of 14 months). As for most tank leaching tests,
demineralised water was used as leachant for both
sand-cement and sand-bitumen materials which simu-
lated the case of owing water. In addition, to simulate
a particular case, i.e., very low leachate renewal (in long
contact time with the material, stagnating water), a
continuous leaching test with synthetic pore water (com-
position described above) was conducted on the sand-
cement materials. The intermittent wetting schedule
consisted of multiple cycles of a single leaching interval
followed by a xed storage interval of seven days. The
Table 4
Number of cycles and cumulative leaching and drying times for intermittent wetting and continuous leaching tests
Tests Sand-cement
Continuous leaching test with demineralised water 14 cycles, 250 days leaching
Continuous leaching test with synthetic pore water 15 cycles, 265 days leaching
Intermittent wetting test 12 cycles, 170 days leaching + 75 days drying
non-leaching duration was based on the time required
to dry samples during preliminary experiments. During
the non-leaching periods, samples were stored in a
chamber containing silica gel to dry the atmosphere
and sodium hydroxide to limit the amount of carbon
dioxide. The latter condition was to prevent the carbon-
ation reaction from occurring between the carbon diox-
ide of the atmosphere and the sand cement. The
duration of the leaching interval for each cycle was iden-
tical to the ones used for the continuous leaching tests.
2.4. Field verication: large-scale test
The sand-cement and sand-bitumen prepared with
ISF slags were tested, along with control materials, at
pilot scale for 16 months. The pilots, set up by Colas
SA, were in Bethunes, France. The four test sections,
each of which had a surface of approximately 160 m2,
are represented in Fig. 1. Each test section, from the
top to the bottom, is made of a 4-cm thick surface layer
of bituminous concrete, a 24-cm layer of sand-bitumen
or a 38-cm layer of sand-cement, a 5-cm draining
layer of calcareous gravel and a 50-cm foundation layer
of red shale. To enhance the contact of the materials
with the water, the surface layer was made highly porous
(roughly 20% porosity), and no impermeable layer was
placed between the surface layer and the sand-bitumen
or sand-cement. Each test section, isolated by a geo-
membrane (thick lines on the gure), had a slope of
2% to drain the water toward one corner equipped with
tanks. Two tanks per test section allowed separate col-
lection of surcial water at the sand-cement or sand-
bitumen surface and the percolation that reached the
geomembrane.
Rainfall measurements were obtained from a local
meteorological oce. Samples of surcial water and per-
colation were collected following precipitation events
and analysed.
3. Results and discussion
3.1. Characterisation of waste and waste materials
3.1.1. Characterisation of the lead and zinc primary
smelting slags
Despite being the by-product of a lead production
system, LBF slags (11.2wt% Zn and 3.5wt% Pb) contain
twice the zinc of the ISF slags (6.9wt% Zn and 0.7wt%
Sand-bitumen
20 cycles, 430 days leaching
10 cycles, 116 days leaching + 62 days drying
 R. Barna et al. / Waste Management 24 (2004) 945955
Pb). The oxide composition of the slags is presented in
Table 3. The particle size of the slag was between 0.1
and 4 mm, D50 = 0.6 mm. The slags density varies be-
tween 3.6 and 3.9 kg/m3.
The base/acid neutralisation capacity of the slags,
presented in Fig. 2 was similar for both slags, except be-
tween 0.05 and 4 mol of acid per kilogram of slag, where
LBF slag presented a higher buering capacity. The pH
of slag in demineralised water after 48 h was about 10,
which was signicantly lowered or increased when in
the presence of a small amount of nitric acid or sodium
hydroxide (0.05 mol/kg slag), indicating that the studied
slags are mostly inert materials. The lead and zinc solu-
bilisation behaviour as a function of pH exhibited a clas-
sic amphoteric behaviour for both slags with a minimum
of solubilisation reached between pH 8 and 10 (Fig. 3).
For pH between 5 and 12, the zinc solubilisation of the
LBF slag was up to one order of magnitude higher com-
pared to the ISF slag. A similar trend was observed for
the solubilisation of lead for pH between 8.5 and 11.
Conversely, for pH higher than 12, the solubilisation
of lead was more important for the ISF slag than for
the LBF slag: at pH 13.2 it was 367 mg/l for the ISF
slags and 263 mg/l for the LBF slags. This result oc-
curred even though the LBF slag had ve times the lead
14
12
10
pH
8
6
4 phase and only 0.5% of the total zinc was leached. Al-
2 most 50% of the total lead from ISF slag was leached,
4 2 0 2 4 6
mol base/kg slags mol acid/kg slags
Fig. 2. Acid neutralizing capacity of ISF and LBF slags.
100000
10000
1000
Zn [mg/L]
100
10
1 1
0,1
0,01
0 2 4 6
(a)
ISF
Total content, ISF
Fig. 3. Solubilisation as a function of pH of (a) zinc and (b) lead for ISF and LBF slags.
949
content of the ISF slag. The lines total content for ISF
and LBF in Fig. 3 represent the maximum concentration
if the metal dissolved completely. Thus total contents
limited the solubilisation of lead at pH greater than 12
for the ISF slag and limited the solubilisation of lead
and zinc at pH lower than 4 for both slags.
The pH of the leachates obtained when in demineral-
ised water was 10.6 for ISF slag and 9.9 for LBF slag.
The increase in pH is likely due to the release of alk-
alines contained in slag. The release of silica was low
at 0.4 and 1 mg/l for ISF and LBF slags, respectively.
In addition, the lead and zinc releases did not exceed
50 and 10 lg/l, respectively, for either slag. This result
indicated that demineralised water did not aect the slag
enough to release the contaminants.
When the slags were contacted with synthetic pore
water, a dierent behaviour was observed (Table 5).
The release of silica from both slags was lower than
when contacted with demineralised water. Because cal-
cium silicate precipitates and adsorbs to calcium
hydroxide surfaces when a large concentration of cal-
cium is present at a pH above 11 (Bishop et al., 1986),
the amount of silica in solution appeared to be limited
by the calcium hydroxide in the pore water solution.
This was veried by using a synthetic pore water without
Ca(OH)2. With the modied pore water the measured
silica in solution increased by a factor of 10.
The amount of silica release from LBF slag is higher
than from ISF slag. However, this result did not corre-
spond with a higher release of zinc and the highest lead
isf lbf
release was observed for the ISF slag. The mineralogical
results reported by Mandin et al. (1997) allow for con-
jecture on the behaviour of slags in this study. For both
slags, 90% (by mass) of the zinc is present in the silicate
8 10 12 which could be because most of the lead appears to be
in the form of metallic droplets (D50 of 100 lm) not
properly embedded in the glassy slag matrix. Con-
versely, lead from the LBF slag seems to have been well
100000
10000
1000
Pb [mg/L]
100
10
0,1
0,01
8 10 12 14 0 2 4 6 8 10 12 14
(b)
pH pH
LBF ISF LBF
Total content,LBF Total content, ISF Total content,LBF
950 R. Barna et al. / Waste Management 24 (2004) 945955

Table 5
Si, Pb and Zn solubilisation of the slags contacted with sand-cement synthetic pore water (pH . 13)
Element: Si (mg/l) Pb (mg/l) Zn (mg/l)
Type of slags: ISF LBF ISF LBF ISF LBF
Average of two tests 0.11 0.45 343 120 5.5 5
Standard deviation 0.01 0.02 7.07 0.00 0.21 0.21
% Solubilised from the total content 49.7 3.4 <0.1 <0.1

Table 6
Total Pb and Zn content in the sand-cements and sand-bitumens
Materials: Sand-cements Sand- bitumens
Elements (g/kg): Pb Zn Pb Zn
Control 0.02 0.05 <1 <1
SCisf 4.5 34.7 3.7 31.8
SClbf 10.7 45.0 14.6 52.9

embedded in the glass matrix, which would explain why
less of it leached.
3.2. Composition and physical characterisation of the
sand-cements and sand-bitumens
The lead and zinc measured in the sand-cement and
sand-bitumen agreed reasonably well with the calculated
values. The very low contents of lead and zinc (trace
concentrations, 10 5 g/g) found in the control materials
were brought in with the binding material and sand (see
Table 6).
The open porosity for the SCisf was 10 times higher
compared to the SBisf, with measured values of 11.7
and 1.8 vol%, respectively. In addition, the permeability
of the SCisf (4 10 6 m/s) was two orders of magnitude
higher compared to the SBisf (7 10 8 m/s). Details on
these tests are reported in Gervais (1999).
4. Leaching behaviour of the sand-cements
4.1. Leaching behaviour at laboratory scale
4.1.1. Leaching behaviour in saturated conditions with
water renewal
The long-term leaching behaviour of the sand-
cements in saturated conditions was assessed through
a continuous leaching test with sequential renewal of
demineralised water. The three sand-cements presented
a similar pH trend: the pH increased with increasing
leaching time from pH 8.5 to pH 11.5 within the six rst
cycles; from cycle 7 onwards, the pH only slightly varied
between 11.3 and 11.7. The cumulative amounts of zinc
and lead released from the sand-cements are reported in
Table 7. Respectively, 30wt% and 43wt% of the zinc and
lead released from the SCisf were leached during the rst
leaching period. It is likely that the freshly cut surfaces
led to an initial surface wash-o of more readily dissolv-
able lead and zinc. Smaller amounts of lead and zinc
were leached from the SClbf compared to the SCisf (Ta-
ble 7). In addition, for both materials (SCisf and SClbf),
the contaminant release took place within the six rst
cycles. For later cycles, the concentration in the leac-
hates was lower than the detection limit of the ICP-
AES. Lead and zinc were leached when the pH was
increasing from 8.3 to 11.2, which is within the range
for the minimum solubilisation of lead and zinc (Fig.
3). Conversely when the pH increased above 11, where
the lead and zinc solubilisation is higher (approximately
0.05 mg/l), no more release was observed. This behav-
iour suggested that the observed release of the contam-
inants was mainly due to surface transfer
phenomenon, while the pH of the sand-cements for
the longest leaching periods was not alkaline enough
to promote further leaching of the contaminants.

Table 7
Cumulative zinc and lead released per unit area by the sand-cements for the saturated and intermittent wetting conditions (measured at laboratory
scale)
mg/m2 at the end of the test Saturated conditions Intermittent wetting conditions
Continuous leaching test with Continuous leaching test with Intermittent wetting test
demineralised water synthetic pore water
Sccont SCisf SClbf Sccont SCisf SClbf SCcont SCisf SClbf
Zn 1.0 27.7 5.8 4 50 123 0.1 2.9 1.7
Pb 0.7 24.0 3.9 38 920 343 0.1 1.4 0.2
 R. Barna et al. / Waste Management 24 (2004) 945955
4.1.2. Leaching behaviour in saturated conditions with
synthetic pore water
A continuous leaching test with synthetic pore water
was performed for 8 months to assess the leaching
behaviour of the sand-cements in saturated conditions
with pore water. Measured leachate pH varied between
13 and 13.5. The total amount of zinc and lead leached
are presented in Table 7. The SClbf released more zinc
and less lead than the SCisf. This behaviour was consist-
ent with leachate pH and lead and zinc solubilisation.
Indeed, at pH 13.2, the zinc solubilisation of the SClbf
and SCisf was, respectively, 8 and 5 mg/l, while the lead
solubilisation was, respectively, 56 and 40 mg/l. The dy-
namic of the contaminants release, as shown Fig. 4, is
important: e.g., the zinc cumulative release from SClbf,
even after 270 days of leaching. In this case, a small liq-
uid/solid ratio, and the one-month duration of each
leaching period allowed solid/liquid transfer to be close
to equilibrium. The pollutant concentrations in the leac-
hates were therefore almost equal to the maximum level
of solubilisation measured for similar pH during the sol-
ubilisation test. The two leaching tests conducted to
evaluate the leaching behaviour of the sand-cement
materials in saturated conditions showed that the con-
taminants release is mainly controlled by the leachates
pH. The contribution of the initial surface transfer
process also seems to be important.
4.1.3. Leaching behaviour of the sand-cements in inter-
mittent wetting conditions
The leaching behaviour of the sand-cements in inter-
mittent wetting conditions was assessed through an
intermittent wetting test. The leachate pHs, measured
after each leaching interval, presented a similar trend
for the three sand-cements. Thus, the pH decreased by
one unit within the rst three cycles and then increased
up to a plateau between pH 11 and 11.5. Compared to
the leachate pHs measured for the continuous leaching
test, pHs are higher for the rst cycle, which could not
be explained as the experimentation conditions were
similar. However, from the third cycle, the leachate
160
SCcont
120 SCisf
Zn [mg/m2 ]
SClbf
80
40
0 0
0 100 200
(a) Leaching time[days]
Fig. 4. (a) Zn and (b) Pb release from the sand-cement under leaching with synthetic sand-cement pore water.
951
pHs for the intermittent wetting test had a similar trend
to the leachate pHs for the continuous leaching test but
were 0.5 pH unit lower. The dierence is probably due
to specic physico-chemical processes like precipitation,
neo-formation or a slight carbonation of the materials
(Sanchez et al., 2002).
The materials were much less carbonated than if
dried in the open air. Indeed, a parallel test where the
sample was stored in open air during the non-leaching
period was conducted for a sample of SCisf and showed
that the leachate pH decreased rapidly and reached a
plateau at around 8.5 after three wetting/drying cycles,
implying that carbonation by CO2 uptake from the
atmosphere was likely.
The amount of lead released from the sand-cement
prepared with LBF slag is similar to that observed for
the control material (Table 7). Ninety percent of the to-
tal lead released from the SCisf was leached during the
rst two wetting/drying cycles. Similarly, 95 wt% of
the zinc was leached from both materials within the rst
four cycles. Therefore, as for the continuous leaching
test with demineralised water, the contaminant release
appears to be associated with initial surface reactions.
For these tests, the cumulative amount of zinc and lead
released was low compared to the continuous leaching
tests with demineralised water, which can be explained
by the combined eects of lower leachate pH and a pos-
sible closing of the pores by precipitation (neoforma-
tion) during the drying phases.
4.2. Leaching behaviour of the sand-cements at pilot scale
The control sand-cement and the ISF slag (but not the
LCF slag) containing sand-cement were tested at pilot
scale for 16 months. During that period the rainfall
measured was 1400 l/m2. The relative amount of surcial
water and percolation were, respectively, estimated at 2%
and 19% of the rainfall. The high ratio of percolation
measured complied with the initial objective of enhanc-
ing the contact between water and material and was
due to a high porosity and permeability of the sand-
1000
800
Pb [mg/m2 ]
600
400 SCcont
SCisf
200 SClbf
300 0 100 200 300
(b) Leaching time [days]
952 R. Barna et al. / Waste Management 24 (2004) 945955

Table 8 concentration of lead in both waters was similar and

Cumulative amount of lead and zinc released from the sand-cement
pilots at 16 months
mg/m2 at 16 months SCcont SCisf
Surcial Percolation Surcial
water water
Zn 0.2 0.9 0.4
Pb 1 2 27
cement. During the rst 50 days, no surcial water or
percolation was collected. This phenomenon could be
due to the water absorption capacity (WAC) of the
sand-cement. This parameter was evaluated by contact-
ing a sample of sand-cement with water until it reached
a constant mass, and the WAC calculated equalled
5.5% on a weight basis. Therefore, up to 7700 l of water
could have been absorbed by each test section, which re-
ceived in that period 9600 l. The dierence could be evap-
orated water as the pilots were set up at the beginning of
the summer.
The pH of the surcial water and percolation collected
for the two sand-cements mainly varied between 12.5 and
11.5. This level of pH was unexpectedly high considering
the leachates pH measured for intermittent wetting con-
ditions at the laboratory scale. Indeed, the leachate pH
measured on site was between the values measured for
the continuous leaching test with demineralised water
(pH 11.5) and for the pore water leaching test (pH be-
tween 13 and 13.5). This result suggests that the eld con-
ditions (percolation with long contact time) are close to
those of a steady-state transfer process where water has
time to chemically equilibrate with the road material.
The total amount of zinc released from the SCisf was
similar compared to the SCcont (Table 8), which was
consistent with leachate pH and zinc solubilisation
(Fig. 5). The zinc solubilisation from the sand-cement
prepared with ISF slags did not exceed 0.05 mg/l. The
amount of lead released from the SCisf was signicantly
higher than that measured for the SCcont. Because the
was apparently controlled by the pH as shown in Fig.
5, the diering amounts released through surcial water
and percolation seems directly related to their relative
Percolation quantities (2% and 19%). While the lead concentration
in the surcial water and percolations decreased over
1.7 time from 2 mg/l down to 0.5 mg/l, the zinc concentra-
204 tion stayed at the same level. This behaviour is similar
to the one reported above for the continuous leaching
test with synthetic alkaline water where the lead release
rate slowed down compared to the zinc one, which was
attributed to a quicker depletion of lead near the inter-
face water/material because of its higher solubilisation.
The leaching behaviour observed at pilot scale dem-
onstrated the importance of the fourth step of the Euro-
pean methodology, which requires a eld verication of
predicted behaviour. In this case, the leaching behaviour
of the sand-cement on site could not have been predicted
in any way by the results from the laboratory intermit-
tent wetting conditions test. Furthermore, the labora-
tory test that most accurately described the leaching
behaviour and level of contaminants released on site
was the continuously leaching test with alkaline water.
The gap between the predicted and observed behaviour
is most probably due to the initial choice to enhance the
contact between the water and material, which appar-
ently changed the system from an intermittent leaching
system to a continuous percolating system with long
contact times.
5. Leaching behaviour of the sand-bitumens
5.1. Leaching behaviour at laboratory scale
5.1.1. Leaching behaviour of the sand-bitumen in satu-
rated conditions
Leachate pH patterns are similar for the three sand-
bitumens. Within the rst two days, pH increased from

100
1000

100
10
Zn [mg/L]

Pb [mg/L]

10
1
1

0,1
0,1

0,01 0,01
10 11 12 13 14 7 8 9 10 11 12 13 14

(a) pH (b) pH

Fig. 5. Comparison of (a) zinc and (b) lead concentration in the surcial () and percolating (s) waters from the SCisf test section to the
solubilisation curves ().
 R. Barna et al. / Waste Management 24 (2004) 945955 953

pH 8.5 to 9.2, then decreased, and from the seventh cy-
cle onward uctuated between 8 and 8.5. The pH for the
control sand-bitumen was slightly higher than for the
slag-containing sand-bitumens. The total amount of re-
leased zinc and lead are presented in Table 9 and the
dynamics of the cumulative release in Fig. 6. The release
of zinc from the SCisf increased steadily over time, while
release from the SClbf increased signicantly from the
ninth cycle but reached a plateau after 350 days of leach-
ing. The concentration data compared to solubilisation
as a function of pH clearly shows that the zinc release
was controlled by the pH of the leachates.
The release of lead mainly happened within the rst
14 days of leaching; beyond this period, the concentra-
tion of lead in the leachates was lower than the detection
limit (10 lg/l) of the ICP-AES. There was no signicant
dierence in the amount of lead released from the con-
trol sand-bitumen compared to the slag-containing
materials. Indeed, almost 50% of the total amount of
lead released by the latter was released during a single
leaching period. This behaviour was consistent with
the leachate pH and the lead solubilisation and indicated
that the lead released during the rst leaching periods
was due to surface transfer phenomenon. Furthermore,
some sort of algae was found growing on the sand-bitu-
men sample surface, yet it has not been possible to study
its impact on the leaching behaviour. Organic matter
can play a role in leaching, for example in modifying
the solubilisation (by complexing) and transport proper-
ties of heavy metals cations (van der Sloot et al., 1997).
5.1.2. Leaching behaviour of the sand-bitumen in inter-
mittent wetting conditions
The leaching behaviour of the sand-bitumens in inter-
mittent wetting conditions was assessed through an
intermittent wetting test. The pH of the leachates was
similar for the three sand-bitumens and presented at
equal leaching duration the same trend described above
for the continuous leaching test. No lead was detected in
the leachates for the three materials and the maximum
amount of zinc released was 4.3 mg/m2 (Table 9). The
zinc release from the slag-containing sand-bitumens in-
creased from the eighth wetting/drying cycle (112 days
or 63 days of leaching). Thus, the zinc release dynamic
was similar to the one observed for the continuous
leaching test but at a lower level. For an equal leaching
duration (110 days), 6 wt% of the zinc released from the
slag-containing sand-bitumens during the continuous
leaching test was released during the intermittent wet-
ting test. This result could be due to a partial sealing
of the pores by ion precipitation during the drying
phase.
5.2. Leaching behaviour of the sand-bitumens at pilot
scale
The control sand-bitumen and the ISF slag-contain-
ing sand-bitumen (but not the LCF slag) were tested
at pilot scale under similar eld conditions to the
sand-cement test sections. The low percentage of perco-
lation compared to the sand-cement was due to the

Table 9
Cumulative zinc and lead released per unit area by the sand-bitumens for the saturated and intermittent wetting conditions (measured at laboratory
scale; DL = detection limit)
mg/m2 at the end of the test Saturated conditions Intermittent wetting conditions
Continuous leaching test with demineralised Intermittent wetting test
water
SBcont SBisf SBlbf SBcont SBisf SBlbf
Zn 9.4 85 290 0.6 2.3 4.3
Pb 7.6 14 24 <DL <DL <DL

300 25

20
200
Zn [mg/m2]

15
Pb [mg/m2]

10
100
5

0 0
0 100 200 300 400 500 0 100 200 300 400 500
(a) Leaching Time [days] (b) Leaching Time [days]

Fig. 6. (a) Zinc and (b) lead release from the sand-bitumens, SBcont (control) (), SBisf (h), SBlbf (), under continuous leaching with
demineralised water.
954 R. Barna et al. / Waste Management 24 (2004) 945955

1000 100

100
10

Pb [mg/L]
Zn [mg/L]
10

1
1

0,1
0,1

0,01 0,01
6 7 8 9 10 11 12 7 8 9 10 11 12
(a) pH (b) pH

Fig. 7. Comparison of (a) zinc and (b) lead concentration in the surcial () and percolating (s) waters from the SBisf to the solubilisation curves
obtained for the ISF slags ().

Table 10
Cumulative amount of lead and zinc released from the sand-bitumen pilots at 16 months
mg/m2 at 16 months SBcont SBisf
Surcial water Percolation Surcial water Percolation
Zn 1.6 No data 4.5 0.63
Pb 1 No data 3.8 0.52

sand-bitumens lower permeability. In contrast to the
sand-cement test section, there was no delay before the
rst surcial water and percolation were collected. After
one month, no more percolation was collected for the
control sand-bitumen probably as a result of a leak in
the geomembrane at the bottom of the test section.
Over the 16 months, the pH of the surcial water and
percolation collected for the two materials varied be-
tween 7.5 and 11.5 with a general trend going from
pH 10 down to pH 8. The pH for the rst 250 days
was 0.52 higher than the pH measured during the lab-
oratory-scale tests. This behaviour indicated, just as for
the sand-cements, that the liquid/solid contact condi-
tions were dierent (closer to steady-state transfer) com-
pared to the laboratory experimental conditions.
Indeed, the pH measured during the buering capacity
test, when the SBisf was contacted with demineralised
water for 48 h was 10.4, which was also the pH meas-
ured for the slag. The release of lead and zinc from
the SBisf was consistent with the pH and the contami-
nants solubilisation as measured on the ISF slags
(Fig. 7). As the pH corresponded to the minimum of
lead and zinc solubilisation, the amounts of contami-
nants released over a period of 16 months were very
low (Table 10).
Considering the amount of contaminants released,
the leaching behaviour on-site of the sand-bitumen pre-
pared with ISF slags was fairly well described by the lab-
oratory test used for intermittent wetting conditions. The
laboratory test did not predict accurately the pH of the
leachates measured on-site, although pH appears to be
the main parameter controlling the release of lead and
zinc. Just as for the sand-cements, the design of the test
section, which enhanced the contact between water and
material, probably can explain the dierence.
6. Conclusions
The main outcomes of the experimental laboratory
and pilot-scale testing of reuse of two metallurgical lead
and zinc slags for road materials are:
 ISF and LBF slags have a small buering capacity.
The solubilisation of lead and zinc from the slags pre-
sented an amphoteric behaviour with a minimum sol-
ubilisation between pH 8 and 10.
 Partial substitution of calcareous sand with slags in
sand-cements decreased the buering capacity,
between 10 and 22 mol of acid per kilogram of mate-
rials. Between pH 7 and 12, the lead and zinc solubi-
lisation from the slag-containing sand-cements was
decreased compared to the slag alone. The ISF slag-
containing sand-bitumen had a small buering capac-
ity similar to the ISF slags, while the lead and zinc
solubilisation were similar to the lead and zinc solubi-
lisation of the ISF slags.
 The release of the studied contaminants from the
sand-cements and sand-bitumens in a saturated sce-
nario, as evaluated at laboratory scale, was mainly
controlled by the pH of the leachates. For the inter-
mittent wetting conditions, despite a similar level of
 R. Barna et al. / Waste Management 24 (2004) 945955
pH compared to the ones measured during continuous
leaching test with demineralised water, the release of
contaminants was signicantly decreased, which was
attributed to a blocking of the pores by precipitation
during the drying phase.
Apparent initial surface leaching (also called wash
o) can play an important role in release, especially
initially.
The leachability of trace metals can be modied by
sample preparation. For example, dry cutting can expose
leachable mineral faces that would not be as likely to be in
contact with leaching waters in eld settings. Comparison
of the results obtained at pilot and laboratory scales, for
both materials, indicated the importance of pilot-scale tri-
als. The leaching behaviour of the sand-cements on site
could not be predicted by the intermittent wetting test used
at laboratory scale; instead, it could have been better pre-
dicted by the continuous leaching test with pore water. The
leaching behaviour of the sand-bitumen used in the pilot
test was well predicted by the intermittent wetting test
set up at laboratory scale.
Based on these results, only the use of ISF slags as a
partial substitute for sand in sand-bitumen materials
should be considered further. However, it is important
to note that only one part of the life cycle of the mate-
rials was thoroughly assessed here: the leaching behav-
iour in normal use conditions. A similar methodology
should be applied to assess the environmental behaviour
of the material for all the dierent stages it can be ex-
posed to, including the construction, repairing, demoli-
tion and recycling phases.
Acknowledgement
This research was supported by the ADEME (French
Environment Agency) and the European Community
under the Brite Euram research Contract Valorisation
of PbZn primary smelting slags, (Bre2-CT94-0585).
The partners of the project managed by Metaleurop
RechercheSA (F) were ve major industrial smelters:
Metaleurop Nord (F), Britannia Zinc Ltd (GB), Eniri-
sorse (I), Berzelius Metallhutten GmbH (D), four re-
search teams: Netherlands Energy Research
Foundation (NL), Institut National des Sciences Appli-
quees-Polden Lyon (F), Technodes SA (F), Rheinisch-
Westfalische Technische Hochschule Aachen (D) and
major industrial end-users: Calcestruzzi SpA (I), Kema
NV (NL) and Colas R&D (F).
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