Innovative solidification/stabilization of lead contaminated soil

using incineration sewage sludge ash

*
Jiangshan Li, Chi Sun Poon
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University,

Hung Hom, Kowloon, Hong Kong

*corresponding author: cecspoon@polyu.edu.hk

Abstract: The proper treatment of lead (Pb) contaminated soils and incinerated sewage sludge ash (ISSA)
has become an environmental concern. In this study, ordinary Portland cement (OPC) and blended OPC
containing incinerated sewage sludge ash (ISSA) were used to solidify/stabilize (S/S) soils contaminated with
different concentrations of Pb. After curing for 7 and 28 d, the S/S soils were subjected to a series of strength,
leaching and microscopic tests. The results showed that replacement of OPC by ISSA significantly reduced
the unconfined compressive strength (UCS) of S/S soils and leached Pb. In addition, the leaching of Pb from
the monolithic samples was diffusion controlled, and increasing the ISSA addition in the samples led to a
lower diffusion coefficient and thus an increase in the feasibility for controlled utilization of S/S soils.
Furthermore, the proposed S/S method significantly decreased the amount of Pb associated with carbonates
and increased the amount of organic and residual Pb in S/S soils, reflecting that the risk of Pb contaminated soils
can be effectively mitigated by the incorporating of ISSA. Overall, the leachability of Pb was controlled by
the combined effect of adsorption, encapsulation or precipitation in the S/S soils.

Key words: solidification/stabilization; lead contaminated soil; incineration sewage sludge ash; leachability
1. Introduction

A recent national survey of soil quality in China has revealed widespread nationwide soil contamination with
heavy metals, of which 1.5 % was contaminated by Pb (CMEP, 2014). Phytoremediation, soil washing, and soil
amendments are potential useful remediation approaches for the Pb contaminated soils (Mani et al., 2015; Li et al.,
2015b; Puga et al., 2015), yet solidification/stabilization (S/S) has received most attentions due to the relatively
low cost and demonstrated effectiveness over many years (Zhang et al., 2015; Li et al., 2015a). In recent years, the
potential application of industrial byproducts as reactive binders for S/S of contaminated soil has attracted
extensive interests (Tang et al., 2015; Cho et al., 2015). This remediation strategy enables resource recycling and
reduces environmental burden of waste management, while accomplishing metal sequestration in the contaminated
soil at a low-to-moderate cost with a low carbon footprint.
To effectively manage the increasing amount of sewage sludge generated, the environmental protection department
(EPD) of Hong Kong has recently commissioned the worlds largest sewage sludge incinerator which was
designed to incinerate a maximum of 2,000 tons of sewage sludge a day. Considering that about 100-200 kg of
ashes are produced per tonne of dewatered sewage sludge (about 30% dry solid) by the Hong Kong
incinerator it is obvious that a huge amount of sewage sludge ash is required to be managed each year. The
improper disposal of incinerated sewage sludge ash (ISSA) has become an environmental concern due to
presence of heavy metal contaminants (Lapa et al, 2007; Donatello et al., 2010a). Some research work has
already been done on the use of this waste in construction materials, such as sintered materials (Cheeseman et
al., 2003), bricks, tiles and pavers (Chen and Lin, 2009), lightweight aggregates (Chiou et al., 2006).
Recently more aggressive efforts have been undertaken to explore the possibility to recycle phosphate from
ISSA (Herzel et al., 2016; Petzet et al., 2012; Donatello et al. 2010b). ISSA has certain pozzolanic
characteristics (Davraz and Gunduz, 2005; Turanli et al., 2004;Pan et al., 2003) and can be used to replace
cement in the cement based S/S processes of heavy metals contaminated soils. The hydraulic reactivity of
ISSA blended cement is affected by the glass content, particle size distribution and chemical composition of
ISSA (Shi et al., 2005). In the S/S process, an interlocking framework of minerals encapsulates the heavy
metals present in the contaminated soil as the blended cement hydration proceeds (Zhou et al., 2006).The
release of heavy metals is reduced as the solidified soil has a lower surface area exposed to the environment
and reduced permeability. In addition, the hydraulic binders with high alkaline pH react during hydration
with heavy metals to form insoluble hydroxides by precipitation (Li et al., 2014).

Previous studies have shown that ISSA can potentially be used for the removal of heavy metals from
wastewater due to the large surface area and porous characteristics (Smith et al., 2009; Panetal., 2003). Thus,
ISSA blended cements can be used to improve the handling characteristics and reduce the environmental
impact of contaminated soils via the immobilization of heavy metals by physical and chemical adsorption,
chemical incorporation (ion exchange, surface complexation, precipitation, diadochy) and micro-
encapsulation.Furthermore, it has been reported that phosphorus amendments was an effective method for
stabilizing soils that were rich in Pb, Zn, Cu, and Cd (Zhang et al., 2010; Fang et al., 2012; Du etal., 2014a).
The main chemical composition of phosphate in ISSA is whitlockite (Donatello and Cheeseman, 2013),
which can be detected if there is enough Ca in the ISSA but that Mg, Al an
Fe will also compete with Ca to form substituted whitlockite type minerals during sewage sludge
incineration. It has been postulated that the mechanism of Pb immobilized by ISSA is mainly due to
dissolution/precipitation (Cao et al., 2004) and adsorption/substitution (Park et al., 2011). To date, however,
ISSA blended cements have not ever been used to S/S of a heavy metal contaminated soil. According to
previous studies (Li et al., 2016; Du et al., 2014b), Pb was not effectively stabilized by cement due to the acid
leaching. In order to propose a new binder for S/S technology and a new method for recycling ISSA, we
attempted to use ISSA blended cements to S/S of Pb contaminated soils and confirm the effect and possible
mechanisms. In view of the above, a systematic study was conducted for the treatment of Pb contaminated
soils by S/S with OPC and ISSA. The effects of binder formulation, Pb concentration and curing time on
response variables including unconfined compressive strength (UCS), leaching characteristics,
fractionation and speciation, and bioavailability of Pb in the S/S products were studied. The SEM-EDS,
adsorption and XRD tests were conducted to reveal the possible mechanisms of Pb immobilization.
2. Materials and methods

2.1 Lead contaminated soil preparation

The soil used in the tests was a silty clay obtained locally in Hong Kong. The soil was composed of 13%
sand, 62% silt, and 25% clay size fractions on a dry mass basis (determined by wet sieving and hydrometer
tests). XRF data showed that the major elements in the soil were Si and Al (60.07 and 33.55% respectively).
The as-received soil had a pH of 7.34 (1:5 dry soil: DI Water) and was confirmed to be free of contamination
with pollutant concentrations not exceeding urban/rural residential soil Risk-Based Remediation Goals
(RBRGs) according to the Guidance
Manual for Use of RBRGs for Contaminated Land Management (HK EPD, 2007). The soil sample was dried,
ground and then sieved through a 2mm sieve. Given the inertness of nitrate in affecting cement hydration
(Cuisinier et al., 2011), Pb(NO3)2 solutions were added to the sieved soil until the Pb concentration in the soil
-1
reached 500, 1000 and 5000 mg kg , respectively, which represents low level (L), medium level(M), and
high level(H) Pb contaminated soil based on the Guidance Manual for Use of Risk-Based Remediation Goals
(RBRGs) for Contaminated Land Management (HK EPD, 2007). These concentrations are also within the
range of many Pb-contaminated soils in China (Deng et al., 2006; Li and Huang, 2007).Deionized water was
then added to the contaminated soil until the water content reached 20%. The Pb-contaminated soil was mixed
evenly, plastic film covered and braised for 10 d under standardcuring conditions (232 , 95% humidity) to
allow Pb(NO3)2 and the soil to react adequately.

2.2 ISSA and OPC

A commercially available OPC, and ISSA from the operational sewage sludge incinerators in Hong Kong
were used as the cementitious materials. The chemical compositions of the cementitious materials are
shown in Table 1. The leaching characteristics of Pb in the two binders based on TCLP tests were analyzed. It
-1
can be concluded that both binders contained only trace amounts of Pb (0.32 mg L for ISSA and below the
limit of detection for OPC) and thus the S/S process would not be affected.

Table1 Physical and chemical properties of OPC and ISSA

Items OPC ISSA

SiO2 22.18 27.24
Chemical Al2O3 5.95 14.44
Composition Fe2O3 3.37 27.35
(%) CaO 62.46 6.34
MgO 1.56

Na2O 0.48
K2O 0.24 2.77
TiO2 0.37 5.04
SO3 2.25 3.45
P2O5 12.28
Loss on ignition(%) 0.64 0.99
3
Physical Density(g/cm ) 3.16 2.49
Properties BET specific surface
3.82 1.83
2
area(m /g)

2.3 S/S of lead contaminated soil

The mix proportions used for the laboratory study are listed in Table 2. For all the Pb

contaminated soils, the S/S soil samples were prepared with a constant water-to-solid ratio of 0.2.

ISSA was used to replace OPC progressively for certain mixes as indicated. All the proportioned
soil and cementitious powder materials were first mixed uniformly for about 1 min using a

mechanical mixer. After that, water was added. A well blended mixture was produced by further

mixing for another 2 min. The S/S materials were then cast into steel molds (with an internal

diameter of 50mm and an effective height of 50mm) by compaction under a force of 50 kPa. The

samples were then demolded. After that, the hardened S/S soils were placed in an environmental
chamber with a temperature and RH of 232 and 501%, respectively, until the time (7 and 28
d) of testing for compressive strength and leachability. The schematic diagram of the Pb

contaminated soil S/S process is shown in Fig. 1.

Table 2 Mix proportions of mortar mixtures (mass ratio)

Cementitious materials
Mix notation Pb contaminated soil Water
OPC ISSA
L0 100 10 0 2
-1
L0.2 500 mg kg 100 8 2 2
L0.5 100 5 5 2
M0 100 10 0 2
-1
M0.2 1000 mg kg 100 8 2 2
M0.5 100 5 5 2
-1
H0 5000 mg kg 100 10 0 2
 H0.2 100 8 2 2
H0.5 100 5 5 2

Water
LCS ISSA OPC

Storage tank

Mixer

S/S product

Fig. 1. Schematic diagram of S/S process of lead contaminated soil (LCS)

2.4 Test methods

124 2.4.1 UCS test

UCS testing is necessary to obtain a rough estimate of the S/S product strength and

measurements were performed by using an universal testing machine (Testometric CXM 500-

-1
50KN) at a loading rate of 0.3 mmmin according to BSEN12390-3(BSI, 2009). To validate the

applicability of S/S treated contaminated soil, the UCS was compared with the criteria for reuse as

fill materials for site formation in Hong Kong (i.e., ground levelling/stabilization to the design

formation level prior to construction works) (HK EPD, 2011). All tests were run in duplicates.

2.4.2 Leaching test

Several leaching methods were used to evaluate the leaching potential of Pb in S/S samples

as follows.

(1) Synthetic precipitation leaching procedure (SPLP). According to the US EPA Method

7
1312 (US EPA, 2011), sulfuric acid/nitric acid solution at mass ratio of 6:4 with a pH of 4.930.

05 was used to assess Pb leaching from the S/S treated soils in environments exposed to acid rain.

The samples were extracted at a liquid to solid (L/S) ratio of 20 in capped polypropylene bottles

on a rotary tumbler at 30 rpm for 18 h.

(2) The availability of Pb in ingested soil to human gastro-intestinal system (GI) was

estimated using a simplified bioavailability extraction test (SBET) which simulated the action of

gastric juices in a single step and has been extensively used by many researchers (Ettler et al.,

2012). Briefly, 0.5 g soil was shaken for one hour at 30 rpm on a shaker with 50 ml of synthetic

gastric solution (0.4 M glycine, pH 1.50 0.05 adjusted using trace metal grade HCl) at 37.

(3) Phytoavailability of Pb was measured by a single step extraction method using

diethylene-triamine penta-acetic acid (DTPA) (Karak et al., 2011). 10 g of sample was shaken for

2 h with 20 mL of 0.005 M DTPA, 0.1 M triethanolamine (TEA) and 0.01 M CaCl2 solution (pH

= 7.3).

(4) A sequential extraction scheme developed by Tessier et al. (1979) was used to partition

Pb in the S/S samples into several fractions. Each fraction was defined as:

-1
F1: Exchangeable (extracted by 1.0 mol L CaCl2)

-1
F2: Carbonate (extracted by 1.0 mol L NaOAc, at pH 5.0)

-1
F3: FeMn oxides (extracted by 0.04 mol L NH4OHHCl)

-1
F4: Organic (extracted by 0.02 mol L HNO3 + 30% H2O2)

F5: Residual (digested by conc.HNO3 + conc. HClO4)

(5) The monolithic S/S samples were subjected to the semi-dynamic leaching tests following

the procedures of ASTM C1308 (ASTM, 2009). The leaching agent was deionized water. The
ratio of volume of the deionized water (1177.5 mL) used to the surface area of the specimen

2
(117.75 cm ) was 10:1. The test duration was 11 d, and a constant temperature of 232 was

maintained through the entire test. During the test, the deionized water was replaced after time

periods of 2, 7, and 24 h in the first day, and then daily for the following 10 d. At each time

interval, 10 mL of leachate was sampled.

After the extraction, the final pH of the leachate was measured and the liquid was separated

from the solids by filtration through a 0.45 m glass fiber filter. After that, the leachate was

acidified by adding concentrated HNO3 until the pH was <2.0 prior to the chemical analysis. The

metal concentrations were determined by using an inductively coupled plasma-atomic emission

spectrometry (ICP-AES, Perkin Elmer Optima 3300DV). The values including plots of the

leachate pH and Pb concentrations versus time, and cumulative fraction leached (CFL) of Pb

1/2
calculated using Eq. (1) versus time square root (t ), are presented. The values of diffusion

coefficient (De) of Pb were computed using Eq. (2).

All experiments were carried out in triplicate, and the average value with standard deviations

less than 5% was used in the results and data analysis.

A 1c V
CFL (1)
t
i L,i
A A
0 0 i

D ( CFL V )2 (2)
e
4 t S
Where At =the cumulative mass of the metal contaminant leached out of the medium surface

V
(mg); A0 =total mass of substance contained in the soil prior to the test (mg); =volume of

3 t
specimen (cm ) ; =leaching time (s); S =surface of the sample used in the semi-dynamic
2
leaching test (cm ); ci =measured concentration of the leached metal contaminant in the leachate

-1
at i th test interval during test (mg L ) and VL,i =volume of the leachant (L).
2.4.3 Microscopic characteristics test

The crystalline-phase mineralogy of the ball milled S/S samples was evaluated by using a

high resolution powdered X-ray diffractometer (Rigaku SmartLab, Japan) using CuK (=

1.54059 ) radiation obtained at 40kV and 30 mA. Scans were taken between 5 and 80 2 with

0.02 step sizes. The surface characteristics of gold-coated S/S samples were examined using a

JEOL JSM-6490 scanning electron microscope with energy dispersive X-ray spectroscopy (SEM-

EDX) to analyze the changes in shape, size, and morphology.

3. Results and discussion

3.1 UCS results

11

10 7d 28d
9
8
UCS (MPa)

7
6
5
4
3
2
1
0
L0 L0.2 L0.5 M0 M0.2 M0.5 H0 H0.2 H0.5

Fig.2. UCS of S/S treated soils

As shown in Fig. 2, the UCS of all S/S soils treated by the blended cement fulfilled the

acceptance criteria (1 MPa) in Hong Kong for reuse as on-site fill materials (HK EPD, 2011),

regardless of the mix proportions and curing time. Replacement of OPC by ISSA significantly

reduced the UCS of S/S soils, and the increase in replacement ratio led to further decrease in UCS.
 -1
Comparing to the S/S 500 mg kg soils with 10% OPC after curing for 7 d, the UCS of the

samples with replacements of 20 and 50% OPC by ISSA was decreased by 2.8 and 3.8 MPa,

respectively. Such trend was also found in other studies (Yin et al., 2006; Garcs et al., 2008;

Donatello et al., 2010c; Wang et al., 2015). The strength development of S/S soils is dominated by

calcium silicate hydrate (C-S-H) and calcium hydroxide (CH) which are generated through cement

hydration (Zeng et al., 2012; Bernal et al., 2013). The decreased UCS can be attributed to the

decreased hydration products and low reactivity of ISSA in the S/S mixture (Garcs et al., 2008;

Donatello et al., 2010c). Besides, the presence of absorbed water, organic matter, heavy metals

and P2O5, SO3 in ISSA affected negatively the UCS and the hydration degree of cement (Naamane

et al., 2016). The compressive strength of 28 d cured samples on average were increased by

53.4 % compared to that of 7 d cured samples, and the increase negatively correlate to the

amounts of ISSA.

-1
The UCS of S/S soils decreased with Pb concentration (from 500 to 1000 mg kg ) in the

soils, albeit a lesser extent. For example, the UCS of soils treated by OPC only decreased from

5.16 and 8.48 to 3.53 and 7.39 MPa, respectively after 7 and 28 d curing. That may be attributed

to the inhibition of the cement reactions by the Pb in the mixtures (Gollmann et al., 2010; Chen et

al., 2011). But it was surprising that the UCS of S/S soils increased significantly when Pb

-1
concentration in soils was increased from 1000 to 5000 mg kg , regardless of the curing time.

2+
Boardman (1999) found that the presence of Pb ions aided the dissolution of the aluminates from

an English China Clay, and re-crystallisation of cementitious reaction products (calcium aluminate

hydrates) on the surfaces of the mineral particles appeared, which increased the UCS of the

stabilized soils. Therefore, the increased UCS of S/S soils with high concentration of Pb might be
attributed to the re-crystallisation of calcium aluminate hydrates at the continued high pH in the

S/S mixtures. XRF data showed that the Al content in tested soil was about 33.55%, and the

leached Al concentration in several leaching tests presented in the following sections increased

with Pb in soils (e.g. leached Al from samples L0.2, M0.2 and H0.2 was 3.27, 5.21 and 14.73 mg

-1
L respectively based on the SPLP test). Furthermore, the XRD and SEM results also confirmed

the calcium aluminate hydrates in abundance were present in S/S soils.

3.2 Granular leaching test results

3.2.1 SPLP test

TCLP method (US EPA, 2011) was commonly used for waste disposal purposes to simulate

225 scenarios of landfilling, while SPLP was utilized to determine the leaching potential of

contaminants from soil into groundwater. The TCLP test is, indeed, criticized for not reflecting the

likely range of field conditions (Voglar and Letan, 2013; Sima et al., 2015). In view of the

leaching environment to be encountered when the S/S treated soil is to be reused, SPLP test was

conducted instead of TCLP method to simulate the scenario of leaching associated with acid rain

in the present study. Fig. 3(a) and (d) displayed the leachate Pb concentrations and pH in the SPLP

test of the S/S soils. The pH values of the leachates were similar (11.2211.87) for all the samples,

decreasing slightly with curing time and ISSA incorporation due to the decreased Ca(OH) 2

content. Mixing OPC with ISSA and soil generated hydration reactions which reduced the pH

2+
values, the amount of Ca , and the free Ca(OH)2 of the mixture, which can be attributed to

pozzolanic or carbonization reactions. It can be concluded from Fig. 3(a) that the leached Pb

-1
concentrations were all below 1 mg L , which were much lower than the theoretical maximum
 -1
leachable Pb concentration in the soils of 25, 50 and 200 mg L that are obtained by dividing the

-1
total Pb concentration (500, 1000 and 5000 mg kg ) by 20 (liquid-to-solid ratio), suggesting that

surface runoff due to acidic rainfall is unlikely to be a problem in the environment. The results

confirmed the effectiveness of S/S treatment of Pb contaminated soil by blending OPC with ISSA.

1000
7d 50 7d 7d
(a) SPLP-Pb 28d (b) SBET-Pb 28d (c) DTPA-Pb 28d

Extractability concentration (mg/kg)

(mg/L)
800

concentration
40
600
20
30
400
Pbleaching

200

10

0 L0 L0.2 L0.5 M0 M0.2 M0.5 H0

L0 L0.2 L0.5 M0 M0.2 M0.5 H0 H0.2 H0.5 L0 L0.2 L0.5 M0 0.2 M0.5 H0 H0.2 H0.5 H0.2 H0.5

(d) SPLP-pH 7d 28d

2.0 (e) SBET-pH 7d 28d
1.8
13 (f) DTPA-pH 7d 28d
12
1.6
11
1.4
10
1.2
LeachatepH
Leachate pH

1.0 9

0.8 8
0.6
7
0.4
6
0.2
L0 L0.2 L0.5 M0 M0.5 H0 0.0 L0 L0.2 5 L0 L0.2 L0.5 M0 M0.2 M0.5 H0 H0.2 H0.5

Fig.3. Leachate pH and Pb concentration from S/S samples based on different leaching tests

The results also show that Pb leaching concentration decreased with ISSA incorporation and

-1
curing time. For S/S soils with 5000 mg kg Pb after 7 d of curing, the leached Pb concentration

-1
decreased from 0.89 to 0.27 mg L when the replacement ratio of ISSA was increased from 20 to

50%. According to the reported theoretical and test results, the amphoteric behaviour of Pb

accounts for the minimum solubility found between pH 8 and 10 combined with the sharp

solubility increases in both acidic and alkaline conditions (Sanchez et al., 2002). Therefore,

leached Pb concentration from S/S soils by OPC and ISSA treatment was not only pH controlled.

Many studies have demonstrated that phosphate containing materials can immobilize soluble Pb

mainly through precipitation with minor surface sorption and induce the formation of stable Pb
 - - -
phosphate minerals, such as PbHPO4 or pyromorphites [Pb5(PO4)3X, where X = Cl , OH , F ] (Cao

et al., 2004; Cao et al., 2008; Xu et al., 2015). These findings may be responsible for Pb

immobilization but needs to be confirmed.

3.2.2 SBET test

The leachate Pb concentrations and pH in SBET test are shown in Fig. 3(b) and (e). The

leached Pb concentrations in the SBET tests were higher than other leaching methods. The

increased availability of Pb can be explained by the pH-dependent characteristics of Pb for the pH

of leachant used in SBET test is 1.5 simulating the gastrointestinal environment. The S/S

treatment hardly changed the pH (1.5 to 1.7) of the leachate due to the strong acidic buffering

capacity of the SBET fluids, but the leached Pb concentration varied drastically. The pH values of

the leachates decreased slightly with curing time and ISSA incorporation, which confirmed that

leaching of Pb was not only pH controlled due to the amphoteric nature of Pb. At the lowest pH,

Pb concentration was not solubility controlled but rather limited by the total Pb content in the S/S

soils according to the reported experimental investigations (Baltpurvins et al., 1996). For OPC

treated soils, the theoretical maximum leachable Pb concentrations were obtained based on SBET

tests, suggesting that the bioavailability risk was not reduced. While blending OPC with ISSA

could notably reduce the bioavailability risk compared to conventional OPC S/S treatment, and the

-1
risk decreased with ISSA incorporation. For S/S soils with 5000 mg kg Pb after 7 d of curing, the

-1
leached Pb concentration decreased from 51.60 to 39.01 mg L when replacement ratio of ISSA

increased from 20 to 50%. It can be deduced that some insoluble Pb containing compounds were

formed in the S/S process, or Pb in soils was tightly bonded on the surface of some minerals.

3.2.3 DTPA test

According to the literature, extraction by DTPA solution provides the prediction (on the high

side) of trace elements uptake by plants from soils (McLaughlin et al., 2000). The values and

ranges of DTPA-extractable Pb concentrations in the soils after S/S treatment are shown in Fig.

3(c). DTPA-extractable Pb in the soils was considerably lower after S/S treatments. Evanylo and

Sukkariyah (2006) reported a highly significant correlation between the DTPA-extractable

contents and the labile fraction of trace elements. Therefore, the results confirmed that the

leachable fraction of Pb and phyto-extractable Pb in soils was reduced after S/S treatments,

especially for the blended binder. The leached Pb concentrations decreased sharply with curing

-1
time, by 49.78% for S/S soils with 5000 mg kg Pb after 7 d of curing, which confirmed that the

effectiveness of S/S treated Pb contaminated soils by the blended binder. The pH values of the

leachates (Figure 3(f)) varied only a little (10.8412.12) for all the samples, decreasing slightly

with curing time and ISSA incorporation, indicating that leached Pb was likely pH controlled in

the high-alkaline scenarios.

3.3 Monolithic leaching results

Fig. 4 showed the variations in the leachate pH and Pb concentrations with the leaching time

-1
of the S/S treated 5000 mg kg Pb-spiked soils. The pH of the leachate increased during the initial

stage (0-2 d) and then remained steady and unchanged in the follow 2 d, but decreased sharply

with time afterwards. The pH values of the leachate for the soils treated by OPC only were the

highest, and the pH values decreased with the ISSA content in the binders. The average values of

the leachate pH ranged from 8.2 to 11.0.

 (a)
11.0
120 (b) H0
H0.2
10.5
100 H0.5

Pb concentration (g/l)
10.0
pH 80
9.5
H0 60
9.0 H0.2
H0.5
40
8.5

8.0 20
0 2 4 6 8 10 12 0 2 4 6 8 10 12

Time (d) Time (d)

Fig.4. Variation of leachate pH (a) and Pb concentration (b) with leaching time

The leached Pb concentrations in OPC treated soils were obviously higher than that of the

other treatments. In all the leachate of the OPC and ISSA treated samples, the Pb concentrations

-1
mainly ranged from 0.04 to 0.08 mg L , indicating a very low concentration even in prolonged

and repetitive leaching. The leached Pb in the leachate increased during the initial stage (0-2 d)

and then decreased slightly afterwards regardless of the S/S treatments. These variations may be

attributed to the physical durability of solidified matrix of the S/S soils (as monolithic materials)

in the prolonged leaching condition. Increasing the ISSA content in the binders led to a decrease

in the leached Pb concentrations. Therefore, ISSA in the S/S soils could reduce the mobility of Pb

due to the adsorption, encapsulation or precipitation effect in the solidified matrix.

1/2
Fig. 5 shows the change of CFL of Pb with t . Very low percentages (below 0.11%) of total

Pb were leached from all the samples over the 11 d. It was obvious that the leached Pb from

monolithic leaching was much lower than those of other leaching processes using crushed samples

due to the encapsulation effect in the solidified matrix and the less aggressive leachant used (DI

1/2
water). The plots of CFL-t for Pb of all the S/S samples were well-represented by linear lines

throughout the entire leaching time, indicating the leaching was mainly through diffusion.

Increasing the ISSA content in samples led to a decrease in CFL at a given leaching time and
16
 -12 2 -13
reduced the slope of the plots. The derived De for Pb decreased from 1.06*10 m /s to 5.69*10

2
m /s with ISSA incorporations from 0 to 50%. In accordance with Wastewater Technology Centre

(1991), the De was used for comparing the relative mobility of different contaminants. For De

-13 2
values below 10 m /s, the treatment was considered effective and the S/S treated wastes were

deemed appropriate for controlled utilization, i.e., quarry rehabilitation, lagoon closure, road

-13 2 -12 2
bases, etc. For De values between 10 m /s and 10 m /s, the S/S treated wastes could be

disposed of in segregated or sanitary landfills. It can be easily concluded that the S/S treated Pb

contaminated by OPC can be disposed of in segregated or sanitary landfills, while S/S treated soils

by the blended binder can be deemed appropriate for controlled utilization. This again

confirmed that the use of ISSA increased the effectiveness of the cement-based stabilization of Pb

contaminated soils.

H0
0.10
H0.2
H0.5
0.08 Linear Fit of CFL
Linear Fit of CFL
Linear Fit of CFL
CFL (%) 0.06

0.04
Equation y = a + b*x
Adj. R-Square 0.99771 0.99045 0.99315
Value Standard Error
CFL Intercept -0.00402 0.00107
0.02 CFL Slope 1.16305E-4 1.6093E-6
CFL Intercept -0.00541 0.00178
CFL Slope 9.44632E-5 2.67712E-6
CFL Intercept -0.00398 0.00136
CFL Slope 8.5115E-5 2.04056E-6
0.00
0 200 400 600 800 1000

t0.5 (s0.5)
Fig.5. Variation of CFL of Pb with leaching time

3.4 Fraction of Pb in S/S soils

The Pb speciation in the soils after S/S treatment for 7 and 28 d are shown in Fig. 6,

17

respectively. The amount of exchangeable Pb accounted for less than 1% of the total Pb in all the

samples. Most of the Pb in S/S soils was bound to carbonates (30-70%) and FeMn oxides (30-
60%), and Pb containing carbonate increased with Pb content in the tested soil, but FeMn oxides

phase decreased. This suggested that Pb may be present as lead carbonate minerals, such as

cerussite or hydrocerussite, or adsorbed on iron oxides which were abundant (34.9 g Fe 2O3/kg) in

the test soil, indicating that most of Pb had not entered the residual phase during the S/S process.

Furthermore, the carbonate phase of Pb in S/S soils decreased with ISSA content and curing time.

The S/S treatment with OPC and ISSA significantly decreased the amount of Pb associated with

carbonates and increased the amount of organic and residual Pb, which were hardly soluble,

reflecting that ISSA was effective to stabilize Pb in the soils. It is most likely that lead carbonate

minerals were transformed to more stable precipitates or insoluble compounds (Li et al., 2001;

Hettiarachchi et al, 2001).

(a) 110 F5 F4 F3 F2 F1 (b)110 F5 F4 F3 F2 F1

100 100
90 90
80 80
70 70
(%)

(%)

60 60
Fraction

Fraction

50 50
40 40
30 30
20 20
10 10
0 0
L0 L0.2 L0.5 M0 M0.2 M0.5 H0 H0.2 H0.5 L0 L0.2 L0.5 M0 M0.2 M0.5 H0 H0.2 H0.5

Fig.6. Fraction of Pb species in soils after S/S treatment for (a)7 d and (b) 28 d

It is evident that Pb associated with different operationally defined fractions was bound to

soils with varying binding strength. According to a widely recognized assumption that the first

two fractions of Pb in soil may be potentially labile (Singh et al., 2005), the leachable Pb from S/S

soils was significantly decreased with ISSA incorporation, reflecting that the leaching risk of Pb

18
spiked soils can be effectively mitigated by using ISSA.

3.5 Discussion

3.5.1 Probable immobilization mechanism of Pb

This study demonstrated that the ISSA could reduce the Pb leaching concentration in the S/S

treated soils based on several leaching tests. The findings can be partly attributed to the effect of

final pH of the leachate or specific minerals in the S/S soils on the stability of Pb. For Pb(II) the

2+ +
geochemical code Visual MINTEQ showed dissolved species in solution were Pb , PbOH ,

0 3 2+ +
Pb(OH)2 , and Pb(OH) . At low pH condition, Pb and PbOH was the dominant dissolved

-
Pb(II) species, but with the increase of pH, Pb(OH)2 and Pb(OH)3 were the main aqueous species

under the alkaline conditions encountered in cement-based soils (Li et al., 2001). It is clear that the

leaching of Pb was not fully pH controlled due to the fact that Pb leaching did not increase with a

decreasing pH for SBET samples. Also, a slightly decrease in pH of the leachate led to sharp

decrease in Pb concentration for the SPLP and DTPA tests. To illustrate the effect of ISSA on Pb

-1
stability, an adsorption test following that of Pan et al. (2003) was conducted, and 100 mg L Pb

solution was used in this test. According to the results presented in Table 3, Pb concentration in

solution decreased with ISSA incorporation due to the high adsorption capacity of ISSA, and Al

and Ca in solution increased with ISSA incorporation. Thus, it is likely that the Pb in solution was

absorbed by ISSA through ion exchange, which was confirmed by XRD results in Fig. 7.

Whitlockite was the main phosphate-based crystalline phase in ISSA, while lead phosphate

appeared after the reaction between ISSA and Pb in solution, which was mainly attributed to the

Pb substitution of Ca. A previous study also pointed out that cation exchange was one of the

19
primary mechanisms for copper removal since the ISSA exhibited significant CEC (Pan et al.,

2003). Furthermore, the hydrous silicon oxide, iron oxide and aluminum oxide on the surface of

ISSA can form complexes with Pb by chemical bonding (Huang and Rhoads, 1989). Considering

the relatively high concentration of Pb in these S/S materials, Pb may be adsorbed onto the oxide

phases in ISSA. However, the XRD patterns failed to show a distinct peak for the Pb containing

precipitate, most likely because the small amount of precipitates could not be detected by XRD.

Table 3 Leachate concentrations of Pb, Al and Ca in the adsorption test

-1
ISSA Leachate concentration (mg L )
incorporation
-1
Pb Al Ca
(g L )
10 0.057 0 51.254
20 0.008 0.337 82.496
*
50 DL 0.761 100.459
*: DL indicates detection limit.
Q
M 50 g L-1 10 g L-1
F F
Q LP
M WF
Q Q Q F

Q F
Q W Q
W LP
F LP W Q
Q Q

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Degree (2Theta)

Fig.7. XRD patterns of ISSA after adsorption test

(Q: Quartz; F: Feldspar strontian; M: Magnetite low; W: Whitlockite; LP: Lead Phosphate)

3.5.2 Microscopic characteristics of S/S soils

20
 H0

378

H0.5

L0.5

Fig.8. SEM micrographs of S/S soils and EDX spectra focused on the area within the square

The SEM micrographs for samples H0, H0.5 and L0.5 are shown in Fig. 8 after the 28 d of curing along with
EDS analysis to provide a semi-quantitative indication of the elemental compositions. The sample H0
consisted of some needle-like crystals of the hydration products,with a shape similar to ettringite (AFt). CSH
or CASH was apparent in the all S/S soils (as analyzed by EDS with significant quantities of Ca, Al and Si
present). The SEM micrographs showed the presence of some amorphous phases plus a porous network in
sample H0.5, which may be attributed to the ISSA incorporation (resulting in less gel formed by less cement)
and responsible for the low strength. The L0.5 showed a clear change in particle morphology with larger
agglomerations in a dense structure. The content of needle-like crystal (AFt) was low in L0.5, but a high
concentration of white globule of CSH was found in the matrix. The results of SEM-EDS analysis
corresponded to those of USC and XRD analysis. However, the SEM-EDS failed to show the Pb containing
compounds in the S/S soils, most likely because the relatively small content was not sufficient for detection.
But the dense network of hydration products in S/S soils facilitated the Pb immobilization through adsorption
and encapsulation (Shi and Fernandez-Jimenez, 2006; Ogundiran et al., 2013).
3.5.3 Comparison of Pb leaching characteristics between different leaching tests

-1
It was obvious that the extractable Pb contents (in terms of mg kg for comparison) followed the order
of SBET > DTPA> SPLP. This indicated that the bioavailability of Pb in S/S soils (via accidental ingestion of
soil particles or soil dust) was higher than other exposure pathways, and the acid rain-extractable Pb was the
lowest. The contrasting results obtained from various leachability tests were the result of the difference in
complexing ability and final pH of the leaching solutions that simulated different environmental conditions
and exposure scenarios. It seemed that the pH of leachate played a big role. The leached Pb from the
monolithic leaching test was much lower than that of other leaching tests using crushed samples. The
monolithic leaching results are more credible because it can better reflect the likely range of field conditions.
According to the total Pb content and the labile pool of Pb in S/S soils (i.e. the sum of the first three fractions),
the SBET results underestimated the effectiveness of S/S treatment if only the labile Pb was released.
Furthermore, it is likely SPLP can only extract the exchangeable Pb form and DTPA can extract exchangeable
and partly carbonate form. This difference between the Pb leachability determined with SPLP, SBET and
DTPA extraction suggested that the leaching results could only be interpreted under their own experimental
conditions.

3.5.4 Limitation and further work

In this laboratory study, a single soil artificially spiked with Pb and ISSA from Hong Kong was used, and the
results should be further validated by testing aged Pb contaminated soils. The S/S treatment should also be
conducted by different types of ISSA to provide practical management and recycling approach for ISSA.
Furthermore, further studies are suggested to increase the reactivity of ISSA through milling or acid-washing
pretreatment. Finally, in order to determine the chemical speciation and immobilization mechanism of Pb in
the S/S soils, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and other
techniques should be carried out.

4. Conclusions
This study investigated the effect of blending OPC with ISSA on Pb immobilization in S/S soils via a series of
leaching tests. The factors including binder formulation, Pb concentration and curing time on UCS and Pb
leaching characteristics of S/S soils were assessed. The Pb immobilization mechanism was revealed according
to the results of adsorption and XRD tests.Based on this study, the following conclusions can be drawn:

1. The UCS of all S/S soils stabilized by the blended binder fulfilled the acceptance criteria
of 1 MPa, and replacing of OPC by ISSA significantly reduced the UCS of the S/S soils due to the low
reactivity of ISSA. High concentrations of Pb increased the UCS of S/S soils due to the dissolution of the
aluminates and re-crystallisation of calcium aluminate hydrates.

2. Leached Pb content and pH of the leachate decreased with ISSA incorporation and curing time. The
extractable Pb contents followed the order of SBET > DTPA> SPLP test due to the difference in complexing
ability and final pH of the leaching solutions that simulated different environmental conditions and exposure
scenarios.

3. The leached Pb from monolithic leaching test was much lower than those of other leaching processes using
crushed samples due to the encapsulation effect in the solidified matrix. Pb leached out from the monolithic
sample mainly through diffusion, and increasing the ISSA content in the samples led to a decrease in diffusion
coefficient and increase in feasibility for controlled utilization.

4. The S/S treatment with OPC and ISSA significantly decreased the amount of Pb associated with carbonates
and increased the amount of organic and residual Pb, reflecting that the leaching risk of Pb spiked soils can be
effectively mitigated by ISSA.

5. Pb immobilization was attributed to the combined effect of adsorption, encapsulation or Pb phosphate

precipitation in the S/S matrix based on adsorption, SEM-EDS and XRD analysis, although these need to be
confirmed by further investigation.
Acknowledgements

The authors appreciate the financial support from the Hong Kong Research Grants Council (PolyU
152132/14E), and the Open Research Fund of State Key Laboratory of Geomechanics and Geotechnical
Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences (NO.Z015003).
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